Method for manufacturing recycled polyester resins

Abstract

The present invention provides a method for easily (simplely) or efficiently producing recycled polyester resins in which the reduction in molecular weight due to recycling (or regeneration) is suppressed (for example, recycled polyester resins exhibiting a molecular weight equal to or greater than that of virgin polyester resins). [Solution] A raw material polyester resin having ester bonds and / or carbonate ester bonds and not containing dicarboxylic acid units derived from terephthalic acid components is provided with a diol component (A d A depolymerization step in which the raw material polyester resin is partially depolymerized in the presence of a transesterification catalyst, A recycled polyester resin is produced by a method that includes a repolymerization step, in which the decomposition products obtained in the depolymerization step are polymerized to produce a recycled polyester resin. The aforementioned diol component (A d ) may contain at least a diol component (A) corresponding to the diol unit (A) in the raw material polyester resin.

Description

[Technical Field]

[0001] This disclosure relates to a method for producing recycled polyester resin (a method for recycling polyester resin) using a specific polyester resin having ester bonds and / or carbonate ester bonds as a raw material (raw material polyester resin). [Background technology]

[0002] Plastics are an indispensable material in modern society, but from the perspective of global warming, CO2 emissions during their manufacture and disposal have become a social problem, making recycling a crucial issue for reducing CO2 emissions. Generally, plastic recycling includes chemical recycling and material recycling.

[0003] Chemical recycling is a method of depolymerizing waste plastics by adding alcohol, acid, base, catalyst, etc., heating them, and then purifying and separating them to return them to monomer-level raw materials for reuse as plastic raw materials (Patent Documents 1-3).

[0004] Material recycling is a method of reusing materials without chemical treatment. For example, a method of melting waste plastics and molding them into a reusable form is known (Patent Document 4). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2000-169623 [Patent Document 2] Japanese Patent Publication No. 2001-294552 [Patent Document 3] Japanese Patent Publication No. 2022-085144 [Patent Document 4] Japanese Patent Publication No. 2022-130008 [Overview of the project] [Problems that the invention aims to solve]

[0006] In chemical recycling, waste plastics are depolymerized down to the raw material (monomer) level before being repolymerized, making it possible to produce high-quality recycled plastics (e.g., equivalent to virgin plastics).

[0007] However, chemical recycling generally requires not only depolymerization and repolymerization, but also the purification and separation of decomposition products obtained from depolymerization, resulting in more complex processes and lower productivity compared to material recycling. In particular, the purification and separation process tends to be extremely complicated in the chemical recycling of polyester resins composed of multiple (especially three or more) monomer components.

[0008] Furthermore, chemical recycling requires depolymerization under harsh conditions (high temperature, long reaction time, etc.) to break down materials to the monomer level. This not only requires a large amount of energy, but also makes it difficult to generate by-products due to the harsh conditions, making it difficult to recover all monomer components that make up waste plastics in the purification and separation process (resulting in a low recovery rate from waste plastics), thus making it difficult to effectively reduce the environmental burden.

[0009] On the other hand, in material recycling, such as in Patent Document 4, where waste plastics are melted and reshaped, depolymerization and purification / separation are unnecessary, allowing for the reuse of waste plastics through a simple process and making it easier to reduce the environmental burden.

[0010] However, in material recycling, the molecular weight decreases under the influence of heat (thermal history) applied during molding before recycling and melt molding during material recycling, and the resulting recycled products tend to be more prone to reductions in mechanical strength, changes in melt viscosity, and the like compared to virgin products. When the mechanical strength decreases, the product may not be reusable in the same applications as before recycling (the applicable uses will be limited). Furthermore, even if it can be used in the same applications, if the melt viscosity changes, it cannot be handled in the same manner as a virgin product, which not only necessitates resetting the molding conditions, but also, since the degree of deterioration of waste plastic is often not constant (the quality is not as stable as that of virgin plastic), it also becomes necessary to adjust or optimize the molding conditions each time recycling is performed, which can cause a reduction in productivity. That is, although material recycling is a simple recycling method, it tends to be difficult to produce recycled plastics that exhibit physical properties (or performance) equivalent to those of virgin plastics, and in particular, unlike the alicyclic structure-containing polymer (COP resin) described in Patent Document 4, the above tendency becomes even more pronounced for polyester resins, as their molecular weight (and physical properties or performance) is more likely to further decrease due to hydrolysis.

[0011] As described above, it has been difficult to achieve both high quality of recycled plastic and simplicity of the recycling method.

[0012] Accordingly, an object of the present disclosure is to provide a method for easily (simply) or efficiently producing a recycled polyester resin in which the decrease in molecular weight due to recycling (or regeneration) is suppressed (for example, a recycled polyester resin exhibiting a molecular weight equal to or higher than that of a virgin polyester resin). [Means for Solving the Problems]

[0013] The present inventors recognized that in order to produce high-quality recycled polyester resin through chemical recycling, the raw material polyester resin must be completely depolymerized (decomposed down to the monomer level). As a result of extensive studies to achieve the aforementioned object, the inventors conceived that even if depolymerization is incomplete (i.e., limited to depolymerization up to the oligomer level, for example, a molecular weight of about 1000 or more), and even if subsequent steps such as the separation and purification step after depolymerization are omitted and simplified, a high-quality recycled polyester resin can be obtained in the repolymerization step. Based on this concept, the present inventors further conducted extensive studies, and as a result, when depolymerizing a raw material polyester resin that does not contain a specific structural unit by a predetermined method, even if the depolymerization is only partial and the product is supplied to the repolymerization step, the inventors found that a recycled polyester resin in which the decrease in molecular weight due to recycling is suppressed (for example, a recycled polyester resin exhibiting a molecular weight equal to or higher than that of virgin polyester resin) can be produced easily or efficiently, and completed the present invention (or the present disclosure). That is, the present disclosure may include the following aspects and the like.

[0014] Aspect [1]: A raw material polyester resin having an ester bond and / or a carbonate bond and containing no dicarboxylic acid unit derived from a terephthalic acid component, to which a diol component (A d ) is added, and the raw material polyester resin is partially depolymerized in the presence of a transesterification catalyst; and a repolymerization step of polymerizing the decomposition product obtained in the depolymerization step to produce a recycled polyester resin. A method for producing a recycled polyester resin.

[0015] Aspect [2]: The diol component (A d ) at least comprises a diol component (A) corresponding to the diol unit (A) in the raw material polyester resin. The production method according to aspect [1].

[0016] Aspect [3]: The raw material polyester resin at least has an ester bond, and The production method according to aspect [1] or [2], wherein the diol unit (A) forming the raw material polyester-based resin comprises at least one diol unit selected from the diol unit (A1) represented by the following formula (A-1), the diol unit (A2) represented by the following formula (A-2), and the diol unit (A3) represented by the following formula (A-3).

[0017]

Chemical Formula

[0018] (In the formula, R 1 represents a substituent, m1 represents an integer of 0 to 8, Z 1a and Z 1b each independently represent an arene ring, R 2a and R 2b each independently represent a substituent, m2a and m2b each independently represent an integer of 0 or more, A 1a and A 1b each independently represent an alkylene group, and n1a and n1b each independently represent an integer of 0 or more.)

[0019]

Chemical Formula

[0020] (In the formula, A 2 represents an alkylene group, and n2 represents an integer of 1 or more.)

[0021]

Chemical Formula

[0022] (In the formula, Y 1 represents a direct bond, an optionally halogenated divalent hydrocarbon group, an oxygen atom, a carbonyl group, a sulfur atom or a sulfonyl group, Z 2a and Z 2b each independently represent an arene ring, R3a and R 3b each independently represent a substituent, m3a and m3b each independently represent an integer of 0 or more, A 3a and A 3b each independently represent an alkylene group, and n3a and n3b each independently represent an integer of 0 or more.)

[0023] Aspect [4]: The raw material polyester-based resin has at least an ester bond, and The production method according to any one of Aspects [1] to [3], wherein in the depolymerization step, a dicarboxylic acid component (B) corresponding to the dicarboxylic acid unit (B) in the raw material polyester-based resin is further added.

[0024] Aspect [5]: The raw material polyester-based resin has at least an ester bond, and The production method according to any one of Aspects [1] to [4], wherein the dicarboxylic acid unit (B) forming the raw material polyester-based resin comprises at least one dicarboxylic acid unit selected from the group consisting of a dicarboxylic acid unit (B1) represented by the following formula (B-1), a dicarboxylic acid unit (B2) represented by the following formula (B-2), and a dicarboxylic acid unit (B4) represented by the following formula (B-4).

[0025]

Chemical Formula

[0026] (wherein R 4 represents a substituent, m4 represents an integer of 0 to 8, A 4a and A 4b each independently represent an alkylene group.)

[0027]

Chemical Formula

[0028] (wherein Z 3 represents a polycyclic arene ring, R 5 (where represents a substituent, and m5 represents a non-negative integer.)

[0029] [ka]

[0030] (In the formula, W 1 It shows an aliphatic hydrocarbon ring, A 5a and A 5b These independently show either a direct bond or an alkylene group. R 7 (where represents a substituent, and m7 represents a non-negative integer.)

[0031] Appearance [6]: The aforementioned raw material polyester resin has at least ester bonds, The aforementioned diol component (A d A method for producing a product according to any one of embodiments [1] to [5], wherein the product comprises at least an alkylene glycol component (E).

[0032] Appearance [7]: The aforementioned raw material polyester resin has at least a carbonate ester bond, and The manufacturing method according to any one of embodiments [1] to [6], wherein the diol unit (A) forming the raw material polyester resin includes at least one diol unit selected from the diol unit (A1) and the diol unit (A3).

[0033] Appearance [8]: The aforementioned raw material polyester resin has at least a carbonate ester bond, The manufacturing method according to any one of embodiments [1] to [7], wherein at least a carbonate bond-forming component (C) is added in the depolymerization step and / or the repolymerization step.

[0034] Appearance [9]: When the ratio of a predetermined constituent unit to the total constituent units of the raw polyester resin is X1 [mol%], and the ratio of the predetermined constituent unit to the total constituent units of the recycled polyester resin is X2 [mol%], The manufacturing method according to any one of embodiments [1] to [8], wherein the absolute value [mol%] of X2-X1 is 15 [mol%] or less for all constituent units.

[0035] Appearance

[10] : In the recycled polyester resin and the raw material polyester resin, The absolute value of the difference in refractive index nD is 0.005 or less. The manufacturing method according to any one of embodiments [1] to [9], wherein the absolute value of the difference in Abbe numbers is 0.5 or less.

[0036] Appearance

[11] : The manufacturing method according to any one of embodiments [1] to

[10] , wherein the ratio of the raw material polyester resin to the recycled polyester resin is 95% by mass or less.

[0037] Appearance

[12] : The manufacturing method according to any one of embodiments [1] to

[11] , wherein the decomposition product obtained in the depolymerization step is subjected to the repolymerization step without purification.

[0038] Appearance

[13] : The manufacturing method according to any one of embodiments [1] to

[12] , wherein the weight-average molecular weight Mw of the decomposition product obtained in the depolymerization step is 5000 or more.

[0039] Furthermore, this disclosure may achieve the following secondary objectives (solve the following secondary problems).

[0040] In other words, another object of this disclosure is to provide a method for easily and efficiently producing recycled polyester resins that exhibit physical properties (e.g., heat resistance such as glass transition temperature, optical properties such as refractive index, Abbe number, and birefringence, molecular weight, etc.) comparable to those of pre-depolymerization (or virgin) polyester resins, even with a high recycling rate (even if a large proportion of the yield of recycled polyester resins originates from or is attributable to the raw polyester resin).

[0041] Another object of this disclosure is to provide a method for easily or efficiently producing a recycled polyester resin that has a composition similar to that of the pre-depolymerized (or virgin) polyester resin, even if the polyester resin is formed from multiple (particularly three or more) monomer components.

[0042] In this specification and in the claims, "diol unit," "constituent unit derived from a diol component," etc., refer to a unit (or divalent group) obtained by removing a hydrogen atom from each of the two hydroxyl groups of the corresponding diol, and "diol component" (including compounds exemplified as diol components) may be used synonymously with the corresponding "diol unit."

[0043] Similarly, terms such as "dicarboxylic acid unit" and "constituent unit derived from a dicarboxylic acid component" refer to the unit (or divalent group) obtained by removing the OH (hydroxyl group) from each of the two carboxyl groups of the corresponding dicarboxylic acid. "Dicarboxylic acid component" (including compounds exemplified as dicarboxylic acid components) is sometimes used synonymously with the corresponding "dicarboxylic acid unit."

[0044] The term "dicarboxylic acid component" is used to mean a component that includes not only dicarboxylic acid but also derivatives that can be used as polymerization components, such as ester-forming derivatives. Examples of ester-forming derivatives of dicarboxylic acid include dicarboxylic acid esters, acid halides, and acid anhydrides. The ester may be a monoester (half-ester) or a diester. In the method of this disclosure, the dicarboxylic acid component is preferably a dicarboxylic acid ester.

[0045] Examples of the dicarboxylic acid ester include alkyl dicarboxylic acid esters, particularly lower alkyl esters, specifically methyl esters, ethyl esters, t-butyl esters, etc. 1-4 Examples include alkyl esters. Examples of the dicarboxylic acid halide include acid chlorides and acid bromides.

[0046] Furthermore, in this specification and the claims, for convenience, the same reference numerals are used for predetermined constituent units of polyester resins (diol units, dicarboxylic acid units, etc.) and the polymerization components (diol components, dicarboxylic acid components, etc.) corresponding to those constituent units (for forming the constituent units). For example, "diol unit (A)" and "diol component (A)", "dicarboxylic acid unit (B)" and "dicarboxylic acid component (B)", "diol unit (A1)" and "diol component (A1)", etc.

[0047] In this specification and the claims, the number of carbon atoms in a substituent is defined as C1, C6, C 10 These are sometimes used to indicate this. For example, an alkyl group with 1 carbon atom is called a "C1 alkyl group," and an aryl group with 6 to 10 carbon atoms is called a "C1 alkyl group." 6-10 It is sometimes referred to as an "aryl group," etc.

[0048] Furthermore, in this specification and the claims, “independently” means that multiple components are independent components, for example, Z 1a and Z 1bIn this case, it means that the arene rings may be the same as the other arene rings, or they may be different arene rings.

[0049] Furthermore, in this specification and the claims, the numerical range indicated by "X~Y" may include the numerical values ​​X and Y. [Effects of the Invention]

[0050] According to this disclosure, it is possible to provide a method for easily (simplely) or efficiently producing recycled polyester resins in which the reduction in molecular weight due to recycling (or regeneration) is suppressed (for example, recycled polyester resins exhibiting a molecular weight equal to or greater than that of virgin polyester resins). [Modes for carrying out the invention]

[0051] The method of this disclosure makes it possible to easily and efficiently produce recycled polyester resins that exhibit physical properties (e.g., heat resistance such as glass transition temperature, optical properties such as refractive index, Abbe number, and birefringence, molecular weight, etc.) comparable to those of the polyester resin before depolymerization (or virgin), even with a high recycling rate (even if a large proportion of the yield of recycled polyester resin originates from or is caused by the raw polyester resin). Furthermore, the method of this disclosure also makes it possible to easily and efficiently produce recycled polyester resins formed with a composition comparable to that of the polyester resin before depolymerization (or virgin), even if the polyester resin is formed from multiple (especially three or more) monomer components.

[0052] In other words, the method for producing recycled polyester resins (or the method for recycling polyester resins) of the present disclosure involves adding a diol component (A) to a specific raw material polyester resin having ester bonds and / or carbonate ester bonds in its main chain. d The process includes a depolymerization step in which a raw material polyester resin is partially depolymerized by adding a transesterification catalyst, and a repolymerization step in which the decomposition products obtained in the depolymerization step are polymerized to produce a regenerated polyester resin.

[0053] In addition, the type or composition (and composition ratio) of the raw polyester resin in the depolymerization step and the recycled polyester resin prepared in the repolymerization step do not necessarily have to be the same [that is, desired polymerization components (additional or supplementary monomer components) may be added in the depolymerization step and / or repolymerization step to regenerate a polyester resin with a different composition (and composition ratio) of constituent units]. However, the method of this disclosure not only suppresses the decrease in molecular weight due to recycling (regeneration), but also makes it easier to regenerate to a composition or physical properties equivalent to that of virgin polyester resin (unused or new polyester resin). Therefore, it is preferable to regenerate to a polyester resin that is substantially the same as or of the same type (same system) as the raw polyester resin (or virgin polyester resin).

[0054] Therefore, it is preferable that the recycled polyester resin obtained in the repolymerization process is substantially identical to the polyester resin disclosed in the section [Raw Material Polyester Resin] below, including preferred embodiments, in terms of the types of constituent units and their composition ratios, representative resins (combinations of representative constituent units), physical properties, etc.

[0055] Furthermore, even when additional or supplementary monomer components are added in the depolymerization and / or repolymerization steps, it is preferable that the composition (and composition ratio) of the additional or supplementary monomer components be substantially the same as the composition (and composition ratio) of the constituent units in the raw polyester resin. That is, it is preferable that the composition (and composition ratio) of the additional monomer components be substantially the same as the types and composition ratios of each constituent unit disclosed in the [Raw Polyester Resin] section below, including preferred embodiments.

[0056] [Raw material: polyester resin] The raw material polyester resin (or waste polyester resin) is a polyester resin that has ester bonds [-C(=O)-O-] and / or carbonate ester bonds [-OC(=O)-O-] (or carbonate bonds) in its main chain, and does not contain dicarboxylic acid units (or terephthalic acid units) derived from terephthalic acid components.

[0057] The polyester resin may have a branched chain structure, but it is preferably a melt-mold polyester resin (linear or non-three-dimensional network polyester resin), and more preferably a linear (linear) polyester resin.

[0058] Examples of polyester resins include polyester resins containing ester bonds, polycarbonate resins (polycarbonate resins) containing carbonate ester bonds, and polyester carbonate resins containing ester bonds and carbonate ester bonds. Polyester resins can be used alone or in combination of two or more types. Preferred polyester resins are polyester resins and polycarbonate resins [for example, polycarbonate resins containing diol units (A) and carbonate units (C) described later], and more preferably polyester resins, and particularly preferably polyester resins containing at least diol units (A) and dicarboxylic acid units (B) described later, as they make it easier to produce recycled polyester resins that exhibit substantially the same physical properties as virgin polyester resins.

[0059] Typical constituent units for forming polyester resins include diol units (A), dicarboxylic acid units (B), and carbonate units (C), with polyester resins containing at least diol units (A) being preferred.

[0060] (Diol unit (A)) The diol unit (A) is not particularly limited as long as it is a constituent unit derived from a diol, but it is preferable to include at least one selected from the diol units (A1), (A2), and (A3) described later. In the case of a polyester resin (especially a polyester resin) having at least an ester bond in its main chain, it is more preferable to include at least one selected from diol units (A1) and (A2), even more preferable to include at least diol unit (A2), and particularly preferable to include both diol units (A1) and (A2). Furthermore, in the case of a polyester resin (especially a polycarbonate resin) having at least a carbonate ester bond in its main chain, it is even more preferable to include at least one selected from diol units (A1) and (A3) [for example, at least diol unit (A1)].

[0061] Diol unit (A1) The diol unit (A1) is a diol unit represented by the following formula (A-1).

[0062] [ka]

[0063] (In the formula, R 1 represents a substituent, and m1 represents an integer from 0 to 8. Z 1a and Z 1b These independently show an arene ring, R 2a and R 2b m2a and m2b independently represent substituents, and m2a and m2b independently represent integers greater than or equal to 0. A 1a and A 1b (Independently, n1a represents an alkylene group, and n1b independently represents a non-negative integer.)

[0064] In the above formula (A-1), R 1 The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 1Examples of substituents represented by [-OR] include halogen atoms, hydrocarbon groups, and groups. h ](where R h (represents a hydrocarbon group), group [-SR h ](where R h ( indicates a hydrocarbon group), acyl group [-C(=O)-R h ](where R h Examples include hydrocarbon groups, nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups).

[0065] In this specification and in the claims, R h The hydrocarbon groups represented by each symbol represent independent hydrocarbon groups, which may be identical or different from one another.

[0066] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0067] Hydrocarbon group (or R h ) may be a saturated or unsaturated hydrocarbon group, an aliphatic (including alicyclic) or aromatic hydrocarbon group, and a hydrocarbon group with a linear (linear or branched) or cyclic structure, or a combination of linear and cyclic structures. Note that the hydrocarbon group (or R) h The number of carbon atoms constituting the group is not particularly limited, but may be as low as 20, for example, and preferably in the following order: 1-16, 1-12, 1-10, 1-8, 1-6. Typical hydrocarbon group (or R h Examples of these groups include alkyl groups, cycloalkyl groups, aryl groups, and groups formed by combining two or more of these hydrocarbon groups.

[0068] Examples of alkyl groups (linear or branched alkyl groups) include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1-10 Examples include alkyl groups, preferably C 1-6 Alkyl alkyl groups, more preferably C 1-4 It is an alkyl group.

[0069] Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and other C groups. 5-10 Examples include cycloalkyl groups.

[0070] Examples of aryl groups include phenyl, biphenylyl, and naphthyl groups. 6-12 Examples include aryl groups.

[0071] Examples of groups formed by combining two or more hydrocarbon groups include alkylcycloalkyl groups (e.g., mono or tri-C). 1-4 Alkyl-C 3-10 Cycloalkyl groups, etc.), cycloalkylalkyl groups (for example, C 3-10 Cycloalkyl-C 1-4 Alkyl groups, alkylaryl groups [for example, mono or tri-C groups such as methylphenyl (or tolyl) group, dimethylphenyl (or xylyl) group] 1-4 Alkyl-C 6-12 [Aryl groups, etc.], Aralkyl groups [e.g., benzyl group, phenethyl group, etc.] C 6-12 Aryl-C 1-4 Alkyl alkyl groups, etc., alkylarylalkyl groups [for example, mono or triC] 1-4 Alkyl-C 6-12 Aryl-C 1-4 Examples include alkyl groups, etc.

[0072] The group [-OR h ], base [-SR h ] and acyl group [-C(=O)-R h In ], R h As a hydrocarbon group represented by R 1 Examples include hydrocarbon groups similar to those exemplified above, including preferred embodiments.

[0073] Examples of substituted amino groups (mono- or disubstituted amino groups) include mono- or dialkylamino groups, mono- or diacylamino groups, etc. Examples of mono- or dialkylamino groups include mono- or dialkylamino groups such as mono- or dimethylamino groups. 1-4 Examples include alkyl)amino groups. Mono or diacylamino groups include mono or diacetylamino groups, etc. 1-7 Examples include acyl(amino) groups.

[0074] Typical R 1 Examples include halogen atoms, hydrocarbon groups (e.g., alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, aralkyl groups, etc.), and groups [-OR h Examples include C11 (alkoxy group, etc.) and acyl group, and preferably hydrocarbon groups such as alkyl groups, aryl groups, and alkylaryl groups. Examples of alkyl groups (linear or branched alkyl groups) include C11, methyl group, ethyl group, t-butyl group, etc. 1-6 Examples include alkyl groups, such as methyl groups and C 1-4 Alkyl groups are preferred. Examples of aryl groups include C such as phenyl groups. 6-10 Examples include aryl groups. Alkylaryl groups include mono- or tri-C groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl) groups. 1-4 Alkyl-C 6-10 Examples include aryl groups.

[0075] R 1 The number of substitutions m1 is an integer from 0 to 8, for example, an integer from about 0 to 6, preferably in stages from 0 to 4, then from 0 to 2, more preferably 0 or 1, and especially 0. Note that if m1 is 2 or more, then 2 or more R 1 The types may be the same or different from each other. Also, of the two benzene rings that form the fluorene skeleton, both benzene rings may have R 1 If substitution occurs, then the R of one of the benzene rings 1 The type and the R of the other benzene ring 1The types of may be the same as or different from each other. In addition, R 1 The substitution position of is not particularly limited, and may be, for example, 2-position, 3-position, 2,7-position, etc.

[0076] Z 1a or Z 1b Examples of the arene ring (aromatic hydrocarbon ring) represented by include monocyclic arene rings such as benzene ring, polycyclic arene rings, and the like. Examples of the polycyclic arene ring include condensed polycyclic arene rings (condensed polycyclic aromatic hydrocarbon rings), ring-assembled arene rings (ring-assembled aromatic hydrocarbon rings), and the like.

[0077] Examples of the condensed polycyclic arene ring include condensed bi- to tetracyclic arene rings such as condensed bicyclic arene rings and condensed tricyclic arene rings. Examples of the condensed bicyclic arene ring include condensed bicyclic C such as naphthalene ring and indene ring 9-16 arene rings and the like. Examples of the condensed tricyclic arene ring include condensed tricyclic C such as anthracene ring and phenanthrene ring 14-20 arene rings and the like. A preferable condensed polycyclic arene ring is a condensed polycyclic C such as naphthalene ring 10-14 arene ring.

[0078] Examples of the ring-assembled arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring and binaphthyl ring; terarene rings such as terphenyl ring, and the like. A preferable ring-assembled arene ring is a bi- or ter-arene ring, more preferably a biarene ring, particularly preferably a C such as biphenyl ring 12-18 biarene ring.

[0079] In the present specification and claims, the term "ring-assembled arene ring" means a structure in which two or more ring systems (arene ring systems) are directly connected via a single bond or a double bond, and the number of bonds directly connecting the rings is one less than the number of the ring systems. For example, as described above, a phenylnaphthalene ring, a binaphthyl ring and the like are classified as ring-assembled arene rings even if they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as a naphthalene ring (non-ring-assembled arene ring).

[0080] Z 1a , Z 1b Preferable arene rings represented by are C such as benzene ring, naphthalene ring, biphenyl ring and the like 6-12 arene rings, more preferably C such as benzene ring, naphthalene ring and the like 6-10 arene rings, particularly preferably benzene ring. Z 1a and Z 1b may be the same or different from each other, and are preferably the same as each other.

[0081] The substitution position (bonding position) of Z bonded to the 9-position of the fluorene ring 1a and Z 1b is not particularly limited. For example, when Z 1a , Z 1b is a benzene ring, the position may be any position; when Z 1a , Z 1b is a naphthalene ring, the position is either the 1-position (1-naphthyl) or the 2-position (2-naphthyl), preferably the 2-position; when Z 1a , Z 1b is a biphenyl ring, the position is any one of the 2-position, 3-position and 4-position, preferably the 3-position.

[0082] R 2a or R 2b The substituent represented by may be a non-reactive group (or non-polymerizable group) that is inert to the reaction. Examples of the substituent represented by R 2a , R 2b include, for example, R in the above formula (A-1) 1Examples of groups similar to the one exemplified, including preferred embodiments, include R. 2a ,R 2b Typical substituents represented include halogen atoms, hydrocarbon groups, and groups [-OR h Examples include alkoxy groups, acyl groups, nitro groups, cyano groups, substituted amino groups, and preferably hydrocarbon groups such as alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, alkylaryl groups, aralkyl groups, and alkoxy groups (linear or branched alkoxy groups). h Examples include ], and more preferably C such as a methyl group. 1-6 C such as alkyl groups and cyclohexyl groups 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 Mono- or tri-C groups such as aryl groups, methylphenyl groups (or tolyl groups), and dimethylphenyl groups (or xylyl groups) 1-4 Alkyl-C 6-12 C such as aryl groups and methoxy groups 1-4 Examples include alkoxy groups. Among these, hydrocarbon groups such as alkyl groups, aryl groups, and alkylaryl groups are preferred, and in particular alkyl groups (such as methyl groups) are preferred. 1-4 Alkyl groups, etc., aryl groups (such as phenyl groups, etc.) 6-10 (An aryl group, etc.) is preferred. 2a and R 2b The types may be the same or different from each other. Also, R 2a ,R 2b When R is an aryl group, 2a ,R 2b These are Z 1a ,Z 1b They may form a ring-assembled arene ring together.

[0083] R 2a ,R 2b The number of substitutions m2a and m2b can each be any integer greater than or equal to 0, Z 1a ,Z 1bThe type can be appropriately selected, for example, it may be an integer of about 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, even more preferably 0 or 1, and especially 0. m2a and m2b may be different from each other, but it is preferable that they be the same. Also, if m2a is 2 or more, then 2 or more R 2a The types may be the same or different from each other; if m2b is 2 or more, then 2 or more R 2b The types may be the same as or different from each other.

[0084] R 2a ,R 2b The substitution position of Z is not particularly restricted, 1a ,Z 1b In this, the bond position with the 9-position of the fluorene ring, and the group [-O-(A 1a O) n1a -],[-O-(A 1b O) n1b Any position other than the bond site with the ether bond [-O-] (i.e., the ether bond [-O-] that forms the main chain), for example, Z 1a ,Z 1b The ether bond [-O-] in the above-mentioned compound may be substituted at the ortho position (the carbon atom adjacent to the bonding position of the ether bond).

[0085] A 1a Or A 1b Examples of alkylene groups (linear or branched alkylene groups) represented by this symbol include ethylene, propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, and tetramethylene groups. 2-6 Examples include alkylene groups, preferably C 2-4 C such as an alkylene group, more preferably an ethylene group, a propylene group, etc. 2-3 Alkylene groups, particularly ethylene groups, are preferred. Also, A 1a and A 1b The types may be the same or different from each other, but it is preferable that they be the same.

[0086] [-(A 1a O)-] or [-(A1b The number of repeating alkylene oxy groups represented by [O)-], n1a and n1b, are each 0 or greater, and may be selected from integers of approximately 0 to 15, preferably in the following increments: integers from 0 to 10, integers from 0 to 8, integers from 0 to 6, integers from 0 to 4, integers from 0 to 2, and more preferably 0 or 1. Furthermore, if the number of repeating groups n1a and / or n1b is 1 or greater, (especially in the case of polyester resins) polymerization reactivity is easily improved, and may be selected from integers of approximately 1 to 15, preferably in the following increments: integers from 1 to 10, integers from 1 to 8, integers from 1 to 6, integers from 1 to 4, integers from 1 to 3, and more preferably 1 or 2, with 1 being particularly preferred. In this specification and in the claims, "number of repeating groups (number of added moles)" may be an average value (arithmetic mean) or average number of added moles. Therefore, n1a and n1b may be selected from a range of approximately 0 to 15, preferably in the following increments: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1, or they may be selected from a range of approximately 1 to 15, preferably in the following increments: 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1 to 2. When n1a and n1b are within a moderate range that is not too large, it tends to be easier to suppress the decrease in refractive index and heat resistance.

[0087] Furthermore, n1a and n1b may be the same or different from each other. If n1a is 2 or more, then 2 or more alkylene oxy groups [-(A 1a The types of O)-] may be different from each other, but are preferably the same; if n1b is 2 or more, 2 or more alkylene oxy groups [-(A 1b The types of O)-] may be different from each other, but it is preferable that they be the same.

[0088] Base [-O-(A 1a O) n1a -],[-O-(A 1b O) n1b -] (i.e., the ether bond forming the main chain) 1a ,Z 1b The substitution position (bonding position) for Z is not particularly limited,1a ,Z 1b You just need to substitute them in the appropriate positions. Base [-O-(A 1a O) n1a -],[-O-(A 1b O) n1b -] of Z 1a ,Z 1b The substitution position for Z is Z 1a ,Z 1b If is a benzene ring, it is preferable to substitute at one of the positions of the phenyl group bonded to the 9-position of the fluorene ring, either the 2-position, 3-position, or 4-position, particularly the 3-position or 4-position, especially the 4-position. Also, Z 1a ,Z 1b When is a naphthalene ring, substitution often occurs at one of the 5-8 position positions of the naphthyl group bonded to the 9-position of the fluorene ring. For example, the 1- or 2-position of the naphthalene ring is substituted for the 9-position of the fluorene ring (substitution in the relationship of 1-naphthyl or 2-naphthyl), and it is preferable that this substitution occurs in the relationship of 1,5-position, 2,6-position, and especially the relationship of 2,6-position. Also, Z 1a ,Z 1b If the ring set is an allene ring, then the base [-O-(A 1a O) n1a -],[-O-(A 1b O) n1b The substitution position of -] is not particularly limited; for example, it may be substituted on an arene ring bonded to the 9-position of fluorene or on an arene ring adjacent to this arene ring. For example, Z 1a ,Z 1b is a biphenyl ring (or Z 1a ,Z 1b is a benzene ring, m2a and m2b are 1, R 2a ,R 2b In the case of a phenyl group, it is preferable that the 3-position of the biphenyl ring is bonded to the 9-position of fluorene, and the 6-position of the biphenyl ring is bonded to the group [-O-(A 1a O) n1a -],[-O-(A 1b O) n1b It is preferable to combine it with -].

[0089] A typical diol unit (A1) is, in the above formula (A-1), R 1 is a halogen atom, hydrocarbon group, group [-OR h ] represents an acyl group, nitro group, cyano group, or substituted amino group, and m1 represents an integer from 0 to 4. Z 1a and Z 1b These are independently C2 rings such as benzene rings, naphthalene rings, and biphenyl rings. 6-12 Showing an arene ring, R 2a and R 2b These are independently halogen atoms, hydrocarbon groups, and groups [-OR h ] represents an acyl group, nitro group, cyano group, or substituted amino group, and m2a and m2b independently represent integers from 0 to 4. A 1a and A 1b C is independent 2-6 Examples include a constituent unit that represents an alkylene group, where n1a and n1b independently represent integers from 0 to 10;

[0090] Preferably, R 1 is a hydrocarbon group (e.g., C 1-10 hydrocarbon group, preferably C 1-7 (Hydrogen group) is shown, and m1 is an integer from 0 to 3. Z 1a and Z 1b These are independently C2 rings such as benzene rings, naphthalene rings, and biphenyl rings. 6-12 Showing an arene ring, R 2a and R 2b These are independently hydrocarbon groups (e.g., C 1-10 hydrocarbon group, preferably C 1-7 (Hydrogen group) is represented, and m2a and m2b independently represent integers from 0 to 3. A 1a and A 1b C is independent 2-4 The constituent units include those that represent an alkylene group, where n1a and n1b independently represent integers from 0 to 6;

[0091] More preferably, R 1 is C 1-6Alkyl or C 6-10 It represents an aryl group such as an aryl group, and m1 represents an integer from 0 to 2. Z 1a and Z 1b These are independently C2 rings such as benzene rings and naphthalene rings. 6-10 Showing an arene ring, R 2a and R 2b C is independent 1-6 Alkyl or C 6-10 It represents an aryl group such as an aryl group, and m2a and m2b independently represent integers from 0 to 2. A 1a and A 1b These are independently C groups such as ethylene or propylene. 2-3 The constituent units include those that represent an alkylene group, where n1a and n1b independently represent integers from 0 to 2;

[0092] Particularly preferred, R 1 is C 1-4 It represents an alkyl group, and m1 represents an integer from 0 to 2 (especially 0). Z 1a and Z 1b These independently represent a benzene ring or a naphthalene ring. R 2a and R 2b These are independently C groups such as methyl groups. 1-4 Representing an alkyl group or a phenyl group, m2a and m2b independently represent integers from 0 to 2 (preferably 0 or 1, especially 0), A 1a and A 1b The constituent units include one in which represents an ethylene group, and n1a and n1b independently represent 0 or 1 (especially 1).

[0093] Specific diol components (A1) that form the diol unit (A1) include, for example, 9,9-bis(hydroxyaryl)fluorenes in formula (A-1) where n1a and n1b are 0; and 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes where n1a and n1b are 1 or more, for example, about 1 to 10.

[0094] In this specification and in the claims, unless otherwise specified, "(poly)alkoxy" is used to mean both alkoxy groups and polyalkoxy groups.

[0095] Examples of 9,9-bis(hydroxyaryl)fluorenes include 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)fluorene, 9,9-bis(aryl-hydroxyphenyl)fluorene, and 9,9-bis(hydroxynaphthyl)fluorene.

[0096] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene.

[0097] Examples of 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, and other 9,9-bis[(mono or di)C 1-4 Examples include alkyl-hydroxyphenyl fluorene.

[0098] Examples of 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-diphenylphenyl)fluorene, and other 9,9-bis[(mono or di)C 6-10 Examples include aryl-hydroxyphenyl fluorene.

[0099] Examples of 9,9-bis(hydroxynaphthyl)fluorene include 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene.

[0100] Examples of 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes include 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene, and 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene.

[0101] Examples of 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, and other 9,9-bis[hydroxy(mono or deca)C 2-4 Examples include alkoxyphenyl fluorene.

[0102] Examples of 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)-3,methylphenyl]fluorene, and other 9,9-bis[(mono or di)C 1-4 Alkyl-hydroxy(mono or deca)C 2-4 Examples include alkoxyphenyl fluorene.

[0103] Examples of 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)-3-phenylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-diphenylphenyl]fluorene, and other 9,9-bis[(mono or di)C 6-10 Aryl-hydroxy(mono or deca)C 2-4 Examples include alkoxyphenyl fluorene.

[0104] Examples of 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene, etc. 2-4 Examples include alkoxy-naphthyl fluorene.

[0105] The diol unit (A1) may be used alone or in combination of two or more types. Preferred diol units (A1) include constituent units derived from 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes, such as 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene and 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene. 6-12 Examples include constituent units derived from arylfluorene; more preferably 9,9-bis[hydroxy(mono or penta)C 2-4 9,9-bis[hydroxy(mono or deca)alkoxyphenyl]fluorene, such as 9,9-bis[hydroxy(mono or deca)alkoxyphenyl]fluorene, 9,9-bis[hydroxy(mono or deca)alkoxynaphthyl]fluorene, such as 9,9-bis[hydroxy(mono or deca)alkoxyC 6-12 Examples of constituent units derived from aryl fluorene include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[(mono or di)C 2-3 9,9-bis[hydroxy(mono or di)C]fluorene, such as alkoxyphenyl]fluorene and 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene. 2-3 Constituent units derived from alkoxy-naphthyl fluorene are preferred.

[0106] Diol unit (A2) The diol unit (A2) is a diol unit represented by the following formula (A-2).

[0107] [ka]

[0108] (In the formula, A 2 (where n2 represents an alkylene group, and n2 represents an integer greater than or equal to 1.)

[0109] In the above formula (A-2), A 2 Examples of alkylene groups (linear or branched alkylene groups) represented by include ethylene, propylene, trimethylene, 1,2-butanediyl, 1,3-butanediyl, tetramethylene, 1,5-pentanediyl, 1,6-hexanediyl, 1,8-octanediyl, and 1,10-decanediyl groups. 2-12 Examples include alkylene groups, preferably in the following steps, C 2-10 Alkylene group, C 2-8 Alkylene group, C 2-6 Alkylene group, C 2-4 The group is an alkylene group, and more preferably a carbon group such as an ethylene group or a propylene group. 2-3 The group is an alkylene group, and an ethylene group is particularly preferred.

[0110] Alkylene oxy group [-(A 2 The number of repeats n2 of O)-] may be selected from an integer of about 1 to 10, for example, and preferably in the following order: an integer from 1 to 4, an integer from 1 to 3, an integer from 1 to 2, and especially preferably 1. The number of repeats n2 may also be an average value (arithmetic mean or arithmetic mean), for example, selected from a range of about 1 to 10, and preferably in the following order: 1 to 4, 1 to 3, 1 to 2. When n2 is in a moderate range that is not too large, it tends to suppress a decrease in refractive index and heat resistance. When n2 is 2 or more, there are 2 or more alkylene oxy groups [-(A 2 The types of O)-] may be the same or different from each other.

[0111] A typical diol unit (A2) is, in the above formula (A-2), A 2 is C 2-6 Examples include a constituent unit that represents an alkylene group, where n2 represents an integer from 1 to 10; Preferably, A 2 is C 2-6 Examples include a constituent unit that represents an alkylene group, where n2 is an integer from 1 to 4; More preferably, A 2 is C 2-4 Examples include a constituent unit that represents an alkylene group, where n2 is an integer between 1 and 2; Particularly preferred, A 2 is C 2-3 Examples include constituent units that represent an alkylene group (particularly an ethylene group) and where n2 represents 1.

[0112] Specific diol components (A2) that form a diol unit (A2) include, for example, alkanediols (or alkylene glycols) and polyalkanediols (or polyalkylene glycols).

[0113] For example, an alkylene glycol is one in which n2 is 1 in formula (A-2) above. 2 C is a linear or branched alkylene glycol corresponding to the alkylene group described above, specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol (or 1,4-butanediol), 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, etc. 2-12 Examples include alkylene glycol, and a preferred embodiment is the alkylene group A 2 The same applies to the corresponding case.

[0114] As for polyalkylene glycol, for example, in formula (A-2), n2 is 2 or more, preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4, A 2This corresponds to the example alkylene group, a polylinear or branched alkylene glycol, specifically diethylene glycol, dipropylene glycol, triethylene glycol, etc., or di or decaC. 2-12 Examples include alkylene glycol, preferably di or hexaC 2-6 Alkylene glycol, more preferably di or tetraC 2-4 Alkylene glycol can be used.

[0115] The diol unit (A2) may be used alone or in combination of two or more types. Preferred diol unit (A2) is C 2-6 Linear or branched alkylene glycols such as alkylene glycols, more preferably C 2-4 Alkylene glycol, more preferably ethylene glycol, propylene glycol, etc. 2-3 These are constituent units derived from alkylene glycol, and more preferably from ethylene glycol.

[0116] Diol unit (A3) The diol unit (A3) is a diol unit represented by the following formula (A-3), and is distinguished from the diol unit (A1) represented by the aforementioned formula (A-1).

[0117] [ka]

[0118] [In the formula, Y 1 This represents a direct bond (single bond), a potentially halogenated divalent hydrocarbon group (except when the divalent hydrocarbon group is a fluorene-9,9-diyl group), an oxygen atom (ether bond), a carbonyl group (ketone bond), a sulfur atom (sulfide bond), or a sulfonyl group. Z 2a and Z 2b These independently show an arene ring, R 3a and R 3b m3a and m3b independently represent substituents, and m3a and m3b independently represent integers greater than or equal to 0. A 3a and A 3b The first element independently represents an alkylene group, and n3a and n3b ​​independently represent non-negative integers.

[0119] In the above formula (A-3), Y 1 The bond may be a direct bond (single bond), a halogenated divalent hydrocarbon group (except when the divalent hydrocarbon group is a fluorene-9,9-diyl group), an oxygen atom (ether bond), a carbonyl group (ketone bond), a sulfur atom (sulfide bond), or a sulfonyl group.

[0120] In the aforementioned halogenated divalent hydrocarbon group, examples of divalent hydrocarbon groups include an alkanediyl group which may be substituted with an aryl group, a cycloalkanediyl group which may be substituted with an alkyl group, a di(alkanediyl)arene group [or alkanediyl-arylene-alkanediyl group], and an alkenylene group.

[0121] Examples of alkanediyl groups that may be substituted with an aryl group include methylene group, 1,1-ethanediyl group, isopropylidene group (2,2-propanediyl group), 2,2-butanediyl group, 1-phenyl-1,1-ethanediyl group, diphenylmethylene group, etc. 6-10 C may be substituted with an aryl group. 1-6 Examples include alkanediyl groups.

[0122] Examples of cycloalkanediyl groups that may be substituted with alkyl groups include C1,1-cyclohexanediyl, 3-methyl-1,1-cyclohexanediyl, 3,3,5-trimethyl-1,1-cyclohexanediyl, and 1,1-cyclododecanediyl. 1-4 C may be substituted with an alkyl group. 5-15 Examples include cycloalkanediyl groups.

[0123] Examples of di(alkanediyl)arene groups [or alkanediyl-arylene-alkanediyl groups] include di(isopropylidene)-1,4-phenylene group [or 2,2-propanediyl-1,4-phenylene-2,2-propanediyl group], di(isopropylidene)-1,3-phenylene group [or 2,2-propanediyl-1,3-phenylene-2,2-propanediyl group], and other di(C) 1-6 Alkandiyl) C 6-10 Examples include arene groups.

[0124] Furthermore, halogenation of divalent hydrocarbon groups can be fluorinated or chlorinated, and halogenated divalent hydrocarbon groups can be exemplified by halogenated (fluorinated and / or chlorinated, etc.) groups of the divalent hydrocarbon groups mentioned above, specifically the hexafluoroisopropylidene group and the 2,2-dichloro-1,1-ethendiyl group.

[0125] Preferred Y 1 is a direct bond (single bond), a potentially halogenated divalent hydrocarbon group, an oxygen atom (ether bond), a sulfur atom (sulfide bond), or a sulfonyl group; more preferably a direct bond (single bond), a potentially halogenated divalent hydrocarbon group (e.g., C 1-13 A divalent hydrocarbon group (e.g., C) may be halogenated (fluorinated, chlorinated, etc.) or a sulfonyl group; more preferably a divalent hydrocarbon group (e.g., C) which may be halogenated. 1-10 (such as hydrocarbon groups); particularly preferably alkanediyl groups (for example, C such as isopropylidene groups) 1-4 (Such as an alkanediyl group)

[0126] Z 2a or Z 2b As an arene ring (aromatic hydrocarbon ring) represented by the above formula (A-1), for example, Z 1a ,Z 1b Examples include the arene ring exemplified above, as well as similar rings, including preferred embodiments. 2a ,Z 2bPreferred arene rings represented by C such as a benzene ring. 6-12 Arene ring, more preferably C 6-10 An arene ring, particularly preferably a benzene ring. 2a and Z 2b The types may be the same or different from each other, but it is preferable that they be the same.

[0127] Note Y 1 Z that joins 2a and Z 2b The substitution position (joining position) is not particularly limited.

[0128] R 3a or R 3b The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 3a ,R 3b A substituent represented by the above formula (A-1) is, for example, R 1 Examples of groups similar to the one exemplified, including preferred embodiments, include R. 3a ,R 3b Typical substituents represented include halogen atoms, hydrocarbon groups, and groups [-OR h Examples include alkoxy groups, acyl groups, nitro groups, cyano groups, substituted amino groups, and preferably hydrocarbon groups such as alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, alkylaryl groups, aralkyl groups, and alkoxy groups (linear or branched alkoxy groups). h Examples include ], and more preferably C such as a methyl group. 1-6 C such as alkyl groups and cyclohexyl groups 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 Mono- or tri-C groups such as aryl groups, methylphenyl groups (or tolyl groups), and dimethylphenyl groups (or xylyl groups) 1-4 Alkyl-C 6-12 C such as aryl groups and methoxy groups 1-4Examples include alkoxy groups. Among these, hydrocarbon groups such as alkyl groups, aryl groups, and alkylaryl groups are preferred, and in particular alkyl groups (such as methyl groups and isopropyl groups) are preferred. 1-4 Alkyl groups, etc., aryl groups (such as phenyl groups, etc.) 6-10 (An aryl group, etc.) is preferred. 3a and R 3b The types may be the same or different from each other. Also, R 3a ,R 3b When R is an aryl group, 3a ,R 3b These are Z 2a ,Z 2b They may form a ring-assembled arene ring together.

[0129] R 3a ,R 3b The number of substitutions m3a and m3b can each be any integer greater than or equal to 0, Z 2a ,Z 2b The type can be appropriately selected, for example, it may be an integer of about 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, even more preferably 0 or 1, and especially 0. m3a and m3b may be different from each other, but it is preferable that they be the same. Also, if m3a is 2 or more, then 2 or more R 3a The types may be the same or different from each other; if m3b is 2 or more, then 2 or more R 3b The types may be the same as or different from each other.

[0130] R 3a ,R 3b The substitution position of Z is not particularly restricted, 2a ,Z 2b In Y 1 The bonding position with the group [-O-(A 3a O) n3a -],[-O-(A 3b O) n3b Any position other than the bond site with the ether bond [-O-] (i.e., the ether bond [-O-] that forms the main chain), for example, Z 2a ,Z 2bThe ether bond [-O-] in the above-mentioned compound may be substituted at the ortho position (the carbon atom adjacent to the bonding position of the ether bond).

[0131] A 3a Or A 3b An alkylene group represented by (linear or branched alkylene group) is, for example, in formula (A-1) above, A 1a ,A 1b Similar groups, including preferred embodiments, can be cited as examples of the groups shown. 3a and A 3b The types may be the same or different from each other, but it is preferable that they be the same.

[0132] [-(A 3a O)-] or [-(A 3b The number of repeating alkylene oxy groups (number of added moles) n3a and n3b, represented by O)-], can be 0 or greater, and may be integers or average values. For example, they can be the same as the repeating numbers exemplified as n1a and n1b in formula (A-1), including preferred embodiments. When n3a and n3b ​​are 1 or greater, polymerization reactivity tends to be improved (especially in the case of polyester resins), and when n3a and n3b ​​are within a moderate range that is not too large, it tends to suppress a decrease in refractive index and heat resistance.

[0133] Furthermore, n3a and n3b ​​may be the same or different from each other. If n3a is 2 or more, then 2 or more alkylene oxy groups [-(A 3a The types of O)-] may be different from each other, but it is preferable that they be the same; if n3b is 2 or more, 2 or more alkylene oxy groups [-(A 3b The types of O)-] may be different from each other, but it is preferable that they be the same.

[0134] Base [-O-(A 3a O) n3a -],[-O-(A 3b O) n3b -] (i.e., the ether bond forming the main chain) 2a ,Z2b The substitution position (joining position) for Z is not particularly limited; for example, Z 2a ,Z 2b If Y is a benzene ring, 1 It is preferable that the bonded phenyl group is at the 4-position.

[0135] A typical diol unit (A3) is, in the above formula (A-3), Y 1 This represents a directly bonded, possibly halogenated, divalent hydrocarbon group, oxygen atom, sulfur atom, or sulfonyl group. Z 2a and Z 2b C is independent 6-12 Showing an arene ring, R 3a and R 3b These are independently halogen atoms, hydrocarbon groups, and groups [-OR h ] represents an acyl group, nitro group, cyano group, or substituted amino group, and m3a and m3b independently represent integers from 0 to 4. A 3a and A 3b C is independent 2-6 Examples include a constituent unit that represents an alkylene group, where n3a and n3b ​​independently represent integers from 0 to 10;

[0136] Preferably, Y 1 This is a directly bonded, possibly halogenated, divalent hydrocarbon group (e.g., C 1-10 hydrocarbon group, preferably C 1-7 Representing a hydrocarbon group or a sulfonyl group, Z 2a and Z 2b C is independent 6-10 Showing an arene ring, R 3a and R 3b These are independently hydrocarbon groups (e.g., C 1-10 hydrocarbon group, preferably C 1-7 (Hydrogen group) is represented, and m3a and m3b independently represent integers from 0 to 3. A 3a and A 3b C is independent2-4 The constituent units include those that represent an alkylene group, where n3a and n3b ​​independently represent integers from 0 to 6;

[0137] More preferably, Y 1 This represents a halogenated divalent hydrocarbon group (for example, an alkanediyl group which may be substituted with an aryl group, a cycloalkanediyl group which may be substituted with an alkyl group, a di(alkanediyl)arene group, etc.), Z 2a and Z 2b C is independent 6-8 Showing an arene ring, R 3a and R 3b These are independently alkyl groups (C 1-6 (Alkyl group, etc.) or aryl group (C 6-10 (e.g., aryl groups), and m3a and m3b independently represent integers from 0 to 2. A 3a and A 3b C is independent 2-3 The constituent units include those that represent an alkylene group, where n3a and n3b ​​independently represent integers from 0 to 2;

[0138] Particularly preferred, Y 1 C may be halogenated (fluorinated, chlorinated, etc.) 1-6 Alkanediyl groups (especially C groups such as isopropylidene groups) 1-4 (shows an alkanediyl group) Z 2a and Z 2b This shows a benzene ring, R 3a and R 3b C is independent 1-4 Alkyl groups (such as methyl groups) 1-3 (Alkyl alkyl groups, etc.) or C 6-8 It represents an aryl group (such as a phenyl group), and m3a and m3b independently represent 0 or 1 (especially 0). A 3a and A 3b C is independent 2-3Examples of constituent units include those that represent an alkylene group (particularly an ethylene group), where n3a and n3b ​​independently represent 0 or 1 (particularly 0).

[0139] Specific diol components (A3) that form the diol unit (A3) include, for example, biphenols (4,4'-biphenol, 2,2'-biphenol, etc.); and halogenated bis(hydroxyphenyl)alkanes [for example, halogenated bis(hydroxyphenyl)C such as bis(4-hydroxyphenyl)methane (or bisphenol F), 1,1-bis(4-hydroxyphenyl)ethane (or bisphenol A), 2,2-bis(4-hydroxyphenyl)propane (or bisphenol A), 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (or bisphenol AF), 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxyphenyl)butane (or bisphenol B), etc.]. 1-4 Alkanes, etc.]; Bis(alkyl-hydroxyphenyl)alkanes [e.g., 2,2-bis(4-hydroxy-3-methylphenyl)propane (or bisphenol C), 2,2-bis(4-hydroxy-3-isopropylphenyl)propane (or bisphenol G), etc., such as bis(C 1-4 (Alkyl-hydroxyphenyl)C 1-4 Alkanes, etc.]; Bis(aryl-hydroxyphenyl)alkanes [e.g., 2,2-bis(4-hydroxy-3-phenylphenyl)propane (or bisphenol PH), etc.] 6-10 Aryl-hydroxyphenyl)C 1-4 Alkanes, etc.]; Bis(hydroxyphenyl) mono or diaryl alkanes [e.g., bis(hydroxyphenyl) mono or diaryl C, such as 1,1-bis(4-hydroxyphenyl)-1-phenylethane (or bisphenol AP), bis(4-hydroxyphenyl)-diphenylmethane (or bisphenol BP)] 1-4 [e.g., alkanes]; bis(hydroxyphenyl)C which may have an alkyl group. 5-15Cycloalkanes [e.g., 1,1-bis(4-hydroxyphenyl)cyclohexane (or bisphenol Z), 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (or bisphenol TMC), 1,1-bis(4-hydroxyphenyl)cyclododecane, etc.] 1-4 Bis(hydroxyphenyl)C which may have an alkyl group 5-15 Cycloalkanes, etc.; Bis[hydroxyphenylalkyl]benzene [e.g., 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (or bisphenol P), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (or bisphenol M), etc., such as bis[hydroxyphenyl C 1-4 Examples include alkylbenzenes, bis(hydroxyphenyl)haloalkenes (e.g., 1,1-bis(4-hydroxyphenyl)-2,2-dichloroethylene), bis(hydroxyphenyl) ethers (e.g., bis(4-hydroxyphenyl) ether), bis(hydroxyphenyl) ketones (e.g., bis(4-hydroxyphenyl) ketone), bis(hydroxyphenyl) sulfides (e.g., bis(4-hydroxyphenyl) sulfide), and bis(hydroxyphenyl) sulfones (e.g., bis(4-hydroxyphenyl) sulfone (or bisphenol S)).

[0140] The diol unit (A3) may be used alone or in combination of two or more types. Preferred diol units (A3) include constituent units derived from bis(hydroxyphenyl)alkanes and bis(alkyl-hydroxyphenyl)alkanes, which may be halogenated, and bis(hydroxyphenyl)C such as bisphenol A. 1-4 Alkane-derived constituent units are preferred.

[0141] Diol units (A4) Furthermore, diol unit (A) may or may not include diol unit (A4), which is different from diol unit (A1), diol unit (A2), and diol unit (A3) [and does not belong to the category of diol units (A1) to (A3)], as needed.

[0142] Examples of diol units (A4) include aromatic diol components [excluding diol components (A1) and (A3)], alicyclic diol components, and constituent units derived from alkylene oxide (or alkylene carbonate, haloalkanol) adducts of these diol components.

[0143] Examples of aromatic diol components [excluding diol components (A1) and (A3)] include dihydroxyarenes such as hydroquinone and resorcinol; and aromatic aliphatic diols such as benzenedimethanol.

[0144] Examples of alicyclic diol components include cycloalkanediols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; hydrogenated aromatic diol components such as hydrogenated bisphenol A (e.g., the above aromatic diol components, diol component (A3), etc.); and polycyclic (bridged ring and / or spirocyclic) diol compounds which may contain heterocycles, such as tricyclodecanedimethanol, isosorbide, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0145] Examples of alkylene oxide (corresponding alkylene carbonate or haloalkanol) adducts of these diol components include, for example, C 2-4 C such as alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. 2-3 Examples include alkylene oxide adducts, and the number of moles added is not particularly limited. Specifically, examples include adducts in which approximately 2 to 10 moles of ethylene oxide are added to 1 mole of the above-mentioned diol component.

[0146] Diol units (A4) may be present alone or in combination of two or more types.

[0147] The proportion of diol units (A4) can be selected from 0 to 100 mol% relative to the total diol units (A), and may be, for example, 50 mol% or less, preferably 30 mol% or less, and even more preferably 10 mol% or less (for example, around 0.1 to 5 mol%), and it is particularly preferable that the mixture substantially does not contain diol units (A4).

[0148] The ratio of the total amount of diol units (A1), (A2), and (A3) to the total amount of diol units (A) (also called A1,2,3 / A) can be selected from 0 to 100 mol%, and may be, for example, 10 mol% or more (for example, 30 to 100 mol%), preferably in stages below 50 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and particularly preferably substantially 100 mol%. When the ratio of the total amount of diol units (A1), (A2), and (A3) is within a moderate range that is not too low, it tends to suppress the decrease in refractive index and heat resistance.

[0149] The ratio of the total amount of diol units (A1) and (A2) to the total amount of diol units (A) (also called A1,2 / A) can be selected from 0 to 100 mol%, and may be, for example, 10 mol% or more (for example, 30 to 100 mol%), preferably in stages below 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and particularly preferably substantially 100 mol%. These may also be embodiments of a polyester resin having at least an ester bond in its main chain, that is, a polyester resin containing diol units (A) and dicarboxylic acid units (B) (particularly a polyester resin) (particularly the embodiment of resin (P1) described later). When the ratio of the total amount of diol units (A1) and (A2) is within a moderate range that is not too small, it tends to be easier to satisfy a good balance of high refractive index, low birefringence, and high heat resistance.

[0150] The ratio of diol units (A1) to (A2) (also called A1 / A2) can be selected from A1 / A2 (molar ratio) = 0 / 100 to 100 / 0, for example, A1 / A2 (molar ratio) = 10 / 90 to 100 / 0, and preferably in the following increments: 30 / 70 to 100 / 0, 40 / 60 to 99 / 1, 50 / 50 to 98 / 2, 60 / 40 to 97 / 3, 70 / 30 to 95 / 5, 75 / 25 to 93 / 7, and 80 / 20 to 90 / 10. These may be embodiments of a polyester resin having at least an ester bond in its main chain, i.e., a polyester resin containing diol units (A) and dicarboxylic acid units (B) (particularly a polyester resin) (particularly the embodiment of resin (P1) described later). When the proportion of diol units (A1) is within a moderate range and not too low, it tends to suppress the decrease in refractive index and heat resistance, and when the proportion of diol units (A2) is within a moderate range and not too low, it tends to suppress the decrease in molecular weight, mechanical properties, and moldability.

[0151] The ratio of diol units (A1) to the total diol units (A) (also called A1 / A) can be selected from 0 to 100 mol%, and may be, for example, 10 mol% or more (for example, 30 to 100 mol%). In the case of a polyester resin having at least ester bonds in its main chain, i.e., a polyester resin containing diol units (A) and dicarboxylic acid units (B) (especially polyester resins), preferred A1 / A are, in stages, 40-99 mol%, 50-98 mol%, 60-97 mol%, 70-95 mol%, 75-93 mol%, and 80-90 mol%, and these may also be embodiments of resin (P1) described later; in the case of a polyester resin having at least carbonate ester bonds in its main chain, i.e., a polyester resin containing diol units (A) and carbonate units (C) (especially polycarbonate resins), preferred A1 / A are, in stages, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and substantially 100 mol%, and these may also be embodiments of resin (P2) described later. When the proportion of diol units (A1) is within a moderate range, not too low, it tends to suppress the decrease in refractive index and heat resistance.

[0152] The ratio of diol units (A2) to the total diol units (A) (also called A2 / A) can be selected from 0 to 100 mol%, and may be, for example, 90 mol% or less (for example, 0 to 70 mol%), and preferably in the following increments: 1 to 60 mol%, 2 to 50 mol%, 3 to 40 mol%, 5 to 30 mol%, 7 to 25 mol%, and 10 to 20 mol%. These may be embodiments of a polyester resin having at least an ester bond in its main chain, that is, a polyester resin containing diol units (A) and dicarboxylic acid units (B) (particularly a polyester resin) (particularly the embodiment of resin (P1) described later). When the ratio of diol units (A2) is within a moderate range that is not too low, it tends to suppress a decrease in molecular weight, mechanical properties, moldability, etc.

[0153] The ratio of diol units (A3) to the total diol units (A) (also called A3 / A) can be selected from 0 to 100 mol%, and may be, for example, 10 mol% or more (for example, 30 to 100 mol%), preferably in stages below 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and substantially 100 mol%. These may be embodiments of a polyester resin having at least a carbonate ester bond in its main chain, that is, a polyester resin containing diol units (A) and carbonate units (C) (particularly polycarbonate resin) (particularly the embodiment of resin (P2) described later). When the ratio of diol units (A3) is within a moderate range that is not too low, it tends to suppress a decrease in refractive index and heat resistance.

[0154] The total amount of diol units (A1) to (A4) may be 100 mol% relative to the total amount of diol units (A). Also, the proportion of diol units (A) [total amount of diol units (A1) to (A4)] may be, for example, 10 mol% or more relative to the total amount of constituent units of the polyester resin (total amount of constituent units derived from all polymer components that make up the resin), and preferably in stages, 20-50 mol%, 30-50 mol%, and 40-50 mol%.

[0155] In the case of a polyester resin having at least ester bonds in its main chain, i.e., a polyester resin containing diol units (A) and dicarboxylic acid units (B) (especially a polyester resin) (especially the resin (P1) described later), the ratio of diol units (A) to dicarboxylic acid units (B) in the polyester resin is preferably 1 / 0.8 to 1 / 1.2, more preferably 1 / 0.9 to 1 / 1.1, and is nearly equimolar (1 / 1).

[0156] In the case of a polyester resin having at least carbonate ester bonds in its main chain, i.e., a polyester resin containing diol units (A) and carbonate units (C) (especially a polycarbonate resin) (especially the resin (P2) described later), the ratio of diol units (A) to carbonate units (C) in the polyester resin is preferably 1 / 0.8 to 1 / 1.2, more preferably 1 / 0.9 to 1 / 1.1, and is nearly equimolar (1 / 1).

[0157] (Dicarboxylic acid unit (B)) The dicarboxylic acid unit (B) is a unit that can link with the diol unit (A) to form an ester bond, that is, a constituent unit derived from a dicarboxylic acid component (dicarboxylic acid or its ester-forming derivative), and is not particularly limited as long as it is a unit other than the terephthalic acid unit, but it is preferable that it contains at least one selected from the dicarboxylic acid units (B1), (B2), and (B4) described later, and more preferably contains at least dicarboxylic acid unit (B1) [particularly containing both dicarboxylic acid units (B1) and (B2)], or at least dicarboxylic acid unit (B4).

[0158] Dicarboxylic acid unit (B1) The dicarboxylic acid unit (B1) is a dicarboxylic acid unit represented by the following formula (B-1).

[0159] [ka]

[0160] (In the formula, R 4 represents a substituent, and m4 represents an integer from 0 to 8. A 4a and A 4b (This independently represents an alkylene group.)

[0161] In the above formula (B-1), R 4 The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 4 A substituent represented by the above formula (A-1) is, for example, R 1 Examples of groups similar to those exemplified, including preferred embodiments, include representative R groups. 4 Examples include halogen atoms, hydrocarbon groups, and groups [-OR h Examples include alkoxy groups, preferably hydrocarbon groups, and more preferably alkyl groups, aryl groups, and alkylaryl groups. Examples of alkyl groups (linear or branched alkyl groups) include methyl groups, ethyl groups, t-butyl groups, etc. 1-6 Examples include alkyl groups, such as methyl groups and C 1-4 Alkyl groups are preferred. Examples of aryl groups include phenyl groups, naphthyl groups (1-naphthyl group, 2-naphthyl group, etc.), and C 6-12 Examples include aryl groups, preferably C 6-10 The group is an aryl group, and more preferably a naphthyl group such as a 2-naphthyl group. Examples of alkylaryl groups include mono- or tri-C groups such as a methylphenyl group (or tolyl group) or a dimethylphenyl group (or xylyl group). 1-4 Alkyl-C 6-12 Examples include aryl groups.

[0162] R 4 The number of substitutions m4 is an integer from 0 to 8, for example, an integer from 0 to 6, preferably an integer from 0 to 4, an integer from 0 to 2, more preferably 0 or 1 or 0 or 2, and especially 0. Note that if m4 is 2 or more, then 2 or more R 4The types may be the same or different from each other. Also, of the two benzene rings that form the fluorene skeleton, both benzene rings may have R 4 If substitution occurs, then the R of one of the benzene rings 4 The type and the R of the other benzene ring 4 The types may be the same or different from each other. Note that if m4 is 1 or more, then 1 or more R 4 Of these, at least one is an aryl group (such as a phenyl group or naphthyl group). 6-10 It may also be an aryl group, etc. Also, R 4 The substitution position is not particularly restricted and may be, for example, 2-position, 2,7-position, etc.

[0163] A 4a Or A 4b Examples of alkylene groups (linear or branched alkylene groups) represented by this symbol include methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl groups. 1-6 Examples include alkylene groups. Preferred A 4a ,A 4b Examples include C groups such as methylene, ethylene, trimethylene, propylene, and 2-methylpropane-1,3-diyl. 1-6 Examples include alkylene groups, more preferably C 1-4 It is an alkylene group, and more preferably C 2-4 These are alkylene groups, and among them, C groups such as ethylene and propylene. 2-3 Alkylene groups are preferred, and ethylene groups are particularly preferred. 4a and A 4b The types may be different from each other, but it is preferable that they be the same.

[0164] A typical dicarboxylic acid unit (B1) is, in the above formula (B-1), R 4 m4 represents an integer from 0 to 6, where m4 represents a hydrocarbon group, halogen atom, or cyano group. A 4a and A 4b C is independent 1-6Examples include constituent units that represent alkylene groups;

[0165] Preferably, R 4 These are hydrocarbon groups such as alkyl groups, aryl groups, and alkylaryl groups (for example, C 1-10 hydrocarbon group, preferably C 1-7 (Hydrogen group) is indicated, and m4 represents an integer from 0 to 4. A 4a and A 4b C is independent 1-4 Examples of constituent units that represent an alkylene group include:

[0166] More preferably, R 4 is C 1-6 Alkyl alkyl group, C 6-12 Aryl group or mono or tri C 1-4 Alkyl-C 6-12 It indicates an aryl group, and m4 represents an integer from 0 to 2. A 4a and A 4b C is independent 2-4 Examples of constituent units that represent an alkylene group include:

[0167] Particularly preferred, R 4 is C 1-4 Alkyl group (such as methyl group), C 6-10 Aryl groups (phenyl groups, naphthyl groups, etc.) or mono- or tri-C 1-3 Alkyl-C 6-10 It represents an aryl group [such as a methylphenyl group (or tolyl group), a dimethylphenyl group (or xylyl group)], and m4 represents an integer from 0 to 2 (e.g., 0 or 1 or 0 or 2, especially 0). A 4a and A 4b C is independent 2-3 Examples of constituent units include those exhibiting an alkylene group (particularly an ethylene group).

[0168] Specific dicarboxylic acid components (B1) that form the dicarboxylic acid unit (B1) include, for example, 9,9-bis(carboxyalkyl)fluorene, more specifically, 9,9-bis(2-carboxyethyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene, etc. 2-6 Alkyl)fluorene; 9,9-bis(carboxyalkyl)-mono or diarylfluorene, more specifically, 9,9-bis(2-carboxyethyl)-2-phenylfluorene, 9,9-bis(2-carboxyethyl)-2-(1-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2-(2-naphthyl)fluorene, 9,9-bis(2-carboxypropyl)-2-(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-diphenylfluorene, 9,9-bis(2-carboxyethyl)-2,7-di(1-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(2-carboxypropyl)-2,7-di(2-naphthyl)fluorene, etc. 2-6 Alkyl)-mono or diC 6-12 Examples include arylfluorenes; preferably 9,9-bis(carboxyC) 2-4 Alkyl)fluorene, 9,9-bis(carboxyC) 2-6 Alkyl)-diC 6-12 Aryl fluorene [especially 9,9-bis(carboxyC] 2-4 Examples include alkyl fluorenes or their ester-forming derivatives.

[0169] The dicarboxylic acid unit (B1) may be used alone or in combination of two or more types. Preferred dicarboxylic acid units (B1) are constituent units derived from 9,9-bis(carboxyalkyl)fluorene, and more preferably 9,9-bis(2-carboxyethyl)fluorene or other 9,9-bis(carboxyC 2-4 It is a constituent unit derived from alkyl fluorene.

[0170] Dicarboxylic acid unit (B2) The dicarboxylic acid unit (B2) is a dicarboxylic acid unit represented by the following formula (B-2).

[0171] [ka]

[0172] (In the formula, Z 3 This shows a polycyclic arene ring, R 5 (where represents a substituent, and m5 represents a non-negative integer.)

[0173] In the above equation (B-2), Z 3 As an example of a polycyclic arene ring (polycyclic aromatic hydrocarbon ring) represented by the above formula (A-1), Z 1a ,Z 1b Examples include polycyclic arene rings as exemplified, as well as similar rings, including preferred embodiments. 3 A preferred polycyclic arene ring represented by C is C 10-20 Polycyclic arene ring (C 10-14 Polycyclic arene rings, more preferably naphthalene rings, biphenyl rings, etc. 10-12 A polycyclic arene ring, particularly preferably a naphthalene ring.

[0174] In the above equation (B-2), Z 3 The substitution positions (bonding positions) of the two carbonyl groups bonded to Z may, for example, be adjacent to each other, preferably at distant positions that are not adjacent, and more preferably at the furthest positions from each other. Specifically, Z 3 When the ring is a naphthalene ring, the other carbonyl group may be substituted at the 5- to 8-position relative to the 1- or 2-position of the other carbonyl group, preferably at the 6-position (2,6-position) relative to the 2-position.

[0175] R 5 The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 5 A substituent represented by the above formula (A-1) is, for example, R 1Examples of groups similar to those exemplified, including preferred embodiments, include representative R groups. 5 Examples include halogen atoms, hydrocarbon groups, and groups [-OR h Examples include alkoxy groups, acyl groups, nitro groups, cyano groups, substituted amino groups, and preferably alkyl groups (linear or branched alkyl groups), cycloalkyl groups (such as cyclohexyl groups). 5-8 Hydrocarbon groups such as cycloalkyl groups, alkoxy groups (linear or branched alkoxy groups, such as methoxy groups, etc.) 1-4 Groups such as alkoxy groups [-OR h ] are examples, and more preferably C 1-6 Alkyl groups such as alkyl groups (especially C groups such as methyl groups) 1-4 It is an alkyl group.

[0176] R 5 The number of substitutions m5 can be 0 or greater, Z 3 Depending on the type, for example, an integer of about 0 to 6, preferably in stages below, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, and especially preferably 0. If m5 is 2 or more, then R is 2 or more. 5 The types may be the same or different from each other. 5 The substitution position (joining position) is Z 3 The position is not particularly limited, as long as it is not the substitution position of the two carbonyl groups bonded to it.

[0177] A typical dicarboxylic acid unit (B2) is, in the above formula (B-2), Z 3 is C 10-20 It shows a polycyclic arene ring, R 5 is a halogen atom, hydrocarbon group or group [-OR h Examples include a constituent unit that represents an alkoxy group, where m5 is an integer between 0 and 4;

[0178] Preferably, Z 3 is C 10-14 It shows a polycyclic arene ring, R 5 is a hydrocarbon group (e.g., C 1-10 hydrocarbon group, preferably C 1-7 Examples of constituent units include a hydrocarbon group, where m5 represents an integer from 0 to 3;

[0179] More preferably, Z 3 C is a ring such as a naphthalene ring or a biphenyl ring. 10-12 It shows a polycyclic arene ring, R 5 is an alkyl group (C 1-6 Examples of constituent units include alkyl groups, where m5 represents an integer between 0 and 2;

[0180] Particularly preferred, Z 3 This shows a naphthalene ring, R 5 is C 1-4 Examples of constituent units include those that represent an alkyl group (such as a methyl group) and where m5 is 0 or 1 (especially 0).

[0181] Specific dicarboxylic acid components (B2) that form a dicarboxylic acid unit (B2) include, for example, condensed polycyclic aromatic dicarboxylic acids (condensed polycyclic arene dicarboxylic acids), ring-assembled aromatic dicarboxylic acids (ring-assembled arene dicarboxylic acids), or their ester-forming derivatives.

[0182] Examples of condensed polycyclic aromatic dicarboxylic acids (condensed polycyclic arene dicarboxylic acids) include naphthalenedicarboxylic acids (such as 1,2-, 1,4-, 1,5-, 1,8-, 2,3-, or 2,6-naphthalenedicarboxylic acids), anthracenedicarboxylic acids, phenantradicarboxylic acids, and other condensed polycyclic C 10-20 Examples include arene-dicarboxylic acids.

[0183] Examples of ring-assembled aromatic dicarboxylic acids (ring-assembled allene dicarboxylic acids) include biaryl dicarboxylic acids (e.g., 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-dicarboxy-1,1'-binaphthyl, etc.).6-10 Examples include aryl dicarboxylic acids, etc.

[0184] The dicarboxylic acid unit (B2) may be used alone or in combination of two or more types. Preferred dicarboxylic acid units (B2) are constituent units derived from condensed polycyclic aromatic dicarboxylic acids (condensed polycyclic arenedicarboxylic acids), and more preferably constituent units derived from naphthalenedicarboxylic acids such as 2,6-naphthalenedicarboxylic acid.

[0185] Dicarboxylic acid unit (B3) In this disclosure, in the depolymerization and repolymerization steps, the presence of terephthalic acid components derived from terephthalic acid units tends to cause polymerization failures, possibly due to their tendency to vaporize (or sublimate) during the process. Therefore, the raw material polyester resin (and recycled polyester resin) does not contain terephthalic acid units, but from the viewpoint of more easily suppressing polymerization failures, it is preferable that it does not contain dicarboxylic acid units (B3) represented by the following formula (B-3).

[0186] [ka]

[0187] (In the formula, R 6 (where represents a substituent, and m6 represents an integer between 0 and 4.)

[0188] In formula (B-3) above, the substitution positions (bonding positions) of the two carbonyl groups bonded to the benzene ring may be, for example, the orthogonal position, preferably the metagonal position, the paragonal position, and more preferably the paragonal position.

[0189] R 6 The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 6 A substituent represented by the above formula (A-1) is, for example, R 1 Examples of groups similar to those exemplified, including preferred embodiments, include representative R groups. 6 Examples include halogen atoms, hydrocarbon groups, and groups [-ORh Examples include alkoxy groups, acyl groups, nitro groups, cyano groups, substituted amino groups, and preferably alkyl groups (linear or branched alkyl groups), cycloalkyl groups (such as cyclohexyl groups). 5-8 Aliphatic hydrocarbon groups such as cycloalkyl groups, alkoxy groups (linear or branched alkoxy groups, such as methoxy groups, etc.) 1-4 Groups such as alkoxy groups [-OR h ] are examples, and more preferably C 1-6 Alkyl groups such as alkyl groups (especially C groups such as methyl groups) 1-4 It is an alkyl group.

[0190] R 6 The number of substitutions m6 is an integer between 0 and 4, for example, an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1, and particularly preferably 0. If m6 is 2 or more, then 2 or more R 6 The types may be the same or different from each other. 6 The substitution position (bonding position) is not particularly limited as long as it is a position other than the substitution positions of the two carbonyl groups bonded to the benzene ring.

[0191] A typical dicarboxylic acid unit (B3) is, in the above formula (B-3), R 6 is a halogen atom, hydrocarbon group or group [-OR h Examples include a constituent unit that represents an alkoxy group, where m6 represents an integer from 0 to 4;

[0192] Preferably, R 6 is a hydrocarbon group (e.g., C 1-10 hydrocarbon group, preferably C 1-7 Examples of constituent units include a hydrocarbon group, where m6 represents an integer from 0 to 3;

[0193] More preferably, R 6 is an alkyl group (C 1-6 Examples of constituent units include alkyl groups, where m6 represents an integer between 0 and 2;

[0194] Particularly preferred, R 6 is C 1-4 Examples of constituent units include those that represent an alkyl group (such as a methyl group) and where m6 represents 0 or 1 (especially 0).

[0195] Specific dicarboxylic acid components (B3) that form a dicarboxylic acid unit (B3) include, for example, benzenedicarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid; alkylbenzenedicarboxylic acids (for example, C-methylisophthalic acid). 1-4 Examples include alkylbenzene dicarboxylic acids.

[0196] Dicarboxylic acid units (B3) may be present individually or in combination of two or more types. Dicarboxylic acid units (B3) that are preferable not to be present in the raw material polyester resin (and recycled polyester resin) are dicarboxylic acid-derived constituent units such as terephthalic acid and isophthalic acid.

[0197] Dicarboxylic acid unit (B4) The dicarboxylic acid unit (B4) is a dicarboxylic acid unit represented by the following formula (B-4). The dicarboxylic acid unit (B4) is an alicyclic dicarboxylic acid unit having an aliphatic hydrocarbon ring skeleton (alicyclic skeleton).

[0198] [ka]

[0199] (In the formula, W 1 It shows an aliphatic hydrocarbon ring, A 5a and A 5b These independently show either a direct bond or an alkylene group. R 7 (where represents a substituent, and m7 represents a non-negative integer.)

[0200] In the above formula (B-4), W 1An aliphatic hydrocarbon ring represented by may be any non-aromatic ring structure formed by an aliphatic chain, and may or may not contain unsaturated bonds such as double bonds. Furthermore, an aliphatic hydrocarbon ring may be monocyclic or polycyclic, containing multiple ring structures. A polycyclic aliphatic hydrocarbon ring may be a bridging ring structure in which adjacent rings share two or more atoms; it may be a spirocyclic structure in which adjacent rings share one atom; or it may be a ring assembly in which two or more ring systems are directly connected by single bonds or double bonds, with the number of bonds directly connecting the rings being one less than the number of ring systems. Representative aliphatic hydrocarbon rings include, for example, monocyclic aliphatic hydrocarbon rings, bridging ring aliphatic hydrocarbon rings, and ring assembly aliphatic hydrocarbon rings.

[0201] Examples of monocyclic aliphatic hydrocarbon rings include cycloalkane rings and cycloalkene rings. Examples of cycloalkane rings include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, and cyclooctane rings. 3-20 Examples include cycloalkane rings. Cycloalkene rings include cyclopentene rings and cyclohexene rings. 3-20 Examples include cycloalkene rings.

[0202] Examples of crosslinked aliphatic hydrocarbon rings include crosslinked cycloalkane rings and crosslinked cycloalkene rings. Examples of crosslinked cycloalkane rings include decalin rings, norbornane rings, tricyclodecane rings, and tetracyclododecane rings. 7-20 Examples include bridged ring-type bi or tetracycloalkane rings. As for tricyclodecane rings, there are adamantane rings (tricyclo[3.3.1.1 3,7 ] Decane ring), tricyclo[5.2.1.0 2,6 Examples include decane rings. Tetracyclododecane rings include tetracyclo[4.4.0.1 2,5 .1 7,10 Examples include the dodecane ring. Examples of bridging cycloalkene rings include the norbornene ring, tricyclodecene ring, and tetracyclododecene ring. 7-20Examples include bridging ring-type vinyl or tetracycloalkene rings.

[0203] Examples of ring-assembled aliphatic hydrocarbon rings include ring-assembled cycloalkane rings such as bi or tercycloalkane rings (bi or tercycloalkyl rings), specifically ring-assembled bi or terC1 rings such as 1,1'-bicyclohexane rings (or 1,1'-bicyclohexyl rings). 3-10 Examples include cycloalkane rings.

[0204] W 1 Preferred aliphatic hydrocarbon rings represented by this formula are monocyclic or bridged aliphatic hydrocarbon rings; more preferably cycloalkane rings (e.g., C 3-10 Cycloalkane rings), bridged ring bi or tetracycloalkane rings (e.g., C 7-14 It is a bridged ring (bi or tetracycloalkane ring); more preferably a cycloalkane ring (e.g., C 4-9 Cycloalkane rings, bridged ring bi or tricycloalkane rings (e.g., decalin ring, tricyclodecane ring, etc.) 7-13 It is a crosslinked cyclic bi or tricycloalkane ring; particularly preferably a cycloalkane ring (e.g., C 5-8 Cycloalkane rings, bridging bicycloalkane rings (e.g., decalin rings, etc.) 7-12 It is a cross-linked bicycloalkane ring; among them, C such as the cyclohexane ring. 5-7 It is a cycloalkane ring.

[0205] A 5a and A 5b The C group may be either a direct bond (or single bond) or an alkylene group (linear or branched alkylene group). Examples of alkylene groups (linear or branched alkylene groups) include methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl groups. 1-8 Examples of alkylene groups include methylene groups, ethylene groups, trimethylene groups, propylene groups, 2-methylpropane-1,3-diyl groups, etc. 1-6Alkylene group, more preferably C 1-4 Alkylene group, particularly preferably C 1-3 Alkylene groups (especially methylene groups and other C groups) 1-2 (Alkylene group)

[0206] A 5a and A 5b It may be an alkylene group, but a direct bond (or single bond), i.e., W 1 It is preferable that the carbonyl group [-C(=O)-] forming the main chain is directly bonded to it. 5a and A 5b The types may be the same or different from each other.

[0207] W 1 And, A 5a and A 5b The bond position with the carbonyl group [-C(=O)-] that forms the main chain is not particularly restricted, W 1 The furthest point in the middle, for example, W 1 If it is a cyclohexane ring, then at the 1,4-position, W 1 If it is a decalin ring, then at the 2,6-position, W 1 If it is a tricyclodecane ring, it may also be at the 4,8-position, etc.

[0208] R 7 The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 7 A substituent represented by the above formula (A-1) is, for example, R 1 Examples of substituents similar to those exemplified are groups, preferably hydrocarbon groups, more preferably aliphatic hydrocarbon groups (e.g., alkyl groups, cycloalkyl groups, combinations thereof), and particularly preferably alkyl groups (such as methyl groups). 1-4 It is an alkyl group.

[0209] R 7 The number of substitutions m7 is an integer greater than or equal to 0, and W 1Depending on the type, it may be an integer of about 0 to 16 (for example, an integer from 0 to 10), preferably an integer from 0 to 4, more preferably an integer from 0 to 2, even more preferably 0 or 1, and particularly preferably 0. If m7 is 2 or more, then R is 2 or more. 7 The types may be the same or different from each other. 7 The substitution position is not particularly restricted.

[0210] A typical dicarboxylic acid unit (B4) is, in the above formula (B-4), W 1 This represents a monocyclic or bridged cyclic aliphatic hydrocarbon ring. A 5a and A 5b They are independently directly bonded or C 1-4 Showing an alkylene group, R 7 is a hydrocarbon group (e.g., C 1-10 hydrocarbon group, preferably C 1-7 Examples include a hydrocarbon group, where m7 represents an integer from 0 to 4;

[0211] Preferably, W 1 This represents a cycloalkane ring or a bridging cyclic bi or tetracycloalkane ring. A 5a and A 5b They are independently directly bonded or C 1-3 Showing an alkylene group, R 7 These are aliphatic hydrocarbon groups such as alkyl groups, cycloalkyl groups, and combinations thereof (e.g., C 1-6 Examples include a constituent unit that represents an aliphatic hydrocarbon group, where m7 represents an integer from 0 to 3;

[0212] More preferably, W 1 is a cycloalkane ring (e.g., C 3-10 Cycloalkane ring) or bridging ring bi or tricycloalkane ring (e.g., decalin ring, tricyclodecane ring, etc.) 7-13 (showing a bi or tricycloalkane ring), A5a and A 5b These independently show a direct bond or a methylene group. R 7 Examples include the fact that represents an alkyl group, and m7 represents an integer between 0 and 2;

[0213] Particularly preferred, W 1 is a cycloalkane ring (e.g., C 4-9 Cycloalkane ring) or bridging cyclic bicycloalkane ring (e.g., decalin ring, etc.) 7-12 Bicycloalkane rings (especially C such as cyclohexane rings) 5-8 (showing a cycloalkane ring), A 5a and A 5b This indicates a direct bond, R 7 is C 1-6 Alkyl (especially C 1-4 Examples include a constituent unit that represents an alkyl group, where m7 represents either 0 or 1.

[0214] Specific dicarboxylic acid components (B4) that form a dicarboxylic acid unit (B4) include, for example, cycloalkanedicarboxylic acids, cycloalkenedicarboxylic acids, crosslinked cyclic cycloalkanedicarboxylic acids, crosslinked cyclic cycloalkenedicarboxylic acids, ring-assembled cycloalkanedicarboxylic acids, or ester-forming derivatives thereof.

[0215] Examples of cycloalkanedicarboxylic acids include cyclohexanedicarboxylic acid (such as 1,4-cyclohexanedicarboxylic acid) and C 3-10 Examples include cycloalkane-dicarboxylic acids.

[0216] Examples of cycloalkenedicarboxylic acids include C15, such as cyclohexenedicarboxylic acid. 5-10 Examples include cycloalkene-dicarboxylic acids.

[0217] Examples of crosslinked cyclic cycloalkanedicarboxylic acids include decalindicarboxylic acid, norbornanedicarboxylic acid, tricyclodecanedicarboxylic acid [for example, adamantanedicarboxylic acid (or tricyclo[3.3.1.1 3,7 ]decanedicarboxylic acid), tricyclo[5.2.1.0 2,6 Examples include cross-linked cyclic bi or tricycloalkanedicarboxylic acids such as decanedicarboxylic acid.

[0218] Examples of crosslinked cyclic cycloalkenedicarboxylic acids include crosslinked cyclic bi or tricycloalkenedicarboxylic acids such as norbornenedicarboxylic acid.

[0219] Examples of ring-assembled cycloalkanedicarboxylic acids include 1,1'-bicyclohexane-4,4'-dicarboxylic acid and other ring-assembled bicycloalkanedicarboxylic acids.

[0220] The dicarboxylic acid component (B4) may be an isomer mixture, for example, selected from trans / cis (molar ratio) = 0 / 100 to 100 / 0, specifically around 1 / 99 to 99 / 1, and preferably in the following increments: 50 / 50 to 100 / 0, 70 / 30 to 100 / 0, 80 / 20 to 100 / 0, and 90 / 10 to 100 / 0.

[0221] The dicarboxylic acid unit (B4) may be used alone or in combination of two or more types. Preferred dicarboxylic acid units (B4) include cycloalkanedicarboxylic acids (e.g., C 3-10 The constituent units are derived from cycloalkane-dicarboxylic acids, and more preferably C such as cyclohexanedicarboxylic acid (1,4-cyclohexanedicarboxylic acid, etc.). 4-9 It is a constituent unit derived from cycloalkane-dicarboxylic acid.

[0222] Dicarboxylic acid unit (B5) The dicarboxylic acid unit (B) may or may not include a dicarboxylic acid unit (B5) which is different from the dicarboxylic acid units (B1), (B2), (B3), and (B4) [not belonging to the category of dicarboxylic acid units (B1) to (B4)], as needed.

[0223] Examples of dicarboxylic acid units (B5) include constituent units derived from aromatic dicarboxylic acid components [excluding dicarboxylic acid components (B1) to (B3)], aliphatic dicarboxylic acid components, and so on.

[0224] Aromatic dicarboxylic acid components include diarylalkane dicarboxylic acids (for example, diC such as 4,4'-diphenylmethanedicarboxylic acid). 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.); diarylketone dicarboxylic acids [for example, di(C) such as 4,4'-diphenylketone dicarboxylic acid] 6-10 [Aryl)ketone-dicarboxylic acids, etc.]; diaryl ether dicarboxylic acids [e.g., 4,4'-diphenyl ether dicarboxylic acid, etc. (C) 6-10 [Aryl) ether-dicarboxylic acids, etc.]; diaryl sulfone dicarboxylic acids [for example, 4,4'-diphenyl sulfone dicarboxylic acid, etc. (C) 6-10 Examples include aryl)sulfone-dicarboxylic acids, etc., and their ester-forming derivatives.

[0225] Examples of aliphatic dicarboxylic acid components include alkanedicarboxylic acids (linear or branched alkanedicarboxylic acids), specifically malonic acid, succinic acid, adipic acid, suberic acid, sebacic acid, decanedicarboxylic acid, etc. 1-12 Alkane-dicarboxylic acids, etc.; unsaturated aliphatic dicarboxylic acids (linear or branched unsaturated aliphatic dicarboxylic acids), specifically, maleic acid, fumaric acid, itaconic acid, etc. 2-10 Examples include alkene-dicarboxylic acids and their ester-forming derivatives.

[0226] The dicarboxylic acid unit (B5) may be present alone or in combination of two or more types.

[0227] The proportion of dicarboxylic acid units (B5) can be selected from 0 to 100 mol% relative to the total dicarboxylic acid units (B), for example, 50 mol% or less, preferably in stages below, 30 mol% or less, 20 mol% or less, 15 mol% or less, 10 mol% or less, 5 mol% or less, and 1 mol% or less, and may be as low as 0.1 to 3 mol%, and it is particularly preferable that the product substantially does not contain dicarboxylic acid units (B5).

[0228] The polyester resin may contain dicarboxylic acid units (B3) to the extent that it does not significantly impair the effects of the present disclosure. The proportion of dicarboxylic acid units (B3) is, for example, 50 mol% or less, preferably in stages, 30 mol% or less, 20 mol% or less, 15 mol% or less, 10 mol% or less, 5 mol% or less, and 1 mol% or less, relative to the total dicarboxylic acid units (B). It may also be, for example, around 0.1 to 3 mol%, and it is particularly preferable that it is substantially free of dicarboxylic acid units (B3).

[0229] The ratio of the total amount of dicarboxylic acid units (B1) and (B2) to the total amount of dicarboxylic acid units (B) (also called B1,2 / B) can be selected from 0 to 100 mol%, and may be 10 mol% or more (for example, 30 to 100 mol%), preferably in stages below 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and 95 mol% or more, with substantially 100 mol% being particularly preferred. These may also be embodiments of a polyester resin having at least an ester bond in its main chain, i.e., a polyester resin containing diol units (A) and dicarboxylic acid units (B) (particularly a polyester resin) (particularly the embodiment of resin (P1) described later). When the ratio of the total amount of dicarboxylic acid units (B1) and (B2) is within a moderate range that is not too small, it tends to be easier to satisfy a good balance of high refractive index, low birefringence, and high heat resistance.

[0230] The ratio of dicarboxylic acid units (B1) to (B2) (also called B1 / B2) can be selected from B1 / B2 (molar ratio) = 0 / 100 to 100 / 0, for example, B1 / B2 (molar ratio) = 10 / 90 to 100 / 0, and preferably in the following increments: 30 / 70 to 95 / 5, 50 / 50 to 90 / 10, 60 / 40 to 80 / 20, and 65 / 35 to 75 / 25. These may be embodiments of a polyester resin having at least an ester bond in its main chain, i.e., a polyester resin containing diol units (A) and dicarboxylic acid units (B) (particularly a polyester resin) (particularly the embodiment of resin (P1) described later). When the proportion of dicarboxylic acid units (B1) is within a moderate range and not too low, it tends to suppress the increase in birefringence, and when the proportion of dicarboxylic acid units (B2) is within a moderate range and not too low, it tends to suppress the decrease in refractive index and heat resistance.

[0231] The ratio of dicarboxylic acid units (B1) to the total dicarboxylic acid units (B) (also called B1 / B) can be selected from 0 to 100 mol%, and may be 10 mol% or more (for example, 30 to 100 mol%), preferably in stages below 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and 95 mol% or more, with substantially 100 mol% being particularly preferred. These may also be embodiments of a polyester resin having at least an ester bond in its main chain, i.e., a polyester resin containing diol units (A) and dicarboxylic acid units (B) (particularly a polyester resin) (particularly the embodiment of resin (P1) described later). When the ratio of dicarboxylic acid units (B1) is within a moderate range that is not too low, it tends to be easier to satisfy a good balance of high refractive index, low birefringence, and high heat resistance.

[0232] The ratio of dicarboxylic acid units (B4) to the total dicarboxylic acid units (B) (also called B4 / B) can be selected from 0 to 100 mol%, and may be 10 mol% or more (for example, 30 to 100 mol%), preferably in stages below 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and 95 mol% or more, with substantially 100 mol% being particularly preferred. These may also be embodiments of a polyester resin having at least an ester bond in its main chain, i.e., a polyester resin containing diol units (A) and dicarboxylic acid units (B) (particularly a polyester resin) (particularly the embodiment of resin (P1) described later). When the ratio of dicarboxylic acid units (B4) is within a moderate range that is not too low, it tends to be easier to satisfy a good balance of high refractive index, low birefringence, and high heat resistance.

[0233] The ratio of the total amount of dicarboxylic acid units (B1), (B2), and (B4) to the total amount of dicarboxylic acid units (B) (also called B1,2,4 / B) can be selected from 0 to 100 mol%, and may be 10 mol% or more (for example, 30 to 100 mol%), preferably in stages below 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and 95 mol% or more, with substantially 100 mol% being particularly preferred. These may also be embodiments of a polyester resin having at least an ester bond in its main chain, i.e., a polyester resin containing diol units (A) and dicarboxylic acid units (B) (particularly a polyester resin) (particularly the embodiment of resin (P1) described later). When the ratio of the total amount of dicarboxylic acid units (B1), (B2), and (B4) is within a moderate range that is not too small, it tends to be easier to satisfy a good balance of high refractive index, low birefringence, and high heat resistance.

[0234] Furthermore, the proportion of the total amount of dicarboxylic acid units (B1) to (B5) [preferably the proportion of the total amount of dicarboxylic acid units (B1), (B2), (B4), and (B5)] may be 100 mol% relative to the total amount of dicarboxylic acid units (B). Also, the proportion of dicarboxylic acid units (B) [the total amount of dicarboxylic acid units (B1) to (B5), preferably the total amount of dicarboxylic acid units (B1), (B2), (B4), and (B5)] may be, for example, about 10 mol% or more relative to the total constituent units of the polyester resin (the total amount of constituent units derived from all polymerization components that make up the resin), and preferably in stages, 20-50 mol%, 30-50 mol%, and 40-50 mol%.

[0235] (Carbonate units (C)) The polyester resin may be a polycarbonate resin or polyester carbonate resin containing a diol unit (A) [and optionally a dicarboxylic acid unit (B)] in addition to a carbonate unit (C).

[0236] In this specification and in the claims, "carbonate unit" means a constituent unit derived from a carbonate bond-forming component that can form a carbonate ester bond (carbonate bond) [-OC(=O)-O-] through reaction with a diol component (A), i.e., a carbonyl group [-C(=O)-]. In other words, a carbonate unit (carbonyl group) can form a carbonate bond together with the terminal oxygen atoms of two adjacent diol units.

[0237] Therefore, the carbonate bond-forming component (C) can be any compound capable of forming a carbonate bond through reaction with the diol component (A). Typical carbonate bond-forming components (C) include, for example, phosgenes such as phosgene and triphosgene, and diesters of carbonates such as diphenyl carbonate (DPC).

[0238] The carbonate bond-forming component (C) can be used alone or in combination of two or more types. Among the carbonate bond-forming components (C), diphenyl carbonate and other diesters are preferred from the viewpoint of safety and other factors.

[0239] The ratio of the total amount of dicarboxylic acid units (B) and carbonate units (C) in the resin to the amount of diol units (A) (also called B,C / A) is preferably approximately equimolar, with a molar ratio of 1 / 0.8 to 1 / 1.2, more preferably 1 / 0.9 to 1 / 1.1. The ratio of dicarboxylic acid units (B) to carbonate units (C) (also called B / C) may be approximately 100 / 0 to 0 / 100 (for example, around 90 / 10 to 10 / 90), and in the case of polycarbonate resin, the molar ratio is 0 / 100. In the case of polyester carbonate resin, the molar ratio may be approximately 80 / 20 to 20 / 80, 70 / 30 to 30 / 70, or 60 / 40 to 40 / 60.

[0240] (Other constituent units (D)) Furthermore, the polyester resin does not necessarily have to contain other constituent units (D) different from the diol units (A), dicarboxylic acid units (B), and carbonate units (C), but may contain them as needed, to the extent that it does not impair the effects of this disclosure.

[0241] Other constituent units (D) include, for example, constituent units derived from hydroxycarboxylic acid components or lactone components, polyfunctional polymer components having three or more polymerizable groups (carboxyl groups and / or hydroxyl groups), diamine components, aminocarboxylic acid components or lactam components, diisocyanate components, etc., with constituent units derived from hydroxycarboxylic acid components or lactone components, polyfunctional polymer components having three or more polymerizable groups (carboxyl groups and / or hydroxyl groups), etc. being preferred.

[0242] Examples of hydroxycarboxylic acid components include aromatic hydroxycarboxylic acids such as hydroxybenzoic acid; aliphatic hydroxycarboxylic acids (hydroxyalkanoic acids) such as lactic acid, 3-hydroxybutyric acid, and 6-hydroxyhexanoic acid; and ester-forming derivatives thereof. Examples of corresponding lactone components include lactones corresponding to hydroxyalkanoic acids such as ε-caprolactone.

[0243] Examples of polyfunctional polymerization components having three or more polymerizable groups (carboxyl groups and / or hydroxyl groups) include trivalent or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid; and trivalent or higher polyhydric alcohols such as glycerin and pentaerythritol.

[0244] The proportion of such other constituent units (D) is, for example, 50 mol% or less, preferably in stages, 0 to 30 mol%, 0 to 10 mol%, and 0.01 to 5 mol%, relative to the total amount of constituent units [total amount of diol units (A), dicarboxylic acid units (B), carbonate units (C), and other constituent units (D)], and it is preferable that the other constituent units (D) are substantially absent.

[0245] (Typical polyester resins) Typical polyester resins include those containing at least diol units (A) but not terephthalic acid units, such as the resins listed below (P1) to (P2).

[0246] (P1): A polyester resin (especially a polyester resin) having at least ester bonds in its main chain, The diol unit (A) includes at least one selected from diol units (A1), (A2), and (A3) [preferably at least one selected from (A1) and (A2); more preferably at least (A2); particularly preferably both (A1) and (A2)], A polyester resin comprising a dicarboxylic acid unit (B), wherein the dicarboxylic acid unit (B) comprises at least one selected from dicarboxylic acid units (B1), (B2), and (B4) [preferably comprising at least (B1) (in particular, both (B1) and (B2)) or comprising at least (B4)].

[0247] (P2): A polyester resin (especially a polycarbonate resin) having at least a carbonate ester bond in its main chain, The diol unit (A) includes at least one selected from diol units (A1) and (A3), A polyester resin containing carbonate units (C).

[0248] Furthermore, in resins (P1) to (P2) [especially resin (P1)], it is preferable that the dicarboxylic acid unit (B) substantially does not contain dicarboxylic acid unit (B3).

[0249] Furthermore, in resins (P1) to (P2), the types of each constituent unit (or the range encompassed by each constituent unit) and the proportion (or composition ratio) of each constituent unit are the same as those described in the preceding sections, including preferred embodiments.

[0250] Of the resins (P1) and (P2), resin (P1) is preferred because it is easier to manufacture recycled polyester resins that exhibit substantially the same physical properties as virgin polyester resins.

[0251] (Method of manufacturing raw material polyester resin) The method for producing the raw polyester resin is not particularly limited and can be done using conventional methods depending on the type of constituent unit (or corresponding polymerization component). For example, the following production methods 1 and 2 can be used.

[0252] Method for manufacturing raw material polyester resin 1 Manufacturing method 1 is a method in which the raw material polyester is a polyester resin (particularly a polyester resin) having at least ester bonds, and includes, for example, a method of reacting (polymerizing or polycondensing) a polymerization component (monomer component) containing a diol component (A) and a dicarboxylic acid component (B). Specifically, it may be prepared by a transesterification method, a melt polymerization method such as direct polymerization, a solution polymerization method, or an interfacial polymerization method. A melt polymerization method is preferred because it can effectively suppress the residue or contamination of solvents and salts, etc., as it is easy to improve moldability (productivity) and transparency.

[0253] Furthermore, the proportion (or composition ratio) of each polymerization component may be the same as the proportion (composition ratio or introduction ratio) described in each section, such as the diol unit (A) and the dicarboxylic acid unit (B), and as will be described later, the diol component (A2) may be used in excess.

[0254] The charging ratio of the dicarboxylic acid component (B) to the diol component (A) is usually the former / latter (molar ratio) = for example, 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9 (especially substantially 1 / 1), but it is not necessarily limited to this range, and at least one component selected from the dicarboxylic acid component (B) and the diol component (A) may be used in excess of the planned introduction ratio. For example, the diol component (A2), such as ethylene glycol, which can be distilled from the reaction system, may be used in excess of the ratio introduced into the polyester resin (or the introduction ratio).

[0255] Furthermore, if the polymerization component also includes a carbonate bond-forming component (C), the ratio of the total amount of the dicarboxylic acid component (B) and the carbonate bond-forming component (C) to the amount of the diol component (A) used is, for example, former / latter (molar ratio) = 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9. Note that the carbonate bond-forming component (C) may be used in slightly excess relative to the planned introduction ratio, taking into account volatilization and decomposition in the reaction. For example, the carbonate bond-forming component (C) may be used in excess of about 0.1 to 5 mol%, preferably 2 to 3 mol%, relative to the total amount of dicarboxylic acid units (B) and carbonate units (C) (total amount to be introduced into the resin).

[0256] The reaction may be carried out in the presence of a catalyst. Conventional transesterification (or esterification) catalysts such as Lewis acids, or metal catalysts, can be used as catalysts. Examples of metal catalysts include metal compounds containing alkali metals such as sodium; alkaline earth metals such as magnesium, calcium, and barium; transition metals such as titanium, manganese, and cobalt; group 12 metals of the periodic table such as zinc and cadmium; group 13 metals of the periodic table such as aluminum; group 14 metals of the periodic table such as germanium and lead; and group 15 metals of the periodic table such as antimony. Examples of metal compounds include alkoxides; organic acid salts such as acetates and propionates; inorganic acid salts such as borates and carbonates; oxides, or hydrates thereof. Representative metal compounds include, for example, germanium compounds such as germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, and germanium-n-butoxide; antimony compounds such as antimony trioxide, antimony acetate, and antimony ethylene glycolate; titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate (or titanium(IV) tetrabutoxide), titanium oxalate, and potassium titanium oxalate; manganese compounds such as manganese acetate tetrahydrate; and calcium compounds such as calcium acetate monohydrate.

[0257] Catalysts can be used individually or in combination of two or more. When multiple catalysts are used, each catalyst can be added according to the progress of the reaction (for example, according to the stage of the reaction, such as the initial transesterification reaction, followed by the polycondensation reaction). Preferred catalysts include manganese acetate tetrahydrate, calcium acetate monohydrate, germanium dioxide, and titanium(IV) tetrabutoxide, with a combination of a manganese compound such as manganese acetate tetrahydrate in the transesterification reaction and a germanium compound such as germanium dioxide in the polycondensation reaction being even more preferred.

[0258] The amount of catalyst used (total amount) is, for example, 0.01 × 10⁻¹⁶ per mole of dicarboxylic acid component (B). -4 ~100×10 -4 Moles, preferably 0.1 × 10⁻⁶ -4 ~40×10 -4 This is expressed in moles. The amount of manganese compounds used, such as manganese acetate tetrahydrate, is, for example, 0.01 × 10⁻¹⁶ per mole of dicarboxylic acid component (B). -4 ~100×10 -4 moles, preferably 0.1 × 10⁻⁶ -4 ~40×10 -4 moles, more preferably 0.5 × 10 -4 ~10×10 -4 The unit is moles. The amount of germanium compounds used, such as germanium dioxide, is, for example, 0.01 × 10⁻¹⁶ per mole of dicarboxylic acid component (B). -4 ~100×10 -4 moles (for example, 0.1 × 10⁻⁶) -4 ~60×10 -4 moles), preferably 1 × 10 -4 ~50×10 -4 moles (for example, 10 × 10) -4 ~40×10 -4 moles), more preferably 20 × 10 -4 ~30×10 -4 It is a mole.

[0259] Furthermore, the reaction may be carried out in the presence of stabilizers such as heat stabilizers or antioxidants, if necessary. Heat stabilizers are commonly used, and examples include phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (or dibutyl phosphate), phosphorous acid, trimethyl phosphate, and triethyl phosphate. Alkyl phosphates such as trimethyl phosphate are preferred. The amount of heat stabilizer used is, for example, 0.01 × 10⁻¹⁶ per mole of dicarboxylic acid component (B). -4 ~100×10 -4 moles, preferably 0.1 × 10⁻⁶ -4 ~40×10 -4 moles, more preferably 1 × 10⁻⁶ -4 ~10×10 -4 It is a mole.

[0260] The reaction may be carried out in an inert gas atmosphere (e.g., nitrogen gas; noble gases such as helium or argon). Alternatively, the reaction may be carried out under reduced pressure, for example, at around 10 kPa or less (e.g., 1 × 10⁻⁶). 2 ~1 × 10 4 The reaction can also be carried out at a pressure of approximately Pa, preferably 1 kPa or less (e.g., 0.1 to 1 kPa), and more preferably 0.2 kPa or less (e.g., 0.1 to 0.15 kPa). The transesterification reaction may be carried out under an inert gas atmosphere such as nitrogen gas, and the polycondensation reaction may be carried out under reduced pressure. The reaction temperature can be selected according to the polymerization method; for example, the reaction temperature in the melt polymerization method is approximately 150 to 320°C (e.g., 250 to 290°C), preferably 250 to 310°C (e.g., 260 to 280°C), and more preferably 270 to 300°C.

[0261] After the reaction is complete, the resulting polyester resin may be separated and purified by conventional methods, such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, or a combination thereof.

[0262] Method for manufacturing raw material polyester resin 2 Method 2 is a method in which the raw material polyester is a polyester resin (particularly polycarbonate resin) having at least a carbonate ester bond, and includes, for example, a method of reacting (polymerizing or polycondensing) a polymerization component (monomer component) containing a diol component (A) and a carbonate bond forming component (C), and specifically includes the phosgene method (solvent method) and the transesterification method (melt method), with the transesterification method being preferred because it does not require a solvent.

[0263] In the transesterification method, the proportion of diester carbonates as the carbonate bond-forming component (C) is, for example, 0.8 to 1.5 moles, preferably 0.9 to 1.2 moles, and more preferably 1 to 1.1 moles, per mole of the diol component (A).

[0264] Transesterification reactions may be carried out in the presence of conventional catalysts. Typically, base catalysts are used as catalysts, such as nitrogen-containing compounds, elemental metals, or metal compounds.

[0265] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides and tertiary amines.

[0266] Examples of quaternary ammonium hydroxides include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; and trialkyl-aralkylammonium hydroxides such as trimethylbenzylammonium hydroxide.

[0267] Examples of tertiary amines include trialkylamines such as trimethylamine and triethylamine; dialkyl-aralkylamines such as dimethylbenzylamine; and triarylamines such as triphenylamine.

[0268] Examples of metals contained in elemental metals or metal compounds include alkali metals such as sodium, alkaline earth metals such as magnesium, calcium, and barium, transition metals such as titanium, manganese, and cobalt, group 12 metals of the periodic table such as zinc and cadmium, group 13 metals of the periodic table such as aluminum, group 14 metals of the periodic table such as germanium and lead, and group 15 metals of the periodic table such as antimony. Examples of metal compounds include alkoxides or phenoxides of the aforementioned metals; organic acid salts such as acetates and propionates; inorganic acid salts such as borates, carbonates, or bicarbonates; oxides; and hydroxides.

[0269] The catalyst can be used alone or in combination of two or more types. Preferred catalysts are alkali metal or alkaline earth metal carbonates or bicarbonates, and more preferably alkali metal carbonates or bicarbonates such as sodium bicarbonate (especially alkali metal bicarbonates). The amount of catalyst used is, for example, 0.001 × 10⁻¹⁶ per mole of diol component (A). -4 ~100×10 -4 Moles, preferably in the following steps: 0.01 × 10 -4 ~40×10 -4 moles, 0.03 × 10⁻⁶ -4 ~10×10 -4 moles, 0.05 × 10⁻⁶ -4 ~1 × 10 -4 moles, 0.08 × 10⁻⁶ -4 ~0.5 × 10 -4 moles, 0.1 × 10⁻⁶ -4 ~0.3 × 10 -4 It is a mole.

[0270] Furthermore, the reaction may be carried out in the presence of additives such as stabilizers, if necessary. Examples of stabilizers include antioxidants and heat stabilizers.

[0271] The reaction can usually be carried out in an inert gas atmosphere (e.g., nitrogen gas; noble gases such as helium or argon). Alternatively, the reaction can be carried out under reduced pressure, for example, around 0.1 to 1 kPa, preferably progressively to 0.5 kPa or less, 0.2 kPa or less, and 0.13 kPa or less. The reaction temperature can be selected according to the polymerization method; for example, in the transesterification method, the reaction temperature is, for example, 150 to 320°C, preferably 200 to 310°C (e.g., 250 to 290°C), and more preferably 250 to 300°C (e.g., 260 to 280°C). In particular, when using diphenyl carbonate as the diester carbonate, polycondensation while distilling off phenol under high temperature and reduced pressure is effective.

[0272] After the reaction is complete, the resulting thermoplastic resin may be separated and purified by conventional methods, such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, or a combination thereof.

[0273] Furthermore, as the diol component used in manufacturing method 2, for example, a polyester diol containing a diol unit (A) (a polyester resin having hydroxyl groups at both ends) may be used to prepare the polyester carbonate resin. The polyester diol may be prepared by manufacturing method 1 or the like.

[0274] (Physical properties of the raw material polyester resin) In the method disclosed herein, the decrease in molecular weight due to recycling is suppressed, that is, the molecular weight is effectively improved by the repolymerization process [for example, regenerated to a molecular weight equivalent to or greater than that of virgin polyester resin (unused or new polyester resin)], so the weight-average molecular weight Mw of the raw polyester resin is not particularly limited. The weight-average molecular weight Mw of the virgin polyester resin (raw polyester resin before molding into a predetermined molded body) may be, for example, around 15,000 or more (for example, around 20,000 to 200,000) in terms of standard polystyrene, and preferably in the following increments: 25,000 to 100,000, 30,000 to 80,000, 35,000 to 60,000, and 40,000 to 50,000. When the weight-average molecular weight Mw is in a moderate range that is not too low, it tends to suppress the decrease in mechanical properties and moldability (or productivity).

[0275] The glass transition temperature (Tg) of the raw polyester resin depends on the constituent units and their composition ratios, but may be as low as 100-180°C (e.g., 110-170°C), and is preferably 120-160°C (e.g., 130-150°C). When the Tg is within a moderate range that is not too low, discoloration (or staining) is more easily suppressed when exposed to high-temperature environments during manufacturing (molding), storage, and use, and deformation or deterioration in high-temperature environments after molding to a predetermined shape tends to be more easily suppressed. When the Tg is within a moderate range that is not too high, it tends to be easier to suppress a decrease in moldability or productivity (especially injection moldability).

[0276] The refractive index nD of the raw polyester resin may be, for example, about 1.5 or higher (for example, about 1.55 to 1.7) at a temperature of 20°C and a wavelength of 589 nm, and preferably in the following increments: 1.6 to 1.68, 1.61 to 1.67, 1.62 to 1.66, and 1.63 to 1.65. The refractive index may be adjusted as appropriate depending on the application. For example, when used in optical lenses, a low refractive index is acceptable, but a high refractive index is often preferred. When used in optical films (such as phase difference films), the refractive index does not necessarily have to be high and is not particularly limited.

[0277] The Abbe number νD of the raw polyester resin may be, for example, 60 or less (e.g., 15 to 40) at a temperature of 20°C, preferably 35 or less (e.g., 17 to 30), and more preferably 28 or less (e.g., 20 to 25). The Abbe number may be adjusted as appropriate depending on the application. For example, when used in optical lenses, a low or high Abbe number may be used depending on the usage conditions. When used in optical films (such as phase difference films), the Abbe number is not particularly limited.

[0278] The birefringence of the raw polyester resin may be evaluated by the birefringence of a stretched film (birefringence at 3x stretching or 3x birefringence) obtained by uniaxially stretching a film formed from the resin alone at 3x its free end, as described later in the examples. The absolute value of the 3x birefringence is, for example, 0 to 100 × 10 at a measurement temperature of 20°C and a wavelength of 600 nm. -4 It may be within a certain range, and when used in applications such as optical lenses, preferably in the following steps: 80 × 10 -4 Below, 50 x 10 -4 Below, 30 x 10 -4 Below, 20 x 10 -4 Below, 10 x 10 -4 Below, 5 x 10 -4 Below, 3 x 10 -4 Below, 2 x 10 -4 Below, 1 x 10 -4 The following applies. Note that the 3x birefringence may be adjusted as appropriate depending on the application. For example, when used in optical lenses, low birefringence is often preferable, and when used in optical films (such as polarizing plate protective films or phase difference films), high or low birefringence may be used depending on the usage conditions.

[0279] In this specification and in the claims, the weight-average molecular weight Mw, glass transition temperature Tg, refractive index nD, Abbe number νD, and birefringence (triple birefringence) can be measured by the methods described in the examples below.

[0280] The raw material polyester resin may be crystalline (crystalline polymer), but it is preferable that it be amorphous (amorphous polymer), especially for applications such as optical lenses and optical films.

[0281] (Additives) The raw polyester resin may contain conventional additives as needed. These additives may include, for example, fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, flame retardant aids, plasticizers, lubricants, stabilizers [e.g., antioxidants, UV absorbers, heat stabilizers, etc., specifically the stabilizers exemplified in the section on (method of manufacturing the raw polyester resin)], mold release agents, antistatic agents, dispersants, compatibilizers, flow regulators, leveling agents, defoamers, surface modifiers, stress reducers, carbon materials, etc. Additives may be used individually or in combination of two or more. Preferred additives include stabilizers (antioxidants, heat stabilizers, etc.) and mold release agents.

[0282] The total proportion of additives is, for example, about 50 parts by mass or less (for example, about 30 parts by mass or less), preferably 10 parts by mass or less (for example, 0.0001 to 5 parts by mass), more preferably 1 part by mass or less (for example, 0.001 to 0.5 parts by mass), and particularly preferably 0.1 parts by mass or less (for example, 0.003 to 0.05 parts by mass), based on 100 parts by mass of the raw material polyester.

[0283] The additive may be added to the raw polyester resin during the manufacturing process (for example, during the polymerization reaction), or it may be mixed with the manufactured raw polyester resin by conventional methods such as dry or wet mixing or melt kneading.

[0284] (Material: Polyester resin form) The raw material polyester resin is not particularly limited, but is usually scrap or waste material (waste polyester resin). Preferred waste polyester resin is scrap or waste material generated in the process of manufacturing a predetermined molded article (or product) containing the raw material polyester resin, and more preferably scrap or waste material generated in the process of manufacturing optical components. Examples include sprues and runners generated during the molding of injection molded articles (e.g., optical lenses), both sides (edges) generated during the molding of film (sheet) molded articles (e.g., optical films), defective molded articles (or products) (lot-out products), out-of-model products, or stock products.

[0285] Such scraps or waste materials typically have a lower molecular weight than the polyester resin before molding [for example, virgin (unused or new) polyester resin used to manufacture a specific molded body (or product)] due to the effects of thermal history during molding (e.g., hydrolysis), resulting in a decrease in mechanical properties and changes in melt viscosity, making material recycling difficult. However, the method of this disclosure not only effectively improves the molecular weight through the repolymerization process, but also depolymerizes only partially (to the oligomer level), allowing for easier and more efficient production (recycling) of recycled polyester resin than chemical recycling, which depolymerizes almost completely (substantially to the monomer level).

[0286] Furthermore, since the composition of the raw material polyester resin (or virgin polyester resin) is known in the aforementioned scraps or waste materials, and impurities or foreign substances are often less likely to be present, they are particularly suitable for use in pre-consumer recycling (or in-process recycling).

[0287] [Depolymerization process] In the depolymerization step, a diol component is added to the raw polyester resin (waste polyester resin), and the raw polyester resin is partially depolymerized in the presence of a transesterification catalyst to prepare the decomposition product. In the depolymerization step of the method disclosed herein, a transesterification catalyst is not necessarily required (depolymerization may be carried out in the absence of a transesterification catalyst), but it is preferable to carry out the reaction in the presence of a transesterification catalyst in order to enable easy or efficient depolymerization.

[0288] In the method of this disclosure, it is not necessary to add additional (or supplemental) monomer components to be introduced into the recycled polyester resin in the depolymerization step and / or repolymerization step, but it is preferable to add them as needed. The recycling rate, as described later, can be adjusted by the additional (or supplemental) monomer components. As mentioned above, from the viewpoint of producing a recycled polyester resin that is substantially identical or of the same type (same system) as the raw material polyester resin (or virgin polyester resin), it is preferable that the composition ratio of each monomer component contained in the additional (or supplemental) monomer component is substantially identical or of the same degree as the composition (and composition ratio) in the raw material polyester resin (i.e., it is preferable that it is substantially identical, including preferred embodiments, to the types of constituent units and their composition ratios, and the combination of representative constituent units of the polyester resin described in the [raw material polyester resin] section above).

[0289] Furthermore, from the viewpoint of suppressing polymerization defects, the additional (or supplemented) monomer component is preferably a component that is difficult to vaporize (or sublimate) in the depolymerization step and / or repolymerization step (for example, a component whose vapor pressure is substantially zero in the depolymerization step and / or repolymerization step).

[0290] (Diol component added in the depolymerization process (A d )) In the depolymerization process, the diol component (A) is mixed with the raw material polyester resin. dAs for the components, they are not particularly limited as long as the raw polyester resin can be at least partially depolymerized by the transesterification reaction, and can be appropriately determined depending on the type or composition (composition of constituent units) of the raw polyester resin, the type or composition of the recycled polyester resin to be prepared, the recycling rate described later, etc. That is, a typical diol component (A d Examples of these include diol compounds as additional or supplementary monomer components to be introduced into recycled polyester resins [for example, a diol component (A) corresponding to a diol unit (A) in the raw material polyester resin], and alkylene glycol components (E) described later. These may be used individually or in combination of two or more.

[0291] Diol component (A d It is preferable that the additional monomer component contains at least a diol component (A) corresponding to the diol unit (A) in the raw polyester resin. d The composition (and composition ratio) of the diol component (A) in the raw polyester resin is preferably substantially the same as or to the same extent as the composition (and composition ratio) of the diol unit (A) in the raw polyester resin [for example, if the diol unit (A) in the raw polyester resin is formed of a predetermined proportion of diol units (A1) and (A2), then the diol component (A d ) preferably contains diol components (A1) and (A2) as diol component (A) in the predetermined proportions. This makes it easier to produce recycled polyester resin that is substantially the same as or of the same type (same system) as the raw polyester resin (or virgin polyester resin) while adjusting the recycling rate described later.

[0292] (Dicarboxylic acid component added during the depolymerization process (B)) When the raw material polyester resin is a polyester resin having at least an ester bond in its main chain, that is, a polyester resin (particularly a polyester resin) containing a diol unit (A) and a dicarboxylic acid unit (B), the dicarboxylic acid component (B) corresponding to the dicarboxylic acid unit (B) is added or supplemented as a monomer component in the depolymerization step, and the diol component (A d ) may be added together with the above. If the dicarboxylic acid component (B) added as an additional monomer component is in the form of an acid (Brønsted acid), it may act as a transesterification catalyst in the depolymerization step, as will be described later.

[0293] Furthermore, the composition (and composition ratio) of the dicarboxylic acid component (B) added in the depolymerization step is preferably substantially the same as or to the same extent as the composition (and composition ratio) of the dicarboxylic acid units (B) in the raw polyester resin. [For example, if the dicarboxylic acid units (B) in the raw polyester resin are formed of dicarboxylic acid units (B1) and (B2) in predetermined proportions, the dicarboxylic acid component (B) added in the depolymerization step preferably contains dicarboxylic acid components (B1) and (B2) in the predetermined proportions.] This makes it easier to produce recycled polyester resins that are substantially the same as or of the same type (same system) as the raw polyester resin (or virgin polyester resin) while adjusting the recycling rate, as described later.

[0294] Furthermore, the diol component (A) added in the depolymerization process d Preferably, the composition (composition ratio) of each polymer component in the mixture (additional or supplementary monomer component) of the diol component (A) in the raw polyester resin and the dicarboxylic acid component (B) added in the depolymerization step is substantially the same as or to the same extent as the composition (and composition ratio) of each constituent unit of the diol unit (A) and dicarboxylic acid unit (B) in the raw polyester resin. In other words, it is preferable that by polymerizing the mixture (additional or supplementary monomer component), a polyester resin exhibiting substantially the same composition (and composition ratio) as the raw polyester resin can be prepared. In particular, the diol component (A) added in the depolymerization step is preferable. dPreferably, the ratio of the total number of moles of diol component (A) in the mixture to the total number of moles of dicarboxylic acid component (B) added in the depolymerization step is substantially about 1 / 1.

[0295] Furthermore, if the raw polyester resin contains constituent units other than diol units (A) and dicarboxylic acid units (B) [for example, carbonate units (C)], it is preferable to add the polymerization component corresponding to this constituent unit [carbonate bond-forming component (C)] as an additional monomer component in the depolymerization step and / or repolymerization step (preferably the depolymerization step) in accordance with the composition ratio in the raw polyester resin.

[0296] (Alkylene glycol component (E)) When the raw material polyester resin is a polyester resin having at least ester bonds in its main chain, i.e., a polyester resin containing diol units (A) and dicarboxylic acid units (B) [preferably a polyester resin containing at least diol units (A2) and dicarboxylic acid units (B), particularly a polyester resin], the diol component (A) added in the depolymerization step is more likely to suppress polymerization defects in the repolymerization step. d Preferably, the compound contains at least an alkylene glycol component (E).

[0297] Diol component (A d The alkylene glycol component (E) in ) is the diol component (A d It is preferable that the diol component (A2), which may be included as diol component (A) (i.e., additional monomer component) in ), is the same diol compound, but the roles of the two are different. For details, see diol component (A dThe diol component (A2) in the mixture is added with the purpose of depolymerizing the raw polyester resin by transesterification and introducing it into the recycled polyester resin in the repolymerization process (incorporating it as a constituent unit). In contrast, the alkylene glycol component (E) also depolymerizes the raw polyester resin by transesterification, but in the repolymerization process, it is basically distilled off or removed from the reaction system under high temperature and reduced pressure conditions, and does not necessarily have to be incorporated as a constituent unit in the recycled polyester resin.

[0298] Specifically, as described in Reference Example 3 in the Examples section, the diol component (A d If the polymer does not contain the alkylene glycol component (E), then if the molar ratio (ratio of the total number of moles of each component) A / B of the diol component (A) and dicarboxylic acid component (B) added as additional monomer components deviates from A / B = 1 / 1 [for example, if the dicarboxylic acid component (B) is slightly in excess], even slight deviations such as weighing errors can lead to polymerization failure. However, if the polymer contains the alkylene glycol component (E), which can be distilled or removed in the repolymerization step, then in the reaction system of the depolymerization step, the diol component will be in excess of the dicarboxylic acid component. However, as the alkylene glycol component (E) is distilled out in the repolymerization step, the molar ratio of the diol component / dicarboxylic acid component in the reaction system approaches 1 / 1, thus effectively suppressing polymerization failure.

[0299] Note that diol component (A d ) may contain an alkylene glycol component (E) without containing additional monomer components. That is, the recycling rate may be substantially 100%, but the glass transition temperature Tg may decrease due to the side reaction of the alkylene glycol component (E), therefore, the diol component (A d It appears that including both the additional monomer component and the alkylene glycol component (E) makes it easier to produce recycled polyester resins that exhibit physical properties equivalent to those of virgin polyester resins.

[0300] Also, diol component (Ad When the reaction system contains an alkylene glycol component (E), it is easier to reduce the viscosity of the reaction system and make the reaction system more homogenized, allowing for smooth depolymerization.

[0301] The alkylene glycol component (E) is a linear or branched alkylene glycol, such as ethylene glycol, trimethylene glycol, propylene glycol, butanediol, etc. 2-6 Examples include alkylene glycols. The alkylene glycol component (E) can be used alone or in combination of two or more types. Preferred alkylene glycol component (E) is C 2-4 Alkylene glycol is preferred, with ethylene glycol being particularly preferred. Note that the diol component (A d If the mixture contains both an alkylene glycol component (E) and a diol component (A2) [as an additional monomer component, diol component (A)], it is preferable that the type of alkylene glycol component (E) is the same as the type of diol component (A2).

[0302] The amount of alkylene glycol component (E) added is not particularly limited, but is, for example, 1 part by mass or more (e.g., 3 to 200 parts by mass), preferably 5 to 150 parts by mass (e.g., 6 to 110 parts by mass), and more preferably 7 to 80 parts by mass (e.g., 8 to 50 parts by mass) per 100 parts by mass of the raw material polyester resin. When the amount of alkylene glycol component (E) is within a moderate range that is not too little, it tends to effectively suppress polymerization defects in the repolymerization process and facilitate the smooth progress of depolymerization (transesterification reaction) in the depolymerization process. When it is within a moderate range that is not too much, it tends to be easily or efficiently distilled off or removed in the repolymerization process.

[0303] (Carbonate bond-forming component added during the depolymerization process (C)) When the raw material polyester resin is a polyester resin having at least a carbonate ester bond in its main chain, i.e., a polyester resin containing a diol unit (A) and a carbonate unit (C) (particularly a polycarbonate resin), a carbonate bond-forming component (C) corresponding to the carbonate unit (C) [preferably a diester carbonate such as diphenyl carbonate (DPC)] is added or supplemented as a monomer component in the depolymerization step and / or repolymerization step (preferably in the depolymerization step) to form the diol component (A). d ) may be added together with this.

[0304] The composition (and composition ratio) of the carbonate bond-forming component (C) added in the depolymerization step may be substantially the same as or to the same extent as the composition (and composition ratio) of the carbonate units (C) in the raw polyester resin, but it is preferable to add a slightly excessive amount of the carbonate bond-forming component (C) (for example, 1 to 10 mol%, preferably about 3 to 7 mol%, more than the composition of the carbonate units (C) in the raw polyester resin). For example, if the molar ratio of carbonate units (C) to diol units (A) in the raw polyester resin is 1 / 1, then the diol component (A d Preferably, a diol component (A) corresponding to the diol unit (A) in the raw polyester resin is added as a component, and for every mole of the added diol component (A), for example, 1.01 to 1.1 moles, preferably 1.03 to 1.07 moles, of a carbonate bond-forming component (C) [preferably diphenyl carbonate (DPC) or other diester carbonates] is added. This makes it easier to produce a recycled polyester resin that is substantially identical or of the same type (same system) as the raw polyester resin (or virgin polyester resin) while adjusting the recycling rate described later.

[0305] (Transesterification catalyst) The depolymerization step may be carried out in the presence of a transesterification catalyst as needed. When carried out in the presence of a transesterification catalyst, catalysts present or remaining in the raw polyester resin [catalysts used in the production of the raw polyester resin, for example, the catalysts described in the section on (method of producing the raw polyester resin)] or dicarboxylic acid component (B) as an additional monomer component [dicarboxylic acid component (B) in the form of an acid (Brønsted acid)] may be used as transesterification catalysts in the depolymerization step, or a new transesterification catalyst may be added separately. The transesterification catalyst added in the depolymerization step is not particularly limited as long as it is a catalyst capable of depolymerizing the raw polyester resin by transesterification reaction, and conventional transesterification catalysts can be used, for example, the catalysts described in the section on (method of producing the raw polyester resin) may be used. Transesterification catalysts can be used alone or in combination of two or more types.

[0306] For example, if the raw material polyester resin is a polyester resin having at least an ester bond in its main chain, that is, a polyester resin containing a diol unit (A) and a dicarboxylic acid unit (B) (particularly a polyester resin), then a conventional transesterification (or esterification) catalyst (metal catalyst) as exemplified in section 1 of the method for producing the raw material polyester resin, such as a Lewis acid, can be used. Specifically, examples include metal catalysts or Lewis acid catalysts active in transesterification (esterification) reactions of manganese compounds (e.g., manganese organic salts or their hydrates, such as manganese acetate tetrahydrate), calcium compounds (e.g., calcium organic salts or their hydrates, such as calcium acetate monohydrate), titanium compounds (e.g., titanium alkoxides such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, titanium organic salts such as titanium oxalate and potassium titanium oxalate), germanium compounds (e.g., germanium oxides such as germanium dioxide, germanium hydroxides such as germanium hydroxide, germanium organic salts such as germanium oxalate, germanium tetraethoxide and germanium-n-butoxide), and antimony compounds (e.g., antimony oxides such as antimony trioxide, antimony organic salts such as antimony acetate, and antimony complexes such as antimony ethylene glycolate). Catalysts can be used individually or in combination of two or more types. Preferred catalysts are manganese compounds, and more preferably manganese organic salts or their hydrates, such as manganese acetate tetrahydrate.

[0307] Furthermore, if the raw material polyester resin is a polyester resin having at least a carbonate ester bond in its main chain, that is, a polyester resin containing diol units (A) and carbonate units (C) (particularly polycarbonate resin), then the base catalyst exemplified in section 2 of the method for producing the raw material polyester resin (preferably an alkali metal or alkaline earth metal carbonate or bicarbonate, more preferably an alkali metal carbonate or bicarbonate such as sodium bicarbonate, and particularly preferably an alkali metal bicarbonate) can be used.

[0308] The amount of transesterification catalyst added in the depolymerization step [excluding the catalyst present or remaining in the raw polyester resin and the dicarboxylic acid component (B) in the form of an acid (Brønsted acid) as an additional monomer component] is, for example, 0 to 30 × 10 parts by mass of the total amount of the raw polyester resin and additional monomer components [total amount excluding alkylene glycol component (E)]. -5 Mass portion (e.g., 0.01 × 10) -5 ~20×10 -5 It may be approximately 0.1 × 10⁻¹⁰ parts by mass, preferably 0.1 × 10⁻¹⁰. -5 ~10×10 -5 This is the mass part.

[0309] When the raw material polyester resin is a polyester resin having at least ester bonds in its main chain, i.e., a polyester resin (especially a polyester resin) containing diol units (A) and dicarboxylic acid units (B), the amount of transesterification catalyst added in the depolymerization step [the amount added excluding the catalyst present or remaining in the raw material polyester resin and the dicarboxylic acid component (B) in the form of an acid (Brønsted acid) as an additional monomer component] is, for example, 0 to 10 × 10 parts by mass of the total amount of the raw material polyester resin and additional monomer components [total amount excluding alkylene glycol component (E)]. -5 Mass portion (e.g., 0.5 × 10) -5 ~8×10 -5 It may be approximately 1 × 10⁻¹⁰ units in mass, preferably 1 × 10⁻¹⁰ units in mass. -5 ~6×10 -5 Mass portion (e.g., 2.5 × 10) -5 ~5×10 -5 (This is the mass part.)

[0310] When the raw material polyester resin is a polyester resin having at least a carbonate ester bond in its main chain, i.e., a polyester resin containing diol units (A) and carbonate units (C) (particularly polycarbonate resin), the amount of transesterification catalyst added in the depolymerization step [excluding the catalyst present or remaining in the raw material polyester resin and the dicarboxylic acid component (B) in the form of an acid (Brønsted acid) as an additional monomer component] is, for example, 0 to 5 × 10 parts by mass of the total amount of the raw material polyester resin and additional monomer components. -5 Mass portion (e.g., 0.05 × 10) -5 ~3×10 -5 It may be approximately 0.1 × 10⁻¹⁰ parts by mass, preferably 0.1 × 10⁻¹⁰. -5 ~0.5 × 10 -5 This is the mass part.

[0311] (Reaction conditions for the depolymerization process) The depolymerization step may be carried out in air or in an inert gas atmosphere (e.g., nitrogen gas; noble gases such as helium or argon), and is preferably carried out in an inert gas atmosphere such as nitrogen gas. The reaction may also be carried out under atmospheric pressure with stirring. The reaction temperature is, for example, about 150 to 300°C, preferably 200 to 280°C, more preferably 230 to 270°C, and particularly preferably 240 to 260°C. The reaction time is not particularly limited and can be adjusted as appropriate according to the amount of components used, and it is sufficient that the depolymerization of the raw material polyester resin proceeds partially or to some extent, resulting in low molecular weight (oligomerization) (it is not necessary to depolymerize completely or almost to the monomer level). For example, as an additional monomer component [as dicarboxylic acid component (B)], a dicarboxylic acid or its ester (e.g., C such as methyl dicarboxylic acid ester) may be used. 1-4 When adding alkyl esters, etc., add water or an alcohol corresponding to the ester portion of the dicarboxylic acid ester (such as methanol). 1-4 Since alkanols (and other substances) are distilled or removed from the reaction system by transesterification during the depolymerization step, the decomposition product obtained may be subjected to the repolymerization step after confirming the completion of the distillation of water or alcohol.

[0312] After the reaction is complete, the resulting decomposition products may be separated and purified from impurities and foreign matter by conventional methods, such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, or a combination thereof. However, with the method disclosed herein, even if the decomposition products are subjected to the repolymerization step without purification, a relatively high-quality recycled polyester resin (for example, equivalent to that of virgin polyester resin) can be produced.

[0313] (decomposition products) Decomposition products include decomposition products of the raw material polyester resin (for example, diol components (A d This includes oligomer components that are transesterified with other monomers (for example, oligomer components that are transesterified with other monomers). If additional monomer components are added during the depolymerization process, these additional monomer components or their transesterified counterparts (for example, oligomer components with a low degree of polymerization such as trimers) may be further included.

[0314] The decomposition products obtained in the depolymerization step only need to have a lower molecular weight than the raw polyester resin before depolymerization. The weight-average molecular weight Mw of the decomposition products may be, for example, 1000 or more (e.g., 2000 to 50000, preferably 3000 to 42000), preferably 5000 or more (e.g., 6000 to 35000), more preferably 7000 to 30000 (e.g., 8000 to 25000), and particularly preferably 10000 to 20000 (e.g., 12000 to 15000). When the weight-average molecular weight (Mw) of the decomposition products is within a moderate range and not too low, they can be easily and efficiently manufactured. When the weight-average molecular weight (Mw) of the decomposition products is within a moderate range and not too high, the molecular weight distribution of the recycled polyester resin obtained in the repolymerization process tends to be similar to that of the virgin polyester resin (less likely to have a bimodal or broad molecular weight distribution), and physical properties such as mechanical properties and melt viscosity tend to be easily adjusted to be similar.

[0315] [Repolymerization process] In the repolymerization process, the decomposition products obtained in the depolymerization process are polymerized (polycondensed) to produce (regenerate) a recycled polyester resin.

[0316] The polymerization method in the repolymerization step can be a conventional method depending on the type of raw polyester resin or recycled polyester resin, for example, the method described in the section above (Method for producing raw polyester resin) can be used. A preferred method is a melt polymerization method in which the decomposition product obtained by heating in the depolymerization step is heated and the pressure is reduced to promote polycondensation.

[0317] (Polymerization catalyst, stabilizer) In the repolymerization step, the reaction may be carried out in the presence of a polymerization catalyst (polycondensation catalyst) and stabilizers (thermal stabilizers, antioxidants, etc.) as needed. The polymerization catalyst and stabilizers are preferably added when the raw material polyester resin is a polyester resin having at least ester bonds in its main chain, i.e., a polyester resin (particularly a polyester resin) containing diol units (A) and dicarboxylic acid units (B).

[0318] Furthermore, if polymerization is possible in the repolymerization step using a transesterification catalyst added in the depolymerization step, the polymerization catalyst (polycondensation catalyst) does not necessarily need to be added in the repolymerization step. The polymerization catalyst (polycondensation catalyst) may be added when the raw material polyester resin is a polyester resin having at least ester bonds in its main chain, as described above. Examples include conventional catalysts usable in polycondensation reactions, specifically conventional transesterification (or esterification) catalysts such as Lewis acids, as exemplified in section 1 of the method for producing the raw material polyester resin [for example, metal catalysts such as the transesterification catalyst exemplified in the section [Depolymerization Step]]. The polymerization catalyst added in the repolymerization step can be used alone or in combination of two or more types. A preferred polymerization catalyst to be added in the repolymerization step is a germanium compound, and more preferably a germanium oxide such as germanium dioxide.

[0319] The amount of polymerization catalyst added in the repolymerization process is, for example, 0.1 × 10⁻¹⁴ parts by mass of the total amount of raw polyester resin and additional monomer components [total amount excluding alkylene glycol component (E)]. -5 ~100×10 -5 Mass part (e.g., 1 × 10) -5 ~50×10 -5 It may be approximately 3 × 10⁻¹⁰ units in mass, preferably 3 × 10⁻¹⁰ units in mass. -5 ~40×10 -5 Mass portion, more preferably 12 × 10 -5 ~25×10 -5 This is the mass part.

[0320] In the repolymerization step, stabilizers (heat stabilizers, antioxidants, etc.) may or may not be added as needed. Stabilizers are preferably added when the polymerization catalyst (polycondensation catalyst) is added in the repolymerization step, and may also be added to deactivate the transesterification catalyst added in the depolymerization step. Examples of stabilizers (heat stabilizers, antioxidants, etc.) include those exemplified in section 1 of the method for producing the raw material polyester resin (e.g., phosphorus compounds such as trimethyl phosphate). Stabilizers can be used alone or in combination of two or more. Preferred stabilizers are phosphorus compounds, and more preferably alkyl phosphates such as trimethyl phosphate.

[0321] The amount of stabilizer added in the repolymerization process is, for example, 0.1 × 10⁻¹⁴ parts by mass of the total amount of raw polyester resin and additional monomer components [total amount excluding alkylene glycol component (E)]. -5 ~50×10 -5 Mass portion (e.g., 0.5 × 10) -5 ~20×10 -5 It may be approximately 1 × 10⁻¹⁰ units in mass, preferably 1 × 10⁻¹⁰ units in mass. -5 ~10×10 -5 Mass portion, more preferably 4 × 10 -5 ~7×10 -5 This is the mass part.

[0322] (Reaction conditions for the repolymerization process) In the repolymerization step, as mentioned above, the reaction is preferably carried out under heating and reduced pressure, and may also be carried out while stirring. The reaction temperature can be selected according to the polymerization method, for example, about 150 to 320°C, preferably 250 to 300°C, more preferably 260 to 290°C, and particularly preferably 265 to 280°C. The reaction pressure may be, for example, about 10 kPa or less (for example, 0.1 to 1 kPa), and preferably, in stages, 0.5 kPa or less, 0.2 kPa or less, 0.15 kPa or less, and 0.13 kPa or less. The reaction time is not particularly limited and should be adjusted as appropriate to obtain a recycled polyester resin exhibiting the desired weight-average molecular weight Mw.

[0323] After the reaction is complete, the generated recycled polyester resin may be separated and purified from impurities and foreign matter by conventional methods, such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, or a combination thereof, but separation and purification are not necessarily required.

[0324] [Recycled polyester resin] As mentioned above, the recycled polyester resin obtained in the repolymerization process does not necessarily have to be of the same type or composition (and composition ratio) as the raw material polyester resin [it may be recycled as a different type of polyester resin]. However, the method disclosed herein not only suppresses the decrease in molecular weight due to recycling (regeneration), but also makes it easier to regenerate to a composition or physical properties equivalent to virgin polyester resin (unused or new polyester resin). Therefore, it is preferable to regenerate to a polyester resin that is substantially the same as or of the same type (same system) as the raw material polyester resin (or virgin polyester resin). For this reason, the preferred embodiment of the recycled polyester resin is substantially the same as the polyester resin disclosed in the section on [raw material polyester resin] [types of each constituent unit and their composition ratios, representative resins (combinations of representative constituent units), physical properties, etc.].

[0325] Therefore, it is preferable that the composition (and composition ratio) of the recycled polyester resin and the composition (and composition ratio) of the raw polyester resin are substantially the same or of similar proportions. When the ratio of a predetermined constituent unit to the total constituent units of the raw polyester resin is X1 [mol%], and the ratio of the predetermined constituent unit to the total constituent units of the recycled polyester resin is X2 [mol%], the absolute value of X2-X1 for all constituent units forming the raw polyester resin and the recycled polyester resin is, for example, about 15 mol% or less, preferably in stages as follows: 10 mol% or less, 8 mol% or less, 5 mol% or less, 3 mol% or less, 2 mol% or less, and 1 mol% or less.

[0326] In this specification and claims, the proportion (composition ratio) of constituent units of raw polyester resin and recycled polyester resin can be measured based on NMR spectroscopy.

[0327] Furthermore, it is preferable that the physical properties of the recycled polyester resin and the physical properties of the raw polyester resin are substantially the same or of the same degree. Therefore, when comparing the recycled polyester resin and the raw polyester resin before recycling, The absolute value of the difference in refractive index nD is, for example, 0.005 or less, preferably in increments of 0.004 or less, 0.003 or less, 0.002 or less, 0.001 or less, 0.0008 or less, 0.0005 or less, 0.0003 or less, 0.0002 or less, and 0.0001 or less; The absolute value of the difference in Abbe numbers is, for example, 0.5 or less, preferably in stages, 0.4 or less, 0.3 or less, 0.2 or less, and 0.1 or less; The absolute value of the difference in triple birefringence is, for example, 20 × 10 -4 (for example, 16 x 10) -4 Preferably, proceed in the following steps: 15 × 10 -4 Below, 12 x 10 -4 Below, 10 x 10 -4 Below, 8 x 10 -4 Below, 5 x 10 -4 Below, 4 x 10 -4 Below, 3 x 10 -4 Below, 2.5 × 10 -4Below, 2 x 10 -4 Below, 1.5 × 10 -4 Below, 1 x 10 -4 Below, 0.8 × 10 -4 Below, 0.5 × 10 -4 The following; The absolute value of the difference in glass transition temperature Tg is, for example, 5°C or less, preferably in the following steps: 4°C or less, 3°C or less, 2.8°C or less, 2.5°C or less, 2°C or less, 1.8°C or less, 1.5°C or less, and 1°C or less.

[0328] Furthermore, the weight-average molecular weight Mw of the recycled polyester resin may be equal to or greater than that of the raw polyester resin Mw, and it is preferable that it be substantially the same or of similar magnitude. The absolute value of the difference in weight-average molecular weight Mw between the recycled polyester resin and the raw polyester resin before recycling is, for example, 10,000 or less, and preferably in stages as follows: 8,000 or less, 5,000 or less, 3,000 or less, and 2,000 or less.

[0329] The ratio of raw polyester resin to recycled polyester resin (recycling rate) may be substantially 100% by mass (i.e., without using additional or supplementary monomer components). The recycling rate may be, for example, 95% by mass or less (e.g., 10-90% by mass), and preferably in stages as follows: 15-85% by mass, 20-80% by mass, 25-75% by mass, 30-70% by mass, 35-65% by mass, 40-60% by mass, and 45-55% by mass. When the recycling rate is within a moderate range that is not too high, it tends to be easier to produce recycled polyester resin that exhibits physical properties equivalent to virgin polyester resin (in particular, it is easier to suppress the decrease in the glass transition temperature Tg), and when it is within a moderate range that is not too low, it is easier to reduce the environmental burden. [Examples]

[0330] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples.

[0331] [Evaluation Method] ( 1 (H-NMR) The sample is dissolved in a deuterated solvent containing tetramethylsilane as an internal standard, and then analyzed using a nuclear magnetic resonance spectrometer (BRUKER AVANCE III HD). 1 The 1H-NMR spectrum was measured.

[0332] (molecular weight) Using gel permeation chromatography (HLC-8320GPC, manufactured by Tosoh Corporation), the sample was dissolved in tetrahydrofuran (THF), and the weight-average molecular weight (Mw) was measured on a standard polystyrene basis.

[0333] (Glass transition temperature (Tg)) A differential scanning calorimeter (SEIKO INSTRUCTIONS DSC 6220) was used to measure the temperature of a sample placed in an aluminum pan under a nitrogen stream at a heating rate of 10°C / min, in accordance with JIS K 7121, from 30°C to 200°C. The value read from the resulting chart as the midpoint glass transition temperature (Tmg) was adopted as Tg.

[0334] (Refractive index and Abbe number) The sample was heat-pressed at 200-280°C to form a film with a thickness of 200-300 μm. This film was then cut into strips measuring 20-30 mm in length and 10 mm in width to prepare test specimens. The refractive indices nF, nD, and nC of the obtained test specimens were measured using a multi-wavelength Abbe refractometer (ATAGO Corporation "DR-M4 (circulating constant temperature water bath 60-C3)") with 1-bromonaphthalene as the contact solution, at a measurement temperature of 20°C and measurement wavelengths of 486 nm (F line), 589 nm (D line), and 656 nm (C line). The Abbe number was calculated using the following formula.

[0335] Abbe number = (nD-1) / (nF-nC)

[0336] (Birefringence) The sample was hot-pressed at 200-280°C to form a film with a thickness of 200-600 μm, and this film was cut into strips measuring 10 mm in length and 50 mm in width to form test specimens. The obtained test specimens were uniaxially stretched at the free end at a stretching speed of 25 mm / min under a temperature condition of Tg + 10°C to achieve a stretching ratio of 3 times. The retardation was measured using a phase difference film / optical material inspection device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.) at a measurement temperature of 20°C and a measurement wavelength of 600 nm using the rotational analyzer method, and the birefringence (3x birefringence) was calculated by dividing the absolute value by the thickness of the measurement area.

[0337] [polymerizing components] (Diol component) BPEF(registered trademark): 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene BNEF(registered trademark): 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene EG: Ethylene glycol BisA: Bisphenol A (Dicarboxylic acid component or carbonate bond forming component) DMT: Dimethyl terephthalate DMN: 2,6-Dimethyl naphthalenedicarboxylic acid FDP-m(registered trademark): 9,9-bis(2-methoxycarbonylethyl)fluorene CHDA: 1,4-cyclohexanedicarboxylic acid DPC: Diphenyl carbonate

[0338] The structural formulas of each polymerization component are shown below.

[0339] [ka]

[0340] [Synthesis Example 1] The reactor contains 0.70 moles of BPEF, 2.30 moles of EG, 1.0 mole of DMT, and 2 × 10⁻¹⁶ manganese acetate tetrahydrate as a transesterification catalyst. -4Add moles and gradually heat and melt while stirring, raising the temperature to 230°C, then add trimethyl phosphate 5 × 10⁻⁶ -4 Moles, germanium dioxide 22 × 10 -4 Moles were added, and the temperature was gradually increased and the pressure reduced while removing EG until the temperature reached 270°C and the pressure was below 0.13 kPa. After reaching the predetermined stirring torque, the contents were removed from the reactor to obtain polyester resin pellets. The obtained pellets were then used to... 1 Analysis by 1H-NMR revealed that 70 mol% of the diol units introduced into the polyester resin originated from BPEF, 30 mol% from EG, and 100 mol% of the introduced dicarboxylic acid units originated from DMT. The resulting polyester resin had a Mw of 43800, a Tg of 142.0°C, an nD of 1.6328, an Abbe number of 23.4, and a birefringence of 55.0 × 10⁻⁶. -4 That was the case.

[0341] [Reference example 1] In the reactor, 50 parts by mass of polyester resin (raw material polyester resin) obtained in Synthesis Example 1, which has dicarboxylic acid units (terephthalic acid units) derived from the terephthalic acid component, 33.68 parts by mass of BPEF, 8.55 parts by mass of EG, 21.31 parts by mass of DMT, and 3.9 × 10⁻¹⁶ parts by mass of manganese acetate tetrahydrate are added. -3 Add parts by mass, gradually heat and melt while stirring, raise the temperature to 250°C (depolymerization step), then add 5.7 × 10⁻⁶ trimethyl phosphate. -3 Parts by mass: Germanium dioxide 18.0 × 10⁻¹⁴ -3 When part by mass was added and the temperature was gradually increased and the pressure reduced (repolymerization process) until it reached 270°C and 0.13 kPa or less, the DMT vaporized (or sublimated) from the reaction system, causing pipe blockage and preventing the reaction from proceeding, resulting in polymerization failure.

[0342] [Reference example 2] We attempted to produce recycled polyester resin by adding a large amount of EG during the depolymerization process to promote oligomerization of DMT and suppress vaporization (or sublimation). Specifically, the procedure was the same as in Reference Example 1, except that the amount of EG added was changed from 8.55 parts by mass to 15.66 parts by mass. However, the DMT vaporized (or sublimated) from the reaction system, causing pipe blockage and preventing the reaction from proceeding, resulting in polymerization failure.

[0343] [Synthesis Example 2] The reactor contains 0.85 moles of BPEF, 2.15 moles of EG, 0.3 moles of DMN, 0.7 moles of FDP-m, and 2 × 10⁻¹⁶ manganese acetate tetrahydrate as a transesterification catalyst. -4 Add moles, gradually heat and melt while stirring, raise the temperature to 230°C, then add trimethyl phosphate 5 × 10⁻⁶ -4 Moles, germanium dioxide 22 × 10 -4 Moles were added, and the temperature was gradually increased and the pressure reduced while removing EG until the temperature reached 270°C and the pressure was below 0.13 kPa. After reaching the predetermined stirring torque, the contents were removed from the reactor to obtain polyester resin pellets. The obtained pellets were then used to... 1 Analysis by 1H-NMR revealed that 85 mol% of the diol units introduced into the polyester resin originated from BPEF and 15 mol% from EG, while 30 mol% of the introduced dicarboxylic acid units originated from DMN and 70 mol% from FDP-m. The resulting polyester resin had a Mw of 40000, a Tg of 133.4°C, an nD of 1.6423, an Abbe number of 22.5, and a birefringence of 1.0 × 10⁻¹⁴. -4 That was the case.

[0344] [Example 1] In the reactor, add 20 parts by mass of the polyester resin obtained in Synthesis Example 2 (raw material polyester resin), 47.5 parts by mass of BPEF, 21.3 parts by mass of EG, 9.3 parts by mass of DMN, 30.2 parts by mass of FDP-m, and 6.3 × 10⁻¹⁵ parts by mass of manganese acetate tetrahydrate. -3 Add parts by mass, gradually heat and melt under a nitrogen gas atmosphere while stirring, raise the temperature to 250°C (depolymerization step), then add 9.0 × 10⁻⁶ trimethyl phosphate. -3Part mass: Germanium dioxide 28.8 × 10⁻¹⁴ -3 Parts by mass were added, and the temperature was gradually increased and the pressure reduced while removing EG until the temperature reached 270°C and the pressure was 0.13 kPa or less (repolymerization step). After reaching a predetermined stirring torque, the contents were removed from the reactor to obtain pellets of recycled polyester resin. The obtained pellets were then used to... 1 Analysis by 1H-NMR revealed that the composition ratio of the recycled polyester resin was 85 mol% diol units from BPEF and 15 mol% from EG, and 30 mol% dicarboxylic acid units from DMN and 70 mol% from FDP-m. The obtained recycled polyester resin had a Mw of 45,000, a Tg of 134.9°C, an nD of 1.6422, an Abbe number of 22.4, and a birefringence of 0.2 × 10⁻¹⁴. -4 That was the case.

[0345] [Example 2] The amounts of the raw materials polyester resin, BPEF, DMN, and FDP-m obtained in Synthesis Example 2 were changed as shown in the table below, and manganese acetate tetrahydrate was added in a quantity of 3.9 × 10⁻⁶. -3 In parts by mass, add 5.6 × 10⁻⁶ trimethylphosphate -3 The mass portion contains 18.0 × 10⁻¹⁴ germanium dioxide. -3 Recycled polyester resin pellets were obtained in the same manner as in Example 1, except that the mass portion was changed. The composition ratio of the obtained recycled polyester resin was also approximately the same as that of the raw material polyester resin obtained in Synthesis Example 2.

[0346] [Examples 3-4, Reference Example 3] Except for changing the amount of EG used as shown in the table below, we attempted to produce recycled polyester resin in the same manner as in Example 2. In Examples 3 and 4, we obtained pellets of recycled polyester resin, and the composition ratio of each recycled polyester resin was almost the same as that of the raw material polyester resin obtained in Synthesis Example 2. On the other hand, in Reference Example 3, the viscosity of the reaction mixture did not increase easily and the predetermined stirring torque was not reached, resulting in polymerization failure.

[0347] [Example 5] The amounts of the raw materials polyester resin, BPEF, DMN, and FDP-m obtained in Synthesis Example 2 were changed as shown in the table below, and manganese acetate tetrahydrate was added in a quantity of 2.3 × 10⁻⁶. -3 In parts by mass, add 3.4 × 10⁻⁶ trimethylphosphate -3 In the mass part, germanium dioxide is added in 10.8 × 10 -3 Recycled polyester resin pellets were obtained in the same manner as in Example 1, except that the mass portion was changed. The composition ratio of the obtained recycled polyester resin was also approximately the same as that of the raw material polyester resin obtained in Synthesis Example 2.

[0348] [Example 6] The amounts of the raw materials polyester resin, BPEF, DMN, and FDP-m obtained in Synthesis Example 2 were changed as shown in the table below, and manganese acetate tetrahydrate was added in a quantity of 0.8 × 10⁻⁶. -3 Add 1.1 × 10 parts by mass of trimethyl phosphate. -3 The mass portion contains 3.6 × 10⁻⁶ germanium dioxide. -3 Recycled polyester resin pellets were obtained in the same manner as in Example 1, except that the mass portion was changed. The composition ratio of the obtained recycled polyester resin was also approximately the same as that of the raw material polyester resin obtained in Synthesis Example 2.

[0349] [Example 7] The amounts of the raw material polyester resin, BPEF, DMN, and FDP-m obtained in Synthesis Example 2 were changed as shown in the table below (i.e., without adding additional monomer components), and manganese acetate tetrahydrate was added in a quantity of 7.8 × 10⁻⁶. -3 In parts by mass, add 11.3 × 10⁻⁶ trimethylphosphate -3 The mass portion contains 36.0 × 10⁻⁶ germanium dioxide. -3 Recycled polyester resin pellets were obtained in the same manner as in Example 1, except that the mass portion was changed. The composition ratio of the obtained recycled polyester resin was also approximately the same as that of the raw material polyester resin obtained in Synthesis Example 2.

[0350] [Examples 8-9] Recycled polyester resin pellets were obtained in the same manner as in Example 7, except that the amount of EG used was changed as shown in the table below. The composition ratio of the obtained recycled polyester resin was also almost the same as that of the raw material polyester resin obtained in Synthesis Example 2.

[0351] The results are shown in the table below.

[0352] [Table 1]

[0353] As is clear from the results in Table 1, in Reference Examples 1 and 2, which attempted to regenerate a raw polyester resin (Synthesis Example 1) containing dicarboxylic acid units (terephthalic acid units) derived from the terephthalic acid component, it was not possible to obtain recycled polyester resin due to the vaporization (or sublimation) of DMT, as mentioned above. In contrast, in the examples that attempted to regenerate a raw polyester resin (Synthesis Example 2) that did not contain terephthalic acid units, recycled polyester resin was successfully produced in all cases. Moreover, the recycled polyester resin obtained in the examples showed physical properties that were almost equivalent to or better than those of the raw polyester resin before regeneration (Synthesis Example 2), even with a high recycling rate.

[0354] In Example 2, when the change in weight-average molecular weight during the depolymerization process was examined, it was found that Mw was 18,800 in the initial stages of the polymerization process and 13,800 in the later stages of the depolymerization process. From this, it was found that the raw polyester resin with an Mw of 40,000 (Synthesis Example 2) was depolymerized (or oligomerized) to a certain extent by transesterification in the depolymerization process, and then regenerated to near its original molecular weight in the repolymerization process. Normally, in the chemical recycling of polyester resins, the raw polyester resin is completely depolymerized to almost the monomer level (not just partially depolymerized to the oligomer level), and the resulting decomposition products are separated and purified to recover reusable monomer components or mixtures thereof. However, in such conventional methods, the recovery rate decreases due to separation and purification. Also, when recovered as a mixture of multiple monomer components, the composition ratio of the monomer components in the mixture often does not match the composition ratio of the polyester resin before depolymerization (or virgin). Therefore, in order to produce a recycled polyester resin with the same composition as before depolymerization using the aforementioned mixture, it is extremely complicated as it is necessary to analyze and accurately determine the composition ratio of monomer components in the mixture, and then adjust the composition ratio by adding new monomer components. In contrast, in the embodiment of the present invention, it is not necessary to depolymerize down to the monomer level, and separation and purification after the depolymerization step can be omitted, allowing the process to proceed to the repolymerization step. Furthermore, it has been found that a recycled polyester resin with a composition (and physical properties) that is almost the same as or better than that of the original material can be easily and efficiently produced without analyzing and adjusting the composition ratio of the decomposition products (i.e., simply by adding monomer components in the same composition ratio as the raw polyester resin).

[0355] Furthermore, Examples 2-4 and Reference Example 3 are all examples in which the recycling rate was adjusted to approximately 50%, and regeneration was attempted by changing the amount of EG. Reference Example 3 is an example that does not include the excess EG [corresponding to alkylene glycol component (E)] obtained by subtracting the amount of EG introduced into the recycled polyester resin from the amount of EG added. However, possibly due to weighing errors, the total number of moles of the dicarboxylic acid component was slightly higher than the total number of moles of the diol component (it did not become 1 / 1), so the degree of polymerization (or viscosity) could not be sufficiently increased, resulting in polymerization failure as described above. On the other hand, in Examples 2-4 which included the excess EG, the excess EG was removed in the repolymerization process, so the ratio of the total number of moles of the dicarboxylic acid component to the total number of moles of the diol component approached 1 / 1, thus improving the degree of polymerization (or viscosity) and allowing recycled polyester resin to be manufactured without problems. From this, it was found that recycled polyester resin can be manufactured more easily or efficiently when the excess alkylene glycol component (E) is included. In Examples 2-4, no significant difference was observed in the physical properties of the recycled polyester resin even when the amount of EG changed.

[0356] Examples 7-9 show regeneration with a 100% recycling rate [addition of only EG, which corresponds to the alkylene glycol component (E), without additional monomer components], by varying the amount of EG. These examples demonstrate that regeneration is possible even with a 100% recycling rate, and no significant differences were observed in the physical properties of the recycled polyester resin in these examples, indicating no effect from the amount of EG.

[0357] Furthermore, among the examples, a tendency was observed for Tg to decrease slightly when the recycling rate was high. The reason for this is not clear, but it is possible that diol units derived from diethylene glycol are formed by a side reaction of EG.

[0358] [Synthesis Example 3] In the reactor, add 1.0 mol of BPEF, 1.05 mol of DPC, and 2 × 10⁻¹⁶ of sodium bicarbonate. -5Moles were added, and the mixture was gradually heated and melted while stirring. The temperature was raised to 250°C, and then gradually increased while reducing the pressure until it reached 270°C and a pressure of 0.13 kPa or less. After reaching the predetermined stirring torque, the contents were removed from the reactor to obtain polycarbonate resin pellets. The obtained pellets were then processed as follows: 1 Analysis by 1H-NMR revealed that 100 mol% of the diol units in the polycarbonate resin were derived from BPEF. The polycarbonate resin had a Mw of 38700, a Tg of 146.1°C, an nD of 1.6394, an Abbe number of 23.5, and a birefringence of 6 × 10⁻¹⁴. -4 That was the case.

[0359] [Example 10] In the reactor, add 50 parts by mass of the polycarbonate resin obtained in Synthesis Example 3 (raw material polycarbonate resin), 47.2 parts by mass of BPEF, 24.2 parts by mass of DPC, and 1.8 × 10⁻¹⁶ sodium bicarbonate. -4 Parts by mass were added, and the mixture was gradually heated and melted while stirring, raising the temperature to 250°C (depolymerization step). Then, the temperature was gradually increased and the pressure reduced until it reached 270°C and a pressure of 0.13 kPa or less (repolymerization step). After reaching a predetermined stirring torque, the contents were removed from the reactor to obtain pellets of recycled polycarbonate resin. The obtained pellets were then used to... 1 Analysis by 1H-NMR revealed that 100 mol% of the diol units in the recycled polycarbonate resin originated from BPEF. The weight-average molecular weight (Mw) of the obtained recycled polycarbonate resin was 46600, Tg was 149.1°C, nD was 1.6389, Abbe number was 23.4, and birefringence was 7.4 × 10⁻⁶. -4 That was the case.

[0360] [Synthesis Example 4] In the reactor, add 1.0 mol of BisA, 1.05 mol of DPC, and 2 × 10⁻¹⁶ of sodium bicarbonate. -5 Moles were added, and the mixture was gradually heated and melted while stirring. The temperature was raised to 250°C, and then gradually increased while reducing the pressure until it reached 270°C and a pressure of 0.13 kPa or less. After reaching the predetermined stirring torque, the contents were removed from the reactor to obtain polycarbonate resin pellets. The obtained pellets were then processed as follows: 1Analysis by 1H-NMR revealed that 100 mol% of the diol units in the polycarbonate resin were derived from BisA. The polycarbonate resin had a Mw of 43700, a Tg of 142.0°C, an nD of 1.5871, an Abbe number of 30.3, and a birefringence of 52.8 × 10⁻¹⁴. -4 That was the case.

[0361] [Example 11] In the reactor, add 50 parts by mass of the polycarbonate resin obtained in Synthesis Example 4 (raw material polycarbonate resin), 44.89 parts by mass of BisA, 44.23 parts by mass of DPC, and 1.8 × 10⁻¹⁶ parts of sodium bicarbonate. -4 Parts by mass were added, and the mixture was gradually heated and melted while stirring, raising the temperature to 250°C (depolymerization step). Then, the temperature was gradually increased and the pressure reduced until it reached 270°C and a pressure of 0.13 kPa or less (repolymerization step). After reaching a predetermined stirring torque, the contents were removed from the reactor to obtain pellets of recycled polycarbonate resin. The obtained pellets were then used to... 1 Analysis by 1H-NMR revealed that 100 mol% of the diol units in the recycled polycarbonate resin were derived from BisA. The resulting recycled polycarbonate resin had a Mw of 50900, a Tg of 146.2°C, an nD of 1.5866, an Abbe number of 30.4, and a birefringence of 68.3 × 10⁻¹⁴. -4 That was the case.

[0362] The results are shown in the table below.

[0363] [Table 2]

[0364] As is clear from the results in Table 2, recycled polycarbonate resin was successfully produced in all of Examples 10-11, and exhibited physical properties that were almost equivalent to or better than those of the raw material polycarbonate resin before recycling (Synthesis Examples 3-4).

[0365] Furthermore, compared to recycled polycarbonate resin (Examples 10-11), recycled polyester resin (Examples 1-9) appears to be easier to regenerate to a degree more equivalent to the physical properties of the corresponding synthesis examples.

[0366] [Synthesis Example 5] Add 0.80 moles of BPEF, 2.20 moles of EG, and 1.0 mole of CHDA to the reactor, and gradually heat and melt while stirring. After raising the temperature to 230°C, add 5 × 10⁻⁶ trimethyl phosphate. -4 Moles, germanium dioxide 22 × 10 -4 Moles were added, and the temperature was gradually increased and the pressure reduced while removing EG until the temperature reached 270°C and the pressure was below 0.13 kPa. After reaching the predetermined stirring torque, the contents were removed from the reactor to obtain polyester resin pellets. The obtained pellets were then used to... 1 Analysis by 1H-NMR revealed that 80 mol% of the diol units introduced into the polyester resin originated from BPEF, 20 mol% from EG, and 100 mol% of the introduced dicarboxylic acid units originated from CHDA. The resulting polyester resin had a Mw of 47200, a Tg of 123.0°C, an nD of 1.6066, an Abbe number of 27.0, and a birefringence of 5.0 × 10⁻⁶. -4 That was the case.

[0367] [Example 12] In the reactor, 50 parts by mass of the polyester resin obtained in Synthesis Example 5 (raw material polyester resin), 35.1 parts by mass of BPEF, 13.7 parts by mass of EG, and 17.2 parts by mass of CHDA were added. Under a nitrogen gas atmosphere, the mixture was gradually heated and melted while stirring, and the temperature was raised to 250°C (depolymerization step). Then, 5.7 × 10⁻⁶ of trimethyl phosphate was added. -3 Parts by mass: Germanium dioxide 18.0 × 10⁻¹⁴ -3 Parts by mass were added, and the temperature was gradually increased and the pressure reduced while removing EG until the temperature reached 270°C and the pressure was 0.13 kPa or less (repolymerization step). After reaching a predetermined stirring torque, the contents were removed from the reactor to obtain pellets of recycled polyester resin. The obtained pellets were then used to... 1 Analysis by 1H-NMR revealed that the composition ratio of the recycled polyester resin was 80 mol% diol units derived from BPEF, 20 mol% diol units derived from EG, and 100 mol% dicarboxylic acid units derived from CHDA. The obtained recycled polyester resin had a Mw of 49000, a Tg of 125.0°C, an nD of 1.6076, an Abbe number of 26.9, and a birefringence of 2.0 × 10⁻⁶. -4That was the case.

[0368] [Synthesis Example 6] The reactor contains 0.75 moles of BNEF, 2.25 moles of EG, 1.0 mole of FDP-m, and 2 × 10⁻¹⁶ manganese acetate tetrahydrate as a transesterification catalyst. -4 Add moles, gradually heat and melt while stirring, raise the temperature to 230°C, then add trimethyl phosphate 5 × 10⁻⁶ -4 Moles, germanium dioxide 22 × 10 -4 Moles were added, and the temperature was gradually increased and the pressure reduced while removing EG until the temperature reached 270°C and the pressure was below 0.13 kPa. After reaching the predetermined stirring torque, the contents were removed from the reactor to obtain polyester resin pellets. The obtained pellets were then used to... 1 Analysis by 1H-NMR revealed that 75 mol% of the diol units introduced into the polyester resin originated from BNEF, 25 mol% from EG, and 100 mol% of the introduced dicarboxylic acid units originated from FDP-m. The resulting polyester resin had a Mw of 42100, a Tg of 147.0°C, an nD of 1.6620, an Abbe number of 20.3, and a birefringence of 12.0 × 10⁻¹⁴. -4 That was the case.

[0369] [Example 13] In the reactor, add 50 parts by mass of the polyester resin obtained in Synthesis Example 6 (raw material polyester resin), 29.1 parts by mass of BNEF, 10.1 parts by mass of EG, 24.4 parts by mass of FDP-m, and 3.9 × 10⁻¹⁵ parts by mass of manganese acetate tetrahydrate. -3 Add parts by mass, gradually heat and melt under a nitrogen gas atmosphere while stirring, raise the temperature to 250°C (depolymerization step), then add 5.7 × 10⁻⁶ trimethyl phosphate. -3 Parts by mass: Germanium dioxide 18.0 × 10⁻¹⁴ -3 Parts by mass were added, and the temperature was gradually increased and the pressure reduced while removing EG until the temperature reached 270°C and the pressure was 0.13 kPa or less (repolymerization step). After reaching a predetermined stirring torque, the contents were removed from the reactor to obtain pellets of recycled polyester resin. The obtained pellets were then used to... 1Analysis by 1H-NMR revealed that the composition of the recycled polyester resin consisted of 75 mol% diol units derived from BNEF, 25 mol% diol units derived from EG, and 100 mol% dicarboxylic acid units derived from FDP-m. The obtained recycled polyester resin had a Mw of 42200, a Tg of 147.8°C, an nD of 1.6621, an Abbe number of 20.2, and a birefringence of 9.6 × 10⁻⁶. -4 That was the case.

[0370] The results are shown in the table below.

[0371] [Table 3]

[0372] As is clear from the results in Table 3, recycled polyester resin could be produced in all of Examples 12-13, in which the types of polymerization components (and additional monomer components) of the raw polyester were changed, and the resin exhibited physical properties that were almost equivalent to or better than those of the raw polyester resin before recycling (Synthesis Examples 5-6).

[0373] In Example 12, unlike the other examples, no new transesterification catalyst was added during the depolymerization process. However, the catalyst remaining in the raw polyester resin (germanium dioxide) and the dicarboxylic acid (CHDA) added as an additional monomer component acted as transesterification catalysts, and depolymerization (transesterification reaction) proceeded.

[0374] In some examples, the Mw is greater than that of the corresponding synthesis example (raw material polyester resin before regeneration). However, by appropriately setting the reaction conditions in the repolymerization process (for example, shortening the reaction time), it is possible to easily adjust the Mw to be similar to that of the corresponding synthesis example.

[0375] The method described herein demonstrates that it is an excellent recycling method because it is possible to produce recycled polyester resin having physical properties equivalent to those of the polyester resin before depolymerization (or virgin polyester resin) more easily and efficiently than conventional methods. [Industrial applicability]

[0376] The method for producing recycled polyester resins described herein is suitable for recycling polyester resins (particularly pre-consumer recycling or in-process recycling), and can be effectively used, for example, for recycling polyester resins used to form optical components such as optical lenses and optical films [e.g., recycling of scraps and waste materials generated during the molding process of optical components].

[0377] Furthermore, the resulting recycled polyester resin can be used in conventional applications (for example, optical components such as optical lenses and optical films), and may be the same as or of the same type as the raw polyester.

Claims

1. A raw material polyester resin having ester bonds and / or carbonate ester bonds and not containing dicarboxylic acid units derived from terephthalic acid components, contains a diol component (A ｄ A depolymerization step is performed by adding ) and partially depolymerizing the raw material polyester resin in the presence of a transesterification catalyst, A method for producing a recycled polyester resin, comprising a repolymerization step of polymerizing the decomposition product obtained in the depolymerization step to produce a recycled polyester resin.

2. The aforementioned diol component (A ｄ The manufacturing method according to claim 1, wherein the material comprises at least a diol component (A) corresponding to the diol unit (A) in the raw material polyester resin.

3. The aforementioned raw material polyester resin has at least ester bonds, and The manufacturing method according to claim 2, wherein the diol unit (A) forming the raw material polyester resin includes at least one diol unit selected from the diol unit (A1) represented by the following formula (A-1), the diol unit (A2) represented by the following formula (A-2), and the diol unit (A3) represented by the following formula (A-3). 【Chemistry 1】 (In the formula, R １ represents a substituent, and m1 represents an integer from 0 to 8. Z １ａ and Z １ｂ These independently show an arene ring, R ２ａ and R ２ｂ m2a and m2b independently represent substituents, and m2a and m2b independently represent integers of 0 or greater. A １ａ and A １ｂ each independently represent an alkylene group, and n1a and n1b each independently represent an integer of 0 or greater.) 【Chemistry 2】 (In the formula, A ２ (where represents an alkylene group, and n2 represents an integer greater than or equal to 1.) 【Transformation 3】 (In the formula, Y １ This represents a directly bonded, possibly halogenated, divalent hydrocarbon group, oxygen atom, carbonyl group, sulfur atom, or sulfonyl group. Z ２ａ and Z ２ｂ These independently show an arene ring, R ３ａ and R ３ｂ m3a and m3b independently represent substituents, and m3a and m3b independently represent integers greater than or equal to 0. A ３ａ and A ３ｂ (Independently, n3a represents an alkylene group, and n3b ​​independently represents an integer greater than or equal to 0.)

4. The aforementioned raw material polyester resin has at least ester bonds, and The manufacturing method according to claim 2, wherein in the depolymerization step, a dicarboxylic acid component (B) corresponding to the dicarboxylic acid unit (B) in the raw material polyester resin is further added.

5. The aforementioned raw material polyester resin has at least ester bonds, and The manufacturing method according to claim 4, wherein the dicarboxylic acid unit (B) forming the raw material polyester resin includes at least one dicarboxylic acid unit selected from the following formulas (B-1) (B1), (B-2) (B2), and (B-4) (B4). 【Chemistry 4】 (In the formula, R ４ represents a substituent, and m4 represents an integer from 0 to 8. A ４ａ and A ４ｂ (This independently represents an alkylene group.) 【Transformation 5】 (In the formula, Z ３ This shows a polycyclic arene ring, R ５ (where represents a substituent, and m5 represents a non-negative integer.) 【Transformation 6】 (In the formula, W １ It shows an aliphatic hydrocarbon ring, A ５ａ and A ５ｂ These independently show either a direct bond or an alkylene group. R ７ (where represents a substituent, and m7 represents a non-negative integer.)

6. The aforementioned raw material polyester resin has at least ester bonds, The aforementioned diol component (A ｄ The manufacturing method according to any one of claims 1 to 5, wherein the component comprises at least an alkylene glycol component (E).

7. The aforementioned raw material polyester resin has at least a carbonate ester bond, and The manufacturing method according to claim 2, wherein the diol unit (A) that forms the raw material polyester resin includes at least one diol unit selected from the diol unit (A1) and diol unit (A3) described in claim 3.

8. The aforementioned raw material polyester resin has at least a carbonate ester bond, The manufacturing method according to any one of claims 1, 2, and 7, wherein at least a carbonate bond-forming component (C) is added in the depolymerization step and / or the repolymerization step.

9. The ratio of a predetermined constituent unit to the total constituent units of the raw material polyester resin is X １ [mol%], the ratio of the predetermined constituent units to the total constituent units of the recycled polyester resin is X ２ When expressed as [mol%], X ２ -X １ The manufacturing method according to any one of claims 1 to 5 and 7, wherein the absolute value [mol%] of is 15 [mol%] or less for all constituent units.

10. In the recycled polyester resin and the raw material polyester resin, The absolute value of the difference in refractive index nD is 0.005 or less. The manufacturing method according to any one of claims 1 to 5 and 7, wherein the absolute value of the difference in Abbe numbers is 0.5 or less.

11. The manufacturing method according to any one of claims 1 to 5 and 7, wherein the ratio of the raw material polyester resin to the recycled polyester resin is 95% by mass or less.

12. The manufacturing method according to any one of claims 1 to 5 and 7, wherein the decomposition product obtained in the depolymerization step is subjected to the repolymerization step without purification.

13. The manufacturing method according to any one of claims 1 to 5 and 7, wherein the weight-average molecular weight Mw of the decomposition product obtained in the depolymerization step is 5000 or more.

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