KR20160055035A - Isoflavone-based polymer, lens and camera module using the same - Google Patents

Abstract

Provided is an isoflavone-based polymer. More specifically, the purpose of the present invention is to provide an isoflavone-based polymer which exhibits excellent optical properties. According to an embodiment of the present invention, the isoflavone-based polymer includes an isoflavone-based skeleton on a main chain and has at least one binding group among ester group and carbonate group.

Description

Isoflavone-based polymer, lens and camera module using the same,

The present invention relates to an isoflavone-based polymer, a lens and a camera module using the same.

As a material of an optical element used in an optical system of various cameras, an optical glass or a transparent resin for optical is used.

Optical glass has various kinds of materials excellent in heat resistance, transparency, dimensional stability, chemical resistance and the like and having various refractive indexes (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, transparent resins for optical use are used as applications for lenses for cameras and the like.

Japanese Laid-Open Patent Publication No. 2001-106761 Korean Patent Publication No. 10-2005-0076282

An object of one embodiment of the present invention is to provide an isoflavone-based polymer exhibiting excellent optical properties.

An object of another embodiment of the present invention is to provide a lens comprising the isoflavone-based polymer.

An object of another embodiment of the present invention is to provide a camera module including the lens.

An embodiment of the present invention provides an isoflavone-based polymer having an isoflavone skeleton in its main chain and having at least one of an ester group and a carbonate group.

The isoflavone-based polymer may include a repeating unit represented by the following formula (1) or (2).

[Chemical Formula 1]

R ₁ to R ₃ are the same or different and each independently represents a substituted or unsubstituted C ₁ -C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ -C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ -C ₂₀ Aromatic rings, or combinations thereof; R ₄ and R ₅ are the same or different and each independently, a deuterium, a substituted or unsubstituted C ₁ ~ C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ ~ ring C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ ~ C ₂₀ aromatic ring, or a combination thereof, and; a is an integer of 0 to 3, b is an integer of 0 to 4, and n may be an integer of 5 to 500.

(2)

R ₆ and R ₇ are the same or different and each independently represents a substituted or unsubstituted C ₁ -C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ -C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ -C ₂₀ Aromatic rings, or combinations thereof; R ₈ and R ₉ are the same or different and each independently, a deuterium, a substituted or unsubstituted C ₁ ~ C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ ~ ring C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ ~ C ₂₀ aromatic ring, or a combination thereof, and; c is an integer of 0 to 3, d is an integer of 0 to 4, and m may be an integer of 5 to 500.

Another embodiment of the present invention provides a lens including the isoflavone-based polymer and a camera module including the lens.

According to one embodiment of the present invention, it is possible to provide an isoflavone-based polymer having a high refractive index, an excellent optical property and a high hardness.

Further, the isoflavone-based polymer according to one embodiment of the present invention is environmentally friendly, and transparency can be improved.

The isoflavone polymer according to one embodiment of the present invention is excellent in processability, can be formed into a lens by injection molding, and has high scratch resistance due to its high hardness.

According to another embodiment of the present invention, it is possible to provide a lens including the isoflavone polymer and improved in optical characteristics and transparency, and a camera module using the same.

1 is a schematic exploded perspective view of a camera module according to an embodiment of the present invention.

First, terms used in the present invention are defined.

(1) In the present specification, an aliphatic chain means an aliphatic compound in the form of a straight chain or branched chain, and includes, but is not limited to, saturated or unsaturated hydrocarbon, alkoxy, alkyl ester, alkyl ether, . At this time, the aliphatic chain may include at least one substituent in the main chain and / or side chain, and the substituent may include, for example, oxygen, a hydroxyl group, a carboxy group, an alkyl group, a cyano group, an ester An ether group, an amide group, an imide group, an alkoxy group, or a combination thereof.

(2) In the present specification, the aliphatic ring refers to a cyclic aliphatic compound, which may be a monocyclic or polycyclic compound formed by condensation of two or more rings, and includes, for example, saturated or unsaturated May be a hydrocarbon ring. In the present specification, aliphatic rings are used as a concept including a heterocyclic ring. Therefore, an element constituting an aliphatic ring may include not only carbon but also atoms other than carbon such as oxygen, phosphorus, and silicon. The aliphatic ring may contain at least one substituent. The substituent may include, but is not limited to, an oxygen, a hydroxy group, a carboxy group, an alkyl group, a cyano group, an ester group, an ether group, An imido group, an alkoxy group, or a combination thereof.

(3) In the present specification, the aromatic ring means an aromatic compound in the form of a ring, which may be a monocyclic or a polycyclic compound formed by condensation of two or more rings, and includes, for example, aryl such as phenyl, naphthalene, Lt; / RTI > The aromatic ring may contain at least one substituent. The substituent may include, but is not limited to, an oxygen, a hydroxy group, a carboxyl group, an alkyl group, a cyano group, an ester group, an ether group, An imido group, an alkoxy group, or a combination thereof.

(4) In the present specification, when two or more rings are directly connected, it means that the ring and the ring are connected by a bond, such as biphenyl, bicyclohexyl and the like, (O) -, -C (= O) O-, -C (= O) NH-, -O [CH ₂ CH ₂ O] _p - , p is an integer of 1 to 20), or the like.

(5) In the present specification, the glass transition temperature (Tg) means a temperature at which a polymer material starts to move with a molecule having an activity due to temperature, and may be measured by a differential scanning calorimeter (DSC) Can be measured.

Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

According to one embodiment of the present invention, there is provided an isoflavone-based polymer having an isoflavone skeleton in its main chain and having at least one of an ester group and a carbonate group.

The isoflavone polymer according to an embodiment of the present invention includes an isoflavone skeleton therein and has an improved refractive index and at least one bonding group selected from an ester group and a carbonate group and has high injection moldability and hardness, When applied to a lens requiring processability, excellent physical properties can be exhibited.

The isoflavone-based polymer according to one embodiment of the present invention may contain at least one of repeating units represented by the following formula (1) and repeating units represented by the following formula (2).

[Chemical Formula 1]

In Formula 1, R ₁ to R ₃ are each independently a substituted or unsubstituted C ₁ to C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ to C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ to C ₂₀ aromatic rings, or combinations thereof; R ₄ and R ₅ are each independently selected from the group consisting of deuterium, a substituted or unsubstituted C ₁ -C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ -C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ -C ₂₀ aromatic ring , Or a combination thereof; a is an integer of 0 to 3, b is an integer of 0 to 4, and n may be an integer of 5 to 500. More preferably, n may be an integer of 20 to 200.

In Formula 1, R ₁ and R ₂ are each independently a single bond, OCH ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ , CH ₂ (CH ₃ ) CH, or CH (CH ₃ ) CH ₂ In this case, the substituent having a low molecular weight in the aryl moiety of the isoflavone skeleton may be introduced to increase the polarity of the isoflavone skeleton and improve the refractive index of the isoflavone polymer.

In Formula 1, R ₃ may be a divalent organic group derived from a dicarboxylic acid or a dicarboxylic acid derivative.

Examples of the dicarboxylic acid include, but are not limited to, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. The aliphatic dicarboxylic acids include alkane dicarboxylic acids and alkydic acids And the alicyclic dicarboxylic acid may include at least one of a cycloalkane dicarboxylic acid, a dicycloalkane dicarboxylic acid, and a tricycloalkane dicarboxylic acid, The aromatic dicarboxylic acid may include at least one of areenedicarboxylic acid and biphenyldicarboxylic acid.

For example, the alkane dicarboxylic acid may include at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid, and the alkenedicarboxylic acid may include at least one of maleic acid and fumaric acid , Said cycloalkanedicarboxylic acid is cyclohexanedicarboxylic acid, said dicycloalkanedicarboxylic acid or tricycloalkanedicarboxylic acid is decarindicarboxylic acid, norbornanedicarboxylic acid and adamantanedicarboxylic acid Lt; RTI ID = 0.0 > and / or < / RTI > In addition, the arene dicarboxylic acid may include at least one of terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid and anthracene dicarboxylic acid, The dicarboxylic acid may include 2,2'-biphenyldicarboxylic acid.

On the other hand, the dicarboxylic acid derivatives include, for example, acid anhydrides such as hexahydrophthalic anhydride, tetrahydrophthalic anhydride, (C ₁ -C ₄ ) alkyl esters such as dimethyl esters and diethyl esters, and dicarboxylic acids Or an ester capable of forming an ester of an acid halide.

The R ₃ may vary depending on the type of the monomer to be used in the polymerization of the actual isoflavone derivative.

Wherein R ₄ and R ₅ are, each independently, a heavy hydrogen, substituted or unsubstituted (C ₁ -C ₄₎ alkyl, substituted or unsubstituted (C ₆ -C ₁₀₎ aryl, substituted or unsubstituted (C ₃ - C ₁₀₎ heteroaryl, substituted or unsubstituted (C ₃ -C ₁₀₎ cycloalkyl, substituted or unsubstituted ring with 5-to 7-heterocycloalkyl, substituted or unsubstituted ring of the circle (C ₆ -C ₁₀₎ ar ( C ₁ -C ₄₎ alkyl, (C ₃ -C ₁₀₎ cycloalkyl are fused one or more of the fused 5-to 7-membered heterocycloalkyl, the substituted or unsubstituted aromatic ring by one or more (C ₃ -C ₁₀ ) < / RTI > cycloalkyl.

(2)

In Formula 2, R ₆ and R ₇ each independently represent a substituted or unsubstituted C ₁ -C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ -C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ -C ₂₀ aromatic rings, or combinations thereof; R ₈ and R ₉ are each independently selected from the group consisting of deuterium, a substituted or unsubstituted C ₁ -C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ -C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ -C ₂₀ aromatic ring , Or a combination thereof; c is an integer of 0 to 3, d is an integer of 0 to 4, and m may be an integer of 5 to 500. More preferably, m may be an integer of 20 to 200. [

In Formula 2, R ₆ and R ₇ are the same or different and each independently represents a single bond, OCH ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ , CH ₂ (CH ₃ ) CH, or CH (CH ₃ ) CH ₂ , wherein a substituent having low molecular weight is introduced into an aryl moiety of the isoflavone skeleton to increase the polarity of the isoflavone skeleton to improve the refractive index of the isoflavone-based polymer .

R ₈ and R ₉ are the same or different and are independently selected from the group consisting of deuterium, substituted or unsubstituted (C ₁ -C ₄ ) alkyl, substituted or unsubstituted (C ₆ -C ₁₀ ) aryl, Substituted or unsubstituted (C ₃ -C ₁₀ ) heteroaryl, substituted or unsubstituted (C ₃ -C ₁₀ ) cycloalkyl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, substituted or unsubstituted (C ₆ -C ₁₀ ) -C ₁₀₎ aralkyl (C ₁ -C ₄₎ alkyl, (C ₃ -C ₁₀₎ cycloalkyl is 5-to 7-membered heterocycloalkyl fused one or more, or a substituted or unsubstituted aromatic rings, one or more fusion a (C ₃ -C ₁₀₎ may be cycloalkyl.

According to one embodiment of the present invention, by including the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2), it is possible to provide an isoflavone polymer having a high refractive index in the visible light region, can do.

In addition, the isoflavone polymer according to one embodiment of the present invention is used for the improvement of optical properties, but a halogen substituent such as bromine (Br) or chlorine (Cl), which has a disadvantage of causing a dioxin problem, Friendly.

The isoflavone-based polymer according to one embodiment of the present invention is an isoflavone-based polymer that does not contain sulfur (S) and does not contain nitrogen (N) directly bonded to at least one hydrogen (H) Polymers can be provided.

For example, the isoflavone-based polymer does not contain -NH ₂ and -NH ₂ , and transparency can be ensured.

The isoflavone polymer according to one embodiment of the present invention is excellent in processability and can be formed by injection molding without decomposition even at a high temperature of 200 ° C or more, and has high scratch resistance due to its high hardness.

On the other hand, the isoflavone-based polymer according to one embodiment of the present invention is a polymer of an isoflavone-based compound represented by the following formula (3), and the polymer is polymerized through at least one of esterification reaction and carbonation reaction .

(3)

Wherein R ₁₀ and R ₁₁ are the same or different and each independently represents a substituted or unsubstituted C ₁ -C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ -C ₁₀ aliphatic ring, A C ₃ to C ₂₀ aromatic ring, or a combination thereof; R ₁₂ and R ₁₃ are the same or different and each independently, a deuterium, a substituted or unsubstituted C ₁ ~ C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ ~ ring C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ ~ C ₂₀ aromatic ring, or a combination thereof, and; e is an integer of 0 to 3, and f may be an integer of 0 to 4.

R ₁₀ and R ₁₁ may be the same or different and each independently represents a single bond, OCH ₂ CH ₂ (R ₁₎ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , , OCH ₂ CH ₂ CH ₂ , CH ₂ (CH ₃ ) CH, or CH (CH ₃ ) CH ₂ .

R ₁₂ and R ₁₃ may be the same or different and each independently selected from the group consisting of deuterium, substituted or unsubstituted (C ₁ -C ₄ ) alkyl, substituted or unsubstituted (C ₆ -C ₁₀ Substituted or unsubstituted (C ₃ -C ₁₀ ) heteroaryl, substituted or unsubstituted (C ₃ -C ₁₀ ) cycloalkyl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, substituted or unsubstituted A 5- or 7-membered heterocycloalkyl in which one or more unsubstituted (C ₆ -C ₁₀ ) aryl (C ₁ -C ₄ ) alkyl, (C ₃ -C ₁₀ ) cycloalkyl is fused, or a substituted or unsubstituted (C ₃ -C ₁₀ ) cycloalkyl wherein one or more aromatic rings are fused together.

Although not limited thereto, the esterification reaction may be a reaction of copolymerizing an isoflavone-based compound represented by Formula 3 with a dicarboxylic acid or a dicarboxylic acid derivative.

Examples of the dicarboxylic acid include, but are not limited to, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. The aliphatic dicarboxylic acids include alkane dicarboxylic acids and alkydic acids And the alicyclic dicarboxylic acid may include at least one of a cycloalkane dicarboxylic acid, a dicycloalkane dicarboxylic acid, and a tricycloalkane dicarboxylic acid, The aromatic dicarboxylic acid may include at least one of areenedicarboxylic acid and biphenyldicarboxylic acid.

For example, the alkane dicarboxylic acid may include at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid, and the alkenedicarboxylic acid may include at least one of maleic acid and fumaric acid , Said cycloalkanedicarboxylic acid is cyclohexanedicarboxylic acid, said dicycloalkanedicarboxylic acid or tricycloalkanedicarboxylic acid is decarindicarboxylic acid, norbornanedicarboxylic acid and adamantanedicarboxylic acid Lt; RTI ID = 0.0 > and / or < / RTI > In addition, the arene dicarboxylic acid may include at least one of terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid and anthracene dicarboxylic acid, The dicarboxylic acid may include 2,2'-biphenyldicarboxylic acid.

On the other hand, the dicarboxylic acid derivatives include, for example, acid anhydrides such as hexahydrophthalic anhydride, tetrahydrophthalic anhydride, (C ₁ -C ₄ ) alkyl esters such as dimethyl esters and diethyl esters, and dicarboxylic acids Or an ester capable of forming an ester of an acid halide.

Meanwhile, although not limited thereto, the carbonation reaction may be a reaction of copolymerizing the isoflavone compound represented by the above formula (3) with phosgene, diphenyl carbonate or the like.

Another embodiment of the present invention provides a lens comprising an isoflavone-based polymer according to an embodiment of the present invention described above. The isoflavone polymer is as described above, and a detailed description thereof will be omitted.

The lens provided by the present embodiment may be formed by molding the isoflavone-based polymer, and may be formed by injection molding.

The lens according to one embodiment of the present invention can be obtained, for example, by injection molding the isoflavone-based polymer into a lens shape in an injection molding machine or an injection compression molding machine. The temperature for injection molding the isoflavone-based polymer may be about 200 캜 to 300 캜 though not limited thereto. More preferably, the temperature at which the isoflavone-based polymer is injection-molded may be about 240 ° C to 280 ° C.

The lens obtained by molding the isoflavone-based polymer exhibits a high refractive index and is excellent in overall optical properties such as transparency.

For example, a lens according to an embodiment of the present invention may have a refractive index of 1.60 or more, more preferably 1.640 or more, for example, 1.641 to 1.655 measured at a wavelength of 587 nm, Abbe number of 22 or more, e.g., 22 To 25%, and the permeability may be 85% or more, for example, about 89% to 93%.

Although not limited thereto, the lens may be formed in the form of an aspherical lens as needed. Aspheric lenses are usefully used 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. For example, 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 mount film, a telescope, a binoculars, a microscope and a projector.

Further, the lens may be applied to a camera module, and another embodiment of the present invention may provide a camera module including the lens.

Hereinafter, the present invention will be described by way of examples. The following examples are intended to illustrate the embodiments of the invention and should not be construed as limiting the scope of the invention.

Example

3- Iodo -7- ( Tetrahydro -2H-pyran-2- Sake ) -4H- Kromen 4-one (Intermediate)

Intermediates can be formed first using 3,4-dihydro-2H-pyran and 1- (2,4-dihydroxyphenyl) ethanone as starting materials, as shown in Scheme 1 below.

[Reaction Scheme 1]

In this example, an intermediate was formed in the following manner.

50 mL of dichloromethane and 9 mL of 3,4-dihydro-2H-pyran were added to a 100 mL round-bottomed flask equipped with a magnetic stir bar and mixed thoroughly. Then, 5 g of 1- (2,4-dihydroxyphenyl) Toluenesulfonate were sequentially added at room temperature and the mixture was stirred for 4 hours. The reaction termination point was confirmed by TLC (Thin Layer Chromatography) and an aqueous solution of sodium hydrogencarbonate was added thereto, followed by extraction with dichloromethane.

The obtained organic layer was dried with sodium sulfate, filtered and concentrated. The obtained product was diluted with 6.5 mL of N, N-dimethylformamide dimethylacetal and heated at 95 캜 for 3 hours. The reaction termination point was confirmed by TLC and concentrated under reduced pressure.

The obtained concentrate was diluted with 50 mL of chloroform, and 2.92 mL of pyridine and 16.68 g of iodine solid were added thereto, followed by stirring at room temperature for 12 hours. The reaction termination point was confirmed by TLC, and an aqueous solution of sodium thiosulfate (Na ₂ S ₂ O ₃ ) was added dropwise, stirred at room temperature for 30 minutes, and then extracted with dichloromethane. The obtained organic layer was dried with sodium sulfate, filtered and concentrated.

Next, the concentrate was purified by column chromatography on silica gel using hexane / ethyl acetate (volume ratio of 5/1 to 2/1) as eluent to obtain 10.78 g of an intermediate as a white solid. (Yield: 88%), NMR was used to confirm that 3-iodo-7- (tetrahydro-2H-pyran-2-yloxy) -4H-chromen-4-one was obtained. ^{(1 H NMR (500MHz, CDCl} 3) δ8.28 (s, 1H), 8.17 (d, 1H), 7.16-7.11 (m, 2H), 5.57 (m, 1H), 3.92-3.79 (m, 1H) , 3.71-3.63 (m, 1H), 2.10-1.90 (m, 3H), 1.83-1.58 (m, 3H)

Synthesis of isoflavone compounds 1 to 5

Next, after the formation of the intermediate, the intermediate may be reacted as shown in the following reaction formula 2 to form the isoflavone-based compound.

[Reaction Scheme 2]

In this Example, isoflavone compounds 1 to 5 were formed by the following method.

[Chemical Formula 4]

The isoflavone compounds 1 to 5 produced in this embodiment can be represented by the above-described formula (4).

Isoflavone compound 1 is a compound in which all of R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are hydrogen (H) in the above formula (4), R ₁₂ is a methyl group and R ₁₃ and R ₁₄ (I), R ₁₅ is hydrogen (H), isoflavone compound 3 is a compound wherein R ₁₃ is a methyl group and R ₁₂ , R ₁₄ and R ₁₅ are hydrogen (H) in the formula (4) 4, R ₁₂ and R ₁₅ are hydrogen (H), R ₁₃ and R ₁₄ are methyl groups, isoflavone compound 5 is a compound wherein R ₁₂ and R ₁₅ are methyl groups and R ₁₃ and R ₁₄ are hydrogen (H ).

First, isoflavone compound 1 was formed as follows.

12 mL of ethylene glycol dimethyl ether and 12 mL of water were added to a 100 mL round-bottomed flask equipped with a magnetic stirring bar, and 1 g of the intermediate formed was dissolved. At room temperature, sodium carbonate (854 mg), 4-methoxyphenylboronic acid (490 mg) and Pd / C (142 mg) were added sequentially. The reaction temperature was maintained at 45 캜 for 4 hours, and the reaction termination point was confirmed by TLC. The reactor was cooled to room temperature and water was added dropwise to dilute the reaction solution, which was then extracted with dichloromethane. The obtained organic layer was dried with sodium sulfate, filtered and concentrated. The reaction was concentrated and the residue was purified by column chromatography on silica gel using hexane / ethyl acetate (3/1 to 1/1 volume ratio) as the eluent. Thereafter, it was confirmed by NMR that 4'-methoxy-7- (tetrahydropyran-2-yloxy) isoflavone. ^{(1 H NMR (500 MHz,} CDCl 3): δ8.22 (d, 1H), 7.93 (s, 1H), 7.48 (dd, 2H), 7.07 (d, 2H), 6.95 (d, 2H), 5.55 (m, 1H), 3.85 (s, 1H), 3.93-3.81 (m, 1H), 3.74-3.61

The obtained material was dissolved in 30 mL of methanol and 30 mL of THF, and 41 mg of p-toluenesulfonic acid was added thereto at room temperature and stirred. After maintaining the reaction temperature at 60 ° C for 1 hour, 300μl of triethylamine was added to neutralize the reaction solution. The reaction was concentrated and the resulting crude was dissolved again in 10 mL of anhydrous dichloromethane. After cooling to 0 ° C in a nitrogen atmosphere, 3 mL of boron tribromide solution 1.0M in dichloromethane was added and the temperature was raised to room temperature. After 6 hours of reaction, the end point was confirmed by TLC. The reaction was terminated by adding ice water and the pH was adjusted to 6 with a 5 wt% aqueous solution of sodium phosphate, followed by extraction with ethyl acetate. The obtained organic layer was dried with sodium sulfate, filtered and concentrated. The obtained crude was dissolved in dichloromethane / methanol and then precipitated in ethyl acetate to give 4 ', 7-dihydroxyisoflavone (isoflavone compound 1, didezane) as an off-white solid having a total yield of 39% and a purity of 98.1% . Thereafter, the structure was confirmed using NMR. ^{(1 H NMR (700 MHz,} DMSO): δ10.74 (brs, 1H), 9.50 (brs, 1H), 8.26 (s, 1H), 7.96 (d, 1H), 7.37 (dt, 2H), 6.93 ( dd, 1 H), 6.84 (d, 1 H), 6.80 (dt, 2 H)

Synthesis of isoflavone compound 2 was carried out in the same manner as in the synthesis example of isoflavone compound 1 except that 4-methoxy-3-methylphenylboronic acid was used instead of 4-methoxyphenylboronic acid to give a total yield of 36 %, Purity: 97.9%.

Synthesis of isoflavone-based compound 3 was carried out in the same manner as in the synthesis example of isoflavone-based compound 1 except that 4-methoxy-2-methylphenylboronic acid was used instead of 4-methoxyphenylboronic acid to give a total yield of 31 %, Purity of 98.4%.

Synthesis of isoflavone compound 4 was carried out in the same manner as in the synthesis example of isoflavone compound 1 except that 4-methoxy-2,6-dimethylphenylboronic acid was used instead of 4-methoxyphenylboronic acid The total yield was 41% and the purity was 97.4%.

Synthesis of isoflavone compound 5 was carried out in the same manner as in the synthesis example of isoflavone compound 1 except that 4-methoxy-3,5-dimethylphenylboronic acid was used instead of 4-methoxyphenylboronic acid The total yield was 29% and purity was 98.9%.

Synthesis and Characterization of Isoflavone Polymers

Monomers of isoflavone derivatives having a purity of 97% or more and represented by isoflavone compounds 1 to 5 synthesized by the above-described method are dissolved in an aqueous solution of sodium hydroxide and a solution of dichloromethane, respectively, to obtain a polymer by a carbonation reaction using phosgene gas, GPC (Gel Permeation Chromatography) molecular weight and glass transition temperature (Tg) were measured, and the results are shown in Table 1 below.

Sample GPC molecular weight DSC TGA Mn, * 1000 Mw, * 1000 Mw / Mn Tg (占 폚) Td 5 wt% (캜) The polymer of isoflavone compound 1 13.4 41.7 3.11 139 398 Polymers of isoflavone compound 2 13.6 42.4 3.12 135 402 Polymer of isoflavone compound 3 13.7 42.1 3.07 135 402 Polymers of isoflavone compound 4 14.5 39.7 2.74 142 407 Polymer of isoflavone compound 5 14.1 39.5 2.80 142 407

Lens formation and evaluation of lens characteristics

Examples of the isoflavone-based polymers (hereinafter referred to as isoflavone-based polymers 1 to 5) formed of the isoflavone-based compounds 1 to 5 and the EP-5000 high-refractive resins of Mitsubishi Gas Chemical Co., , A mold having a thickness of 1 mm was melted by heating, and then a mold was removed to prepare a plate-shaped lens optical property evaluation specimen. The refractive index, Abbe's number and transmittance were measured, Are shown in Table 2 below.

Sample Refractive Index
(587 nm, 25?) ABBE's number Permeability Isoflavone-based polymer 1 1.651 24 91% Isoflavone-based polymer 2 1.648 25 92% Isoflavone-based polymer 3 1.649 25 92% Isoflavone-based polymer 4 1.651 24 93% Isoflavone-based polymer 5 1.652 24 93% Comparative Example (Mitsubishi Gas Chemical Co.) 1.635 24 85%

Referring to Table 1, the isoflavone polymer according to one embodiment of the present invention has a low glass transition temperature (Tg) suitable for extrudability, and with reference to Table 2, the isoflavone polymer according to one embodiment of the present invention The lens formed of the polymer has a refractive index of 1.640 or more, a high refractive index of 1.65, and a high transmittance of 90% or more.

Camera module

Hereinafter, a camera module according to an embodiment of the present invention will be described with reference to the drawings. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventive concept. Other embodiments falling within the scope of the inventive concept may be easily suggested, but are also included within the scope of the present invention.

1 is a schematic exploded perspective view of a camera module according to an embodiment of the present invention.

1, a camera module 1000 according to an exemplary embodiment of the present invention includes a housing 200, a first frame 400 accommodated in the housing 200, A second frame 500 and a lens module 300, a case 100 coupled with the housing 200, and lens driving devices 600 and 700.

The lens module 300 may include a lens barrel 310 and a third frame 330 for receiving the lens barrel 310 therein.

The lens barrel 310 may have a hollow cylindrical shape so that a plurality of lenses for capturing an object may be accommodated in the lens barrel 310. The plurality of lenses may be provided in the lens barrel 310 along an optical axis.

The plurality of lenses are stacked as many as necessary according to the design of the lens barrel 310, and each of the lenses may have the same or different optical characteristics such as a refractive index.

The lens barrel 310 may engage with the third frame 330.

The third frame 330 may be received in the first frame 400 together with the second frame 500. For example, the second frame 500 and the third frame 330 may be arranged in the first frame 400 in order.

The second frame 500 and the third frame 330 may be spaced apart from the inner bottom surface of the first frame 400 in the optical axis direction (Z direction).

For example, the inner bottom surface of the first frame 400 and the bottom surface of the second frame 500 are spaced apart from each other in the optical axis direction (Z direction) And the lower surface of the third frame 330 may be spaced apart from each other in the optical axis direction (Z direction).

The first frame 400, the second frame 500, and the third frame 330 may be received in the housing 200.

A first substrate 800 on which the image sensor 810 is mounted may be coupled to the lower portion of the housing 200.

The housing 200 may be provided in an open shape in the optical axis direction (Z direction) so that external light is incident and received by the image sensor 810.

Meanwhile, the first frame 400, the second frame 500, and the third frame 330 may be driven in the optical axis direction (Z direction) in the housing 200 for automatic focus adjustment .

At this time, a stopper 210 may be mounted on the upper portion of the housing 200 to limit the moving distance of the first frame 400, the second frame 500, and the third frame 330.

The stopper 210 also has a function of preventing the third frame 330 from being released to the outside of the housing 200 due to an external impact or the like.

The case 100 may be coupled to the housing 200 so as to surround the outer surface of the housing 200, and may shield electromagnetic waves generated during driving of the camera module.

The first frame 400, the second frame 500, and the third frame 330 may be arranged to be movable relative to the housing 200.

The third frame 330 and the second frame 500 may be disposed so as to be movable relative to the first frame 400 within the first frame 400.

The camera module 1000 according to an embodiment of the present invention may include lens driving devices 600 and 700. [

The lens driving apparatuses 600 and 700 include an image stabilization unit 600 and an auto focusing driving unit 700.

The camera shake correcting unit 600 may be used to compensate for blurring of an image or shaking of a moving image due to factors such as a user's hand motion during image shooting or moving image shooting.

For example, the hand shake correcting unit 600 can compensate for hand shake by giving a relative displacement corresponding to the hand shake to the third frame 330 when the shaking of the user occurs during image shooting.

The autofocusing driver 700 may be used for autofocusing or zooming.

The auto focus adjustment or zoom function can be performed by driving the third frame 330 in the optical axis direction (Z direction) by the auto focusing driving unit 700.

For example, the auto focusing driving unit 700 includes a third magnet 710 provided on one side of the first frame 400, a third coil 730 disposed to face the third magnet 710, A third substrate 770 for applying power to the third coil 730 and a third Hall sensor 750 for sensing the position of the third magnet 710.

The third coil 730 is mounted on a third substrate 770 and disposed opposite to the third magnet 710 and the third substrate 770 is fixed to one surface of the housing 200.

The autofocusing driver 700 can move the first frame 400 in the optical axis direction (Z direction) by an electromagnetic influence between the third magnet 710 and the third coil 730 .

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 (18)

An isoflavone skeleton in the main chain,
An isocyanate group, an ester group and a carbonate group.
The method according to claim 1,
Wherein the isoflavone-based polymer comprises a repeating unit represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

R ₁ to R ₃ are the same or different and each independently represents a substituted or unsubstituted C ₁ -C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ -C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ -C ₂₀ Aromatic rings, or combinations thereof;
R ₄ and R ₅ are the same or different and each independently, a deuterium, a substituted or unsubstituted C ₁ ~ C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ ~ ring C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ ~ C ₂₀ aromatic ring, or a combination thereof, and;
a is an integer of 0 to 3, b is an integer of 0 to 4, and n is an integer of 5 to 500.
3. The method of claim 2,
Wherein R ₁ and R ₂ are the same or different, each independently, a single _{bond, OCH 2 CH 2, OCH 2} CH 2 CH 2, CH 2 (CH 3) CH, or CH (CH ₃₎ CH ₂ in the isoflavone-based polymer.
3. The method of claim 2,
Wherein R < ₃ > is a divalent organic group derived from a dicarboxylic acid or a dicarboxylic acid derivative.
3. The method of claim 2,
Wherein R ₄ and R ₅ are the same or different and each independently selected from the group consisting of deuterium, substituted or unsubstituted (C ₁ -C ₄ ) alkyl, substituted or unsubstituted (C ₆ -C ₁₀ ) aryl, (C ₃ -C ₁₀ ) heteroaryl, substituted or unsubstituted (C ₃ -C ₁₀ ) cycloalkyl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, substituted or unsubstituted (C ₆ -C 10) ₁₀ ) heterocycloalkyl of 5 to 7 members in which one or more of (C ₁ -C ₄ ) alkyl, (C ₃ -C ₁₀ ) cycloalkyl is fused, or a substituted or unsubstituted aromatic ring is fused C ₃ -C ₁₀ ) cycloalkyl.
The method according to claim 1,
Wherein the isoflavone-based polymer comprises a repeating unit represented by the following formula (2): < EMI ID =
(2)

R ₆ and R ₇ are the same or different and each independently represents a substituted or unsubstituted C ₁ -C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ -C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ -C ₂₀ Aromatic rings, or combinations thereof;
R ₈ and R ₉ are the same or different and each independently, a deuterium, a substituted or unsubstituted C ₁ ~ C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ ~ ring C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ ~ C ₂₀ aromatic ring, or a combination thereof, and;
c is an integer of 0 to 3, d is an integer of 0 to 4, and m is an integer of 5 to 500.
The method according to claim 6,
Wherein R ₆ and R ₇ are the same or different and each independently, a single _{bond, OCH 2 CH 2, OCH 2} CH 2 CH 2, CH 2 (CH 3) CH, or CH (CH ₃₎ CH ₂ in the isoflavone-based polymer.
The method according to claim 6,
Wherein R ₈ and R ₉ are the same or different and are each independently selected from the group consisting of deuterium, substituted or unsubstituted (C ₁ -C ₄ ) alkyl, substituted or unsubstituted (C ₆ -C ₁₀ ) (C ₃ -C ₁₀ ) heteroaryl, substituted or unsubstituted (C ₃ -C ₁₀ ) cycloalkyl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, substituted or unsubstituted (C ₆ -C 10) ₁₀ ) heterocycloalkyl of 5 to 7 members in which one or more of (C ₁ -C ₄ ) alkyl, (C ₃ -C ₁₀ ) cycloalkyl is fused, or a substituted or unsubstituted aromatic ring is fused C ₃ -C ₁₀ ) cycloalkyl.
The method according to claim 1,
Wherein the isoflavone-based polymer does not contain a halogen substituent.
The method according to claim 1,
Wherein the isoflavone-based polymer does not contain a sulfur (S) atom.
The method according to claim 1,
Wherein the isoflavone-based polymer does not contain nitrogen (N) directly bonded to at least one hydrogen (H).
A polymer of an isoflavone-based compound represented by the following formula (3)
Wherein the polymer is polymerized through at least one of an esterification reaction and a carbonation reaction:
(3)

In the above formula 3,
R ₁₀ and R ₁₁ are the same or different and each independently represents a substituted or unsubstituted C ₁ -C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ -C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ -C ₂₀ Aromatic rings, or combinations thereof;
R ₁₂ and R ₁₃ are the same or different and each independently, a deuterium, a substituted or unsubstituted C ₁ ~ C ₁₀ aliphatic chain, a substituted or unsubstituted C ₃ ~ ring C ₁₀ aliphatic ring, a substituted or unsubstituted C ₃ ~ C ₂₀ aromatic ring, or a combination thereof, and;
e is an integer of 0 to 3, and f is an integer of 0 to 4;
13. The method of claim 12,
Wherein R ₁₀ and R ₁₁ are, and independently the same or different, a single _{bond, OCH 2 CH 2, OCH 2} CH 2 CH 2, CH 2 (CH 3) CH, or CH (CH ₃₎ CH ₂ in the isoflavone-based polymer.
13. The method of claim 12,
Wherein R ₁₂ and R ₁₃ are the same or different and are each independently selected from the group consisting of deuterium, substituted or unsubstituted (C ₁ -C ₄ ) alkyl, substituted or unsubstituted (C ₆ -C ₁₀ ) (C ₃ -C ₁₀ ) heteroaryl, substituted or unsubstituted (C ₃ -C ₁₀ ) cycloalkyl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, substituted or unsubstituted (C ₆ -C 10) ₁₀ ) heterocycloalkyl of 5 to 7 members in which one or more of (C ₁ -C ₄ ) alkyl, (C ₃ -C ₁₀ ) cycloalkyl is fused, or a substituted or unsubstituted aromatic ring is fused C ₃ -C ₁₀ ) cycloalkyl.
15. A lens comprising the isoflavone-based polymer of any one of claims 1 to 14.
16. The method of claim 15,
Wherein the lens is formed by injection molding the isoflavone-based polymer.
16. The method of claim 15,
Wherein the lens has a refractive index measured at a wavelength of 587 nm of 1.60 or more.
A camera module comprising a lens comprising the isoflavone-based polymer of any one of claims 1 to 14.

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