JP2015131918A - Polymer, compound, resin composition, resin pellet and resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer having a high refractive index and having a low glass transition temperature and a low birefringence.SOLUTION: A polymer has a structural unit comprising a divalent group represented by the formula (1) in a main chain. (In the formula (1), Ris a univalent group represented by a specific formula, Ris a hydrogen atom or a cyano group, Ris a 2-4C alkylene group, and a is an integer of 0-2.

Description

  The present invention relates to a polymer, a compound, a resin composition, a resin pellet, and a resin molded body.

  Optical components such as optical lenses and optical films are used in display devices such as liquid crystal display devices, camera module lenses such as digital cameras and mobile phone cameras, and optical sensors such as image sensors. In recent years, an optical component has been formed using a polymer having a high refractive index as a resin component from the viewpoint of thinning and high added value.

  Such an optical component is formed by, for example, injection molding or extrusion molding using a resin material containing the polymer at a temperature equal to or higher than the glass transition temperature of the polymer. For this reason, the polymer is required to have a low glass transition temperature from the viewpoint of facilitating molding, preventing deterioration of the polymer during molding, and reducing production costs. In addition, when an optical component is used in a camera module or the like, the optical component is also required to have low birefringence in order to increase the image definition.

  In response to such demands, polyethers, polycarbonates, polyesters, and the like having structures derived from bisphenol compounds such as bisphenolfluorene derivatives have been developed as polymers forming optical components (Japanese Patent Laid-Open No. 2012-224863). Gazette, JP 2010-132782 A and JP 2013-64117 A). The polymers described in these publications exhibit low birefringence because the refractive index is modulated in the direction perpendicular to the main chain due to the fluorene cardo structure. On the other hand, it is difficult to sufficiently lower the glass transition temperature of a polymer having a rigid and bulky skeleton such as a fluorene cardo structure. Thus, in order to lower the glass transition temperature, it may be possible to introduce an alkylene group. However, the introduction of an alkylene group has the disadvantage that the refractive index is lowered.

  In addition, the following compound is also well-known as a bisphenol compound (refer nonpatent literature 1). However, the following bisphenol compound is an intermediate during pharmaceutical synthesis in Non-Patent Document 1, and the use of such a bisphenol compound as a monomer that gives a polymer as a main component of an optical component is described in Non-Patent Document. From the description of 1, it cannot be easily conceived.

JP 2012-224863 A JP 2010-132782 A JP 2013-64117 A

Bioorganic & Medicinal Chemistry Letters. Volume 16, Issue 6, 15 March 2006, Pages 1616-1620.

  This invention is made | formed based on the above-mentioned situation, The objective is to provide a polymer with a high refractive index, a low glass transition temperature, and low birefringence.

（式（１）中、Ｒ^１は、下記式（２）又は式（３）で表される１価の基である。Ｒ^２は、水素原子又はシアノ基である。Ｒ^３は、炭素数２〜４のアルキレン基である。ａは、０〜２の整数である。）

（式（２）中、Ｒ^４は、炭素数１〜１２の１価の有機基である。ｂは、０〜７の整数である。ｂが２以上の場合、複数のＲ^４は、同一であっても異なっていてもよい。複数のＲ^４のうちの２以上のＲ^４は、互いに結合して環構造の一部を形成してもよい。ｃは、０又は１である。
式（３）中、ｄ、ｅ及びｆは、それぞれ独立して、０又は１である。） The invention made to solve the above problems is a polymer having a structural unit containing a divalent group represented by the following formula (1) in the main chain.

(In Formula (1), R ¹ is a monovalent group represented by the following Formula (2) or Formula (3). R ² is a hydrogen atom or a cyano group. R ³ is the number of carbon atoms. An alkylene group of 2 to 4. a is an integer of 0 to 2.)

(In Formula (2), R ⁴ is a monovalent organic group having 1 to 12 carbon atoms. B is an integer of 0 to 7. When b is 2 or more, the plurality of R ⁴ are the same. 2 or more R ⁴ of which may be be different also. more R ⁴ is is good .c also form part of the ring structure bonded to each other, it is 0 or 1.
In formula (3), d, e, and f are each independently 0 or 1. )

（式（５）中、Ｒ^１は、下記式（６）又は（７）で表される１価の基である。Ｒ^３は、炭素数２〜４のアルキレン基である。Ｒ^５は、水素原子又は炭素数１〜５のアルキル基である。ａは、０〜２の整数である。）

（式（６）中、Ｒ^４は、炭素数１〜１２の１価の有機基である。ｂは、０〜７の整数である。ｂが２以上の場合、複数のＲ^４は、同一であっても異なっていてもよい。複数のＲ^４のうちの２以上のＲ^４は、互いに結合して環構造の一部を形成してもよい。ｃは、０又は１である。
式（７）中、ｄ、ｅ及びｆは、それぞれ独立して、０又は１である。） The present invention includes a compound represented by the following formula (5).

(In formula (5), ^{R 1} is .R ³ is a monovalent group represented by the following formula (6) or (7), the .R ⁵ is an alkylene group having 2 to 4 carbon atoms, A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a is an integer of 0 to 2)

(In Formula (6), R ⁴ is a monovalent organic group having 1 to 12 carbon atoms. B is an integer of 0 to 7. When b is 2 or more, the plurality of R ⁴ are the same. 2 or more R ⁴ of which may be be different also. more R ⁴ is is good .c also form part of the ring structure bonded to each other, it is 0 or 1.
In formula (7), d, e, and f are each independently 0 or 1. )

  The present invention further includes a resin composition containing the polymer and an organic solvent, and resin pellets and a resin molded body containing the polymer as a main component. The “main component” is the most abundant component, for example, a component having a content of 50% by mass or more.

  According to the present invention, a polymer having a high refractive index and a low glass transition temperature and low birefringence can be provided. Therefore, the polymer of the present invention can provide an optical component having a high refractive index and a low birefringence, and can provide a resin pellet and a resin composition capable of easily and cost-effectively molding such an optical component. Furthermore, according to this invention, the compound which can form the said polymer is provided.

  Hereinafter, the polymer, compound, resin composition, resin pellet, and resin molded body of the present invention will be described in detail.

[Polymer]
The polymer of the present invention (hereinafter also referred to as “(A) polymer”) is a structural unit (hereinafter referred to as “structural unit”) containing a divalent group (hereinafter also referred to as “X group”) represented by the following formula (1). (Also referred to as (a) ") in the main chain.

<X group>
The X group is derived from, for example, an aromatic diol compound, a derivative or precursor thereof.

In the above formula (1), R ¹ is a monovalent group represented by the following formula (2) or formula (3). R ² is a hydrogen atom or a cyano group, preferably a hydrogen atom. R ³ is an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, and an i-butylene group. a is an integer of 0 to 2, and 0 is preferable. Two a's in the above formula (1) may be the same or different.

(A) The polymer can have a high refractive index and low glass transition temperature and birefringence because R ¹ is a monovalent group represented by the following formula (2) or formula (3). The reason for this is not clear, but (A) by containing an aromatic ring in the side chain of the polymer, the concentration of the aromatic ring in the polymer (A) increases, so that a high refractive index can be achieved, and (A) It is considered that the refractive index can be modulated in the direction orthogonal to the main chain of the polymer, thereby realizing low birefringence. In particular, when R ¹ is a monovalent group represented by the following formula (3), the side chain of the polymer (A) contains a sulfur atom, so that the sulfur concentration in the polymer (A) increases. It is considered suitable for realizing a high refractive index and a low birefringence. In addition, since the X group of the above formula (1) is not a rigid structure like the fluorene cardo structure, the repeating unit has a small molecular weight and can increase the number of binding groups having flexibility. (A) It is considered that the glass transition temperature of the polymer can be lowered.

In the above formula (2), ^{R 4} is a monovalent organic group having 1 to 12 carbon atoms. b is an integer of 0-7. When b is 2 or more, the plurality of R ⁴ may be the same or different. 2 or more R ⁴ of the plurality of R ⁴ may form a part of the bond to ring structure. c is 0 or 1.
In the above formula (3), d, e and f are each independently 0 or 1. In addition, the bond with the divalent group represented by the above formula (1) in the above formula (3) penetrates the parenthesis of the repeating number d, and this is because the above bond is a benzene ring and sulfur. It means that any ring of the heterocyclic ring containing an atom may have a bonding site.

Examples of the monovalent organic group having 1 to 12 carbon atoms represented by R ⁴ include a monovalent hydrocarbon group having 1 to 12 carbon atoms and at least one atom of an oxygen atom and a nitrogen atom. Examples thereof include a monovalent hydrocarbon group having 1 to 12 carbon atoms.

  Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 6 carbon atoms. And 12 aromatic hydrocarbon groups.

  Examples of the linear or branched hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n- A hexyl group, n-heptyl group, etc. are mentioned.

  The linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and the linear or branched hydrocarbon group having 1 to 5 carbon atoms. The hydrocarbon group is more preferable.

  Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; cycloalkenyl groups such as cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group. Group and the like.

  The alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, and more preferably an alicyclic hydrocarbon group having 3 or 4 carbon atoms.

  Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group.

  As a C1-C12 hydrocarbon group containing an oxygen atom, a C1-C12 hydrocarbon group etc. which have an ether bond, a carbonyl group, an ester group etc. are mentioned, for example.

  Examples of the hydrocarbon group having 1 to 12 carbon atoms having an ether bond include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 2 to 12 carbon atoms, and 6 to 6 carbon atoms. 12 aryloxy group, C2-C12 alkoxyalkyl group, etc. are mentioned. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group, and a methoxymethyl group.

  Moreover, as a C1-C12 hydrocarbon group which has a carbonyl group, a C2-C12 acyl group etc. are mentioned, for example. Specific examples include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.

  As a C1-C12 hydrocarbon group which has ester group, a C2-C12 acyloxy group etc. are mentioned. Specific examples include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and a benzoyloxy group.

  As a C1-C12 hydrocarbon group containing a nitrogen atom, an imidazole group, a triazole group, a benzimidazole group, a benztriazole group etc. are mentioned, for example.

  As a C1-C12 hydrocarbon group containing an oxygen atom and a nitrogen atom, an oxazole group, an oxadiazole group, a benzoxazole group, a benzoxadiazole group etc. are mentioned, for example.

  Examples of the monovalent group represented by the formula (2) include monovalent groups represented by the following formulas (2-1) to (2-3).

  As the monovalent group represented by the above formula (2), when c = 1, the bonding site with the benzene ring in the divalent group represented by the above formula (1) is represented by the following formula (2-4). The monovalent group of the position represented by these is preferable.

In said formula (2-4), R < ⁴ > and b are synonymous with said formula (2).

  Examples of the monovalent group represented by the above formula (3) include monovalent groups represented by the following formulas (3-1) to (3-6).

  The monovalent group represented by the above formula (3) is preferably a monovalent group represented by the following formula (4). (A) When a polymer contains group represented by following formula (4), it becomes possible to implement | achieve more highly refractive index and low birefringence more suitably. From this point, as the monovalent group represented by the above formula (3), the monovalent group represented by the above formula (3-3) and the monovalent group represented by the formula (3-4) Is more preferable.

<Structural unit (a)>
As the structural unit (a), an ester group-containing structural unit represented by the following formula (9), a carbonate group-containing structural unit represented by the formula (10), and an ether group-containing structural unit represented by the formula (11) The ether group-containing structural unit represented by the following formula (11) is more preferable.

In the above formulas (9) to (11), X is an X group represented by the above formula (1).
In said formula (9), Y is a divalent organic group which has an alicyclic ring or an aromatic ring.
In said formula (11), Z is a divalent organic group which has a methylene group, a C2-C4 alkylene group, or an aromatic ring.

  Examples of the divalent organic group having an alicyclic ring represented by Y in the formula (9) include an alicyclic group having 4 to 20 carbon atoms. Examples of the alicyclic group having 4 to 20 carbon atoms include a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, an adamantanediyl group, and a norbornanediyl group.

  Examples of the divalent organic group having an aromatic ring represented by Y in the above formula (9) or Z in the above (11) include substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms. Examples of the unsubstituted aromatic group having 6 to 20 carbon atoms include a phenylene group, a naphthalenylene group, and an anthracenylene group. Examples of the substituted aromatic group having 6 to 20 carbon atoms include a group in which at least one hydrogen atom of an unsubstituted aromatic group having 6 to 20 carbon atoms is substituted with a substituent. Examples of this substituent include a halogen atom, a cyano group, and an alkyl group.

  (A) As a content rate of the structural unit (a) in a polymer, it is 25 mol% or more normally with respect to all the structural units in (A) polymer, and 50 mol% or more is preferable. Although it does not specifically limit as an upper limit of the content rate of a structural unit (a), 100 mol% may be sufficient.

  In addition, the (A) polymer may contain other structural units other than the structural unit (a). Another structural unit will not be specifically limited if it is a range which does not impair the effect of this invention. (A) As a content rate of the other structural unit in a polymer, it is 75 mol% or less normally, Preferably it is 50 mol% or less.

<(A) Synthesis of polymer>
(A) The polymer is a known method, for example, an aromatic diol compound or the like that gives the structural unit (a) and other compounds, and if necessary, other compounds in the presence of an organic solvent under predetermined reaction conditions. It can be synthesized by reacting with

  Examples of the aromatic diol compound include an aromatic diol compound, a derivative and a precursor thereof, and a compound (a) described later.

  Other compounds may be appropriately selected according to the structure of the structural unit (a). Examples of other compounds include alkali metal compounds, “— (CO) Y (CO) —” in the above formula (9), “—CO—” in the above formula (10), and “Z” in the above formula (11). The compound which gives is mentioned. Further, other compounds and the like may be appropriately selected according to the structure of the structural unit other than the structural unit (a).

  Here, as a compound which gives "Z" of the said Formula (11), a dihalogenated benzonitrile compound etc. are mentioned, for example. Examples of the dihalogenated benzonitrile include 2,6-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, precursors and derivatives thereof, and the like. . Among these, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferable and 2,6-difluorobenzonitrile is more preferable from the viewpoint of reactivity and economy.

(Alkali metal compound)
The alkali metal compound reacts with an aromatic diol compound or the like in the process of synthesizing the polymer (A) to form an alkali metal salt. Examples of such alkali metal compounds include alkali metals such as lithium, sodium, and potassium;
Alkali metal hydrides such as lithium hydride, sodium hydride, potassium hydride;
Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide;
Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate;
Examples thereof include alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate. Of these, alkali metal carbonates are preferred, and potassium carbonate is more preferred.

  With respect to the amount of the alkali metal compound used, the amount of the metal atom in the alkali metal compound is usually 1 to 3 times equivalent, preferably 1. with respect to the phenolic hydroxyl groups of all compounds used in the synthesis of the polymer (A). The amount is 1 to 2 equivalents, more preferably 1.2 to 1.5 equivalents.

(Organic solvent)
Examples of the organic solvent include N, N-dimethylacetamide (DMAc), N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, sulfolane, dimethyl Sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, methylene chloride, dialkoxybenzene (1 to 4 carbon atoms of alkoxy group), trialkoxybenzene (1 to 4 carbon atoms of alkoxy group) ) And the like. These organic solvents may be used alone or in combination of two or more. Among the exemplified organic solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, and dimethylsulfoxide are preferable because they are polar solvents having a high dielectric constant.

  In addition to the organic solvents exemplified above, azeotropic solvents such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetole can be used in combination.

(Reaction conditions)
(A) As reaction temperature at the time of the synthesis | combination of a polymer, 60 to 250 degreeC is preferable and 80 to 200 degreeC is more preferable. The reaction time during the synthesis is preferably 15 minutes to 100 hours, more preferably 1 hour to 24 hours.

[Compound]
The compound of the present invention (hereinafter also referred to as “(a) compound”) is represented by the following formula (5). This (a) compound can give the said X group.

In the above formula (5), R ¹ is a monovalent group represented by the following formula (6) or (7). R ³ is an alkylene group having 2 to 4 carbon atoms. R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. a is an integer of 0-2.

^R 4, b and c in the formula (6) has the same meaning as ^R 4, b and c in the formula (2).
D, e and f in the above formula (7) have the same meanings as d, e and f in the above formula (3).

  The monovalent group represented by the above formula (7) is preferably a monovalent group represented by the following formula (8).

<Synthesis Method of Compound (a)>
Compound (a) can be obtained, for example, by the following synthesis scheme. Specifically, first, a compound represented by the following formula (12) is reacted with R ¹ B (OH) ₂ or the like in the presence of tetrakistriphenylphosphine palladium (0) (Pd (PPh ₃ ) ₄ ). The bromine atom can be substituted with R ¹ to obtain an aromatic diol compound precursor of the following formula (13). The aromatic diol compound precursor represented by the following formula (13) corresponds to an example of the compound (a).

  Next, an aromatic diol compound represented by the following formula (14) can be obtained by reacting an aromatic diol compound precursor represented by the following formula (13) with boron tribromide or the like. This aromatic diol compound also corresponds to an example of the compound (a).

Here, in the above formula (12) and formula (13), R ¹ is a monovalent group represented by the above formula (6) or formula (7). R ³ is an alkyl group having 2 to 4 carbon atoms. R ⁵ ′ is an alkyl group having 1 to 5 carbon atoms. a is an integer of 0-2.

[Resin composition]
The resin composition (hereinafter also referred to as “(A) resin composition”) contains (A) a polymer and an organic solvent. This (A) resin composition may contain other components as long as the effects of the present invention are not impaired. This (A) resin composition can be suitably used for forming resin pellets and resin molded articles described later.

  Examples of the organic solvent include those similar to the organic solvent used when the (A) polymer is synthesized. These solvents may be used alone or in combination of two or more.

  Examples of other components include an antioxidant and a polymer other than the polymer (A).

  Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, sulfur compounds, metal compounds, and hindered amine compounds. As this antioxidant, a hindered phenol compound is preferable.

  As the hindered phenol compound, those having a molecular weight of 500 or more are preferable. Examples of hindered phenol compounds having a molecular weight of 500 or more include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) proonate], 1,6-hexanediol-bis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino)- 3,5-triazine, pentaerythritol tetrakis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris [2-methyl-4- [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane, 2 2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di -Tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and 3,9-bis [2- [3- (3 -Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 5] undecane, and the like.

[Other optional ingredients]
(A) The resin composition may contain other arbitrary components other than (A) polymer, antioxidant, and polymers other than (A) polymer. Examples of the other optional components include known additives such as a flame retardant, an antibacterial agent, a colorant, a release agent, and a foaming agent in addition to a lubricant that improves processability. These other optional components may be used alone or in combination of two or more.

  (A) As content of the antioxidant in a resin composition, it is 0.01 mass part or more and 10 mass parts or less with respect to 100 mass parts of (A) polymers, for example.

  (A) As content of (A) polymer in a resin composition, it is 10 to 100 mass% in the total solid of (A) resin composition, for example.

  (A) As content of the organic solvent in a resin composition, it is 50 mass parts or more and 100,000 mass parts or less with respect to 100 mass parts of (A) polymers, for example.

<(A) Preparation method of resin composition>
(A) The resin composition is prepared by uniformly mixing other components such as (A) a polymer and an organic solvent, and, if necessary, an antioxidant and other resins. The resin composition is prepared in a solid form such as a powder form, a pellet form, or a chip form, or is dissolved in an appropriate solvent to prepare a liquid form or a paste form.

  As the solvent, a solvent that uniformly dissolves the contained component and does not react with the contained component is used. Examples of such a solvent include the same solvents as those exemplified as the organic solvent used in the synthesis of the polymer (A).

  When the resin composition is prepared in a solid state, the melt flow rate (hereinafter also referred to as “MFR”) at 300 ° C. and 10 kg load of the resin composition is 0.1 g / 10 min or more and 1000 g / 10 min or less. preferable. If the MFR is less than the lower limit, sufficient fluidity cannot be ensured during molding such as extrusion molding, and the moldability may be deteriorated. On the other hand, if the MFR exceeds the above upper limit, the strength of the molded product cannot be maintained, and cracking may occur when removing from the mold.

[Resin pellets]
The resin pellet of the present invention (hereinafter also referred to as “(A) resin pellet”) has (A) a polymer as a main component. This (A) resin pellet may contain another component in the range which does not impair the effect of this invention.

  Examples of other components include the same components as those exemplified as the other components of the (A) resin composition.

  This (A) resin pellet is obtained by dissolving (A) a polymer and, if necessary, a solution in which other components are dissolved, for example, (A) a resin composition using a twin screw extruder, and melt-kneading. It can be obtained by cutting the extruded strand into a predetermined size with a pelletizer.

[Resin molding]
The resin molded body of the present invention (hereinafter referred to as “(A) resin molded body”) contains (A) a polymer as a main component. (A) As a resin molding, an optical component is mentioned, for example.

<Optical parts>
Examples of the optical component include optical films such as a wave plate and a retardation plate, various special lenses such as a conical lens, a spherical lens, and a cylindrical lens, and a lens array.

<(A) Manufacturing method of resin molding>
(A) As a manufacturing method of a resin molding, a metal mold molding method, an extrusion molding method, a solvent cast method etc. are mentioned, for example. A mold forming method is suitable for manufacturing the lens. For the production of an optical film, an extrusion molding method and a solvent casting method are preferable, and an extrusion molding method is more preferable. Hereinafter, the extrusion molding method will be described.

(Extrusion molding method)
Examples of the extrusion molding method include a melt extrusion method and a semi-melt extrusion method, and the melt extrusion method is preferable. Examples of the melt extrusion method include methods using dies having various shapes, and among them, methods using a T die and a coat hanger die are preferable.

  In such melt-extrusion, a heat-melted resin composition is extruded from a die, and is then brought into close contact with a metal belt, a cooling roll or the like to form a sheet. Is obtained.

  The optical sheet may be stretched before being wound into a roll or after being wound into a roll, or may be cut into a predetermined dimension. In order to make the polymer sheet melt-extruded from the die adhere to the metal belt, air controlled to the same temperature as that of the metal belt may be blown or may be brought into close contact by charging and fixing. The stretching treatment may be uniaxial stretching or biaxial stretching.

[Physical properties of (A) polymer and (A) resin molding]
<(A) Glass transition temperature (Tg) of polymer>
(A) As a glass transition temperature (Tg) of a polymer, 200 degrees C or less is preferable, 190 degrees C or less is more preferable, 180 degrees C or less is further more preferable. Since the glass transition temperature of such a polymer (A) is 200 ° C. or less, the resin pellets and resin composition containing the polymer (A) as a main component can be molded at the time of extrusion molding such as melt extrusion. Excellent. Here, the glass transition temperature (Tg) can be measured by, for example, “8230 type DSC measuring apparatus” (temperature rising rate 20 ° C./min) manufactured by Rigaku.

<(A) Weight average molecular weight of polymer (Mw)>
(A) The lower limit of the weight average molecular weight (Mw) of the polymer is preferably 10,000, more preferably 20,000, and even more preferably 30,000. The upper limit of the weight average molecular weight (Mw) is preferably 75,000 or less, and more preferably 60,000 or less. The weight average molecular weight (Mw) is a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

<Thickness of optical film>
(A) As thickness of the optical film as a resin molding, it is 10 micrometers or more and 1,000 micrometers or less, and 10 micrometers or more and 500 micrometers or less are still more preferable. If the thickness of the optical film is less than 10 μm, the sheet strength may not be sufficiently secured. on the other hand. If the thickness of the polymer sheet exceeds 1,000 μm, the transparency of the sheet may not be ensured.

<(A) Total light transmittance of polymer and optical component>
The total light transmittance of the optical component (A) polymer and (A) resin molded body is preferably 85% or more, more preferably 90% or more when prepared as a sheet having a thickness of 50 μm. Here, the total light transmittance is a value of a transparency test method (JIS-K-7105: 1981) for a sheet having a thickness of 50 μm. The transparency of (A) optical components, such as an optical film, can be ensured because the total light transmittance of a sheet | seat is 85% or more. Therefore, an optical component such as an optical film can be suitably used for a display device or the like.

<(A) Refractive index (nD) and Abbe number (D) of polymer and optical component>
(A) As a refractive index (nD) of a polymer and an optical component, 1.65 or more are preferable, 1.66 or more are more preferable, and 1.67 or more are further more preferable.
(A) The Abbe number (D) of the polymer and the optical component is preferably 21 or less, more preferably 20 or less, and even more preferably 19 or less.
(A) The refractive index (nD) of the polymer and the optical component is 1.65 or more, and the Abbe number (D) is 21 or less, thereby realizing thinning of lenses and films and high added value. It becomes possible to do.

<(A) Stress optical coefficient of polymer and (A) optical component ( _CR )>
The upper limit of the absolute value of the stress optical coefficient (C _R ) of the polymer (A) and the optical component (A) is preferably 2,000 Br or less, more preferably 1,500 Br or less, and even more preferably 1,000 Br or less. By making the absolute value of the stress optical coefficient (C _R ) of the optical film not more than the above upper limit, the birefringence of the optical film can be reduced. That is, the optical distortion of the molded body can be reduced, and when applied to a camera module lens or the like, high-definition imaging can be performed. On the other hand, the lower limit of the absolute value stress optical coefficient _{(C R),} is not particularly limited, preferably 100Br, 0Br is more preferable. The unit “Br” of the stress optical coefficient (C _R ) corresponds to “10 ⁻¹² Pa ⁻¹ ”.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to a following example.

[Example 1] (Synthesis of aromatic diol compound precursor (compound (a-1)))
After attaching a three-way cock and a condenser tube to a 100 mL two-necked eggplant type flask containing a stir bar, 1-bromo-3,5-dimethoxybenzene 3.60 g (16.6 mmol), benzothiophene-2-boronic acid 2.95 g (16.6 mmol), tetrakistriphenylphosphine palladium (0) 1.92 g (1.66 mmol), and sodium carbonate 3.52 g (33.2 mmol) were weighed in. After replacing the inside of the container with nitrogen, 160 mL of toluene and 18 mL of ethanol were added, and the temperature was raised to 123 ° C. and reacted for 6 hours. Next, 50 mL of water was added to the obtained reaction mixture, and the separated and recovered organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and then the solvent was distilled off from the filtrate to obtain a crude product. Was recovered. This crude product was purified by silica gel column chromatography (developing solvent: normal hexane: ethyl acetate = 95: 5 (weight ratio)) to give 2- (3,3) as compound (a) (aromatic diol compound precursor). 2.81 g (10.4 mmol) of a powder of 5-dimethoxyphenyl) benzothiophene (compound (a-1)) was obtained. The yield of this compound (a-1) was 63%.

In addition, ¹ H-NMR analysis was performed on the compound (a). This ¹ H-NMR analysis was measured using “JNM-ECA400” manufactured by JEOL RESONANCE. The results are as follows.

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 3.86 (s, 6H), 6.46 (t, 1H), 6.87 (d, 2H), 7.29-7.37 (m, 2H) ), 7.53 (s, 1H), 7.76 (d, 1H), 7.81 (d, 1H)

[Example 2] (Synthesis of aromatic diol compound (compound (a-2)))
After attaching a three-way cock and a flat stopper to a 100 mL two-necked eggplant-shaped flask containing a stir bar, 2.81 g (10.4 mmol) of 2- (3,5-dimethoxyphenyl) benzothiophene was weighed in. After replacing the inside of the container with nitrogen, 12 mL of dichloromethane was added, and 41.56 mL (41.56 mmol) of boron tribromide in 1 mol / L dichloromethane was added dropwise while cooling at -78 ° C. After the addition, the reaction mixture was gradually warmed and reacted at room temperature for 6 hours. Next, 50 mL of water was added to the obtained reaction mixture, and the separated and recovered organic layer was washed with saturated brine, dried over magnesium sulfate and filtered, and then the solvent was distilled off from the filtrate to obtain a crude product. It was collected. The crude product was purified by cyclohexane washing, and 1.84 g (powder of 5-benzothiophenylbenzene-1,3-diol (compound (a-2)) as compound (a) (aromatic diol compound) ( 7.60 mmol). The yield of this compound (a-2) was 73%. Further, ¹ H-NMR measured in the same manner as in Example 1 was as follows.

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 5.03 (s, 2H), 6.35 (s, 1H), 6.79 (s, 2H), 7.30-7.36 (m, 2H) ), 7.50 (s, 1H), 7.76 (d, 1H), 7.83 (d, 1H)

[Example 3] (Synthesis of polymer (A-1))
A 100 mL three-necked flask containing a stirrer was fitted with a nitrogen inlet tube, a Dean-Stark tube, and a condenser tube, and the aromatic diol compound (compound (a-2)) (0 967 g, 3.99 mmol), 2,2-bis (4-hydroxyphenyl) propane (Bis-A, 0.911 g, 3.99 mmol), 2,6-difluorobenzonitrile (DFBN, 1.11 g, 8. 00 mmol), potassium carbonate (2.21 g, 16.0 mmol), N, N-dimethylacetamide (DMAc) 5.6 mL, and toluene 1.4 mL were charged. After the atmosphere in the flask was replaced with nitrogen, the mixture was heated and stirred at 130 ° C., and the resulting water was reacted for 9 hours while being removed by a Dean-Stark tube. After cooling to room temperature, the resulting salt was removed by filtration. An appropriate amount of ion exchange resins (“Diaion RCP160M” and “Diaion WA21J” from Mitsubishi Chemical Corporation) were added to the filtrate, and the mixture was stirred with a mix rotor for 2 hours. After removing the ion exchange resin with filter paper, the filtrate was poured into methanol to precipitate a solid. The precipitated solid was vacuum-dried at 80 ° C. to obtain 1.87 g of a polymer (A-1) powder as a polymer (A). The yield of polymer (A-1) was 70%.

[Example 4] (Synthesis of aromatic diol compound precursor (compound (a-3)))
Compound (a) (aromatic diol compound precursor) was prepared in the same manner as in Example 1 except that 2.86 g (16.6 mmol) of 2-naphthaleneboronic acid was used instead of benzothiophene-2-boronic acid. As a result, 2.63 g (9.96 mmol) of 2- (3,5-dimethoxyphenyl) naphthalene (compound (a-3)) powder was obtained. The yield of compound (a-3) was 60%. Further, ¹ H-NMR measured in the same manner as in Example 1 was as follows.

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 3.86 (s, 6H), 6.46 (t, 1H), 6.87 (d, 2H), 7.57-7.60 (m, 3H) ), 7.73 (dd, 1H), 7.92 (dd, 1H), 8.00 (m, 2H)

[Example 5] (Synthesis of aromatic diol compound (compound (a-4)))
The same operation as in Example 2 was performed except that 2.75 g (10.4 mmol) of 2- (3,5-dimethoxyphenyl) naphthalene was used instead of 2- (3,5-dimethoxyphenyl) benzothiophene, 1.84 g (7.80 mmol) of powder of 5-naphthylbenzene-1,3-diol (compound (a-4)) as compound (a) (aromatic diol compound) was obtained. The yield of compound (a-4) was 75%. Further, ¹ H-NMR measured in the same manner as in Example 1 was as follows.

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 5.35 (s, 2H), 6.45 (s, 1H), 6.88 (s, 2H), 7.48-7.52 (m, 3H ), 7.73 (dd, 1H), 7.92 (dd, 1H), 8.00 (m, 2H)

[Comparative Example 1] (Synthesis of Comparative Polymer (CA-1))
The same operation as in Example 3 was performed except that 1.40 g (3.99 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene (BPFL) was used in place of the compound (a-2). 2.79 g of polymer (CA-1) powder was obtained. The yield of the comparative polymer (CA-1) was 90%.

[Comparative Example 2] (Synthesis of Comparative Polymer (CA-2))
As polymerizable monomers, 2,2-bis (4-hydroxyphenyl) propane (Bis-A) 1.82 g (7.98 mmol) and 2,6-difluorobenzonitrile (DFBN) 1.11 g (8.00 mmol) were used. Except having used, it operated similarly to Example 3 and obtained 2.30g of powders of the comparison polymer (CA-2). The yield of the comparative polymer (CA-2) was 88%.

<Evaluation>
For the polymers of Example 3 and Comparative Examples 1 and 2, the glass transition temperature (Tg), refractive index (nD), Abbe number (νD), and stress optical coefficient (C _R ) were evaluated according to the following methods. The results are shown in Table 1. Table 1 also shows the amount (mmol) of each compound used for the synthesis of each polymer. In Table 1, “-” indicates that the corresponding compound was not used.

[Glass transition temperature (Tg) [° C]]
The glass transition temperature of the polymer was measured using a DSC apparatus (“Thermo Plus DSC8230” manufactured by Rigaku) under a temperature increase rate of 20 ° C./min under nitrogen.
The glass transition temperature (Tg) was evaluated as “◯” when the temperature was 200 ° C. or lower, and “X” when the glass transition temperature was higher than 200 ° C.

[Refractive index (nD) [−] and Abbe number (νD) [−]]
A polymer dissolved in an appropriate amount of methylene chloride was cast on a glass plate and dried overnight at room temperature and normal pressure. Next, the residual methylene chloride was removed with a vacuum dryer to obtain a polymer film. The refractive index of this film was measured by “Prism Coupler Model 2010” manufactured by Metricon. The refractive index was measured at three wavelengths of 408 nm, 633 nm, and 828 nm, and the refractive index (nD) at the D line (589 nm) was determined using the Cauchy equation. The refractive index of F line (486 nm) and C line (656 nm) was determined in the same manner, and the Abbe number (νD) was calculated.
The case where the refractive index (nD) was 1.660 or more was evaluated as “◯”, and the case where it was less than 1.660 was evaluated as “x”.
The Abbe number (νD) was evaluated as “◯” when the value was 21.0 or less, and “x” when the value was more than 21.0.

Stress optical coefficient _(C R) [Br]]
Stress optical coefficient _{C R} a known method (Polymer Journal, Vol.27, No.9, P.943~950 (1995)) was determined by). Several kinds of loads were applied to the film formed for evaluation of the refractive index, and the film was stretched by heating under a temperature condition of Tg + 20 ° C., and slowly cooled to room temperature while the load was applied. A stress applied to the film, resulting phase difference and the from _{C R} (measurement wavelength 550 nm) was calculated. A “RETS spectrometer” manufactured by Otsuka Electronics Co., Ltd. was used for measuring the phase difference.
The stress optical coefficient (C _R ) was evaluated as “◯” when the absolute value (| C _R |) was 1,000 Br or less, and “X” when the absolute value was more than 1,000 Br.

As is apparent from Table 1, the polymer (A-1) of Example 3 was evaluated in terms of glass transition temperature (Tg), refractive index (nD), Abbe number (νD), and stress optical coefficient (C _R ). Good results were obtained.

According to the present invention, a polymer having a high refractive index and a low glass transition temperature and low birefringence can be provided. Therefore, the polymer of the present invention can provide an optical component having a high refractive index and a low birefringence, and can provide a resin pellet and a resin composition capable of easily and cost-effectively molding such an optical component. Furthermore, according to this invention, the compound which can form the said polymer is provided.

Claims (8)

The polymer which has a structural unit containing the bivalent group represented by following formula (1) in a principal chain.

(In Formula (1), R ¹ is a monovalent group represented by the following Formula (2) or Formula (3). R ² is a hydrogen atom or a cyano group. R ³ is the number of carbon atoms. An alkylene group of 2 to 4. a is an integer of 0 to 2.)

(In Formula (2), R ⁴ is a monovalent organic group having 1 to 12 carbon atoms. B is an integer of 0 to 7. When b is 2 or more, the plurality of R ⁴ are the same. 2 or more R ⁴ of which may be be different also. more R ⁴ is is good .c also form part of the ring structure bonded to each other, it is 0 or 1.
In formula (3), d, e, and f are each independently 0 or 1. ) The polymer according to claim 1, wherein the monovalent group represented by the formula (3) is represented by the following formula (4).

The compound represented by following formula (5).

(In formula (5), ^{R 1} is .R ³ is a monovalent group represented by the following formula (6) or (7), the .R ⁵ is an alkylene group having 2 to 4 carbon atoms, A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a is an integer of 0 to 2)

(In Formula (6), R ⁴ is a monovalent organic group having 1 to 12 carbon atoms. B is an integer of 0 to 7. When b is 2 or more, the plurality of R ⁴ are the same. 2 or more R ⁴ of which may be be different also. more R ⁴ is is good .c also form part of the ring structure bonded to each other, it is 0 or 1.
In formula (7), d, e, and f are each independently 0 or 1. ) The compound according to claim 3, wherein the monovalent group represented by the formula (7) is represented by the following formula (8).

  A resin composition comprising the polymer according to claim 1 or 2 and an organic solvent.   The resin pellet which has the polymer of Claim 1 or Claim 2 as a main component.   The resin molding which has the polymer of Claim 1 or Claim 2 as a main component.   The resin molded product according to claim 7, which is an optical component.