JP2015160914A - Polymer, compound, resin composition, resin pellet and resin molded body - Google Patents

Abstract

［Ｒ^１は置換又は非置換のＣ６〜１８のアリール基又は複素環を含む１価の基；Ｒ^２はＣ２〜４のアルキレン基；ａは１又は２；ｂ及びｃは０又は１；ａが２の場合、２つのＲ^１は同一であっても異なっていてもよい］
【選択図】なしThe present invention provides a polymer for optical materials having a high refractive index and a low Abbe number and glass transition temperature.
A polymer having a structural unit represented by the formula (1) in a main chain.

[R ¹ is a monovalent group containing a substituted or unsubstituted C 6-18 aryl group or heterocyclic ring; R ² is a C 2-4 alkylene group; a is 1 or 2; b and c are 0 or 1; a When R is 2, two R ¹ may be the same or different.]
[Selection figure] None

Description

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

  In recent years, in the field of optical components such as optical lenses and optical films, polymers having a high refractive index are often used as resin components from the viewpoints of reducing the thickness of lenses and films and increasing the added value. For this reason, the development of monomer components for obtaining a polymer having a high refractive index, the design of polymers using such monomer components, and the like are widely performed. As the monomer component, a novel dibenzofluorene compound has been developed (see JP 2013-32547 A).

  Here, when designing an optical component, it is generally performed to combine materials having different refractive indexes and Abbe numbers in order to correct aberration. Therefore, from the viewpoint of increasing variations in optical design, polymers having various refractive indexes and Abbe numbers, for example, polymers having a high refractive index and a low Abbe number, have been demanded. In addition, these optical components are usually obtained by injection molding, extrusion molding, or the like using raw materials such as a polymer at a temperature equal to or higher than the glass transition temperature of the polymer using a mold. For this reason, the polymer is required to have a low glass transition temperature from the viewpoints of easy molding, prevention of deterioration of the polymer, reduction in production cost, and the like. However, generally, when the refractive index of a polymer is increased, the glass transition temperature is increased accordingly. Therefore, it is very difficult to lower the glass transition temperature while increasing the refractive index of the polymer. Therefore, conventional polymers for optical materials are not always satisfactory for the requirement of high refractive index and low Abbe number and glass transition temperature.

  For reference, Non-Patent Documents 1 and 2 describe compounds represented by the following formula as aromatic diol compounds. However, these aromatic diol compounds are intermediates in the synthesis of other compounds. Therefore, the use of such an aromatic diol compound as a monomer that gives a polymer that is a main component of an optical component cannot be easily conceived from the descriptions in Non-Patent Documents 1 and 2.

JP 2013-32547 A

J. et al. Am. Chem. Soc. , 1951, 73 (10), 4720-4721 “Some Thiazolythio Hydroquinones” Chem. Lett. 2012, 41, 950-951 “Facile Synthesis of Quinone Dimer Derivatives Substituted with Sulfuryl Group and Thirr Properties”

  The present invention has been made based on the above circumstances, and an object thereof is to provide a polymer having a high refractive index and a low Abbe number and glass transition temperature.

（式（１）中、Ｒ^１は、置換又は非置換の炭素数６〜１８のアリール基又は複素環を含む１価の基である。Ｒ^２は、炭素数２〜４のアルキレン基である。ａは、１又は２である。ｂ及びｃは、０又は１である。ａが２の場合、２つのＲ^１は同一であっても異なっていてもよい。） This invention made | formed in order to solve the said subject is a polymer which has a structural unit represented by following formula (1) in a principal chain.

(In Formula (1), R ¹ is a monovalent group containing a substituted or unsubstituted aryl group having 6 to 18 carbon atoms or a heterocyclic ring. R ² is an alkylene group having 2 to 4 carbon atoms. A is 1 or 2. b and c are 0 or 1. When a is 2, the two R ¹ may be the same or different.

（式（６）中、Ｒ^２は、炭素数２〜４のアルキレン基である。ｂ及びｃは、０又は１である。） Another aspect of the present invention is a compound represented by the following formula (6).

(In the formula (6), ^{R 2} is the .b and c is an alkylene group having 2 to 4 carbon atoms, is 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.

  Here, the “organic group” refers to a group containing at least one carbon atom. 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 Abbe number and glass transition temperature can be provided. Therefore, the polymer of the present invention can provide an optical component having a high refractive index and a low Abbe number and a glass transition temperature, and a resin pellet and a resin composition capable of easily and cost-effectively molding such an optical component. Can provide. 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”) has a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (a)”) in the main chain. (A) The polymer may contain other structural units other than the structural unit (a).

<Structural unit (a)>
The structural unit (a) is represented by the following formula (1). The structural unit (a) is preferably contained in the polymer main chain via an ester bond, a carbonate bond or an ether bond, and preferably contained in the polymer main chain via an ether bond. More preferred. The structural unit (a) is derived from, for example, an aromatic diol compound, a derivative or a precursor thereof.

In formula (1), R ¹ is a monovalent group containing a substituted or unsubstituted aryl group having 6 to 18 carbon atoms or a heterocyclic ring. R ² is an alkylene group having 2 to 4 carbon atoms. a is 1 or 2. b and c are 0 or 1. When a is 2, two R ¹ may be the same or different.

  (A) Since the polymer has the structural unit (a), the refractive index is high, and the Abbe number and the glass transition temperature can be lowered. (A) Since the polymer contains an aromatic ring derived from the structural unit (a), the concentration (ratio) of the aromatic ring in the polymer (A) increases, so that a high refractive index and a low Abbe number are possible. it is conceivable that. Furthermore, since the structural unit (a) is not a rigid structure like the fluorene cardo structure, the molecular weight of the structural unit (a) is small, and the number of flexible bonding groups can be increased. (A) It is considered that the glass transition temperature of the polymer can be lowered.

Examples of the substituted or unsubstituted aryl group having 6 to 18 carbon atoms represented by R ¹ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-anthryl group, a 9-anthryl group, and a 3-phenanthryl group. , 9-phenanthryl group and the like.

The monovalent group containing a heterocyclic ring represented by R ¹ may be any group containing at least one heterocyclic ring. This heterocyclic ring may be either an unsaturated heterocyclic ring or a saturated heterocyclic ring. Examples of the unsaturated heterocyclic ring include a pyridine ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, a benzoxazole ring, a triazole ring, an imidazoline ring, a benzoimidazoline ring, and a pyrimidine ring. Examples of the saturated heterocyclic ring include a morpholine ring and a piperidine ring.

Examples of the alkylene group having 2 to 4 carbon atoms represented by R ² include an ethylene group, a propylene group, an i-propylene group, a butylene group, and an i-butylene group.

R ^{1 in the} above formula (1) is preferably a monovalent group represented by the following formula (2) or formula (3).

In Formula (2), R ³ is a monovalent organic group having 1 to 12 carbon atoms. d is an integer of 0-7. When d is 2 or more, the plurality of R ³ may be the same or different, and may be bonded by any combination to form a part of the ring structure. e is 0 or 1.

In formula (3), R ⁴ is a monovalent organic group having 1 to 12 carbon atoms. f is an integer of 0-4. When f is 2 or more, the plurality of R ⁴ may be the same or different, and may be bonded by any combination to form a part of the ring structure.

Examples of the monovalent organic group having 1 to 12 carbon atoms represented by R ^{3 in the} above formula (2) and R ⁴ in the above formula (3) include, for example, linear or branched carbonization having 1 to 12 carbon atoms. A hydrogen group, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, a part of these hydrocarbon groups selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom And a group containing at least one hetero atom.

  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.

  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 monovalent organic 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, for example. Specific examples include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and a benzoyloxy group.

  Examples of the monovalent organic group having 1 to 12 carbon atoms containing a sulfur atom include a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, a 2-methylpropylthio group, and a 1-methyl group. Alkylthio groups such as propylthio group, t-butylthio group, n-pentylthio group, neopentylthio group, n-hexylthio group; phenylthio group, 4-hydroxyphenylthio group, o-tolylthio group, m-tolylthio group, p- Examples include arylthio groups such as tolylthio group, 1-naphthylthio group, and 2-naphthylthio group.

  As a C1-C12 organic 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 organic 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.

  As a C1-C12 organic group containing an oxygen atom and a sulfur atom, an alkyl sulfonate group, an aryl sulfonate group, an alkyl sulfonyl group, an alkyl sulfinyl group etc. are mentioned, for example.

In the monovalent organic group having 1 to 12 carbon atoms represented by R ³ or R ⁴ , examples of the organic group containing a sulfur atom and a nitrogen atom include thiazole group; arylthiazole group such as benzothiazole group, and the like. .

  The structural unit (a) is preferably at least one selected from the group consisting of a structural unit represented by the following formula (4) and a structural unit represented by the following formula (5).

In formula (4) and formula (5), R ² , b and c are as defined in formula (1) above.

  When the structural unit (a) is a structural unit represented by the above formula (4) or formula (5), the side chain of the (A) polymer contains a sulfur atom, so that the sulfur concentration in the (A) polymer. (Proportion) becomes high, and it is considered that it is preferable to realize a high refractive index and a low Abbe number.

  (A) As a content rate of the structural unit (a) in a polymer, 5 mol% or more and 55 mol% or less are preferable in all the structural units of (A) polymer, and 10 mol% or more and 55 mol% or less are more preferable. .

<Other structural units>
(A) The polymer may contain other structural units other than the structural unit (a). Another structural unit will not be specifically limited if it does not impair the effect of this invention.

  (A) As a content rate of the other structural unit in a polymer, 45 mol% or more and 95 mol% or less are preferable in all the structural units of (A) polymer, and 45 mol% or more and 90 mol% or less are more preferable.

<(A) Polymer Synthesis Method>
(A) The polymer is obtained by reacting a known method, for example, an aromatic diol compound that gives the structural unit (a), with another compound as necessary, in the presence of an organic solvent, under predetermined reaction conditions. Can be synthesized.

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

  Examples of other compounds include alkali metal compounds and monomers that give other structural units other than the structural unit (a).

(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 metal atoms in the alkali metal compound is usually 1 to 3 times equivalent, preferably 1.1 with respect to the phenolic hydroxyl groups of all compounds used in the synthesis of the polymer (A). The amount is such that it is double equivalent to 2 equivalents, more preferably 1.2 equivalents to 1.5 equivalents.

(Monomer giving other structural units)
Examples of monomers that give other structural units include 4,4′-difluorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-chlorofluorobenzophenone, bis (4-chlorophenyl) sulfone, and bis (4- Fluorophenyl) sulfone, 4-fluorophenyl-4′-chlorophenylsulfone, bis (3-nitro-4-chlorophenyl) sulfone, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,4-dichlorobenzo Aromatic dihalide compounds such as nitrile and 2,4-difluorobenzonitrile, dihydroxyphenyl compounds such as hydroquinone, resorcinol, catechol and phenylhydroquinone, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4 -Hydroxy-3-methylphen Nyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, 1,1 ′-(4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2 -Bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 2,2-bis (2-hydroxy) -5-biphenylyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,4-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,3-bis [2- And bisphenol compounds such as (4-hydroxyphenyl) -2-propyl] benzene.

(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 (6). The compound (a) can give the structural unit (a) represented by the above formula (4).

Wherein ^{(6), R} 2, b and c is as defined in the above formula (1).

  As the compound represented by the above formula (6), a compound represented by the following formula (7) (2- (2 ′, 5′-dihydroxyphenyl) thionaphthalene) is preferable.

  Compound (a) can be synthesized, for example, by reacting naphthalenethiol with benzoquinone or naphthoquinone in a solvent.

  Examples of naphthalenethiol include 1-naphthalenethiol and 2-naphthalenethiol, and 2-naphthalenethiol is preferable.

  Examples of benzoquinone include 1,2-benzoquinone and 1,4-benzoquinone, and 1,4-benzoquinone is preferable. Examples of naphthoquinone include 1,2-naphthoquinone and 1,4-naphthoquinone, and 1,4-naphthoquinone is preferable.

[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. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

  Other components include, for example, antioxidants, polymers other than (A) polymers, lubricants that improve processability, known additives such as flame retardants, antibacterial agents, colorants, mold release agents, foaming agents Agents. These arbitrary components may be used individually by 1 type, and may use 2 or more types together.

  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, 3,9-bis [2- [3- (3-tert -Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] Decane, and the like.

  (A) Content of the antioxidant in a resin composition 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) Content of (A) polymer in a resin composition is 10 to 100 mass% normally in the total solid of (A) resin composition.

  (A) Content of the organic solvent in a resin composition is 50 mass parts or more and 100,000 mass parts or less with respect to 100 mass parts of (A) polymers normally.

<(A) Preparation method of resin composition>
(A) The resin composition is prepared by uniformly mixing the (A) polymer and the above-described organic solvent, and other components such as an antioxidant and other polymers as necessary. The resin composition is prepared in a solid form such as a powder form, a pellet form, a chip form or the like, or is dissolved in an appropriate solvent to prepare a liquid form or a paste form, and is used for the production of a resin molded product.

  When the resin composition is prepared in a solid state, the resin composition has a melt flow rate (hereinafter also referred to as “MFR”) at 300 ° C. and 10 kg load of 0.1 g / 10 min to 1,000 g / 10 min. The following is preferred. If the MFR is less than 0.1 g / 10 min, sufficient fluidity cannot be ensured at the time of molding such as extrusion molding, and the moldability may be deteriorated. On the other hand, if the MFR exceeds 1,000 g / 10 min, the strength of the molded product cannot be maintained, and there is a risk of cracking 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. The resin pellet (A) may contain other components as long as the effects of the present invention are not impaired.

  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 phase difference plate, 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 a method using a die having a predetermined shape, and among them, a method using a T die and a coat hanger die is preferable.

  In such a melt extrusion method, after extruding a heat-melted resin composition from a die, it is made to adhere to a metal belt, a cooling roll or the like to form a sheet, and the polymer sheet thus obtained is wound up after cooling. Thus, a roll-shaped optical sheet can be 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. The polymer sheet melt-extruded from the die may be blown with air controlled at the same temperature as the metal belt in order to adhere to the metal belt, 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, 175 degrees C or less is more preferable, 160 degrees C or less is further more preferable. Thus, since the glass transition temperature of the polymer (A) is 200 ° C. or lower, the resin pellets and resin composition containing the polymer (A) as a main component are moldable 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) The thickness of the optical film as a resin molded body is usually 10 μm or more and 1,000 μm or less, preferably 10 μm or more and 500 μm or less. 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 optical 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 measured in accordance with a transparency test method (JIS-K-7105: 1981) for a sheet having a thickness of 50 μm. The transparency of optical parts, 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, 1.660 or more are preferable and 1.670 or more are 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 still more preferably 18 or less.
(A) The refractive index (nD) of the polymer and the optical component is 1.660 or more, and the Abbe number (D) is 21 or less, thereby realizing thin film and high added value of lenses and films. It becomes possible to do.

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

<Synthesis of aromatic diol compound>
[Synthesis Example 1] (Synthesis of aromatic diol compound (a-1))
In a 1,000 mL eggplant-shaped flask containing a stir bar, 35.71 g (214 mmol) of 2-benzothiazolethiol, 23.07 g (213 mmol) of 1,4-benzoquinone, 469 g of methanol, and 67 g of ion-exchanged water were weighed. . The reaction was allowed to proceed for 1 hour at room temperature with stirring with a magnetic stirrer. Next, the obtained reaction mixture was poured into hot water at 80 ° C. to precipitate a solid and filtered to recover the product. 2- (2 ′, 5′-dihydroxyphenyl represented by the following formula (8) ) 26.19 g of a solid of thiobenzothiazole (aromatic diol compound (a-1)) was obtained. The yield of this aromatic diol compound (a-1) was 45%.

Moreover, < ¹ > H-NMR analysis was performed about the aromatic diol compound (a-1). This ¹ H-NMR analysis was measured using “JNM-ECA400” manufactured by JEOL RESONANCE. The results are as follows.

¹ H-NMR (400 MHz, DMSO-d6) δ: 5.25 (s, 2H), 7.02 (m, 1H), 7.20 (m, 1H), 7.33 (m, 1H), 7 .73 (dd, 2H), 8.80 (d, 1H), 8.99 (d, 1H)

[Example 1] (Synthesis of aromatic diol compound (a-2))
The same operation as in Example 1 was carried out except that 25.15 g (157 mmol) of 2-naphthalenethiol, 16.21 g (150 mmol) of 1,4-benzoquinone and 485 g of methanol were used as reactants, and the above formula (7 ) 28-38 g of a solid of 2- (2 ′, 5′-dihydroxyphenyl) thionaphthalene (aromatic diol compound (a-2)) represented by The yield of this aromatic diol compound (a-2) was 71%.

The aromatic diol compound (a-2) was subjected to ¹ H-NMR analysis in the same manner as in Example 1. The results are as follows.

¹ H-NMR (400 MHz, DMSO-d6) δ: 6.46 (s, 1H), 6.57 (d, 1H), 6.75 (d, 1H), 7.33 (d, 1H), 7 .50 (t, 2H), 7.85 (m, 4H), 8.81 (s, 1H), 9.21 (s, 1H)

<Synthesis of polymer>
[Example 2] (Synthesis of polymer (a-1))
A 100 mL three-necked flask containing a stirring bar was fitted with a nitrogen introduction tube, a Dean-Stark tube, and a cooling tube, and 15.27 g (55.5 mmol) of the aromatic diol compound (a-1), 2,6- Difluorobenzonitrile (DFBN) 7.19 g (51.7 mmol), potassium carbonate 15.45 g (111.8 mmol), N, N-dimethylacetamide (DMAc) 61 mL, and toluene 11 mL were charged. After the atmosphere in the flask was replaced with nitrogen, the mixture was heated and stirred at 130 ° C., and the reaction was carried out for 19.5 hours while removing generated water through a Dean-Stark tube. After cooling to room temperature, the produced salt was removed with filter paper. 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 6.5 g of polymer (a-1) powder. The yield of this polymer (a-1) was 32%.

[Example 3] (Synthesis of polymer (a-2))
As a reactant, 22.02 g (82.1 mmol) of aromatic diol compound (a-2), 11.39 g (81.9 mmol) of DFBN, 22.54 g (163.1 mmol) of potassium carbonate, 94 mL of DMAc, and 22 mL of toluene were used. Except for the above, the same operation as in Example 3 was carried out to obtain 21.7 g of polymer (a-2) powder. The yield of this polymer (a-2) was 72%.

[Example 4] (Synthesis of polymer (a-3))
As reactants, aromatic diol compound (a-2) 12.68 g (47.3 mmol), 2,2-bis (4-hydroxyphenyl) propane (Bis-A) 9.84 g (43.1 mmol), DFBN 12. The same operation as in Example 3 was performed except that 05 g (86.6 mmol), potassium carbonate 23.84 g (172.5 mmol), DMAc 97 mL, and toluene 22 mL were used, and the polymer (a-3) powder was changed to 21. 0.0 g was obtained. The yield of this polymer (a-3) was 70%.

[Comparative Example 1] (Synthesis of polymer (RA-1))
As reactants, 9,9-bis (4-hydroxyphenyl) fluorene (BPFL) 3.60 g (10.3 mmol), DFBN 1.43 g (10.3 mmol), potassium carbonate 2.85 g (20.6 mmol), DMAc 15 mL, The same operation as in Example 3 was performed except that 3 mL of toluene was used, and 4.3 g of polymer (RA-1) powder was obtained. The yield of this polymer (RA-1) was 93%.

[Comparative Example 2] (Synthesis of polymer (RA-2))
As reactants, BPFL 1.40 g (3.99 mmol), Bis-A 0.911 g (3.99 mmol), DFBN 1.11 g (8.00 mmol), potassium carbonate 2.21 g (16.0 mmol), DMAc 5.6 mL, and toluene The same operation as in Example 3 was performed except that 1.4 mL was used, and 2.79 g of a polymer (RA-2) powder was obtained. The yield of this polymer (RA-2) was 90%.

<Evaluation>
The polymers of Examples 3 to 5 and Comparative Examples 1 and 2 were evaluated for glass transition temperature (Tg), refractive index (nD), and Abbe number (νD) according to the following methods. The results are shown in Table 1. Table 1 also shows the charged amount (mmol) and charged ratio (mol ratio) 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.

  As is apparent from Table 1, the polymers (a-1) to (a-3) of Examples 3 to 5 were evaluated in terms of glass transition temperature (Tg), refractive index (nD), and Abbe number (νD). Good results were obtained.

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

Claims (8)

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

(In Formula (1), R ¹ is a monovalent group containing a substituted or unsubstituted aryl group having 6 to 18 carbon atoms or a heterocyclic ring. R ² is an alkylene group having 2 to 4 carbon atoms. A is 1 or 2. b and c are 0 or 1. When a is 2, the two R ¹ may be the same or different. The polymer according to claim 1, wherein R ^{1 in the} formula (1) is a monovalent group represented by the following formula (2) or formula (3).

(In Formula (2), R ³ is a monovalent organic group having 1 to 12 carbon atoms. D is an integer of 0 to 7. When d is 2 or more, a plurality of R ³ may be the same. They may be different and may be bonded together by any combination to form a part of the ring structure, and e is 0 or 1.
In formula (3), R ⁴ is a monovalent organic group having 1 to 12 carbon atoms. f is an integer of 0-4. When f is 2 or more, the plurality of R ⁴ may be the same or different, and may be bonded by any combination to form a part of the ring structure. ) The weight according to claim 1 or 2, wherein the structural unit is at least one selected from the group consisting of a structural unit represented by the following formula (4) and a structural unit represented by the following formula (5). Coalescence.

(In formula (4) and formula (5), R ² , b and c have the same meaning as in formula (1) above). A compound represented by the following formula (6).

(In the formula (6), ^{R 2} is the .b and c is an alkylene group having 2 to 4 carbon atoms, is 0 or 1.)   The resin composition containing the polymer of any one of Claims 1-3, and an organic solvent.   The resin pellet which has the polymer of any one of Claim 1 to 3 as a main component.   The resin molding which has as a main component the polymer of any one of Claims 1-3. The resin molded product according to claim 7, which is an optical component.