Polyester-based resin, and production method and usage for same

Abstract

Provided is a polyester-based resin that is capable of achieving a highly sufficient balance between mechanical characteristics, heat resistance, optical characteristics, and fabricability. The polyester-based resin is formed from: diol units (A) including a first diol unit (A1) represented by formula (1) (in the formula, A1 and A2 each independently represent an alkylene group, n1 and n2 each independently represent an integer of 0 or greater, R1 and R2 each independently represent a substituent, m1 and m2 each independently represent an integer from 0 to 6, and A3 represents a direct bond (single bond) or an alkylene group), a second diol unit (A2) having a diphenylfluorine skeleton, and a third diol unit (A3) having an alkylene skeleton; and dicarboxylic acid units (B) including a dicarboxylic acid unit (B1) having a fused polycyclic arene ring skeleton. The proportion of the first diol unit (A1) is adjusted to 5-60 mol% of the total of the diol units (A), and the proportion of the dicarboxylic acid unit (B1) is adjusted to 50 mol% or more of the total of the dicarboxylic acid units (B).

Description

Polyester resin, its manufacturing method and use

[0001] The present disclosure relates to a polyester resin containing a specific aromatic diol unit and a specific aromatic dicarboxylic acid unit, as well as a method for producing the same and uses thereof.

[0002] Polyester resins have a high refractive index and a high glass transition temperature due to the inclusion of aromatic units (aromatic skeletons) as structural units, and are therefore used as optical materials with a high refractive index and excellent heat resistance. In particular, in recent years, in fields such as optical lenses, a highly satisfactory balance of mechanical properties, heat resistance, optical properties, and moldability has been required. Since a naphthalene skeleton can improve the refractive index and heat resistance of polyester resins, polyester resins incorporating a binaphthalene skeleton have also been proposed.

[0003] Japanese Patent No. 6,631,514 (Patent Document 1) discloses a polyester resin containing, as dihydroxy components, 63 to 81 mol % of structural units having a binaphthalene skeleton and 9 to 27 mol % of structural units having a bisphenylfluorene skeleton, and, as dicarboxylic acid components, structural units derived from naphthalenedicarboxylic acid, terephthalic acid, or esters thereof.

[0004] Japanese Patent Laid-Open Publication No. 2022-154123 (Patent Document 2) discloses a polyester resin or polyester carbonate resin that contains a repeating unit (1) having a bisarylfluorene skeleton and a binaphthalene skeleton, and a repeating unit (2) having a binaphthalene skeleton, in which the ratio of the repeating unit (1) to the repeating unit (2) is (1):(2)=15:85 to 85:15, and the amount of terminal carboxylic acid is 0.8 equivalents / ton or less.

[0005] Japanese Patent No. 6968642 (Patent Document 3) discloses a polyester resin containing a diol component having a bisarylfluorene skeleton and a binaphthyl skeleton, and a dicarboxylic component having at least one skeleton selected from the group consisting of a fluorene skeleton, a bisarylfluorene skeleton, and a binaphthyl skeleton.

[0006] Japanese Patent No. 7210148 (Patent Document 4) discloses a polyester resin containing first dicarboxylic acid units having a bifluorene skeleton, second dicarboxylic acid units having an arene skeleton, first diol units having a bisarylfluorene skeleton, second diol units having a linear or branched alkylene skeleton, and third diol units having a binaphthalene skeleton.

[0007] Japanese Patent No. 6631514 Japanese Patent Laid-Open No. 2022-154123 Japanese Patent No. 6968642 Japanese Patent No. 7210148

[0008] However, introducing a binaphthalene skeleton into a polyester resin makes it difficult to increase the molecular weight. Therefore, when introducing a binaphthalene skeleton into a polyester resin, the proportion of structural units that reduce the refractive index and heat resistance inevitably increases in order to ensure the molecular weight. That is, when introducing a binaphthalene skeleton into a polyester resin, it is difficult to increase the molecular weight to improve mechanical properties while simultaneously improving optical properties and heat resistance. Furthermore, polyester resins are often molded by injection molding, but increasing the glass transition temperature to improve heat resistance reduces moldability, so strict adjustment of the glass transition temperature is required. That is, there is a trade-off between improving mechanical properties and moldability and improving heat resistance and optical properties, and it is very difficult to simultaneously satisfy these properties. Therefore, even with the polyester resins described in Patent Documents 1 to 4, there is room for improvement in terms of achieving a high level of balance between mechanical properties, heat resistance, optical properties, and moldability.

[0009] Therefore, an object of the present disclosure is to provide a polyester resin that can highly satisfactorily balance mechanical properties, heat resistance, optical properties, and moldability, as well as a production method and uses thereof.

[0010] As a result of intensive research to achieve the above object, the present inventors have found that a polyester resin can be formed by combining specific aromatic diol units and specific aromatic dicarboxylic acid units in a specific ratio, thereby achieving a high level of balance between mechanical properties, heat resistance, optical properties, and moldability, and have completed the present disclosure.

[0011] That is, the present disclosure includes the following aspects.

[0012] Aspect [1]: A polyester resin containing a diol unit (A) and a dicarboxylic acid unit (B), wherein the diol unit (A) is represented by the following formula (1):

[0013]

[0014] (In the formula, A １ and A ２ each independently represents an alkylene group, n1 and n2 independently represent an integer of 0 or more, R １ and R ２ each independently represents a substituent, m1 and m2 independently represent an integer of 0 to 6, ３ represents a direct bond (single bond) or an alkylene group), a first diol unit (A1) represented by the following formula (2):

[0015]

[0016] (In the formula, A ４ and A ５ each independently represents an alkylene group; k1 and k2 each independently represents an integer of 0 or more; R ３ and R ４ each independently represents a substituent, p1 and p2 independently represent an integer of 0 to 4, R ５ represents a substituent, and q represents an integer of 0 to 8), and a second diol unit (A2) represented by the following formula (3):

[0017]

[0018] (In the formula, A ６ represents an alkylene group, and t represents an integer of 1 to 10), the proportion of the first diol units (A1) is 5 to 60 mol % in the diol units (total diol units) (A), and the dicarboxylic acid units (B) are represented by the following formula (4):

[0019]

[0020] (In the formula, Z １ represents a fused polycyclic arene ring, R６ represents a substituent, and s represents an integer of 0 or greater), and the proportion of the dicarboxylic acid units (B1) in the dicarboxylic acid units (total dicarboxylic acid units) (B) is 50 mol % or greater.

[0021] Aspect [2]: In the formula (1), A １ and A ２ became independent and became C ２－４ represents an alkylene group, n1 and n2 independently represent integers of 0 to 10, A ３ represents a direct bond, and the proportion of the first diol unit (A1) is 35 to 55 mol % in the diol unit (A).

[0022] Aspect [3]: In the formula (2), A ４ and A ５ became independent and became C ２－４ The polyester resin according to the above aspect [1] or [2], wherein k1 and k2 each independently represent an integer of 0 to 10, and each represents an alkylene group.

[0023] Aspect [4]: ​​In the formula (3), A ６ is C ２－４ The polyester resin according to any one of the above aspects [1] to [3], wherein t represents an alkylene group and t represents 1.

[0024] Aspect [5]: In the formula (4), Z １ represents a naphthalene ring, and the proportion of the dicarboxylic acid units (B1) in the dicarboxylic acid units (B) is 80 mol % or more.

[0025] Aspect [6]: The polyester-based resin according to any one of Aspects [1] to [5], wherein the molar ratio of the first diol unit (A1) to the second diol unit (A2) is 80 / 20 to 60 / 40.

[0026] Aspect [7]: The polyester-based resin according to any one of Aspects [1] to [6], wherein the molar ratio of the first diol unit (A1) to the third diol unit (A3) is 80 / 20 to 30 / 70.

[0027] Aspect [8]: The polyester-based resin according to any one of aspects [1] to [7], having a glass transition temperature of 130 to 160°C and a refractive index of 1.655 or more.

[0028] Aspect [9]: The polyester-based resin according to any one of aspects [1] to [8], having a weight-average molecular weight of 30,000 or more.

[0029] Aspect

[10] : Chromaticity b ＊ The polyester-based resin according to any one of the above aspects [1] to [9], wherein the absolute value of

[0030] Aspect

[11] : A method for producing the polyester resin according to any one of aspects [1] to

[10] , by polymerizing a diol corresponding to the diol unit (A) and a dicarboxylic acid component corresponding to the dicarboxylic acid unit (B).

[0031] Aspect

[12] : The method according to aspect

[11] , wherein the diol and the dicarboxylic acid component are polymerized in the presence of a titanium compound and / or a manganese compound.

[0032] Aspect

[13] : The method according to aspect

[11] or

[12] , wherein the diol and the dicarboxylic acid component are polymerized in the presence of a phosphorus compound.

[0033] Aspect

[14] : A molded article comprising the polyester-based resin according to any one of aspects [1] to

[10] .

[0034] Aspect

[15] : The molded article according to aspect

[14] , which is an optical lens.

[0035] Aspect

[16] : A polyester resin comprising diol units (A) and dicarboxylic acid units (B), wherein the diol units (A) comprise first diol units (A1) represented by formula (1), second diol units (A2) represented by formula (2), and third diol units (A3) represented by formula (3), the total amount of the first diol units (A1), the second diol units (A2), and the third diol units (A3) being 50 mol% or more in the diol units (A), the molar ratio of the first diol units (A1) to the second diol units (A2) being 80 / 20 to 60 / 40, and the molar ratio of the first diol units (A1) to the third diol units (A3) being 80 / 20 to 30 / 70, The polyester resin of the present invention is characterized in that the dicarboxylic acid units (B) contain dicarboxylic acid units (B1) represented by the formula (4), and the proportion of the dicarboxylic acid units (B1) in the dicarboxylic acid units (B) is 50 mol % or more.

[0036] In addition, the present disclosure may achieve the following secondary objectives (solve the problems).

[0037] Another object of the present disclosure is to provide a polyester-based resin that has excellent non-coloring properties due to reduced coloring such as yellowish tinge, and that can highly satisfies the balance of mechanical properties, heat resistance, optical properties, and moldability, as well as a production method and uses thereof.

[0038] Still another object of the present disclosure is to provide a polyester-based resin that has excellent non-coloring properties with reduced coloring such as yellowish tinge, has a large molecular weight, and is able to highly satisfactorily balance mechanical properties, heat resistance, optical properties, and moldability, as well as a production method and uses thereof.

[0039] In this specification and claims, the terms "dicarboxylic acid unit" and "structural unit derived from a dicarboxylic acid component" refer to a unit (or divalent group) obtained by removing OH (hydroxyl group) from each of the two carboxyl groups of the corresponding dicarboxylic acid, and a "dicarboxylic acid component" (including compounds exemplified as dicarboxylic acid components) may be used synonymously with the corresponding "dicarboxylic acid unit." Similarly, a "diol unit" and a "structural unit derived from a diol" 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 a "diol" (including compounds exemplified as diols) may be used synonymously with the corresponding "diol unit."

[0040] In this specification and claims, the term "dicarboxylic acid component" is used to mean not only dicarboxylic acids but also their ester-forming derivatives. Examples of the ester-forming derivatives include alkyl esters, acid halides such as acid chlorides, and acid anhydrides. Examples of the alkyl esters include lower alkyl esters, such as C alkyl esters, methyl esters, ethyl esters, and t-butyl esters. １－４ Alkyl esters, etc. The ester-forming derivatives may be monoesters (half esters) or diesters.

[0041] In this specification and claims, the number of carbon atoms in a substituent or the like is represented by C １ , C ６ , C １０ For example, "C １ "Alkyl group" means an alkyl group having one carbon atom, ６－１０ The term "aryl group" refers to an aryl group having 6 to 10 carbon atoms.

[0042] In the present specification and claims, the term "independently" means that two components are independent components, for example, an alkylene group A １ and A ２ In this case, A １ and A ２ and do not necessarily have to be the same alkylene group, but may be different alkylene groups.

[0043] Furthermore, in the present specification and claims, when a numerical range is indicated using "X to Y," the endpoints X and Y may be included.

[0044] In the present disclosure, the polyester-based resin is formed by combining specific aromatic diol units and specific aromatic dicarboxylic acid units in a specific ratio, and therefore can achieve a highly balanced combination of mechanical properties, heat resistance, optical properties, and moldability.

[0045] [Polyester-based resin] (A) Diol unit The polyester-based resin of the present disclosure is characterized by including, as the diol unit (A), a first diol unit (A1) represented by the formula (1), a second diol unit (A2) represented by the formula (2), and a third diol unit (A3) represented by the formula (3).

[0046] (A1) First Diol Unit In the present disclosure, the diol unit (A) contains the first diol unit (A1), thereby improving the optical properties and heat resistance.

[0047] In the formula (1), A １ and A ２ Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C alkylene groups such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. ２－１２ These alkylene groups can be used alone or in combination of two or more. ２－６ An alkylene group is preferred, and C ２－４ Alkylene groups are more preferred, and C groups such as ethylene groups and propylene groups are preferred. ２－３ An alkylene group is more preferred, and an ethylene group is most preferred. １ and an alkylene group A ２ may be the same or different from each other.

[0048] The repeat numbers n1 and n2 are each 0 or greater and can be selected from the range of integers from 0 to 15, for example, preferably in the following stepwise order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, and 0 to 1. Furthermore, when the repeat numbers n1 and n2 are each 1 or greater, polymerization reactivity is easily improved, and preferably in the following stepwise order: 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2, with 1 being the most preferred. When n1 and n2 are below the upper limit, the heat resistance and refractive index of the polyester resin tend to be improved. Furthermore, n1 and n2 may be the same or different from each other. When n1 and n2 are each an integer of 2 or greater, two or more alkylene groups A １ and A ２ The types may be the same or different from each other.

[0049] In this specification and claims, the "number of repetitions (number of moles added)" may be an average value (arithmetic mean value, additive mean value) or an average number of moles added, and preferred embodiments may be the same as the above-mentioned preferred range of integers.

[0050] The group [—O—(A １ O) ｎ１ -] and the group [-O-(A ２ O) ｎ２ The bonding positions of each of A and A- in the naphthalene skeleton are not particularly limited. ３ With respect to the 1,1′-binaphthyl skeleton via the bond, the positions may be the 2,2′-positions or the 4,4′-positions, etc., but the 2,2′-positions are preferred in terms of ease of preparation (synthesis) or procurement, improving productivity, and facilitating a high refractive index in terms of conformation.

[0051] A ３ Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C alkylene groups such as methylene group, ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group. １－４ alkylene groups. ３ From the viewpoint of optical properties such as a high refractive index, a low Abbe number, and a low birefringence, a C bond such as a direct bond or a methylene group is preferred. １－２An alkylene group is preferred, and a direct bond (single bond) is particularly preferred.

[0052] R １ and R ２ The substituent represented by may be a non-reactive substituent that is inert to the reaction, and examples thereof include a halogen atom, a hydrocarbon group, an alkoxy group (a linear or branched alkoxy group), an acyl group, a nitro group, a cyano group, and a substituted amino group.

[0053] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0054] The hydrocarbon group includes an alkyl group (straight-chain or branched-chain alkyl group), a cycloalkyl group, an aryl group, an aralkyl group, and the like.

[0055] Examples of the alkyl group include a C methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. １－１０ Examples of the cycloalkyl group include a C alkyl group such as a cyclopentyl group and a cyclohexyl group. ５－１０ Examples of the aryl group include a C cycloalkyl group, such as a phenyl group, a biphenylyl group, and a naphthyl group. ６－１２ Aryl group: mono- to tri-C such as methylphenyl group (or tolyl group), dimethylphenyl group (or xylyl group) １－４ Examples of the aralkyl group include C alkyl-phenyl groups, benzyl groups, phenethyl groups, etc. ６－１０ Aryl-C １－４ Examples of suitable alkyl groups include:

[0056] Examples of the alkoxy group include a C alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, and a t-butoxy group. １－１０ Examples of the acyl group include C alkoxy groups such as acetyl groups. １－６ The substituted amino group includes mono- or di-C groups such as dimethylamino group. １－４ alkylamino group; bis(C １－４ alkyl-carbonyl)amino groups.

[0057] These substituents may be used alone or in combination of two or more.

[0058] Representative Substituent R １ and R ２ Examples of the C include an alkyl group, an aryl group, an alkoxy group, an acyl group, a nitro group, and a cyano group. Among these, an alkyl group and an alkoxy group are preferred, and １－６ Alkyl group, C １－４ An alkoxy group is more preferred, and C １－４ Alkyl groups are more preferred, and C groups such as methyl groups are １－２ Alkyl groups are most preferred. １ and substituent R ２ may be the same or different from each other.

[0059] The numbers of substitutions m1 and m2 are each an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. The numbers of substitutions m1 and m2 may be the same or different from each other. When m1 and m2 are integers of 2 or more, two or more substituents R １ and substituent R ２ The types may be the same or may be different combinations.

[0060] substituent R １ and R ２ The substitution position of is not particularly limited, and is preferably any one of the 3- to 8-positions of each naphthalene ring.

[0061] The first diol unit (A1) is preferably a diol unit represented by the following formula (1a):

[0062]

[0063] (In the formula, A １ , A ２ , n1, n2, R １ , R ２ , m1 and m2 are the same as those in formula (1) above.

[0064] Examples of diols corresponding to the diol unit represented by the formula (1a) include dihydroxy-1,1'-binaphthyls such as 2,2'-dihydroxy-1,1'-binaphthyl; bis[hydroxy(poly)alkoxy]-1,1'-binaphthyls, etc. Examples of bis[hydroxy(poly)alkoxy]-1,1'-binaphthyls include 2,2'-bis[hydroxy(mono- to deca)C such as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxypropoxy)-1,1'-binaphthyl, and 2,2'-bis[2-(2-hydroxyethoxy)ethoxy]-1,1'-binaphthyl. ２－４ These diols can be used alone or in combination of two or more. Among these, 2,2'-dihydroxy-1,1'-binaphthyl, 2,2'-bis[hydroxy(mono- to tetra)C ２－４ alkoxy]-1,1'-binaphthyl is preferred, and 2,2'-bis[hydroxy(mono to tri)C such as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl is preferred. ２－３ Alkoxy]-1,1'-binaphthyl is more preferred.

[0065] The proportion of the first diol units (A1) is 5 to 60 mol % of all diol units (A), and preferably 10 to 60 mol %, 20 to 58 mol %, 30 to 55 mol %, 35 to 55 mol %, 40 to 55 mol %, 45 to 55 mol %, and 48 to 52 mol % in the following stepwise manner. When the proportion of the first diol units (A1) is at least the lower limit, the optical properties and heat resistance of the polyester-based resin tend to be improved, while when it is at most the upper limit, the mechanical properties and moldability of the polyester-based resin tend to be improved.

[0066] (A2) Second Diol Unit In the present disclosure, the diol unit (A) contains the second diol unit (A2), thereby improving optical properties.

[0067] In the formula (2), A ４ and A ５ As the group A in the formula (1), including preferred embodiments thereof, １ and A２ That is, A can be selected from the alkylene groups exemplified as ４ and A ５ The alkylene group A is most preferably an ethylene group. ４ and an alkylene group A ５ may be the same or different from each other.

[0068] A ４ and A ５ The repeating numbers k1 and k2 of A in the formula (1), including preferred embodiments, １ and A ２ In other words, k1 and k2 are most preferably 1. When k1 and k2 are each an integer of 2 or more, two or more alkylene groups A ４ and A ５ The types may be the same or different from each other.

[0069] The group [—O—(A ４ O) ｋ１ -] and the group [-O-(A ５ O) ｋ２ The substitution position of [—] (also referred to as an ether bond-containing group) is not particularly limited, and is preferably any one of the 2-, 3-, and 4-positions of the phenyl group bonded to the 9-position of the fluorene ring, more preferably the 3- or 4-position, and even more preferably the 4-position.

[0070] R ３ and R ４ The substituent represented by the formula (1), including preferred embodiments thereof, is １ and R ２ That is, R ３ and R ４ C such as methyl group １－２ Alkyl groups are most preferred. ３ and substituent R ４ may be the same or different from each other.

[0071] The numbers of substitutions p1 and p2 are each an integer of 0 to 4, preferably an integer of 0 to 3, an integer of 0 to 2, 0 or 1, and most preferably 0. When the numbers of substitutions p1 and p2 are an integer of 2 or more, two or more groups R ３ and R ４ The types may be the same or different from each other.

[0072] substituent R ３ and R ４ The substitution position of is not particularly limited, and is usually a position where the group [—O—(A ４ O) ｋ１ -] or [-O-(A ５ O) ｋ２ In many cases, the substituent is at least at the ortho position (the carbon atom adjacent to the bonding position of the ether bond-containing group) relative to the ether bond-containing group.

[0073] R ５ The substituent represented by the formula (I) may be a non-reactive substituent inactive to the reaction, and examples thereof include a cyano group; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; an alkyl group (a linear or branched alkyl group), an aryl group, or other hydrocarbon group. The aryl group includes a C ６－１０ Aryl groups are preferred. ５ is a cyano group, a halogen atom, or an alkyl group, particularly an alkyl group. Examples of the alkyl group include C methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, and t-butyl groups. １－１２ Alkyl group, preferably C １－８ alkyl group, more preferably C １－６ C such as an alkyl group, more preferably a methyl group １－４ Examples of suitable alkyl groups include:

[0074] In addition, the group R ５ When the number of substitutions q is 2 or more, two or more groups R ５ The types of groups may be the same or different, and two or more groups R substituted on both benzene rings (different benzene rings)５ The types of groups R may be the same or different. ５ The bonding positions (substitution positions) of are not particularly limited as long as they are the 1st to 8th positions of the fluorene ring, and examples thereof include the 2nd, 7th, and 2,7th positions of the fluorene ring.

[0075] The number of substitutions q may be, for example, an integer of 0 to 6, and is preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, 0 or 1, and most preferably 0. In addition, in the two benzene rings constituting the fluorene ring, the group R ５ The number of substitutions in each of the above may be the same or different from each other.

[0076] The second diol corresponding to the second diol unit (A2) can be roughly classified into 9,9-bis(hydroxyphenyl)fluorenes and 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorenes.

[0077] Examples of 9,9-bis(hydroxyphenyl)fluorenes include 9,9-bis(hydroxyphenyl)fluorenes such as 9,9-bis(4-hydroxyphenyl)fluorene; 9,9-bis(alkyl-hydroxyphenyl)fluorenes, specifically 9,9-bis[(mono- or di-)C] such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene. １－４ 9,9-bis(aryl-hydroxyphenyl)fluorene, specifically, 9,9-bis(C such as 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene; ６－１０ aryl-hydroxyphenyl)fluorene and the like.

[0078] Examples of the 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorenes include alkylene oxide (or alkylene carbonate, haloalkanol) adducts of the 9,9-bis(hydroxyphenyl)fluorenes, for example, 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorenes, specifically, 9,9-bis[hydroxy(mono to deca)C such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)phenyl]fluorene, and 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene. ２－４ 9,9-bis[(mono or di)C alkyl-hydroxy(poly)alkoxyphenyl]fluorene, specifically, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene, etc. １－４ Alkyl-hydroxy (mono to deca) C ２－４ 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorenes, specifically 9,9-bis[C such as 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-phenylphenyl]fluorene, and 9,9-bis(4-(2-hydroxypropoxy)-3-phenylphenyl)fluorene. ６－１０ Aryl-hydroxy (mono to deca) C ２－４ alkoxy-phenyl]fluorene and the like.

[0079] These diols can be used alone or in combination of two or more. Among these diols, 9,9-bis[hydroxy(mono- to tri)C such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene is preferred. ２－４Alkoxy-phenyl]fluorene is preferred.

[0080] The proportion of the second diol units (A2) can be selected from the range of about 1 to 90 mol % of all diol units (A), preferably 1 to 80 mol %, 2 to 60 mol %, 3 to 50 mol %, 5 to 40 mol %, 10 to 30 mol %, 15 to 25 mol %, and most preferably 18 to 22 mol %. When the proportion of the second diol units (A2) is equal to or greater than the lower limit, the optical properties of the polyester resin tend to be improved.

[0081] The molar ratio of the first diol units (A1) to the second diol units (A2) (former / latter) can be selected from a range of about 99 / 1 to 10 / 90, preferably in the following stepwise order: 95 / 5 to 30 / 70, 90 / 10 to 50 / 50, 80 / 20 to 60 / 40, 75 / 25 to 65 / 35, and 73 / 27 to 69 / 31. As the ratio of the first diol units (A1) increases, optical properties such as refractive index tend to improve, and as the ratio of the second diol units (A2) increases, mechanical properties tend to improve.

[0082] In the present disclosure, the diol unit (A) contains the third diol unit (A3), which can improve mechanical properties and moldability. In particular, by combining the third diol unit (A3) with the first diol unit (A1) and the second diol unit (A2) in a specific ratio, it is possible to improve optical properties, heat resistance, mechanical properties, and moldability in a well-balanced manner.

[0083] In the formula (3), A ６ The alkylene group (linear or branched alkylene group) represented by the formula (1) includes, including preferred embodiments thereof, A １ and A ２ That is, the alkylene group represented by A can be selected from the alkylene groups exemplified as the alkylene group represented by A ６ The alkylene group represented by the formula (I) is most preferably an ethylene group.

[0084] The number of repetitions t may be selected, for example, from the range of about 1 to 10, preferably 1 to 4, 1 to 3, 1 to 2, and particularly preferably 1. When t is equal to or less than the upper limit, the optical properties tend to be improved. When t is 2 or more, two or more alkylene groups A ６ The types may be the same or different from each other.

[0085] Examples of the third diol corresponding to the third diol unit (A3) include alkanediols (or alkylene glycols), polyalkanediols (or polyalkylene glycols), and the like.

[0086] The alkylene glycol may be, for example, a compound represented by the formula (3) where t is 1 and A ６ alkylene glycols corresponding to the alkylene groups exemplified above, specifically, C such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol (or 1,4-butanediol), 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol ２－１２ alkylene glycol, etc., and a preferred embodiment is the alkylene group A ６ The same applies to

[0087] The polyalkylene glycol may be, for example, a polyalkylene glycol represented by the formula (3) in which t is 2 or more, preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4; ６ Polyalkylene glycols corresponding to the alkylene groups exemplified above, specifically di- or deca-C such as diethylene glycol, dipropylene glycol, and triethylene glycol ２－１２ alkylene glycols, and preferably di- to hexa-C ２－６ Alkylene glycol, more preferably di- or tetra-C ２－４ Alkylene glycols are included.

[0088] These diols can be used alone or in combination of two or more. ２－６It is preferred to include alkylene glycols such as alkylene glycols, preferably C ２－４ Alkylene glycols are more preferred, and C alkylene glycols such as ethylene glycol and propylene glycol are preferred. ２－３ Alkylene glycols are more preferred, most preferably including ethylene glycol.

[0089] The proportion of the third diol units (A3) can be selected from the range of about 1 to 90 mol% of all diol units (A), preferably in the following stepwise manner: 3 to 80 mol%, 5 to 70 mol%, 10 to 60 mol%, 20 to 50 mol%, 23 to 40 mol%, 25 to 35 mol%, and most preferably 28 to 32 mol%. When the proportion of the third diol units (A3) is at least the lower limit, the mechanical properties and optical properties of the polyester-based resin tend to be improved, whereas when it is at most the upper limit, the optical properties and heat resistance of the polyester-based resin tend to be improved.

[0090] The molar ratio of the first diol unit (A1) to the third diol unit (A3) can be selected from a range of about 99 / 1 to 10 / 90 (former / latter), preferably in the following stepwise order: 95 / 5 to 10 / 90, 90 / 10 to 20 / 80, 80 / 20 to 30 / 70, 75 / 25 to 40 / 60, 73 / 27 to 45 / 55, 70 / 30 to 48 / 52, 68 / 32 to 50 / 50, 67 / 33 to 55 / 45, and most preferably 65 / 35 to 60 / 40. As the ratio of the first diol unit (A1) increases, optical properties and heat resistance tend to improve, and as the ratio of the third diol unit (A3) increases, mechanical properties and moldability tend to improve.

[0091] The molar ratio of the second diol unit (A2) to the third diol unit (A3) can be selected from a range of about 95 / 5 to 1 / 99 (former / latter), preferably in the following stepwise manner: 90 / 10 to 5 / 95, 80 / 20 to 10 / 90, 70 / 30 to 15 / 85, 60 / 40 to 20 / 80, 50 / 50 to 30 / 70, and most preferably 45 / 55 to 35 / 65. As the ratio of the second diol unit (A2) increases, the mechanical properties tend to improve, and as the ratio of the third diol unit (A3) increases, the mechanical properties and moldability tend to improve.

[0092] (A4) Fourth Diol Unit The diol unit (A) may further contain a fourth diol unit (A4) different from the first diol unit (A1), the second diol unit (A2), and the third diol unit (A3), as necessary.

[0093] Examples of the fourth diol unit (A4) include an aromatic diol unit and an alicyclic diol unit.

[0094] Examples of the aromatic diol unit include structural units derived from aromatic diols (excluding diols corresponding to the first diol unit (A1) and the second diol unit (A2)), and alkylene oxide (alkylene carbonate or haloalkanol) adducts of these diols.

[0095] Examples of aromatic diols include bisarylfluorenes such as 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF) (bisarylfluorenes other than the bisarylfluorenes corresponding to the second diol unit (A2)); bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; and biphenols such as p,p'-biphenol.

[0096] Examples of alkylene oxide (corresponding alkylene carbonate or haloalkanol) adducts of these diols include C ２－４ C alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. ２－３ The number of moles of ethylene oxide added is not particularly limited, and specific examples thereof include an adduct in which about 1 to 10 moles of ethylene oxide are added to 1 mole of an aromatic diol such as BNF or bisphenol A.

[0097] Examples of the alicyclic diol unit include structural units derived from alicyclic diols and alkylene oxide (alkylene carbonate or haloalkanol) adducts of the diols. Examples of the alicyclic diol include cycloalkanediols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; bis(hydroxy C) such as adamantanedimethanol and tricyclodecanedimethanol. １－３ alkyl) bicycloalkanes or tricycloalkanes.

[0098] Examples of alkylene oxide adducts of these diols include C ２－４ C alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. ２－３ The number of moles of ethylene oxide added is not particularly limited, and specific examples thereof include an adduct in which about 2 to 10 moles of ethylene oxide are added to 1 mole of an alicyclic diol such as a cycloalkanediol.

[0099] These fourth diol units (A4) may be contained alone or in combination of two or more kinds.

[0100] The proportion of the fourth diol unit (A4) in the diol unit (A) may be 50 mol % or less, preferably 30 mol % or less, 10 mol % or less, and 5 mol % or less in the following stepwise manner. It is preferable that the diol unit (A) is substantially free of the fourth diol unit (A4).

[0101] The total proportion of the first diol unit (A1), the second diol unit (A2), and the third diol unit (A3) in the diol unit (A) may be 50 mol % or more, preferably 70 mol % or more, 90 mol % or more, and 95 mol % or more in the following stepwise manner. The diol unit (A) may be a unit consisting only of the first diol unit (A1), the second diol unit (A2), and the third diol unit (A3).

[0102] (B) Dicarboxylic Acid Unit The polyester resin of the present disclosure is characterized by including a first dicarboxylic acid unit (B1) represented by the above formula (4) as the dicarboxylic acid unit (B).

[0103] (B1) First Dicarboxylic Acid Unit In the present disclosure, the dicarboxylic acid unit (B) contains the first dicarboxylic acid unit (B1), thereby improving the refractive index and heat resistance of the polyester resin.

[0104] In the formula (4), Z １ The fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring) represented by the following formula may be a fused bicyclic to tetracyclic arene ring. The fused bicyclic arene ring may be a fused bicyclic C ring such as an indene ring or a naphthalene ring. ８－２０ Examples of the fused tricyclic arene ring include fused tricyclic C arenes such as an acenaphthylene ring, a fluorene ring, a phenalene ring, an anthracene ring, and a phenanthrene ring. １４－２０ The fused tetracyclic arene ring includes a fused tetracyclic C arene ring such as a pyrene ring and a naphthacene ring. １６－２２ These fused polycyclic arene rings can be used alone or in combination of two or more. １０－１６ Arene rings (especially C １０－１６ fused bicyclic hydrocarbon rings) are preferred, and fused polycyclic C １０－１４ An arene ring is more preferred, and a fused bicyclic C ring such as a naphthalene ring is more preferred. １０－１４ An arene ring is more preferred, and a naphthalene ring is particularly preferred.

[0105] The carbonyl group that forms the ester bond is bonded to the ring Z. １ can be selected appropriately depending on the type of Z １ When is a naphthalene ring, the bonding positions include 1,2-positions, 1,4-positions, 1,5-positions, 1,8-positions, 2,3-positions, and 2,6-positions. Of these bonding positions, 1,5-positions and 2,6-positions are preferred, and 2,6-positions are most preferred.

[0106] R ６ The substituent represented by the formula (1), including preferred embodiments thereof, is １ and R ２That is, R ６ C such as methyl group １－２ Alkyl groups are most preferred.

[0107] R ６ The number of substitutions s in the ring Z may be an integer of 0 or more. １ The number of substitutions s can be appropriately selected depending on the type of the group, and may be, for example, an integer of 0 to 6. Preferred substitution numbers s are, in the following stepwise order, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, 0 or 1, and 0 is the most preferred.

[0108] Examples of the first dicarboxylic acid component corresponding to the first dicarboxylic acid unit (B1) include naphthalenedicarboxylic acids or ester-forming derivatives thereof, such as 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid; anthracenedicarboxylic acid or ester-forming derivatives thereof; and condensed polycyclic C carboxylic acids such as phenanthrenedicarboxylic acid. １０－２４ Arene-dicarboxylic acids (especially fused polycyclic C １０－１４ arene-dicarboxylic acid) or its ester-forming derivatives.

[0109] These dicarboxylic acid units can be used alone or in combination of two or more. A preferred first dicarboxylic acid unit (B1) is a dicarboxylic acid unit represented by the formula (4) above, wherein Z １ is a naphthalene ring and s is 0; more preferably, it is a dicarboxylic acid unit derived from 2,6-naphthalenedicarboxylic acid. １ is a naphthalene ring and s is 0) can be selected from a range of about 10 to 100 mol % in the first dicarboxylic acid units (B1), and is preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, and more preferably 100 mol % in the following stepwise manner. When the preferred proportion of the first dicarboxylic acid units (B1) is the lower limit or more, the refractive index and heat resistance of the polyester resin tend to be improved.

[0110] The first dicarboxylic acid units (B1) may account for 50 mol% or more of the total dicarboxylic acid units (B), and can be selected, for example, from a range of about 50 to 100 mol%, preferably 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, 99 mol% or more, and most preferably 100 mol%. When the proportion of the first dicarboxylic acid units (B1) is equal to or greater than the lower limit, the refractive index and heat resistance of the polyester resin tend to be improved.

[0111] (B2) Second Dicarboxylic Acid Unit The dicarboxylic acid unit (B) may further contain a second dicarboxylic acid unit (B2) different from the first dicarboxylic acid unit (B1), as necessary.

[0112] Examples of the second dicarboxylic acid unit (B2) include a monocyclic aromatic dicarboxylic acid unit, a ring-assembled polycyclic aromatic dicarboxylic acid unit, an aliphatic dicarboxylic acid unit, and an alicyclic dicarboxylic acid unit.

[0113] Examples of the monocyclic aromatic dicarboxylic acid component corresponding to the monocyclic aromatic dicarboxylic acid unit include benzenedicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, or ester-forming derivatives thereof; C carboxylic acids such as 5-methylisophthalic acid, etc. １－４ Examples thereof include alkyl-benzenedicarboxylic acids or ester-forming derivatives thereof.

[0114] Examples of the ring-assembled polycyclic aromatic dicarboxylic acid component corresponding to the ring-assembled polycyclic aromatic dicarboxylic acid unit include bi-C such as 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. ６－１０ arene-dicarboxylic acids or ester-forming derivatives thereof.

[0115] In this specification and claims, the term "ring assembly polycyclic" refers to a ring assembly polycyclic structure in which two or more ring systems (arene ring systems) are directly linked by a single bond or a double bond, and the number of bonds directly linking the rings is one less than the number of ring systems. For example, phenylnaphthalene rings and binaphthyl rings are classified as ring assembly polycyclic structures even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic structures" such as naphthalene rings (non-ring assembly arene rings).

[0116] Examples of the aliphatic dicarboxylic acid component corresponding to the aliphatic dicarboxylic acid unit include C carboxylic acids such as malonic acid, succinic acid, and adipic acid. １－２０ Alkane-dicarboxylic acids or their ester-forming derivatives; C such as maleic acid and fumaric acid ２－１０ Alkene-dicarboxylic acids or ester-forming derivatives thereof are included.

[0117] Examples of the alicyclic dicarboxylic acid component corresponding to the alicyclic dicarboxylic acid unit include C cyclohexanedicarboxylic acid and the like. ４－１２ Cycloalkane-dicarboxylic acids or their ester-forming derivatives; (bi- or tri-)cycloC such as norbornanedicarboxylic acid ７－１０ Alkane-dicarboxylic acids or their ester-forming derivatives; C such as cyclopentene dicarboxylic acid ５－１０ Cycloalkene-dicarboxylic acids or ester-forming derivatives thereof; (bi- or tri-)cycloC such as norbornene dicarboxylic acid ７－１０ Alkene-dicarboxylic acids and the like.

[0118] These second dicarboxylic acid units (B2) may be used alone or in combination of two or more.

[0119] The proportion of the second dicarboxylic acid units (B2) may be 50 mol % or less, preferably 30 mol % or less, 10 mol % or less, and 5 mol % or less in the following stepwise manner based on the total dicarboxylic acid units (B). It is preferred that the dicarboxylic acid units (B) are substantially free of the second dicarboxylic acid units (B2).

[0120] [Method for Producing Polyester Resin] The method for producing a polyester resin according to the present disclosure is not particularly limited, except that it uses as polymerization components the diol (A1) corresponding to the first diol unit (A1), the diol (A2) corresponding to the second diol unit (A2), the diol (A3) corresponding to the third diol unit (A3), and the dicarboxylic acid component (B1) corresponding to the first dicarboxylic acid unit (B1), and conventional methods can be used. For example, the polyester resin can be produced by reacting (polymerizing) the diol (A) corresponding to the diol unit (A) with the dicarboxylic acid component (B) corresponding to the dicarboxylic acid unit (B). This can be produced by conventional methods such as transesterification, melt polymerization such as direct polymerization, solution polymerization, and interfacial polymerization, with melt polymerization being preferred. The reaction typically proceeds via a transesterification reaction step in which the dicarboxylic acid component is transesterified, followed by a polycondensation reaction step in which the resulting transesterification reaction product is polycondensed. Depending on the polymerization method, the reaction may be carried out in the presence or absence of a solvent.

[0121] In a polyester resin containing diol units (A) and dicarboxylic acid units (B), the ratio of the diol (A) to the dicarboxylic acid component (B) used (or the charging ratio) can usually be selected from the range of 1 / 1.2 to 1 / 0.8 (molar ratio) of the former / the latter, and is preferably 1 / 1.1 to 1 / 0.9, but this range is not necessarily required, and at least one component contained in the polymerization components may be used in excess of the intended introduction ratio. For example, a diol such as ethylene glycol that can be distilled from the reaction system may be used in excess of the ratio (or the introduction ratio) introduced into the polyester resin.

[0122] The reaction may be carried out in the presence of a catalyst. A conventional esterification catalyst, such as a metal catalyst, can be used as the catalyst. Examples of the metal catalyst 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; metals in Group 12 of the periodic table such as zinc and cadmium; metals in Group 13 of the periodic table such as aluminum; metals in Group 14 of the periodic table such as germanium and lead; and metals in Group 15 of the periodic table such as antimony. Examples of the metal compounds include alkoxides; organic acid salts such as acetates and propionates; inorganic acid salts such as borates and carbonates; oxides, and hydrates thereof. Representative examples of metal compounds include 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 (titanium (IV) tetrabutoxide), titanium oxalate, and titanium potassium oxalate; manganese compounds such as manganese acetate tetrahydrate; and calcium compounds such as calcium acetate monohydrate.

[0123] These catalysts can be used alone or in combination of two or more. When using multiple catalysts, each catalyst can be added according to the progress of the reaction. Among these catalysts, germanium compounds, titanium compounds, manganese compounds, and calcium compounds are preferred, titanium compounds and / or manganese compounds are more preferred, and a combination of a titanium compound and a manganese compound is more preferred because it is easy to improve the non-coloring properties of the polyester resin. Among these catalysts, manganese acetate tetrahydrate, calcium acetate monohydrate, germanium dioxide, titanium (IV) tetrabutoxide, etc. are commonly used. The amount of catalyst used is, for example, 0.01 × 10 per 1 mole of the dicarboxylic acid component (B). －４ ~100 x 10 －４It may be 0.1 × 10 moles, and from the viewpoint of facilitating the improvement of the molecular weight of the polyester resin, it is preferably 0.1 × 10 moles. －４ ~40 x 10 －４ mole, more preferably 0.5×10 －４ ~20 x 10 －４ It is a mole.

[0124] When a titanium compound and a manganese compound are combined as a catalyst, the molar ratio of the two (titanium compound / manganese compound) can be selected from within a range of 90 / 10 to 1 / 99, preferably 70 / 30 to 5 / 95, more preferably 50 / 50 to 10 / 90, and even more preferably 40 / 60 to 20 / 80.

[0125] The proportion of the titanium compound may be, in terms of elemental titanium (by mass) relative to the obtained polyester resin, for example, 1 to 30 ppm, preferably 2 to 25 ppm, further preferably 3 to 20 ppm, even more preferably 5 to 15 ppm, and most preferably 8 to 12 ppm.

[0126] The proportion of the manganese compound may be, in terms of elemental manganese (by mass) relative to the obtained polyester resin, for example, 1 to 100 ppm, preferably 5 to 50 ppm, further preferably 10 to 30 ppm, more preferably 15 to 25 ppm, and most preferably 18 to 22 ppm.

[0127] When a titanium compound and a manganese compound are combined as catalysts, the manganese compound may be added in the transesterification reaction step and the titanium compound may be added in the polycondensation reaction step, since this facilitates improving the non-coloring properties of the polyester resin.

[0128] The reaction may be carried out in the presence of a stabilizer such as a heat stabilizer or an antioxidant, if necessary. A heat stabilizer is usually used, and examples thereof include phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (dibutyl phosphate or dibutyl phosphate), phosphorous acid, trimethyl phosphite, and triethyl phosphite. Among these, dibutyl phosphate is often used. The amount of the heat stabilizer used is, for example, 0.01 × 10 relative to 1 mole of the dicarboxylic acid component (B). －４~100 x 10 －４ mole, preferably 0.1 x 10 －４ ~40 x 10 －４ It is a mole.

[0129] In particular, the amount of the phosphorus compound used is preferably 0.1 × 10 moles per mole of the dicarboxylic acid component (B) in order to reduce the yellowish or other coloring of the polyester resin and improve its non-coloring properties. －４ ~100 x 10 －４ The range can be selected from the range of about 1×10 －４ ~50 x 10 －４ moles, preferably 2 x 10 －４ ~40 x 10 －４ moles, more preferably 5 x 10 －４ ~30 x 10 －４ moles, more preferably 8 x 10 －４ ~20 x 10 －４ moles, most preferably 10 x 10 －４ ~15 x 10 －４ It is a mole.

[0130] The proportion of the phosphorus compound is, in terms of phosphorus element (mass basis), for example, 1 to 200 ppm, preferably 10 to 200 ppm, further preferably 30 to 150 ppm, even more preferably 50 to 100 ppm, and most preferably 70 to 90 ppm, relative to the obtained polyester resin.

[0131] The reaction is usually carried out in an atmosphere of an inert gas, such as nitrogen gas or a rare gas such as helium or argon. ２ ~1 x 10 ４ The reaction temperature can be selected depending on the polymerization method. For example, the reaction temperature in the melt polymerization method is 150 to 320°C, preferably 180 to 310°C, and more preferably 200 to 300°C.

[0132] [Characteristics of Polyester-Based Resin] The polyester-based resin of the present disclosure has excellent optical properties and high heat resistance, and also has excellent mechanical properties and moldability.

[0133] The polyester resin of the present disclosure has a high refractive index. Specifically, the refractive index nD of the polyester resin of the present disclosure is, at a temperature of 20°C and a wavelength of 589 nm, for example, 1.6 or more, preferably 1.655 or more, and can be selected, for example, from a range of about 1.6 to 1.7, preferably from 1.655 to 1.695, 1.660 to 1.690, 1.665 to 1.685, and most preferably from 1.670 to 1.680.

[0134] The glass transition temperature Tg of the polyester resin of the present disclosure may be 130° C. or higher, for example, 130 to 160° C., preferably 135 to 155° C., further preferably 140 to 150° C., more preferably 142 to 148° C., and most preferably 143 to 147° C. When the glass transition temperature Tg is equal to or higher than the lower limit, heat resistance tends to be improved.

[0135] The Abbe number of the polyester resin of the present disclosure at a temperature of 20°C is, for example, 5 to 50, and preferred ranges are 10 to 30, 13 to 25, 15 to 23, 16 to 20, and more preferably 17 to 19, in the following stepwise order.

[0136] The polyester-based resin of the present disclosure has high transparency and low coloring. In particular, the polyester-based resin of the present disclosure has a color (L ＊ a ＊ b ＊ In the color space, chromaticity b ＊ The absolute value of chromaticity b may be 25 or less, and yellowness and blueness (particularly yellowness) are reduced. ＊ The absolute value of chromaticity b is preferably 23 or less, 21 or less, 20 or less, and 18 or less in the following stepwise manner, and may be, for example, about 1 to 25 or about 10 to 20. ＊ When the absolute value of is equal to or less than the upper limit, yellowish or blueish tint can be reduced, and the non-coloring property of the polyester resin tends to be improved.

[0137] The weight average molecular weight Mw of the polyester resin of the present disclosure may be 10,000 or more, preferably 30,000 or more, and more preferably 35,000 or more, in terms of standard polystyrene. For example, it can be selected from a range of about 10,000 to 1,000,000. Preferred ranges are the following stepwise: 15,000 to 90,000, 20,000 to 80,000, 25,000 to 70,000, 30,000 to 50,000, 32,000 to 45,000, 35,000 to 43,000, and most preferably 38,000 to 41,000. When the weight average molecular weight Mw is equal to or greater than the lower limit, mechanical properties and heat resistance tend to be improved.

[0138] In this specification and claims, the refractive index nD, the glass transition temperature Tg, the Abbe number, the chromaticity b ＊ The weight average molecular weight Mw can be measured by the method described in the examples below.

[0139] As a preferred polyester resin, the diol unit (A) in the formula (1) is １ and A ２ became independent and became C ２－６ represents an alkylene group, n1 and n2 independently represent integers of 0 to 10, R １ and R ２ independently represent an alkyl group, an aryl group, an alkoxy group, an acyl group, a nitro group, or a cyano group; m1 and m2 independently represent an integer of 0 to 4; A ３ is a direct bond or C １－４ a first diol unit (A1) representing an alkylene group; ４ and A ５ became independent and became C ２－６ represents an alkylene group, k1 and k2 independently represent integers of 0 to 10, R ３ and R ４ independently represent an alkyl group, an aryl group, an alkoxy group, an acyl group, a nitro group, or a cyano group; p1 and p2 independently represent an integer of 0 to 3; R ５ represents a cyano group, a halogen atom or an alkyl group, and q represents an integer of 0 to 6; and ６ is C ２－６and a third diol unit (A3) representing an alkylene group, wherein t represents an integer of 1 to 4, the total amount of the first diol unit (A1), the second diol unit (A2), and the third diol unit (A3) is 50 mol % or more in the diol unit (A), the molar ratio of the first diol unit (A1) to the second diol unit (A2) is 90 / 10 to 50 / 50, the molar ratio of the first diol unit (A1) to the third diol unit (A3) is 90 / 10 to 20 / 80, and the dicarboxylic acid unit (B) is represented by the formula (4), Z １ represents a fused polycyclic arene ring, and R ６ represents an alkyl group, an aryl group, an alkoxy group, an acyl group, a nitro group, or a cyano group, and s represents an integer of 0 to 6, the dicarboxylic acid unit (B1) is contained, and the proportion of the dicarboxylic acid unit (B1) in the dicarboxylic acid unit (B) is 50 mol % or more, the refractive index nD is 1.6 or more, the glass transition temperature Tg is 130° C. or more, and the chromaticity b ＊ and a weight average molecular weight Mw of 10,000 or more.

[0140] More preferably, the polyester resin is one in which the diol unit (A) in the formula (1) is: A １ and A ２ became independent and became C ２－４ represents an alkylene group, n1 and n2 independently represent integers of 1 to 6, R １ and R ２ each independently represents an alkyl group or an alkoxy group; m1 and m2 each independently represent an integer of 0 to 2; A ３ is a direct bond or C １－２ a first diol unit (A1) representing an alkylene group; ４ and A ５ became independent and became C ２－４ represents an alkylene group, k1 and k2 independently represent integers of 1 to 6, R ３ and R ４ each independently represents an alkyl group or an alkoxy group, p1 and p2 each independently represents an integer of 0 to 2, and R５ a second diol unit (A2) in which A represents an alkyl group and q represents an integer of 0 to 4; and ６ is C ２－４ and a third diol unit (A3) representing an alkylene group, wherein t represents an integer of 1 to 3; the total amount of the first diol unit (A1), the second diol unit (A2), and the third diol unit (A3) is 70 mol % or more in the diol unit (A); the molar ratio of the first diol unit (A1) to the second diol unit (A2) is 80 / 20 to 60 / 40; the molar ratio of the first diol unit (A1) to the third diol unit (A3) is 80 / 20 to 30 / 70; and the dicarboxylic acid unit (B) is represented by the formula (4), Z １ is a fused polycyclic C １０－１６ represents an arene ring, and R ６ represents an alkyl group or an alkoxy group, and s represents an integer of 0 to 2; and the proportion of the dicarboxylic acid units (B1) in the dicarboxylic acid units (B) is 70 mol % or more; the refractive index nD is 1.655 or more; the glass transition temperature Tg is 135 to 155°C; and the chromaticity b ＊ and a weight average molecular weight Mw of 30,000 or more.

[0141] As a more preferred polyester resin, the diol unit (A) in the formula (1) is １ and A ２ became independent and became C ２－３ represents an alkylene group, n1 and n2 independently represent 1 or 2, R １ and R ２ became independent and became C １－２ represents an alkyl group, m1 and m2 independently represent 0 or 1, A ３ a first diol unit (A1) in which A represents a direct bond; ４ and A ５ became independent and became C ２－３ represents an alkylene group, k1 and k2 independently represent 1 or 2, R ３and R ４ became independent and became C １－２ represents an alkyl group, p1 and p2 independently represent 0 or 1, R ５ is C １－４ a second diol unit (A2) which represents an alkyl group and q represents an integer of 0 to 2; and ６ is C ２－３ a diol unit (A1) containing a third diol unit (A3) which represents an alkylene group and t represents 1 or 2, the total amount of the first diol unit (A1), the second diol unit (A2) and the third diol unit (A3) being 70 mol % or more in the diol unit (A), a molar ratio of the first diol unit (A1) to the second diol unit (A2) being 75 / 25 to 65 / 35, a molar ratio of the first diol unit (A1) to the third diol unit (A3) being 75 / 25 to 40 / 60, and the dicarboxylic acid unit (B) being, in the formula (4), Z １ is a fused polycyclic C １０－１４ represents an arene ring, and R ６ is C １－２ The dicarboxylic acid unit (B1) contains a dicarboxylic acid unit (B1) which represents an alkyl group and s represents 0 or 1, and the proportion of the dicarboxylic acid unit (B1) in the dicarboxylic acid unit (B) is 90 mol % or more, and the refractive index nD is 1.66 to 1.69, the glass transition temperature Tg is 140 to 150°C, and the chromaticity b ＊ and a weight average molecular weight Mw of 35,000 or more.

[0142] [Molded article] The molded article of the present disclosure contains at least the polyester-based resin and exhibits excellent optical properties, and therefore can be used as an optical component such as an optical lens. Since it combines a high refractive index, heat resistance, and moldability, it can be effectively used as an optical lens.

[0143] The molded article of the present disclosure may contain conventional additives. Examples of additives include fillers or reinforcing agents such as carbon materials, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, release agents, antistatic agents, dispersants, flow control agents, leveling agents, antifoaming agents, surface modifiers, hydrolysis inhibitors, stabilizers, and stress-reducing agents. Examples of stabilizers include antioxidants, UV absorbers, and heat stabilizers. Examples of stress-reducing agents include silicone oil, silicone rubber, various plastic powders, and various engineering plastic powders. These additives can be used alone or in combination of two or more. The total proportion of these additives relative to 100 parts by mass of the thermoplastic resin may be, for example, 50 parts by mass or less, preferably 30 parts by mass or less, 0 to 10 parts by mass, or approximately 0.1 to 5 parts by mass, in increments of 100 parts by mass.

[0144] The molded article of the present disclosure can be produced using, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, etc. Of these, injection molding is preferred.

[0145] The shape of the molded body is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous (or fiber-like) and thread-like structures, two-dimensional structures such as film-like, sheet-like and plate-like structures, and three-dimensional structures such as lens-like structures such as concave or convex lenses, rod-like structures and hollow (tubular) structures.

[0146] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Details of evaluation items and raw materials are shown below.

[0147] [Evaluation Method] (Molecular Weight) A sample was dissolved in chloroform, and the weight average molecular weight Mw in terms of polystyrene was determined using gel permeation chromatography ("HLC-8320GPC" manufactured by Tosoh Corporation).

[0148] (Refractive Index and Abbe Number) Using a multi-wavelength Abbe refractometer ("DR-M2 / 1550" manufactured by Atago Co., Ltd.), the refractive indices nF, nD, and nC were measured at a measurement temperature of 20°C and measurement wavelengths of 486 nm (F-line), 589 nm (D-line), and 656 nm (C-line) using 1-bromonaphthalene as a contact liquid. The Abbe number was calculated using the following formula.

[0149] Abbe number = (nD-1) / (nF-nC)

[0150] The test pieces for measuring the refractive index and Abbe number were prepared by hot pressing the sample at 200 to 280°C to form a film with a thickness of 10 to 100 μm, and then cutting this film into strips with a length of approximately 10 mm and a width of 10 to 20 mm.

[0151] (Glass Transition Temperature Tg) Measurement was carried out using a differential scanning calorimeter ("EXSTAR6000 DSC6220 ASD-2" manufactured by SII Nanotechnology Inc.) in a nitrogen atmosphere at a temperature rise rate of 10°C / min.

[0152] [Strength] A cylindrical resin piece 5 cm long and 1 mm in diameter was used, and strength was judged based on whether or not there was breakage when it was bent 1 cm from each end so that the ends were in contact. The evaluation was carried out using 10 samples, and the evaluation criteria were as follows: ○: when 10 samples could be bent without breakage, △: when 5 to 9 samples could be bent without breakage, and ×: when 0 to 4 samples could be bent without breakage.

[0153] [Hue] Using a spectrophotometer ("CM-5" manufactured by Konica Minolta, Inc.), a sample was packed in a petri dish with a measurement diameter of 30 mm in accordance with JIS Z 8722 condition c, and chromaticity b was measured under the conditions of reflection measurement, specular reflection light processing SCI, and observation illuminant D65. ＊ Measurements were carried out.

[0154] [Raw materials] (Dicarboxylic acid components) DMN: 2,6-dimethyl naphthalenedicarboxylate FDP-m: 9,9-bis(2-methoxycarbonylethyl)fluorene (Diol) BINOL-2EO: 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene EG: Ethylene glycol

[0155] [Example 1] BINOL-2EO (18.72 g, 50.0 mmol), BPEF (8.77 g, 20.0 mmol), and EG (14.28 g, 230 mmol) were used as diols, DMN (24.42 g, 100 mmol) was used as a dicarboxylic acid component, titanium (IV) tetrabutoxide (6.8 mg, 18 μmol) was used as a catalyst for the transesterification and polycondensation reaction, and dibutyl phosphate (4.5 mg, 24 μmol) was used as a thermal stabilizer. The mixture was stirred under a nitrogen atmosphere and gradually heated to 285 ° C. to carry out a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually increased to 290 ° C. and 130 Pa, the pressure was reduced, and a polycondensation reaction was carried out while removing EG. After completion of the reaction, the contents were removed from the reactor to obtain a polyester resin.

[0156] [Example 2 and Reference Examples 1 to 6] Polyester resins were obtained in the same manner as in Example 1, except that the compositions of diol units and dicarboxylic acid units were changed to the polymer compositions shown in Table 1. Note that, as in Example 1, an excess amount of ethylene glycol was charged.

[0157] The results are shown in Table 1.

[0158]

[0159] As is clear from Table 1, the polyester resins obtained in the examples had excellent strength, a high refractive index, and a low Abbe number. The glass transition temperature was about 145°C, and the polyester resins had an excellent balance between moldability and heat resistance.

[0160] Example 3 A polyester resin was obtained in the same manner as in Example 1, except that the amount of dibutyl phosphate used was changed to 51.5 mg, 245 μmol.

[0161] Example 4 A polyester resin was obtained in the same manner as in Example 1, except that the types, amounts, and timing of addition of the catalyst and heat stabilizer were changed as follows: BINOL-2EO (18.72 g, 50.0 mmol), BPEF (8.77 g, 20.0 mmol), and EG (14.28 g, 230 mmol) were charged as diols, DMN (22.42 g, 100 mmol) was charged as a dicarboxylic acid component, and manganese acetate tetrahydrate (13.0 mg, 53 μmol) was charged as a transesterification catalyst, and the mixture was stirred under a nitrogen atmosphere while gradually heating to 285° C. to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, titanium (IV) tetrabutoxide (3.4 mg, 10 μmol) was added as a catalyst for the polycondensation reaction and dibutyl phosphate (25.6 mg, 122 μmol) as a thermal stabilizer, and the temperature was gradually increased to 290° C. and the pressure was reduced to 130 Pa, and the polycondensation reaction was carried out while removing EG. After completion of the reaction, the content was removed from the reactor to obtain a polyester resin.

[0162] Examples 5 to 10 Polyester resins were obtained in the same manner as in Example 4, except that the amounts of manganese acetate tetrahydrate and dibutyl phosphate added were changed to the compositions shown in Table 2.

[0163] The results are shown in Table 2. In Table 2, the proportion (ppm) of catalyst or heat stabilizer indicates the mass proportion of each element (Ti, Mn, P) relative to the obtained polyester resin (the mass of the polyester resin assuming that all of the catalyst used is incorporated into the resin).

[0164]

[0165] As can be seen from Table 2, when dibutyl phosphate was used as the heat stabilizer, the yellowness decreased as the proportion of phosphorus increased.

[0166] The polyester-based resin of the present disclosure exhibits excellent optical properties and the like, and therefore may be used in a variety of applications, for example, coating agents or coating films, specifically, protective films for paints, inks, electronic devices, liquid crystal components, and the like; adhesives, pressure-sensitive adhesives; resin fillers; electric and electronic materials or electric and electronic components (electrical and electronic devices), specifically, antistatic agents, carrier transport agents, light-emitting bodies, organic photoreceptors, thermosensitive recording materials, photochromic materials, hologram recording materials, antistatic trays, conductive sheets, optical disks, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, and the like; and mechanical materials or mechanical parts (equipment), specifically, automotive materials or parts, aerospace-related materials or parts, sliding members, and the like.

[0167] The polyester resin of the present disclosure can be particularly effectively used as an optical component, such as an optical lens for glasses or a camera, a prism, a hologram, or an optical fiber.

[0168] Examples of optical lenses include eyeglass lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar concentrating lenses, objective lenses, and rod lens arrays, and are particularly suitable for use in lenses that require a low Abbe number, such as camera lenses. Typical examples of devices or apparatuses that can incorporate such optical lenses include small or mobile devices with camera functions, such as smartphones, mobile phones, and digital cameras; and in-vehicle cameras, such as drive recorders and backup cameras (rear cameras).

Claims

1. A polyester resin containing a diol unit (A) and a dicarboxylic acid unit (B), wherein the diol unit (A) is represented by the following formula (1): (In the formula, A １ and A ２ each independently represents an alkylene group; n1 and n2 each independently represent an integer of 0 or more; R １ and R ２ each independently represents a substituent; m1 and m2 each independently represent an integer of 0 to 6; ３ represents a direct bond or an alkylene group), a first diol unit (A1) represented by the following formula (2): (In the formula, A ４ and A ５ each independently represents an alkylene group; k1 and k2 each independently represent an integer of 0 or more; R ３ and R ４ each independently represents a substituent, p1 and p2 independently represent an integer of 0 to 4, R ５ represents a substituent, and q represents an integer of 0 to 8), and a second diol unit (A2) represented by the following formula (3): (In the formula, A ６ represents an alkylene group, and t represents an integer of 1 to 10), the proportion of the first diol unit (A1) is 5 to 60 mol % in the diol unit (A), and the dicarboxylic acid unit (B) is represented by the following formula (4): (In the formula, Z １ represents a fused polycyclic arene ring; R ６ represents a substituent, and s represents an integer of 0 or more), and the proportion of the dicarboxylic acid units (B1) in the dicarboxylic acid units (B) is 50 mol % or more.

2. In the formula (1), A １ and A ２ became independent and C ２－４ represents an alkylene group, n1 and n2 each independently represent an integer of 0 to 10, A ３ 2. The polyester resin according to claim 1, wherein: represents a direct bond; and the proportion of the first diol unit (A1) in the diol unit (A) is 35 to 55 mol %.

3. In the formula (2), A ４ and A ５ became independent and C ２－４ 3. The polyester resin according to claim 1, wherein k1 and k2 each independently represent an integer of 0 to 10.

4. In the formula (3), A ６ C ２－４ 3. The polyester resin according to claim 1, wherein t is an alkylene group and t is 1.

5. In the formula (4), Z １ 3. The polyester resin according to claim 1, wherein: represents a naphthalene ring; and the proportion of the dicarboxylic acid units (B1) in the dicarboxylic acid units (B) is 80 mol % or more.

6. A polyester resin according to claim 1 or 2, wherein the molar ratio of the first diol unit (A1) to the second diol unit (A2) is from 80 / 20 to 60 / 40.

7. A polyester resin according to claim 1 or 2, wherein the molar ratio of the first diol unit (A1) to the third diol unit (A3) is from 80 / 20 to 30 / 70.

8. The polyester resin according to claim 1 or 2, which has a glass transition temperature of 130 to 160° C. and a refractive index of 1.655 or more.

9. The polyester resin according to claim 1 or 2, which has a weight average molecular weight of 30,000 or more.

10. Chromaticity b ＊ 3. The polyester resin according to claim 1, wherein the absolute value of 11. A method for producing the polyester resin according to claim 1 or 2, comprising polymerizing a diol corresponding to the diol unit (A) and a dicarboxylic acid component corresponding to the dicarboxylic acid unit (B).

12. The method of claim 11, wherein said diol and said dicarboxylic acid component are polymerized in the presence of a titanium compound and / or a manganese compound.

13. The method of claim 11, wherein said diol and said dicarboxylic acid components are polymerized in the presence of a phosphorus compound.

14. A molded article comprising the polyester resin according to claim 1 or 2.

15. The molded article according to claim 14, which is an optical lens.

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