KR20160013784A - 6-hydroxy-2-naphthalenyl fluorene derivatives for producing lens and camera module, using the same - Google Patents

Abstract

The present invention relates to a 6-hydroxy-2-naphthalenyl fluorene derivative, and a camera module and a lens using the same. The 6-hydroxy-2-naphthalenyl fluorene derivative is represented by chemical formula 1. Provided in one aspect of the present invention is a 6-hydroxy-2-naphthalenyl fluorene derivative, which has high polarity and low molecular volume so as to express excellent optical properties.

Description

The present invention relates to a 6-hydroxy-2-naphthalenyl fluorene derivative and a lens and a camera module using the 6-hydroxy-2-naphthalenyl fluorene derivative.

The present invention relates to a 6-hydroxy-2-naphthalenyl fluorene derivative and a lens and a camera module using the same.

Optical glass or transparent resin for optical is used as a material of an optical element used in an optical system of various cameras such as a camera for a smart phone and a video camera.

Optical glass has various kinds of materials excellent in heat resistance, transparency, dimensional stability, chemical resistance, and various refractive indices (nD) and Abbe numbers (v), but the material cost is high, Bad, and low productivity. In particular, in order to process an aspherical lens used for aberration correction, a very high technology and high cost are required, which is a great obstacle for practical use.

On the other hand, an optical lens for optical use, in particular, an optical lens made of a thermoplastic transparent resin, can be mass-produced by injection molding, has an advantage of easily producing an aspherical lens, and is currently used as a lens for a camera.

Patent Document 1 discloses a resin composition containing a fluorene compound as a monomer unit and containing a polycondensation or heavier polymer having at least one sulfur atom in the repeating unit, and an optical element obtained by injection molding the resin composition.

1. Japanese Laid-Open Patent Publication No. 2001-106761

One aspect of the present invention is to provide a 6-hydroxy-2-naphthalenyl fluorene derivative having high polarity and low molecular weight so as to exhibit excellent optical properties.

Another aspect of the present invention is to provide a 6-hydroxy-2-naphthalenyl fluorene derivative having a low glass transition temperature (Tg) for ease of operation and molding.

Another aspect of the present invention is to provide a 6-hydroxy-2-naphthalenyl fluorene derivative having high transparency.

Another aspect of the present invention is to provide an eco-friendly 6-hydroxy-2-naphthalenyl fluorene derivative.

Another aspect of the present invention is to provide a copolymer of the 6-hydroxy-2-naphthalenyl fluorene derivative.

Another aspect of the present invention is to provide a lens in which a copolymer of the 6-hydroxy-2-naphthalenyl fluorene derivative is molded.

Another aspect of the present invention is to provide a camera module made from a lens molded from a copolymer of the 6-hydroxy-2-naphthalenyl fluorene derivative.

According to one aspect of the present invention, there is provided a 6-hydroxy-2-naphthalenyl fluorene derivative represented by the following formula:

[Chemical Formula 1]

Wherein R, R _1, R _2, R ₃ are each the same or different from each other, may be represented by H or the following formula 2, wherein R _1, R _2, R ₃ to at least one having of from the compound represented by the formula (2) Is selected. The substitution position of R _{1 in} the naphthyl group is not particularly limited. Z ₁ may be selected from H, a phenyl group having a C1-C4 alkyl substituent, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group.

Z _{2 ,} Z _{3 and} Z ₄ may be the same or different and each may be represented by a group of -H, -OH or -OCH ₂ CH ₂ OH, and any one of Z _{2 ,} Z _{3 and} Z ₄ is -H. The substitution position in the fluorenebenzene ring of the formula (1) of Z ₄ is not particularly limited.

(2)

In the above formula, R ₄ is a C1 to C5 alkyl group, and Ar is an C6 to C22 aryl group.

The Ar may also be selected from among H, a phenyl group having a C1-C4 alkyl substituent, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group.

According to another aspect of the present invention, there is provided a copolymer of the compound represented by the formula (1).

According to another aspect of the present invention, there is provided a lens formed by molding a copolymer of the compound represented by Formula 1 above.

The features and advantages of the present invention will become more apparent from the following detailed description based on the accompanying drawings.

Prior to that, terms and words used in the present specification and claims should not be construed in a conventional and dictionary sense, and the inventor may properly define the concept of the term to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention.

The 6-hydroxy-2-naphthalenyl fluorene derivative according to the present invention has a high polarity and a low molecular weight, and the 6-hydroxy-2-naphthalenyl fluorene derivative A lens manufactured by molding a combination may have excellent optical properties.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a schematic synthesis scheme for a copolymer of 6-hydroxy-2-naphthalenyl fluorene derivatives according to an embodiment of the present invention. FIG.

BRIEF DESCRIPTION OF THE DRAWINGS The objectives, specific advantages and novel features of the present invention will become more apparent from the following detailed description and examples taken in conjunction with the accompanying drawings. It should be noted that, in the present specification, the reference numerals are added to the constituent elements of the drawings, and the same constituent elements are assigned the same number as much as possible even if they are displayed on different drawings. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail. In this specification, the terms first, second, etc. are used to distinguish one element from another, and the element is not limited by the terms.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

6-hydroxy-2- Naphthalenyl Fluorene  derivative

The 6-hydroxy-2-naphthalenyl fluorene derivative according to an embodiment of the present invention is represented by the following formula 1:

Wherein at least one of R ₁ , R ₂ and R ₃ is represented by the following general formula (2): wherein R ₁ , R ₂ and R ₃ are the same or different and each is hydrogen (H) ≪ / RTI > The substitution position of R _{1 in} the naphthyl group is not particularly limited. Z ₁ may be selected from H, a phenyl group having a C1-C4 alkyl substituent, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group. Z _{2 ,} Z _{3 and} Z ₄ may be the same or different from each other and may be represented by -H, -OH or -OCH ₂ CH ₂ OH group, and any one of Z _{2 ,} Z _{3 and} Z ₄ is -H. The substitution position of Z ₄ in the fluorene benzene ring of the above formula (1) is not particularly limited.

In the above formula, R ₄ is a C1 to C5 alkyl group, and Ar is an C6 to C22 aryl group.

The Ar may be selected from the group consisting of a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group.

In the above 6-hydroxy-2-naphthalenyl fluorene derivative, it is preferable that the 6-hydroxy-2-naphthalenyl fluorene derivative has low molecular weight to at least one aryl moiety in 6-hydroxy- By introducing an aryl group, the refractive index can be improved by increasing the polarity of the 6-hydroxy-2-naphthalenyl fluorene derivative itself.

In addition, since the alkyl group having a rotatable bond is disposed at the front end of the aryl group, the glass transition temperature (Tg) is lowered, and as a result, the viscosity is lowered and the moldability and workability can be improved.

The 6-hydroxy-2-naphthalenyl fluorene derivative is usually used for improving optical properties. However, a halogen substituent such as bromine (Br) or chlorine (Cl), which has a disadvantage of causing dioxin problems, Naphthalenyl fluorene structural unit, which is environmentally friendly, and no sulfur (S) or nitrogen (N) atom is used, ensuring transparency.

The formula (1) may be a compound represented by the following formula (3).

Z _{2 and} Z ₃ may be the same or different from each other and may be represented by -OH or -OCH ₂ CH ₂ OH group.

The formula (1) may be a compound represented by the following formula (4).

Specifically, the compound represented by the above-mentioned formula (4) has a benzyl group introduced into two aryl moieties of the 6-hydroxy-2-naphthalenyl fluorene structural unit, The refractive index can be improved by increasing the polarity. In addition, the methyl group of the benzyl group can be arranged at the front end to enable rotation of the substituent itself, thereby lowering the viscosity of the derivative, thereby improving the moldability and workability. Wherein Z ₁ can be selected from H, a phenyl group having an alkyl substituent of C1-C4, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group. At this time, the substitution position of the benzyl group in the naphthyl group is not particularly limited.

The formula (1) may also be a compound represented by the following formula (5).

Specifically, the compound represented by the above-mentioned general formula (5) has a structure in which two arylmethylmethanaphthyl groups in the 6-hydroxy-2-naphthalenylfluorene structural units are introduced to form a 6-hydroxy-2-naphthalenylfluorene derivative The refractive index can be improved by increasing the polarity of itself. In addition, the methyl naphthyl group can be placed at the front end of the methyl naphthyl group so that the substituent itself can be rotated, thereby lowering the viscosity of the derivative, thereby improving moldability and workability. Wherein Z ₁ can be selected from H, a phenyl group having an alkyl substituent of C1-C4, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group. At this time, the substitution position of the methylnaphthyl group in the naphthyl group is not particularly limited.

The formula (1) may also be a compound represented by the following formula (6).

Specifically, the compound represented by the above-mentioned general formula (6) has a benzyl group introduced into two aryl moieties of the 6-hydroxy-2-naphthalenylfluorene structural unit, The refractive index can be improved by increasing the polarity. In addition, the methyl group of the benzyl group can be arranged at the front end to enable rotation of the substituent itself, thereby lowering the viscosity of the derivative, thereby improving the moldability and workability. Wherein Z ₁ can be selected from H, a phenyl group having an alkyl substituent of C1-C4, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group. At this time, the substitution position of the benzyl group in the naphthyl group is not particularly limited. The substitution position of the -OCH ₂ CH ₂ OH group of the formula (6) substituted in the Z ₄ position of the formula (1) in the fluorene benzene ring is not particularly limited.

The formula (1) may also be a compound represented by the following formula (7).

Specifically, the compound represented by the above-mentioned general formula (7) can be obtained by introducing two arylmethylmethanaphthyl groups in the 6-hydroxy-2-naphthalenylfluorene structural units, thereby synthesizing 6-hydroxy-2-naphthalenylfluorene derivatives The refractive index can be improved by increasing the polarity of itself. In addition, the methyl naphthyl group can be placed at the front end of the methyl naphthyl group so that the substituent itself can be rotated, thereby lowering the viscosity of the derivative, thereby improving moldability and workability. Wherein Z ₁ can be selected from H, a phenyl group having an alkyl substituent of C1-C4, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group. At this time, the substitution position of the methylnaphthyl group in the naphthyl group is not particularly limited. The substitution position of the -OCH ₂ CH ₂ OH group of the formula (7) substituted in the Z ₄ position of the formula (1) in the fluorene benzene ring is not particularly limited.

6-hydroxy-2- Naphthalenyl Fluorene  Method for producing derivatives

Hereinafter, a method for producing a 6-hydroxy-2-naphthalenyl fluorene derivative according to an embodiment of the present invention will be described in detail. However, specific reaction schemes to be described later are for illustrative purposes only, and those skilled in the art will recognize that the process for preparing the 6-hydroxy-2-naphthalenylfluorene derivative is not particularly limited thereto will be.

The compound represented by Formula 3 may be synthesized according to an embodiment using 2-bromo-6-methoxynaphthalene and 9-fluorenone as starting materials as shown in Formula 8 below.

The compound represented by Formula 4 may be synthesized according to an embodiment using naphthalene-2-ol and 9-fluorenone as starting materials, as shown in Formula 9 below.

According to another embodiment, the compound represented by Formula 4 may be synthesized through the reaction shown in Formula 10 below.

Here, a basic catalyst may be used instead of an acid catalyst (acid catalyst), and benzyl chloride may be used instead of benzyl alcohol reacting with 6-hydroxy-2-naphthalenyl fluorene bisnaphthol.

The compound represented by Formula 5 may be synthesized according to an embodiment using 6-hydroxy-2-naphthalenyl fluorene bisnaphthol as a starting material, as shown in Formula 11 below.

An acidic catalyst can be used instead of a base catalyst, and 1-naphthylmethanol can be used instead of 1- (chloromethyl) naphthalene reacting with 6-hydroxy-2-naphthalenyl fluorene bisnaphthol have.

The compound represented by the formula (6) may be synthesized according to one embodiment by a reaction as shown in the following formula (12).

According to another embodiment, the compound represented by Formula 6 may be synthesized through the reaction shown in Formula 13 below.

A base catalyst may be used instead of the acid catalyst, and benzyl chloride may be used instead of the benzyl alcohol reacting with the 6-hydroxy-2-naphthalenyl fluorene derivative.

The compound represented by the general formula (7) may be synthesized according to an embodiment, as shown in the following general formula (14).

In place of the basic catalyst, an acid catalyst may be used instead of the basic catalyst, and 1- (chloromethyl) naphthalene which reacts with the 6-hydroxy-2-naphthalenylfluorene derivative may be used instead of the 1- Naphthyl methanol can be used.

Copolymer

The copolymer according to one embodiment of the present invention is a copolymer of the 6-hydroxy-2-naphthalenyl fluorene derivative represented by the above formula (1). Hereinafter, the copolymer will be described with specific examples, but the following compounds are presented for the purpose of illustration for the purpose of detailed explanation, and the copolymer of the present invention is not particularly limited thereto.

The copolymer can be produced, for example, by reacting a 6-hydroxy-2-naphthalenyl fluorene derivative represented by the formula (3) in which a benzyl group is introduced into two aryl moieties of 6-hydroxy- When copolymerized, they may be represented by the following general formula (15).

In the above formula, R is a dicarboxylic acid component, and may include a dicarboxylic acid, a dicarboxylic acid derivative (a dicarboxylic acid derivative capable of forming an ester bond, or an ester-forming dicarboxylic acid derivative) . The dicarboxylic acid component may be used singly or in combination of two or more. For example, dicarboxylic acid and derivatives thereof may be used as the dicarboxylic acid component. Representative dicarboxylic acids include, for example, aliphatic dicarboxylic acids such as alkanedicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid), aldendicarboxylic acids (maleic acid, fumaric acid, etc.) Bicic acid; (Cyclohexanedicarboxylic acid, cyclohexanedicarboxylic acid, etc.), di- or tricycloalkanedicarboxylic acid (decarindicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid, etc.) Alicyclic dicarboxylic acid; 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracenedicarboxylic acid, etc.), biphenyl dicarboxylic acid (2,2-dicarboxylic acid, '-Biphenyl dicarboxylic acid, etc.), and the like. Further, these reactive derivatives (such as acid anhydrides such as hexahydrophthalic anhydride and tetrahydrophthalic anhydride, lower (C1-4) alkyl esters such as dimethyl ester and diethyl ester, esters such as acid halide corresponding to dicarboxylic acid Can be used. It is needless to say that the R may vary depending on the type of the monomer to be used in the actual copolymerization.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a reaction scheme showing a schematic synthesis scheme for the copolymer represented by the formula (13).

Referring to FIG. 1, a polymer can be obtained by mixing a 6-hydroxy-2-naphthalenyl fluorene derivative with a monomer to be copolymerized in a mixed solution of an aqueous base solution and an organic solvent.

There is no particular limitation on the method for producing the copolymer, and conventional conventionally known copolymerization methods can be applied.

Lens and camera module

A lens according to an embodiment of the present invention is obtained by molding a copolymer of a 6-hydroxy-2-naphthalenyl fluorene derivative represented by the formula (1).

The 6-hydroxy-2-naphthalenyl fluorene derivative and the copolymer thereof are as described above, and a detailed description thereof is omitted here.

The lens obtained by molding the copolymer of the 6-hydroxy-2-naphthalenyl fluorene derivative exhibits a high refractive index with a refractive index of 1.60 or more, and is excellent in overall optical properties such as transparency and the like.

The lens according to one embodiment of the present invention can be obtained, for example, by injection molding a copolymer of the 6-hydroxy-2-naphthalenyl fluorene derivative into a lens shape in an injection molding machine or an injection compression molding machine.

The lens can be used in the form of an aspherical lens if necessary. Aspherical lenses are useful as camera lenses among optical lenses. On the surface of the lens, a coat layer such as an antireflection layer or a hard coat layer may be formed if necessary.

The lens may also be used in various lenses such as a pickup lens, an f-theta lens, and a spectacle lens. Specifically, it can be used as a lens such as a single lens reflex camera, a digital still camera, a video camera, a camera-equipped mobile phone, a lens mounting film, a telescope, a binoculars, a microscope and a projector. Also, the lens may be manufactured as a camera module and used.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are not intended to limit the scope of the present invention.

Synthesis of 9- (6-methoxynaphthalen-2-yl) -9H-fluoren-9-ol, intermediate 1

2.37 g (10 mmol) of 2-bromo-6-methoxynaphthalene was dissolved in 10 mL of anhydrous THF in a 100 mL round-bottomed flask equipped with a magnetic stirring bar. 480 mg of magnesium and a small amount of iodine were added and stirred in a nitrogen atmosphere to check that the solution turned gray, and then cooled in an ice bath. 901 mg (5 mmol) of 9-fluorenone dissolved in 5 mL of anhydrous THF was slowly added dropwise in a nitrogen atmosphere. The temperature was raised to room temperature and stirring was maintained for 4 hours. The reaction termination point was confirmed by TLC (Thin Layer Chromatography) and then cooled with an ice bath and the reaction was terminated with 30 mL of saturated ammonium chloride aqueous solution. The mixture was extracted with dichloromethane. The organic layer was washed with brine, dried over magnesium sulfate, filtered, and concentrated to obtain crude oil. The crude oil phase was purified by silica eluting with 5% to 20% ethyl acetate / hexane to obtain 1.68 g of yellow oil. Thereafter, 9- (6-methoxynaphthalen-2-yl) -9H-fluoren-9-ol was confirmed using NMR. Yield ^{99%, 1 H NMR (700} MHz, CDCl 3) δ8.09 (d, J = 1.4 Hz, 1H), 7.74 (d, J = 9.0 Hz, 1H), 7.70 (d, J = 7.6 Hz, 2H 7.35 (d, J = 7.5 Hz, 2H), 7.26-7.23 (m, 2H), 7.13 (d, J = (dt, J = 8.6, 2.4 Hz, 2H), 7.07 (d, J = 2.4 Hz, 1H), 3.88 (s, 3H).

4- (9- (6- Methoxynaphthalene Yl) -9H- Fluorene -9-yl) phenol, intermediate 2 Synthesis

All the intermediate 1 and phenol (847 mg, 9 mmol) were added to a 100 mL round-bottomed flask equipped with a magnetic stirring bar and dissolved in 10 mL of dichloromethane. 20 drops of methanesulfonic acid was added dropwise while stirring at room temperature. (Reactant turns dark blue.)

After stirring for about 18 hours under a nitrogen atmosphere, the reaction termination point was confirmed by TLC (Thin Layer Chromatography). After cooling with an ice bath, the reaction was terminated with 30 mL of a saturated aqueous sodium hydrogen carbonate solution. The organic layer was washed with brine, dried over magnesium sulfate, filtered, and concentrated to obtain crude foam. The foamy crude was purified by silica eluting with 20% ethyl acetate / hexane to give 1.34 g of a white foamy material. Thereafter, it was confirmed to be 4- (9- (6-methoxynaphthalen-2-yl) -9H-fluoren-9-yl) phenol using NMR. Yield ^{65%, 1 H NMR (700} MHz, CDCl 3) δ7.80 (d, J = 7.5 Hz, 2H), 7.64 (d, J = 8.7 Hz, 1H), 7.56 - 7.53 (m, 1H), 7.52 (d, J = 1.8 Hz, 1H), 7.46 (d, J = 7.6 Hz, 2H), 7.40-7.38 (m, 1H), 7.38-7.36 (M, 2H), 7.14-7.11 (m, 2H), 7.10-7.07 (m, 2H), 6.72-6.69 (m, 2H), 3.90-3.88

4- Hydroxyphenyl Fluorene  Synthesis of naphthol (Formula 1)

1.01 g (2.44 mmol) of Intermediate 2 was dissolved in 10 mL of dichloroethane into a 100 mL round-bottomed flask equipped with a magnetic stir bar. After maintaining the nitrogen atmosphere, 5 mL (5 mmol) of boron tribromide solution 1.0 M in hexane was added at room temperature, and the mixture was heated at 60 ° C. for 1 hour. The reaction termination point was confirmed by TLC (Thin Layer Chromatography). After cooling with an ice bath, the reaction was terminated with 30 mL of a saturated aqueous sodium hydrogen carbonate solution. The organic layer was washed with brine, dried over magnesium sulfate, filtered, and concentrated to obtain yellow crude on a foam. Silica was purified from crude oil in the foam phase.

(* Ratio sequence legend - ethyl acetate: hexane: dichloromethane)

1: 8: 1 (top impurity separation) →

1: 8: 1 + 1v / v% (intermediate impurity separation) →

1: 4: 1 + 1 v / v% methanol addition (target separation)

Purity 99.2%, yield 58%, 569 mg in the form of a yellow foam, which was then confirmed to be 4-hydroxyphenylfluorene naphthol of formula 1 using NMR. ^{1 H NMR (500 MHz, CDCl} 3) δ7.78 (d, J = 7.6 Hz, 2H), 7.57 -7.51 (m, 2H), 7.48 (d, J = 1.7 Hz, 1H), 7.43 (d, J 2H), 7.26 (d, J = 1.0 Hz, 1H), 7.12-7.09 (m, 2H), 7.39-7.33 , 7.07 (d, J = 2.5 Hz, 1H), 7.00 (dd, J = 8.8, 2.5 Hz, 1H), 6.72-6.67 (m, 2H), 5.07 (s,

One- Benzyl naphthalene Ol, intermediate 3 Synthesis

1.44 g of naphthalene-2-ol, 1.23 mL of benzaldehyde, 50 mg (catalyst) of p-toluenesulfonic acid and 0.99 mL of pyrrolidine were mixed in a 35 mL sealed tube for microwave equipped with a magnetic stir bar and sealed and stirred While microwaves were irradiated at 900 W for 1 minute, the process was performed twice for 30 seconds in order to prevent overheating.

The reaction mixture was cooled to room temperature, 20 mL of methanol was added, and the mixture was heated to dissolve the mixture, which was cooled to obtain crystals. The crystalline phase was obtained by filtration, washed twice with 5 mL of cold methanol, and dried to obtain crude crystals in a yield of about 80%.

The crystals obtained were placed in a 100 mL reactor equipped with a reflux condenser, and 631 mg of Ammonium formate and 15 mL of methanol were added to dissolve. 60 mg of Pd / C as a reaction catalyst was added and the solvent was refluxed while maintaining the reaction temperature at 67 ° C for 2 hours. The reaction termination point was confirmed by TLC (Thin Layer Chromatography) and the reactor was cooled to maintain the room temperature. The mixture was filtered through a Celite bed, washed with methanol and concentrated. The resulting crude was dissolved in ethyl acetate and washed with water. The ethyl acetate layer was dried over sodium sulfate, filtered and concentrated to give a solid which was washed with 4 mL of cold dichloromethane to give a solid in 72% yield. Thereafter, 1-benzylnaphthalen-2-ol was confirmed using NMR. ¹ H NMR (300 MHz, CDCl ₃ )? 4.49 (2H, s), 7.07-7.23 (5H, m), 7.29-7.51 , 7.93-7.98 (2H, m)

2-substitution  benzyl Fluorene Bisnaphthol  Ethanol (Formula 3) Synthesis

In a 250 mL reactor equipped with a reflux condenser, 70 ml of acetonitrile was added as a reaction solvent, and 9-fluorenone, intermediate 1, and 3-mercaptopropionic acid were sequentially added and dissolved at 25 ± 2 ° C. Sulfuric acid as a reaction catalyst was gradually added dropwise and maintained at a reaction temperature of 80 ° C for 1 hour, and the reaction termination point was confirmed by TLC.

The reactor was cooled to room temperature and an aqueous solution of potassium carbonate was added dropwise to neutralize the reaction solution to obtain crude crystals. The resultant product was recrystallized from hexane and dichloromethane to obtain a bis-substituted benzylfluorene bisnaphthol intermediate with a purity of 99.1% by HPLC (High Performance Liquid Chromatography) at a yield of 81%.

10 g of the obtained disubstituted benzyl fluorene bisnaphthol was placed in a 500 ml three-necked reactor equipped with a reflux condenser and dissolved in dimethylsulfoxide as a reaction solvent. Ethylene carbonate and 2-methylimidazole were sequentially added thereto, and the mixture was refluxed at 145 ° C After completion of the reaction, the reactor was cooled to 50 DEG C, and 100 mL of methanol was added dropwise to crystallize, and then the reactor was cooled to room temperature. The obtained crude was dissolved in ethyl acetate and precipitated in distilled water to obtain disubstituted benzyl fluorene bisnaphthol ethanol of formula (3), followed by drying under reduced pressure. Subsequently, NMR was used to confirm the disubstituted benzyl fluorene bisnaphthol of the formula (3). Purity 99.0%, yield ^{45%, 1 H NMR (300} MHz, CDCl 3) δ3.87 (4H, t), 4.11 (4H, t), 4.49 (4H, s), 7.07-7.23 (10H, m), (2H, d), 7.93-7.98 (4H, m), 7.75-7.

6-hydroxy-2- Naphthalenyl Fluorene  Derivative-based Homopolymer Synthesis

A 4-hydroxyphenylfluorene naphthol monomer having a purity of 99% or more was dissolved in an aqueous solution of sodium hydroxide and a dichloromethane, and a polymer was obtained by a carbonation reaction using a phosgene gas. Disubstituted benzyl fluorene bisnaphthol and disubstituted benzyl fluorene bisnaphthol ethanol were also prepared by the same synthetic method, and the molecular weight and glass transition temperature (Tg) of GPC (Gel Permeation Chromatography) were measured and the results are shown in the following Table 1 .

Evaluation of lens characteristics

The polymer obtained in the process of synthesizing the dibasic benzyl fluorene bisnaphthol monomer and the EP-5000 high refractive resin reference of Mitsubishi Gas Chemical Co. were placed in a mold having a width of 2 cm and a thickness of 1 mm, After melting and melting, the mold was removed to prepare a plate-shaped lens optical property evaluation specimen, and the refractive index, Abbe's number and transmittance were measured, and the results are shown in Table 2 below.

Referring to Tables 1 and 2, it can be seen that the polymer for a lens according to the present invention exhibits a high refractive index of 1.655, a high transmittance of 90% or more, and a low glass transition temperature (Tg) suitable for injection molding.

As described above, the 6-hydroxy-2-naphthalenyl fluorene derivative according to an embodiment of the present invention may include one or more aryl moieties (e.g., 6-hydroxy-2-naphthalenyl fluorene) Low-molecular-weight aryl group is introduced to increase the polarity of the 6-hydroxy-2-naphthalenyl fluorene derivative itself, thereby improving the refractive index.

Further, since the alkyl group having a single bond capable of rotation is disposed at the front end of the aryl group, the glass transition temperature (Tg) is lowered, and consequently, the viscosity can be lowered, thereby improving workability and moldability.

The 6-hydroxy-2-naphthalenyl fluorene derivative according to one embodiment of the present invention is a 6-hydroxy-2-naphthalenyl fluorene derivative having bromine (Br) or chlorine (Cl) Lt; RTI ID = 0.0 > halogen-substituted < / RTI >

In addition, the 6-hydroxy-2-naphthalenyl fluorene derivative according to an embodiment of the present invention is a compound having 6-hydroxy-2-naphthalenyl fluorene structural unit ) Or nitrogen (N) atoms are not used, so transparency can be ensured.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the present invention. It is obvious that the modification or improvement is possible.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

6-hydroxy-2-naphthalenylfluorene derivative represented by the following formula (1): < EMI ID =
(Formula 1)

In Formula 1, R _1, R _2, R ₃ each may be represented by one another the same or different, hydrogen (H) or the following formula 2, wherein R _1, R _2, R ₃ to at least one having the formula 2 ≪ / RTI > The substitution position of R _{1 in} the naphthyl group is not particularly limited. Z ₁ may be selected from H, a phenyl group having a C1-C4 alkyl substituent, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group. Z _{2 ,} Z _{3 and} Z ₄ may be the same or different from each other and may be represented by -H, -OH or -OCH ₂ CH ₂ OH group, and any one of Z _{2 ,} Z _{3 and} Z ₄ is -H. The substitution position of Z ₄ in the fluorene benzene ring of the above formula (1) is not particularly limited.
(2)

In the above formula, R ₄ is a C1 to C5 alkyl group, and Ar is an C6 to C22 aryl group.
The method according to claim 1,
And Ar is a 6-hydroxy-2-naphthalenyl fluorene derivative selected from the group consisting of a phenyl group, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group.

The method according to claim 1,
Wherein the formula 1 is a 6-hydroxy-2-naphthalenyl fluorene derivative represented by the following formula 3:
(Formula 3)

Z _{2 and} Z ₃ may be the same or different from each other and may be represented by -OH or -OCH ₂ CH ₂ OH group.
The method according to claim 1,
Wherein the compound represented by Formula 1 is a 6-hydroxy-2-naphthalenylfluorene derivative represented by Formula 4:
(Formula 4)

The method according to claim 1,
Wherein the compound represented by Formula 1 is a 6-hydroxy-2-naphthalenylfluorene derivative represented by Formula 5:
(Formula 5)

The method according to claim 1,
Wherein the formula 1 is a compound represented by the following formula 6: 6-hydroxy-2-naphthalenyl fluorene derivative:
(Formula 6)

The method according to claim 1,
Wherein the compound represented by Formula 1 is a 6-hydroxy-2-naphthalenylfluorene derivative represented by Formula 7:
(Formula 7)

A copolymer of a compound represented by the following formula (1):
(Formula 1)

In Formula 1, R _1, R _2, R ₃ each may be represented by one another the same or different, hydrogen (H) or the following formula 2, wherein R _1, R _2, R ₃ to at least one having the formula 2 ≪ / RTI > The substitution position of R _{1 in} the naphthyl group is not particularly limited. Z ₁ may be selected from H, a phenyl group having a C1-C4 alkyl substituent, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group. Z _{2 ,} Z _{3 and} Z ₄ may be the same or different from each other and may be represented by -H, -OH or -OCH ₂ CH ₂ OH group, and any one of Z _{2 ,} Z _{3 and} Z ₄ is -H. The substitution position of Z ₄ in the fluorene benzene ring of the above formula (1) is not particularly limited.
(2)

In the above formula, R ₄ is a C1 to C5 alkyl group, and Ar is an C6 to C22 aryl group. A lens comprising a copolymer of a compound represented by the following formula (1):
(Formula 1)

In Formula 1, R _1, R _2, R ₃ each may be represented by one another the same or different, hydrogen (H) or the following formula 2, wherein R _1, R _2, R ₃ to at least one having the formula 2 ≪ / RTI > The substitution position of R _{1 in} the naphthyl group is not particularly limited. Z ₁ may be selected from H, a phenyl group having a C1-C4 alkyl substituent, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group. Z _{2 ,} Z _{3 and} Z ₄ may be the same or different from each other and may be represented by -H, -OH or -OCH ₂ CH ₂ OH group, and any one of Z _{2 ,} Z _{3 and} Z ₄ is -H. The substitution position of Z ₄ in the fluorene benzene ring of the above formula (1) is not particularly limited.
(2)

In the above formula, R ₄ is a C1 to C5 alkyl group, and Ar is an C6 to C22 aryl group.
A camera module using a lens comprising a copolymer of a compound represented by the following formula (1)
(Formula 1)

In Formula 1, R _1, R _2, R ₃ each may be represented by one another the same or different, hydrogen (H) or the following formula 2, wherein R _1, R _2, R ₃ to at least one having the formula 2 ≪ / RTI > The substitution position of R _{1 in} the naphthyl group is not particularly limited. Z ₁ may be selected from H, a phenyl group having a C1-C4 alkyl substituent, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group. Z _{2 ,} Z _{3 and} Z ₄ may be the same or different from each other and may be represented by -H, -OH or -OCH ₂ CH ₂ OH group, and any one of Z _{2 ,} Z _{3 and} Z ₄ is -H. The substitution position of Z ₄ in the fluorene benzene ring of the above formula (1) is not particularly limited.
(2)

In the above formula, R ₄ is a C1 to C5 alkyl group, and Ar is an C6 to C22 aryl group.

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