KR102112704B1 - Novel Reactive Mesogen Compound, Composition For Negative Dispersion Compensation Film Comprising The Same, And Negative Dispersion Compensation Film Comprising The Same - Google Patents

Abstract

The present invention relates to a hydrogen bonding mixture for a reverse wavelength dispersion compensation film and a compensation film comprising the same, which exhibits reverse wavelength dispersion characteristics according to a self-assembly arrangement between a host-guest reactive mesogen capable of hydrogen bonding as a single layer structure. The film produced by the present invention induces self-assembly between host-guest reactive mesogens which is more stable due to intermolecular host-guest interaction through hydrogen bonding, and thus improves compared to the conventional single-layer reverse wavelength dispersion compensation film. It is characterized by having an alignment property and a wavelength dispersion characteristic closer to an ideal value. Therefore, the reverse wavelength dispersion compensation film proposed in the present invention can be used for the anti-reflection function of the OLED or the viewing angle compensation of the LCD. The reverse wavelength dispersion compensation film of the present invention has the advantage that the thickness of the device can be reduced and the manufacturing process is simple compared to the conventional stacked type reverse wavelength dispersion compensation film.

Description

Novel Reactive Mesogen Compound, Composition For Negative Dispersion Compensation Film Comprising The Same, And Negative Dispersion Compensation Film Comprising The Same }

The present invention relates to a composition for a host-guest type coating type reverse wavelength dispersion compensation film and a reverse wavelength dispersion compensation film comprising the same, and more specifically, a more stable host due to intermolecular host-guest interaction through hydrogen bonding. It relates to a composition for a reverse wavelength dispersion compensation film and a compensation film comprising the same for inducing self-assembly between guest reactive mesogen compounds and thereby providing a compensation property for reverse wavelength dispersion.

As the phase difference film used for the LCD compensation film and the OLED anti-reflection film, a material having a constant wavelength dispersion property has been used in the past, but recently, a material having a reverse wavelength dispersion property capable of obtaining the phase difference property equal to the wavelength has been studied. have. When applied to the LCD compensation film, the compensation characteristics for each wavelength can be made equal, and when applied to the OLED, it is advantageous to lower the reflectance.

In the case of OLED, since the external light reflected from the metal electrode has a large influence on the image, it is necessary to impart anti-reflection performance. As a method currently used to prevent radiation, a method of attaching a circularly polarizing film laminated with a linearly polarizing film and a λ / 4 retardation film to the outside of a transparent electrode is exemplified. The reverse wavelength dispersion compensation film is used for the λ / 4 phase difference film currently used for commercially available circularly polarized films. In the manufacturing method, a stretched film or a reactive mesogen (RM) layer exhibiting a constant wavelength dispersion property is laminated. The method is used. However, the stretched film lamination method is difficult to produce in a thin thickness, so it is difficult to increase the thickness or flexibility, and the reactive mesogen lamination method requires solvent resistance to the reactive mesogen used in another layer in which the reactive mesogen dispersed in each film layer is used. It has the disadvantage of being.

Recently, due to the development of the display industry, flexible displays have been actively researched and are being prepared for commercialization. Accordingly, display material parts are also required to be smaller, thinner, and more flexible. Therefore, the compensation film for viewing angle and reflection ring also solves the problems of the stacking method, and the development of a single layer compensation film is urgent to apply to the next generation display products such as flexible displays.

US 828252389 discloses a reactive mesogen dimer having reverse wavelength dispersion properties and a single layer film comprising the same. In the registered patent, compounds were synthesized on a molecular basis to have reverse wavelength dispersion characteristics. However, the registered patent has a problem that the synthesis of the compound is complicated, and it is difficult to arrange the compound into a desired structure, and thus there is a problem of poor compatibility and poor viewing angle characteristics.

Korean Patent No. 10-1482878-0000 discloses a single layer film in which reactive mesogen molecules having a constant wavelength dispersion property are mixed and have reverse wavelength dispersion properties by self-assembly between the molecules. The registered patent has the advantage that the synthesis of the compound is relatively easy and the process temperature range is wide, but the viewing angle characteristic is still narrow.

In Korean Patent No. 10-2016-0077181, a single layer film having reverse wavelength dispersion property by self-assembly between these molecules by mixing host reactive mesogen molecule having constant wavelength dispersion property and X-type or T-type guest molecule Is disclosed. The registered patent has the advantage of easy compound synthesis and excellent reverse wavelength dispersion and viewing angle characteristics, but there is a problem that it does not appear uniformly in all regions due to phase separation between molecules during self-assembly.

The present invention is to provide a composition for a reverse wavelength dispersion compensation film and a compensation film comprising the same, which can improve the orientation of the conventional single layer reverse wavelength dispersion compensation film.

The present invention provides a composition for a reverse wavelength dispersion compensation film and a compensation film comprising the conventional one-layer reverse wavelength dispersion compensation film capable of improving non-uniformity due to intermolecular phase separation when self-assembling between host and guest molecules Is to provide.

In order to solve the above problems, the first aspect of the present invention provides a novel host-reactive mesogen compound represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

A and B are aromatic or cyclic compounds,

R ₁ and R ₂ are a flexible chain group having 4 to 12 carbon atoms,

X is any one of the compounds represented by the formula (3),

Y is any one of the compounds represented by the formula (4),

Z includes a functional group capable of hydrogen bonding, which is any one selected from the group consisting of OH, -COOH, -NH and -SH.

[Formula 3]

[Formula 4]

The second aspect of the present invention provides a novel guest reactive mesogen compound represented by the following formula (6).

[Formula 6]

In Chemical Formula 6, D is

Compound represented by the formula (7):

[Formula 7]

(In the formula 7, A, B, R _1, R ₂ , X and Y are as defined above)

or

Any one of the compounds represented by the formula (9):

[Formula 9]

(In the formula 9, R is a flexible chain group having 4 to 12 carbon atoms, D ₁ is a compound represented by the formula (7));

X is any functional group capable of photopolymerization and thermal polymerization.

The third aspect of the present invention provides a composition for a reverse wavelength dispersion compensation film comprising 40 to 80% by weight of the host reactive mesogen compound and 20 to 60% by weight of the guest reactive mesogen compound.

The fourth aspect of the present invention provides an inverse wavelength dispersion compensation film comprising the composition.

Since the film manufactured according to the present invention has a reverse wavelength dispersion characteristic as a single layer structure, it can be used for an anti-reflection function of OLED or compensation of a phase difference of LCD, as well as a flexible display.

In addition, compared to the conventional stacked-type reverse wavelength dispersion compensation film, the reverse wavelength dispersion characteristic can be realized only by a single layer process, the thickness can be reduced, and the manufacturing process is simple, so that the manufacturing cost can be lowered. It is easy.

1 shows a synthesis process of H-6BPBA as an example of a host reactive mesogen compound according to the present invention.
Figure 2 shows the results of ¹ H-NMR analysis of H-6BPBA as an example of a host-reactive mesogen compound according to the present invention.
3 shows the results of ¹ H-NMR analysis of N2 as an example of a guest reactive mesogen compound according to the present invention.
4 shows a conceptual diagram of a reverse wavelength dispersion film according to an embodiment of the present invention.
5 shows the wavelength dispersion characteristics of the film according to Comparative Example 1.
6 shows wavelength dispersion characteristics of the films according to Comparative Example 2 and Example 1.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the description of the present invention, when it is determined that a detailed description of related known technologies may obscure the subject matter of the present invention, the detailed description will be omitted. Throughout the specification, when a part “includes” a certain component, this means that other components may be further included instead of excluding other components, unless specifically stated to the contrary.

The present invention can be applied to various transformations and can have various embodiments, and thus, specific embodiments will be illustrated and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention.

The terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present invention, terms such as include or have are intended to designate the existence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and one or more other features, numbers, or steps. It should be understood that it does not preclude the existence or addition possibility of the operation, components, parts or combinations thereof.

One aspect of the present invention provides a host-reactive mesogen compound represented by Formula 1 below.

[Formula 1]

In Formula 1, A and B are each independently an aromatic or cyclic compound, R ₁ and R ₂ are each independently a flexible chain group having 4 to 12 carbon atoms, and X is any one of the compounds represented by Formula 3 , Y is any one of the compounds represented by the following formula (4), Z includes a functional group capable of hydrogen bonding to any one selected from the group consisting of OH, -COOH, -NH and -SH.

[Formula 3]

[Formula 4]

The aromatic or cyclic compound represented by A and B of Formula 1 includes a benzene ring compound, a fused benzene ring compound or a hetero ring compound. A and B may be the same or may be aromatic or cyclic compounds which may be different from each other. For example, it may be a compound represented by the following formula (2).

[Formula 2]

In Formula 2, one or two carbons of the aromatic ring may be substituted with a nitrogen or sulfur atom having a non-covalent electron pair to form a heterocyclic compound, and Br, Cl, I, F atoms or the side of the ring of the Formula Molecules such as CH ₃ , CF ₃ , CN, NO ₂ and the like can be substituted.

In Formula 1, X may be any functional group capable of photopolymerization and thermal polymerization. As an example, it may be any one of the compounds represented by the formula (3).

[Formula 3]

The compounds are substituted at the terminal of the compound to facilitate structure control. Therefore, the host-reactive mesogen compound of Formula 1 may be polymerized through polymerization after coating, and maintain a desired liquid crystal phase through polymerization.

In Formula 1, Y is a functional group that serves to link the aromatic or cyclic compound with any one of the compounds represented by Formula 4 below.

[Formula 4]

In Formula 1, Z is a functional group capable of hydrogen bonding, which is any one selected from the group consisting of OH, -COOH, -NH and -SH.

In Formula 1, Z has hydrogen attached to an atom having a high electronegativity on one side of the host, and when mixed with a guest reactive mesogen, interacts with a non-covalent electron pair of the guest to form a hydrogen bond.

Therefore, the host-reactive mesogen compound of Chemical Formula 1 may have a hydrogen-bonding functional group in the molecular structure to react with the guest-reactive mesogen compound to form a hydrogen bond between the host and the guest-reactive mesogen molecule. It is possible to avoid phase separation between molecules, which is a problem of the single-layer coating type reverse wavelength dispersion compensation film.

For example, the compound of Formula 1 may be represented by Formula 5 below.

[Formula 5]

The host-reactive mesogen compound may be a smectic liquid crystal at a specific temperature range. Smectic liquid crystal is a liquid crystal phase having a layered structure, which means that the arrangement is more regular and has a layered structure compared to a nematic liquid crystal, and the layer at this time is called a layer. The Smectic liquid crystal phase is a liquid crystal phase that has not only an directional order but also a positional order. The molecules representing the Smectic liquid crystal phase tend to make a layer by themselves.

  The smectic liquid crystal usable in the present invention may be a known smectic liquid crystal in which liquid crystal molecules form a layer on their own. The host-reactive mesogenic compounds that can be used in the present invention include smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smect And matic J phase, smetic K phase, smetic L phase, and the like, and preferably smectic A, smectic C, or smectic CA phase.

Reactive mesogen can be used as the host liquid crystal. The reactive mesogen represents a reactive mesogen or a reactive liquid crystal compound. The term "reactive mesogen" in the present application refers to a substance having a functional group that reacts with light or heat at the end of the mesogenic molecule, that is, a mesogenic vinyl monomer. In the present application, the term "mesogen compound" refers to a compound having a mesogen structure, and the term "mesogen" refers to a structure capable of inducing structural order in a crystal.

In the present invention, the "host-reactive mesogen compound" may be a reactive smectic liquid crystal having at least one reactor and a functional group capable of hydrogen bonding at one end.

Another aspect of the present invention provides a novel guest reactive mesogen compound represented by Formula 6 below.

[Formula 6]

In Chemical Formula 6, D may be a compound represented by Chemical Formula 7 or Chemical Formula 9.

[Formula 7]

[Formula 9]

In Chemical Formula 7, A and B are each independently an aromatic or cyclic compound, R ₁ and R ₂ are each independently a flexible chain group having 4 to 12 carbon atoms, and X is any one of the compounds represented by the following Chemical Formula 3 And Y is any one of the compounds represented by the following formula (4).

The aromatic or cyclic compound represented by A and B in Chemical Formula 7 includes a benzene ring compound, a fused benzene ring compound, or a hetero ring compound. A and B may be the same or may be aromatic or cyclic compounds which may be different from each other. For example, it may be a compound represented by the following formula (2).

[Formula 2]

Formula 7 is an example of D, instead of the alkyl chain of the guest reactive mesogen, mesogen was introduced between the alkyl chains so that it can be more mixed with the host reactive mesogen, and if necessary, a photopolymerizer X was introduced at the terminal. . The guest-reactive mesogen including the compound represented by the formula (7) exhibits an X-type molecular structure.

The compound represented by the following general formula (8) is mentioned as an example of the said general formula (7). The following formula is suggested as an example of the newly proposed X-type guest reactive mesogen, but is not limited thereto.

[Formula 8]

In Chemical Formula 9, R is a flexible chain group having 4 to 12 carbon atoms, and D ₁ may have the same structure as Chemical Formula 7.

As an example of D in Chemical Formula 9, two or more alkyl chains or mesogen side chains are introduced in place of the alkyl chain of the guest reactive mesogen, and a polymerizable functional group may be introduced at the terminal if necessary. The guest-reactive mesogen comprising the compound represented by the formula (9) exhibits a dendritic X-type molecular structure, and ideally, this material does not mix host-reactive mesogens and implements reverse wavelength dispersion properties only with dendritic X-type reactive mesogens. Can be.

However, the length of D represented by the above formulas (7) and (9) should not be too long to show the reverse wavelength dispersion characteristics. Preferably, the length of D may be 0.4 nm to 1.3 nm.

In Chemical Formula 6, X may be any functional group capable of photopolymerization and thermal polymerization. As an example, it may be any one of the compounds represented by the formula (3).

[Formula 3]

The compound represented by Chemical Formula 6 is an aromatic or cyclic compound, and may be a compound having an X-type or dendritic X-type molecular structure substituted with D.

The guest-reactive mesogen compound of Formula 6 depends on whether X or D can be positioned vertically on the host liquid crystal.

For example, the compound of Chemical Formula 6 may be represented by Chemical Formula 10 below.

[Formula 10]

Another aspect of the present invention provides a composition for a compensation film for reverse wavelength dispersion.

The composition for a reverse wavelength dispersion compensation film according to the present invention is a composition for a host-guest type coating type reverse wavelength dispersion compensation film, wherein the host reactive mesogen 40 to 80% by weight and the guest reactive mesogen 20 to 60% by weight It is preferred to include.

The host reactive mesogen compound used in the present invention absorbs a short wavelength compared to the guest reactive mesogen. In the present invention, the host reactive mesogen absorbs light in a wavelength range of 10 to 400 nm, preferably 100 to 400 nm, and the guest reactive mesogen compound absorbs light in a wavelength range of 100 to 430 nm, preferably 200 to 430 nm. do.

The guest reactive mesogen compound may be located between the host reactive mesogen compound layer and interact with the host reactive mesogen compound through hydrogen bonding.

The composition may contain a host reactive mesogen, a guest reactive mesogen, a polymerization initiator, and a solvent.

The solvent may be N-methylpyrrolidone (NMP), cyclohexane, cyclohexanone, cyclopentanone, acetone, methyl ethyl ketone, ethanol, methanol, methyl alcohol, isopropyl alcohol, toluene, chloroform, dichloromethane, etc. Can be.

The photopolymerization initiator may be a known compound, for example, benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts and sulfonium salts.

According to an embodiment of the present invention, instead of separately setting the host-guest material, a material having the structure of a host and a guest reactive mesogen at the same time may be used alone to exhibit reverse wavelength dispersion characteristics.

Another aspect of the present invention provides a reverse wavelength dispersion compensation film comprising the composition for the reverse wavelength dispersion compensation film.

The reverse wavelength dispersion compensation film of the present invention can be prepared by coating the composition for the reverse wavelength dispersion compensation film on a substrate and performing a photocuring reaction. To explain this in detail, first, a polyimide-based alignment layer is coated on a substrate to cure. The alignment film used can be formed using known rubbing and photo-alignment methods. After coating the composition on the alignment layer, the solvent may be evaporated to remove it, and then irradiated with UV to form a film. When the composition is coated on the alignment layer, the guest reactive mesogen compound is positioned between the layer and the layer of the host reactive mesogen compound and aligned parallel to the layer plane. At this time, since the affinity of the host-guest is weak compared to the affinity of the host-host, the reactive guest mesogen compound is separated into the space between the layers of the host reactive mesogen compound. Subsequently, the self-assembly of the molecule is achieved through the interaction of the host-reactive mesogen compound and the guest-reactive mesogen compound through hydrogen bonding, so that the stability of the two-dimensional structure is given and the alignment is improved.

4 shows a conceptual diagram of a reverse wavelength dispersion compensation film prepared in the present invention. Referring to FIG. 4, the reverse wavelength dispersion compensation film of the present invention includes a layer of a host reactive mesogen compound and a guest reactive mesogen compound positioned between them.

Since the guest reactive mesogen compound is polymerized by arranging the guest reactive mesogen compound in an empty space between the layer and the layer of the host reactive mesogen compound, the host reactive mesogen is relatively large in vertical direction as shown in FIG. 4 (layered ).

The layers have a width of 1 to 3 nm, but are not limited thereto.

The host reactive mesogen absorbs shorter wavelengths than the guest reactive mesogen. Preferably, the host reactive mesogen absorbs light in the wavelength range of 100 to 400 nm, and the guest reactive mesogen absorbs light in the wavelength range of 200 to 430 nm.

방향에서 광을 강하게 흡수하고, 상기 호스트 반응성 메조겐 화합물은

방향에서 광을 강하게 흡수한다.The guest reactive mesogen compound on a film made using a composition for a reverse wavelength dispersion compensation film

Strong absorption of light in the direction, the host reactive mesogen compound

Strong absorption of light in the direction.

The reverse wavelength dispersion compensation film may have a thickness of 1 to 10 μm.

The host reactive mesogen compound has a positive dispersion property, but the film of the present invention prepared by the host reactive mesogen compound and the guest reactive mesogen compound interposed therebetween is negatively dispersed. ) Has characteristics.

The birefringence of the liquid crystal changes with polarization anisotropy. Polarizability refers to the ease with which the distribution of electrons within an atom or molecule can be distorted. Polarization increases as the number of electrons increases and the number of diffusion electron clouds increases.

에서 액정 또는 복굴절 물질의 Retardation은 하기 수학식 1에 따라, 상기 파장에서의 복굴절률

및 층 두께

의 곱으로서 정의되며 Phase retardation은 Retardation 값과

의 곱으로 정의된다.Predetermined wavelength

In the retardation of the liquid crystal or birefringent material according to Equation 1 below, the birefringence at the wavelength

And layer thickness

Is defined as the product of and phase retardation is equal to the retardation value

It is defined as the product of.

[Equation 1]

Retardation =

) =

Birefringence (

) =

Phase retardation =

편광방향에 따라 다른 속력을 갖는 방향의 굴절률을

라고 정의한다.Refractive index in the direction with constant speed regardless of the polarization direction of light

Refractive index in the direction with different speed depending on the polarization direction

Is defined as

Retardation decreases as the wavelength increases for the constant wavelength dispersion characteristic, whereas retardation increases as the wavelength increases for the reverse wavelength dispersion characteristic.

When the wavelength dispersion material is manufactured so that the phase retardation value has a specific value for light of a specific wavelength (550 nm), a problem occurs in which the phase retardation value is changed for light of a short wavelength (450 nm) and a long wavelength (650 nm). On the other hand, the reverse wavelength dispersion material can exhibit a constant phase retardation regardless of the wavelength. Therefore, it can be seen that it is much more advantageous to use a retardation film having a reverse wavelength dispersion property than a constant wavelength dispersion property for an OLED antireflection film or LCD compensation film.

가 된다. 호스트 반응성 메조겐화합물의 단축방향, 다시 말해 호스트 반응성 메조겐 레이어에 평행한 방향이

가 된다. 필름에 입사되어

방향으로 편광된 빛은 100 내지 300 nm의 단파장 영역을 흡수하는 호스트 반응성 메조겐 화합물에 의해 흡수되고,

방향으로 편광된 빛은 300 내지 430 nm의 장파장 영역을 흡수하는 게스트 반응성 메조겐 화합물에 의해 흡수된다.Referring to FIG. 4, the long axis direction of the host reactive mesogen compound, that is, the direction perpendicular to the host reactive mesogen layer

Becomes. The shortening direction of the host reactive mesogen compound, that is, the direction parallel to the host reactive mesogen layer

Becomes. Joined the film

The light polarized in the direction is absorbed by the host reactive mesogen compound absorbing a short wavelength region of 100 to 300 nm,

Light polarized in the direction is absorbed by the guest reactive mesogen compound absorbing a long wavelength region of 300 to 430 nm.

또는

각각이 가시광선 영역에서 급격하게 감소하느냐, 완만하게 감소하느냐에 영향을 준다. 다시 말해,

방향에서 메조겐이 250 nm 파장의 빛을 흡수하면, 250 nm 흡수파장 바로 근처에서는

가 급격하게 감소하고, 250 nm 흡수파장으로부터 멀어질수록 완만하게 감소된다. 즉, 흡수가 일어나는 파장에서 굴절률이 극대가 된다.More specifically, the absorption wavelength

or

Each affects whether it decreases rapidly or slowly in the visible region. In other words,

If the mesogen in the direction absorbs light with a wavelength of 250 nm, in the vicinity of the absorption wavelength of 250 nm,

Decreases rapidly, and gradually decreases away from the absorption wavelength of 250 nm. That is, the refractive index becomes maximum at the wavelength at which absorption occurs.

방향에서 메조겐이 365 nm 파장의 빛을 흡수하면, 365 nm 근처에서는

가 급격히 감소하고, 365 nm에서 멀어질수록 완만하게 감소하게 된다.Meanwhile,

If the mesogen in the direction absorbs light of 365 nm wavelength, in the vicinity of 365 nm

Decreases rapidly, and gradually decreases as it moves away from 365 nm.

는 완만하게 감소하고,

는 급격하게 감소하게 되므로, 본 발명의 필름은 파장이 길어질수록 복굴절 (

)이 증가하는 역파장분산 특성이 나타나게 된다.As a result, in the visible region (450 to 650 nm)

Is slowly decreasing,

Since is rapidly reduced, the longer the wavelength of the film of the present invention is birefringence (

) Increases the inverse wavelength dispersion characteristic.

Hereinafter, the preparation of the host reactive mesogen and reverse wavelength dispersion compensation film will be described in more detail through examples. However, the following examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention.

(Production Example 1)

Preparation of 4 '-((6-hydroxyhexyl) oxy)-[1,1'-biphenyl] -4-yl 4-((6- (methacryloyloxy) hexyl) oxy) benzoate

Figure 1 shows the synthesis process of the host reactive mesogen (H-6BPBA) of the formula (5). 1, a host-reactive mesogen compound containing Formula 5 was synthesized.

First, 4,4'-Biphenol (7 g, 37.6 mmol) was mixed with purified dimethylformamide (DMF) (50 ml), and 6-Bromohexyloxy- tert- butyldimethylsilane (2 g, 6.8 mmol) was slowly added. . After refluxing at 90 ° C for about 12 hours, the temperature was lowered to room temperature. After putting the compound in water and precipitated, the precipitate was filtered out. 4 '-((6-((tert-butyldimethylsilyl) oxy) hexyl) oxy)-[1,1'-biphenyl by purification by column chromatography using a developing solvent with a chloroform to methanol ratio of 20: 1 ] -4-ol (Compound 1) was synthesized.

Next, 4-Hydrobenzoic acid (2 g, 14.5 mmol), KOH (5 g, 89.1 mmol), and KI (0.25 g, 1.5 mmol) were dissolved in ethanol, followed by ethanol (30 ml) and 6-Chloro-1-hexanol ( 3 g, 22 mmol) was added slowly. After refluxing at 70 ° C for 2 days, KOH (5 g, 89.1 mmol) was further added to reflux the day. After lowering the temperature to room temperature, it was poured into cold water and neutralized by adding 2N HCl solution (10 ml). The precipitate was filtered, and washed with water and hexane several times to synthesize 4-((6-hydroxyhexyl) oxy) benzoic acid (2.9 g).

The synthesized 4-((6-hydroxyhexyl) oxy) benzoic acid (1 g, 4.2 mmol) and Triethylamine (1 ml, 16.9 mmol) were dissolved in 1,4-dioxane (20 ml). After the mixture was cooled to 0 ° C, Methacyloyl chloride (1 ml, 9.6 mmol) was slowly added. After stirring at room temperature for 10 to 15 hours, it was poured into cold water. After the reaction was extracted with ethyl acetate (EA), all of the solvent was evaporated. Acetic acid was added and boiled at 100 ° C for 30 minutes. After the reaction was sufficiently cooled, it was precipitated in cold water and filtered. The filtered precipitate was washed several times with water and hexane to synthesize 4-((6- (methacryloyloxy) hexyl) oxy) benzoic acid (Compound 2) with polymerizable methacrylate.

Next, Compound 1 (0.3 g, 0.7 mmol) and Compound 2 (0.36 g, 1.2 mmol) were dissolved in methylene chloride with excess EDC (0.3 g) and trace amount of DMAP (0.003 g), and then at 0 ° C. for 10 hours. It was stirred for about 12 hours. After the reaction, extraction was performed with water and methyl chloride, and purified by column chromatography using a developing solvent having a ratio of chloroform and methanol of 10: 1 (v / v) to 4 '-((6-(( tert-butyldimethylsilyl) oxy) hexyl) oxy)-[1,1'-biphenyl] -4-yl-4-((6- (methacryloyloxy) hexyl) oxy) benzoate (Compound 3) was synthesized.

Finally, compound 3 (0.45 g, 0.7 mmol) was dissolved in tetrahydrofuran and cooled to 0 ° C. Then 1M Tetrabutylammonium fluoride (2 ml) was added slowly. When the reaction is over, the solvent is evaporated, extracted several times with Ethyl acetate and water, and purified by column chromatography using a developing solvent with a ratio of tetrahydrofuran and hexane of 4: 3, and then using methanol. By recrystallization, 4 '-((6-hydroxyhexyl) oxy)-[1,1'-biphenyl] -4-yl 4-((6- (methacryloyloxy) hexyl) oxy) benzoate of Chemical Formula 5 (hereinafter referred to as H-6BPBA) ) (Compound 4).

The results of ¹ H-NMR analysis of H-6BPBA of Chemical Formula 5 are shown in FIG. 2.

The results of NMR analysis in FIG. 2 were as follows.

¹ H-NMR (400 MHz, CHCl ₃ ): δ = 8.1 (d, 2H), 7.5 (d, 2H), 7.4 (d, 2H), 7.2 (d, 2H), 6.9 (m, 4H), 6.1 (s, 1H), 5.5 (s, 1H), 4.1 (t, 2H), 3.9-4.0 (m, 4H), 3.6 (t, 2H), 1.9 (s, 3H), 1.8 (m, 4H), 1.6-1.8 (m, 2H), 1.4-1.5 (m, 18H)

(Production Example 2)

((1E, 1'E)-((3,3'-bis (octyloxy)-[1,1'-biphenyl] -4,4'-diyl) bis (azanylylidene)) bis (methanylylidene)) bis (4 Preparation of, 1-phenylene) bis (2-methylacrylate)

A guest reactive mesogen compound represented by Chemical Formula 10 was synthesized.

First, 3,3′-Dihydroxybenzidine (2g, 1.01 mmol), phthalic anhydride (5.47g, 4 mmol) and isoquinoline were mixed in 25 ml of purified N-Methyl-2-pyrrolidone in a 250 ml round flask. After refluxing at 120 ° C. for 6 hours, the temperature was lowered to room temperature. Pour 150ml of methanol into a round flask to precipitate, and then 2,2 '-(3,3'-dihydroxy- [1,1'-biphenyl] -4,4'-diyl) bis (isoindoline-1,3- dione). Subsequently, the compound, (1 g, 1 mmol), 1-bromooctane (1.6 g, 3.8 mmol), potassium carbonate, and potassium iodide were refluxed at 60 ° C. for 24 hours using a purified dimethylformamide (20 ml) in a 100 ml round flask. After completion of the reaction, it was purified by column chromatography using a developing solvent with a ratio of methanol and chloroform of 1: 5 (v / v). Subsequently, an excessive amount of Hydrazin monohydrate was added to remove phthalic anhydride. 3,3′-bis (octyloxy)-[1,1′-biphenyl] -4,4′-diamine (0.3g, 0.68mmol) and 4-formylphenyl methacrylate (0.39g, 2.0mmol), sodium in 100ml round flask The carbonate was mixed with purified tetrahydrofuran (30 ml). After refluxing at 60 ° C for 48 hours, the temperature was lowered to room temperature. After completion of the reaction, acetone and hexane were purified by column chromatography using a developing solvent having a ratio of 1: 7 (v / v). Subsequently, the compound was precipitated in 50 ml ethanol, precipitated, and then filtered and dried to form ((1E, 1'E)-((3,3'-bis (octyloxy)-[1,1'-biphenyl) ] -4,4'-diyl) bis (azanylylidene)) bis (methanylylidene)) bis (4,1-phenylene) bis (2-methylacrylate) (hereinafter, N2) was obtained.

The results of ¹ H-NMR analysis of N2 in Chemical Formula 10 are shown in FIG. 3.

The results of NMR analysis in FIG. 3 were as follows.

¹ H-NMR (400 MHz, CHCl ₃ ): δ = 0.86 (t, 6H), 1.25-1.58 (m, 20H), 1.82 (m, 4H), 2.08 (t, 6H), 4.1 (t, 4H) , 5.79 (s, 2H), 6.38 (s, 2H), 7.24-7.26 (m, 4H), 7.95 (d, 4H), 8.57 (s, 2H)

(Comparative Example 1)

After coating and drying the alignment layer on the ITO substrate, the substrate was prepared by rubbing. HCM026 (HCCH), previously used as a host reactive mesogen material, was mixed with a chloroform solvent in a weight ratio of 1: 9, and the composition was spin coated on an alignment layer. Thereafter, the solvent was dried at 130 ° C. for 3 minutes, and then irradiated with UV at an intensity of 30 mW / cm ² for 5 minutes to cure the composition to obtain a film.

)을 나타낸 것으로, 파장이 증가할수록 그 값이 감소하는 정파장분산 보상필름의 특성을 나타냈다.5 is a value measured by the wavelength dispersion characteristics of the compensation film prepared in Comparative Example 1 (

). As the wavelength increased, the value of the constant wavelength dispersion compensation film decreased.

(Comparative Example 2)

After coating and drying the alignment layer on the ITO substrate, the substrate was prepared by rubbing. As a host reactive mesogen material, 60% by weight of HCM026 (HCCH) previously used, and 40% by weight of N2 as a guest reactive mesogen material were mixed. The mixture and chloroform solvent were mixed at a weight ratio of 1: 9, and the composition was spin coated on an alignment layer. Thereafter, the solvent was dried at 110 ° C. for 3 minutes, and then irradiated with UV at an intensity of 30 mW / cm ² for 5 minutes to cure the composition to obtain a film.

(Example 1)

After coating and drying the alignment layer on the ITO substrate, the substrate was prepared by rubbing. 60% by weight of H-6BPBA synthesized in Preparation Example 1 as a host reactive mesogen material, and 40% by weight of N2 synthesized in Preparation Example 2 as a guest reactive mesogen material were mixed. The mixture and chloroform solvent were mixed at a weight ratio of 1: 9, and the composition was spin coated (1500 rpm, 15 s) on an alignment layer. Thereafter, the solvent was dried at 95 ° C for 3 minutes, and then irradiated with UV at an intensity of 30 mW / cm ² for 5 minutes to cure the composition to obtain a film.

(Test Example 1): Analysis of wavelength dispersion characteristics

Wavelength dispersion characteristics of the compensation film produced in Comparative Example 2 and the compensation film produced in Example 1 were performed.

)을 측정한 결과로서, 비교예 2에서 제작한 보상필름의 파장분산특성 값은 사각표식으로 나타내었고, 실시예 1에서 제작한 보상필름의 파장분산특성 값은 원형표식으로 나타내었다.6 is a wavelength dispersion characteristic of the compensation film produced in Comparative Example 2 and the compensation film prepared in Example 1 (

As a result of measuring), the wavelength dispersion characteristic value of the compensation film prepared in Comparative Example 2 was represented by a square marker, and the wavelength dispersion characteristic value of the compensation film prepared in Example 1 was represented by a circular marker.

Referring to FIG. 6, it can be seen that both of the compensation films exhibit the characteristics of the reverse wavelength dispersion compensation film in which the measurement value of the wavelength dispersion property increases as the wavelength increases.

In addition, referring to Figure 6, compared with the compensation film of Comparative Example 2 made using a previously used host reactive mesogen, between the host and the guest reactive mesogen using the newly synthesized host reactive mesogen according to the present invention It can be seen that the newly proposed compensation film, which induces hydrogen bonding and improves stability, exhibits wavelength dispersion characteristics closer to more ideal values.

The above description is merely illustrative of the technical idea of the present invention, and those of ordinary skill in the art to which the present invention pertains may make various modifications and variations without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain them, and the scope of the technical spirit of the present invention is not limited by these embodiments.

The scope of protection of the present invention should be interpreted by the following claims, and all technical spirits within the equivalent range should be interpreted as being included in the scope of the present invention.

1: Layer structure of host reactive mesogen
2: guest reactive mesogen
3: host reactive mesogen

Claims (12)

A novel host reactive mesogen compound represented by Formula 5 below:
[Formula 5]

delete delete According to claim 1,
The host-reactive mesogen compound is a polymerizable, smectic liquid crystal compound that induces hydrogen bonding. A novel guest reactive mesogen compound represented by the following formula (10):
[Formula 10]

delete delete A composition for a reverse wavelength dispersion compensation film comprising 40 to 80% by weight of a host reactive mesogen compound according to claim 1, and 20 to 60% by weight of a guest reactive mesogen compound according to claim 5. delete The method of claim 8,
The host reactive mesogen compound absorbs light in a wavelength range of 10 to 400 nm, the guest reactive mesogen compound absorbs light in a wavelength range of 100 to 430 nm, and the guest reactive mesogen compound is attached to the host reactive mesogen compound Comparative composition for a reverse wavelength dispersion compensation film, characterized in that it absorbs long wavelengths. The method of claim 8,
The guest reactive mesogen compound is a composition for a reverse wavelength dispersion compensation film, which is located between the host reactive mesogen compound layer and interacts with a host reactive mesogen compound through hydrogen bonding. A reverse wavelength dispersion compensation film comprising the composition of claim 8.

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