KR102209495B1 - Polarizing film and Preparing method thereof - Google Patents

Abstract

The present invention relates to a polarizing film and a method for manufacturing the same, and more specifically, relates to a polarizing film in which a specific side chain liquid crystal crystalline polymer is introduced as a polarizing dichroic dye of a polarizing film, and has heat resistance, durability and polarization properties. It relates to this excellent polarizing film and a manufacturing method thereof.

Description

Polarizing film and its manufacturing method TECHNICAL FIELD

The present invention relates to a polarizing film containing a dichroic dye and a method for manufacturing the same, and more particularly, to a polarizing film including a dichroic dye having excellent heat resistance, durability and polarization properties, and a method for manufacturing the same.

Polarizing film is in earnest demand as an important component of a liquid crystal display (LCD), and recently, the demand is increasing for manufacturing industrial colored safety glasses and sunglasses for sports and leisure. In general, such a polarizing film is a dichroic dye iodine or a dichroic dye adsorbed onto a polyvinyl alcohol (PAC) film, and then a protective film made of triacetyl cellulose is adhered to one or both sides through an adhesive to form a polarizing plate. Thus, it can be used for liquid crystal display devices.

A polarizing plate composed of a polarizing film using iodine as a dichroic dye is called an iodine-based polarizing plate, and a polarizing plate composed of a polarizing film using a dichroic dye as a dichroic dye is called a dye-based polarizing plate.

Iodine polarizing films are widely used in general liquid crystal displays, liquid crystal televisions, mobile phones, PDAs, etc. in that they exhibit high transmittance and high polarization, that is, high contrast, compared to dye polarizing films. However, the iodine polarizing plate is superior to the dye polarizing plate in terms of optical characteristics, but is inferior to the dye polarizing plate in terms of optical durability. The iodine-based polarizing plate has a problem in that it is decolorized or deteriorated by moisture, heat, or pressure during processing, and thus a polarizing film requiring high durability is required.

A dichroic dye-based polarizing film is a highly durable polarizing film with little change in optical properties even under high temperature and high humidity conditions, and is used in LCDs that require high durability because of its high durability. In addition, in the case of a dye-based polarizing film, since color control is relatively easy, a polarizing film of various colors can be manufactured, which is also used in fields such as sunglasses.

In general, a commercially available polarizing film uses a film having polarization characteristics treated with iodine or dichroic dye as a polarizer as a polarizer, and a protective layer is formed to prevent deformation of the film due to high sublimation and low durability of iodine. In general, it is known to use triacetyl cellulose (TAC), polyester-based (PE), polycarbonate-based (PC), etc., which do not have birefringence, have high transmittance, have no wavelength dependence, and have high heat resistance, moisture resistance, and mechanical strength. In addition, it is known that an adhesive treatment is applied in the meantime and a protective film is covered on the outermost surface. The principle of the polarizing film made in this way is as follows.

The polarizing film has a function of vibrating in several directions and making incident natural light vibrating in only one direction (that is, polarization). In particular, since LCD uses the birefringence of liquid crystal, it is very important to control the vibration direction of light incident on the liquid crystal molecules.

The function of such a polarizing film is obtained by stretching a PVA film and dyeing it with iodine or a dichroic dye solution to arrange iodine molecules or dye molecules side by side in the stretching direction. Since iodine or dye molecules have dichroic properties, light that vibrates in the stretching direction of the polarizing film is absorbed and light that vibrates in the vertical direction is transmitted.

Currently generally used polarizing film is a PVA-I2 polarizing film which is stretched after immersing polyvinyl alcohol for optics in an aqueous solution of iodine and iodine-potassium, followed by dyeing. PVA has characteristics such as excellent linearity, film formation, high crystallinity, adhesiveness, and excellent alkali resistance to withstand pH 13.5 or higher, and thus the commercially available PVA-I2 polarizing film for LCD shows sufficient electric and optical performance.

However, despite its excellent properties, the PVA-I2 polarizing film has a disadvantage in that polarization properties and durability are very poor when left in high temperature, high humidity, and sunlight for a long time due to strong sublimation of iodine.

Due to this problem, in recent years, a method of using a dichroic dye instead of an iodine compound has been studied, and when a dichroic dye is simply dyed and used, there is a problem in that it does not exhibit polarization and transmittance comparable to iodine despite high durability.

In addition, since dichroic dyes have properties of absorbing intrinsic region light within visible light, only one type of dye cannot produce optical properties like iodine-based compounds. Therefore, at least three or more types of dyes must be combined in order for the degree of polarization to appear in the entire visible wavelength range.

Japanese Patent Application Laid-Open No. 62-156602 has the Color Index General Name of direct dye blue 168, direct dye red 81, direct dye orange 26 in three basic colors, direct dye green 1, and direct dye purple 22. A polarizing film was prepared with five dyes in which two dyes were added, but satisfactory results of a transmittance of 42% or more and a polarization degree of 95% were not obtained.

In addition, Japanese Laid-Open Patent Publication No. 62-123405 classified dichroic dyes into five groups based on the wavelength range, and three to six dyes were selected from these five groups to create a composition with an appropriate ratio. The composition was dyed to prepare a polarizing film, but a polarizing film having a high degree of polarization was not manufactured.

On the other hand, LCP (Liquid crystalline polymer) is a polymer that exhibits liquid crystalline properties in a solution or dissolved state, and it is called a lyotropic liquid crystal when it functions as a liquid crystal in a solution state, and a thermotropic liquid crystal when it is dissolved. . LCP has anisotropic properties, supramolecular and excellent mechanical and electrical properties.Since it has been mass-produced since the 1980s, it has been widely used from structural materials for spacecraft and aircraft to sports goods, and recently, electrical devices and bio devices. Not only is it widely used for such as, but also the application field is in the trend of expanding further.

Korea Publication No. (KR 2013-0014032) mentions LCP having excellent fluidity during molding, but these LCPs have poor thermal properties, so their application fields are narrow, and the process of manufacturing LCP is very complex, so the productivity is good. There is no problem.

Among LCPs, SC-LCP (Side-chain Liquid crystalline polymers, hereinafter referred to as SC-LCP) is one having mesogenic groups connected to the side or elongated of the backbone (or main polymer). Dynamics and side chains tend to have different properties.

Accordingly, the inventors of the present invention learned a method of manufacturing a specific SC-LCP with high productivity after special research, and also found that the manufactured SC-LCP can have polarization property with dichroic dyeing, so that the product applied to polarizing film Was invented. That is, the present invention is to provide a polarizing film including a compound (SC-LCP) represented by a specific formula and a method of manufacturing the same.

The present invention for solving the above problem relates to a polarizing film, comprising: a polymer resin; And a polarizing dichroic dye containing a compound represented by the following Chemical Formula 1;

[Formula 1]

In Formula 1, R ¹ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, an alkoxyl group having 1 to 15 carbon atoms, -CN or -(Ph-CN), and n is a weight average molecular weight of 30,000 to 210,000. Is a rational number.

According to a preferred embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by the following Formula 2.

[Formula 2]

In Formula 2, R ¹ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, an alkoxyl group having 1 to 15 carbon atoms, -CN or -(Ph-CN), and n is a weight average molecular weight of 30,000 to 210,000. Is a rational number.

According to a preferred embodiment of the present invention, the polarizing dichroic dye may have a glass transition temperature (Tg) of 200°C to 350°C, and a thermal decomposition temperature (Td) of 300°C to 420°C.

According to a preferred embodiment of the present invention, the polymer resin is a polycarbonate (PC) resin, a polyethylene terephthalate (PET) resin, a cycloolefin copolymer (COC) resin, a cycloolefin polymer (COP) resin, a triacetylcellulose ( TAC) resin, polyether sulfone (PES) resin, and may include at least one selected from polyetherimide (PEI) resin.

According to a preferred embodiment of the present invention, the polarizing film of the present invention may be characterized in that it further comprises a dichroic auxiliary dye represented by the following Chemical Formulas 10 to 19.

[Formula 10]

In Formula 10, R ¹ is a C1 to C5 alkyl group or -SO ₃ H.

[Formula 11]

In Formula 11, R ¹ is -H, a C1 to C5 alkyl group, -SO ₃ H, -CHO, a C1 to C5 alkoxy or aryl group, and R ² , R ³ , R ⁴ and R ⁵ are each independently As being, -H, C1 ~ C5 alkyl group or isopropyl group, R ⁶ and R ⁹ are each independently, C1 ~ C5 alkyl group, phenyl group, halogen group or isopropyl group, R ⁷ and R ⁸ are each As independent, it is a hydrogen atom or a C1-C5 alkyl group.

[Formula 12]

[Formula 13]

In Formula 13, R ¹ And R ² are each independently a C1 to C5 alkyl group or -SO ₃ H.

[Formula 14]

In Formula 14, R ¹ And R ² are each independently a C1 to C5 alkyl group or -SO ₃ H.

[Formula 15]

In Formula 15, R ¹ Is a C1 to C5 alkyl group or -SO ₃ H.

[Formula 16]

[Formula 17]

In Formula 17, R ¹ Is a C1 to C5 alkyl group or -SO ₃ H.

[Formula 18]

[Formula 19]

According to another preferred embodiment of the present invention, the polarizing film of the present invention may be characterized in that 10㎛ ~ 100㎛.

According to another preferred embodiment of the present invention, the polarizing film of the present invention may be characterized in that it further includes a transparent protective film on one side or both sides.

According to another preferred embodiment of the present invention, in the polarizing film of the present invention, the transparent protective film is polycarbonate (PC), polyethylene terephthalate (PET), cycloolefin copolymer (COC), cycloolefin polymer (COP). ), triacetylcellulose (TAC), polyethersulfone (PES), and polyetherimide (PEI).

According to another preferred embodiment of the present invention, when measured using a spectrophotometer (Minolta, CM 3500d), the polarizing film of the present invention has a transmittance of 42% to 50%, and the retardation film optical material inspection equipment According to the measurement, it may be characterized in that the degree of polarization is 92 to 99%.

According to another preferred embodiment of the present invention, the polarizing film of the present invention may have a glass transition temperature of 200°C to 350°C, and a thermal decomposition temperature of 300°C to 420°C.

According to another preferred embodiment of the present invention, the polarizing film of the present invention is a dye-based polarizing film, an iodine-based polarizing film, a retardation polarizing film, a transflective polarizing film, a highly reflective transflective film, a surface anti-reflective film, LC ( It may be characterized in that it is one type of film selected from a liquid crystal) film or a reflective polarizing film.

Another aspect of the present invention relates to a method of manufacturing a polarizing film described above, comprising: preparing a mixed solution by mixing a polymer resin and a polarizing dichroic dye containing a compound represented by the following Formula 1; An extrusion step of extruding the mixed solution into a film; And a stretching step of stretching the extruded film; it may be characterized in that it is manufactured by performing a process including.

[Formula 1]

In Formula 1, R ¹ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, an alkoxyl group having 1 to 15 carbon atoms, -CN or -(Ph-CN), and n is a weight average molecular weight of 30,000 to 210,000. Is a rational number.

According to a preferred embodiment of the present invention, the compound represented by Formula 1, which is the polarizing dichroic dye component, comprises the steps of preparing a compound represented by the following Formula 3; And under a radical initiator, radical polymerization of the compound represented by the following formula (3); can be prepared by performing a process including.

[Formula 3]

또는

이며, 상기 화학식 3의 R³는 탄소수 1 ~ 15의 알킬기이고, R⁴는 페닐기, 알킬페닐기, 바이페닐기, 알킬바이페닐기, -CN 또는 -(Ph-CN)이다.In Formula 3, R ² is

or

And R ³ in Formula 3 is an alkyl group having 1 to 15 carbon atoms, and R ⁴ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN).

According to a preferred embodiment of the present invention, the step of preparing the compound represented by Chemical Formula 3 is performed under a temperature of 60°C to 100°C, and a halogenbenzene mixture containing a halogenbenzene compound represented by the following Chemical Formula 5 is subjected to a Suzuki coupling reaction ( Suzuki coupling reaction) to prepare a styrene compound represented by the following formula (6); And performing an amidation reaction of a styrene compound represented by the following Formula 6, a primary amine represented by the following Formula 7 or Formula 8, a reaction catalyst, and an organic solvent.

[Formula 3]

또는

이며, 상기 화학식 3의 R³는 탄소수 1 ~ 15의 알킬기이고, R⁴는 페닐기, 알킬페닐기, 바이페닐기, 알킬바이페닐기, -CN 또는 -(Ph-CN)이며,In Formula 3, R ² is

or

And R ³ in Formula 3 is an alkyl group having 1 to 15 carbon atoms, and R ⁴ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN),

[Formula 5]

[Formula 6]

In Formulas 5 and 6, X is F-, Br- or Cl-, and R ⁵ is an alkyl group having 1 to 10 carbon atoms,

[Formula 7]

[Formula 8]

R ³ in Formulas 7 and 8 is an alkyl group having 1 to 15 carbon atoms, and R ⁴ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN).

According to another preferred embodiment of the present invention, as another method of preparing the compound represented by Formula 3, the step of preparing the compound represented by Formula 3 is a compound represented by the following Formula 4, SOCl ₂ , pyridine, A halogenbenzene compound represented by the following formula 3-1 by mixing a primary amine represented by Formula 7 or Formula 8, 4-Dimethylaminopyridine (DMAP), and methylene chloride, and then performing an amidation reaction at 70°C to 90°C. Manufacturing a; And performing a Suzuki coupling reaction with the halogen benzene compound under 60°C to 100°C.

[Formula 3]

[Formula 3-1]

또는

이며, 상기 화학식 3의 R³는 탄소수 1 ~ 15의 알킬기이고, R⁴는 페닐기, 알킬페닐기, 바이페닐기, 알킬바이페닐기, -CN 또는 -(Ph-CN)이며,In Formulas 3 and 3-1, R ² is

or

And R ³ in Formula 3 is an alkyl group having 1 to 15 carbon atoms, and R ⁴ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN),

[Formula 4]

In Formula 4, X is -F, -Br or -Cl.

[Formula 7]

[Formula 8]

R ³ in Formulas 7 and 8 is an alkyl group having 1 to 15 carbon atoms, and R ⁴ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN).

In addition, as another preferred embodiment of the present invention, in the step of preparing the mixed solution, the mixed solution may be prepared by further adding a dichroic auxiliary dye represented by Chemical Formulas 10 to 19.

The compound used as the polarizing dichroic dye of the present invention is simpler than the existing LCP (Liquid crystalline polymer) manufacturing process, so that a polarizing dichroic dye can be manufactured with high economic efficiency. Using this polarizing dichroic dye, heat resistance, durability and It is possible to provide a polarizing film excellent in transparency along with polarization properties.

1 is a DSC measurement result for measuring the glass transition temperature of Example 1 carried out in Experimental Example 1.
FIG. 2 is a photograph of a polarization microscope (Motic, BA300pol) to measure the nematic structure of the polarizing film of Example 1 conducted in Experimental Example 1. FIG.

The terms "about", "substantially", etc. of the degree used in the present specification are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, and To assist, accurate or absolute numerical values are used to prevent misuse by unscrupulous infringers of the stated disclosure.

The term "film" used in the present invention has a broad meaning not only in the form of a film generally used in the art, but also in the form of a sheet.

The terms "C1", "C2", and the like used in the present invention mean carbon number, for example, "C1 to C5 alkyl group" means an alkyl group having 1 to 5 carbon atoms.

로 표현된 화학식에서, R₁은 독립적으로 수소원자, 메틸기 또는 에틸기이며, a는 1 ~ 3이다"라고 치환기에 대해 표현되어 있을 때, a가 3인 경우, 복수의 R¹, 즉 R¹ 치환기가 3개가 있고, 이들 복수 개의 R¹들 각각은 서로 같거나 다른 것으로서, R¹들 각각은 모두 수소원자, 메틸기 또는 에틸기일 수 있으며, 또는 R¹들 각각은 다른 것으로서, R¹ 중 하나는 수소원자, 다른 하나는 메틸기 및 또 다른 하나는 에틸기일 수 있음을 의미하는 것이다. 그리고, 상기 내용은 본 발명에서 표현된 치환기를 해석하는 일례로서, 다른 형태의 유사 치환기도 동일한 방법으로 해석되어야 할 것이다.
In the present invention "

In the formula represented by, R ₁ is independently a hydrogen atom, a methyl group, or an ethyl group, and a is 1 to 3" when expressed for a substituent, when a is 3, a plurality of R ¹ , that is, R ¹ There are three substituents, and each of the plurality of R ^1s is the same as or different from each other, and each of R ^1s may be a hydrogen atom, a methyl group or an ethyl group, or each of R ^1s is different, R ¹ One of the It means that a hydrogen atom, the other is a methyl group, and the other is an ethyl group. In addition, the above contents are an example of interpreting the substituents expressed in the present invention, and similar substituents of other forms should be interpreted in the same manner.

Hereinafter, the present invention will be described in more detail.

The present invention is a polymer resin; And it relates to a polarizing film comprising a polarizing dichroic dye containing a compound represented by the following formula (1).

[Formula 1]

The compound represented by Formula 1 may be included in an amideside chain liquid crystalline polymer (hereinafter referred to as SC-LCP), and in Formula 1, R ¹ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkyl bi A phenyl group, an alkoxyl group having 1 to 15 carbon atoms, -CN or -(Ph-CN), and preferably a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN). And, the n is a rational number that satisfies the weight average molecular weight of 30,000 to 210,000, preferably 100,000 to 150,000, and if n is less than 30,000, the polydispersity index (PDI) of SC-LCP may drop, and if n exceeds 210,000 Since a problem may occur in the film state, it is better to be within the above range.

In the polarizing film of the present invention, the polymer resin is polycarbonate (PC) resin, polyethylene terephthalate (PET) resin, cycloolefin copolymer (COC) resin, cycloolefin polymer (COP) resin, triacetylcellulose (TAC) Resin, polyether sulfone (PES) resin, and polyetherimide (PEI) resin, it is preferable to use at least one selected from polyethylene terephthalate (PET) resin, polycarbonate (PC) and polyether sulfone (PES). It is better to use at least one selected.

In addition, the amount of the polarizing dichroic dye is preferably 1 to 10 parts by weight, preferably 1 to 8 parts by weight, and more preferably 1 to 5 parts by weight, based on 100 parts by weight of the polymer resin. If the amount of the photosensitive dichroic dye is less than 1 part by weight, sufficient polarization effect and dichroic effect may not be seen, and if it is used in excess of 10 parts by weight, the transmittance of the polarizing film may be lowered.

The polarizing dichroic dye containing the compound represented by Formula 1 will be described in more detail.

In the present invention, the compound represented by Formula 1 may improve the heat resistance of the polarizing film, and the glass transition temperature of the compound represented by Formula 1 is 200°C to 350°C, preferably 220°C to 320°C. I can. In this case, the glass transition temperature means heat resistance. In addition, it may be characterized in that the thermal decomposition temperature (Td) is 300 ℃ ~ 420 ℃, preferably 340 ℃ ~ 400 ℃.

In addition, the compound represented by Formula 1 may be preferably a compound represented by Formula 2 or Formula 2-1, and more preferably may be a compound represented by Formula 2.

[Formula 2]

[Formula 2-1]

R ¹ in Formula 2 and Formula 2-1 is the same as the description for R ¹ in Formula 1.

In addition, the polarizing film of the present invention may further include a dichroic auxiliary dye in addition to the polymer resin and a polarizing dichroic dye, and the dichroic auxiliary dye is visible that the polarizing dichroic dye cannot absorb or is weakly absorbed. As an auxiliary role for absorbing the light ray region, at least one selected from the compounds represented by the following Formulas 10 to 19 may be included, preferably 2 or more, and more preferably 3 or more.

In addition, the amount of the dichroic auxiliary dye may be 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, and more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the polymer resin. At this time, if the amount of the dichroic auxiliary dye is less than 0.1 parts by weight, an additional visible light absorption effect may not be expected due to its use, and if it is used in excess of 5 parts by weight, the transmittance of the polarizing film decreases and the polarization property is rather poor. It is recommended to use within the above range.

[Formula 10]

In Formula 10, R ¹ is a C1 to C5 alkyl group or -SO ₃ H.

[Formula 11]

In Formula 11, R ¹ is -H, a C1 to C5 alkyl group, -SO ₃ H, -CHO, a C1 to C5 alkoxy or aryl group, and R ² , R ³ , R ⁴ and R ⁵ are each independently As being, -H, C1 ~ C5 alkyl group or isopropyl group, R ⁶ and R ⁹ are each independently, C1 ~ C5 alkyl group, phenyl group, halogen group or isopropyl group, R ⁷ and R ⁸ are each As independent, it is a hydrogen atom or a C1-C5 alkyl group.

[Formula 12]

[Formula 13]

In Formula 13, R ¹ And R ² are each independently a C1 to C5 alkyl group or -SO ₃ H.

[Formula 14]

In Formula 14, R^One And R²Are each independently, a C1 ~ C5 alkyl group or -SO₃H.

[Formula 15]

In Formula 15, R ¹ Is a C1 to C5 alkyl group or -SO ₃ H.

[Formula 16]

[Formula 17]

In Formula 17, R ¹ Is a C1 to C5 alkyl group or -SO ₃ H.

[Formula 18]

[Formula 19]

In addition, the polarizing film of the present invention may further use a crosslinking agent such as boric acid in addition to the polymer resin, polarizing dichroic dye, and dichroic auxiliary dye.

The polarizing film of the present invention has an average thickness of 10 μm to 150 μm, preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm, and polarization when the average thickness is less than 10 μm It may be difficult to process the film because it is too thin, and if it exceeds 150 µm, it is unsuitable for delamination of recent parts, so having a thickness within the above range is appropriate in terms of transparency, mechanical strength, and the like.

In addition, the polarizing film of the present invention may further include a transparent protective film on one side or both sides, and as the transparent protective film, a material having excellent transparency generally used in the art may be used, and preferably polycarbonate, polyethylene At least one selected from terephthalate, cycloolefin copolymer, cycloolefin polymer, triacetylcellulose, polyethersulfone, and polyetherimide may be used.

In addition, an adhesive layer may be formed between the polarizing film and the transparent protective layer, and as an adhesive used for the adhesive layer, one selected from triacetyl cellulose, cycloolefin copolymer and cycloolefin polymer capable of securing transparency It is better to use an adhesive containing the above.

The method of manufacturing the polarizing film of the present invention using the above-described composition will be described below.

The polarizing film of the present invention comprises the steps of preparing a mixed solution by mixing a polymer resin and a polarizing dichroic dye containing the compound represented by Formula 1; An extrusion step of extruding the mixed solution into a film; And it can be produced by performing a process comprising a; stretching step of stretching the extruded film.

In this case, the compound represented by Formula 1 is the same as described above.

Further, in the manufacturing method of the present invention, in the step of preparing the mixed solution, the mixed solution may be prepared by further adding a dichroic auxiliary dye represented by Chemical Formulas 10 to 19.

The extrusion step may use a general extrusion method used in the art, for example, it may be extruded using a T-die.

The stretching step is aimed at aligning the polarizing dichroic dye (and dichroic auxiliary dye), and the draw ratio is preferably 3 to 7 times, more preferably 5 to 6 times. The degree of orientation becomes accurate within the above range, and the spreading effect is excellent. In addition, during the stretching, it is preferable that the stretching temperature is 200°C to 280°C.

Meanwhile, a method of preparing the compound represented by Formula 1 of the present invention will be described below.

In the present invention, the compound represented by the following formula (1) is a step (1) of preparing a compound represented by the following formula (3); And radical polymerization of the aminocarbonylstyrene compound represented by the following Formula 3 under a radical initiator (2), which may be prepared in the same manner as in Scheme 1 below.

In addition, the method of preparing the compound represented by Formula 1 may further include washing and filtering the polymer generated by radical polymerization, and at this time, the washing liquid used for washing may be a general one used in the art. And, preferably, distilled water, methanol, or the like may be used.

[Scheme 1]

Formula 1 is the same as described above, and Formula 3 is as follows.

[Formula 3]

또는

이며, 바람직하게는

,

,

또는

이며, 더욱 바람직하게는

또는

이다.In Formula 3, R ² is

or

And, preferably

,

,

or

And more preferably

or

to be.

And, R ³ in Formula 3 is a C 1 to C 15 alkyl group, preferably a C 1 to C 10 linear alkyl group, more preferably -CH ₃ , -CH ₂ CH ₃ , -(CH ₂ ) ₃ CH _{3 , - (CH 2) 7 CH} 3, or - (CH _{2) 11} CH _{3, and,} at this time, the R ³ since the number of carbon atoms is the production chain amide side LCP by using this, when it is more than 15, it can decrease the LCP yield It is preferable to have within the above carbon number range. In addition, R ⁴ in Formula 3 is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN), preferably a phenyl group, an alkylphenyl group or -CN in terms of the LCP manufacturing process and the LCP yield. Good in

In the step (1) of preparing the compound represented by Formula 3, the compound represented by Formula 3 may be aminocarbonylstyrene, and Formula 3 is the same as described above.

The aminocarbonylstyrene compound represented by Formula 3 of the present invention is an intermediate used in the preparation of the amideside chain LCP, and the amideside chain LCP is a compound represented by the following Formula 1, preferably represented by the following Formula 2. Can contain.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, R ⁵ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, an alkoxyl group having 1 to 15 carbon atoms, -CN or -(Ph-CN), preferably a phenyl group, an alkylphenyl group, It is a biphenyl group, an alkylbiphenyl group, -CN, or -(Ph-CN). In addition, n in Formulas 1 and 2 is a rational number that satisfies a weight average molecular weight of 30,000 to 210,000, preferably 100,000 to 150,000.If n is less than 30,000, the polydispersity index (PDI) of LCP may drop, and n is 210,000. If it is exceeded, the film may break, so it is better to be within the above range.

In addition, the aminocarbonylstyrene compound represented by Chemical Formula 3 of the present invention can be prepared with high productivity through the following method.

The aminocarbonylstyrene compound represented by Formula 3 of the present invention can be prepared through the same process as in Scheme 2 below.

[Scheme 2]

In Formula 5 and/or Formula 6, X is -F, -Br or -Cl, preferably -Br. In addition, R ⁵ is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, where, when the number of carbon atoms exceeds 10, the reaction yield may decrease. And, R ² in Formula 3 is the same as described above, R ³ in Formulas 7 and 8 is an alkyl group having 1 to 15 carbon atoms, and R ⁴ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or- (Ph-CN), and X is -F, -Br or -Cl.

When explaining in detail the method for preparing the aminocarbonylstyrene compound represented by Chemical Formula 3 according to Scheme 2, a halogenbenzene mixture containing the halogenbenzene compound represented by Chemical Formula 5 is prepared under 60°C to 100°C. Preparing a styrene compound represented by Formula 6 by performing a Suzuki coupling reaction (1-1-1); And performing an amidation reaction of the styrene compound, a styrene mixture containing the primary amine represented by Formula 7 or Formula 8, a reaction catalyst, and an organic solvent to prepare a compound represented by Formula 3 (1-1. The aminocarbonyl styrene compound can be produced through a process including -2).

In the step (1-1-1) of preparing a styrene compound represented by Formula 6, the Suzuki coupling reaction is under 60°C to 100°C, preferably under 70°C to 90°C, more preferably 75°C. It is good to carry out under ~85℃, but if it is carried out at less than 60℃, the reaction yield may drop, and when reacting in an atmosphere exceeding 100℃, there may be a problem that a large amount of by-products may be generated. It is good.

In addition, the halogenbenzene mixture is 1 selected from the halogenbenzene compound represented by Formula 5, vinyl borate, palladium (Pd) catalyst, cesium carbonate (Cs ₂ CO ₃ ) and potassium carbonate (K ₂ CO ₃ ) It may contain more than a kind of salt (base) and a polar solvent, and the halogen benzene mixture is a halogenbenzene compound represented by Chemical Formula 5, a vinyl borate, a palladium (Pd) catalyst, the salt and a polar solvent 1: 1.5 ~ 3: 0.05 ~ 0.2: 2.5 ~ 4: 3 ~ 6 may be characterized in that it comprises a molar ratio.

Here, if the molar ratio of the halogenbenzene compound and the vinyl borate is less than 1: 1.5, the yield of the styrene compound may decrease, and even if the molar ratio of the vinyl borate exceeds 1: 3, there is no effect of increasing the yield, so that the molar ratio within the above range is used. It is good.

In addition, when the molar ratio of the halogenbenzene compound and the palladium catalyst is less than 1:0.05, the reaction temperature proposed by the present invention must be increased, and in this case, there may be a problem of lowering productivity, and the palladium catalyst is used in a 1:0.2 molar ratio. Even if it is used in excess, it is uneconomical because there is no further effect of increasing the yield.

In addition, the cesium carbonate and/or potassium carbonate serve as a salt in the present invention, and if the molar ratio of the halogenbenzene compound and the salt is less than 1:2.5, there may be a problem of inferior reactivity, so it is used within the above range. It is good to do.

In addition, the polar solvent is dimethylformamide (DMF), tetrahydrofuran (THF), toluene, isopropyl alcohol and water (H ₂ O) At least one selected from It may contain at least one selected from among, and it is preferable from the viewpoint of smooth reaction to use in an amount of 3 to 6 moles per 1 mole of the halogenbenzene compound.

Through the step of preparing the styrene compound represented by Formula 6, the styrene compound can be obtained in a high yield of 90% or more, preferably 94% or more.

In the step (1-1-2) of preparing a compound represented by the following Formula 3, the amidation reaction is good to be carried out under 50 ℃ ~ 100 ℃, preferably under 70 ℃ ~ 90 ℃, less than 50 ℃ When carried out at, the yield of the aminocarbonyl styrene compound, which is a reaction product, may be lowered, and if it exceeds 100°C, there may be a problem that by-products are generated, so it is preferable to perform it within the above temperature range.

In a preferred embodiment of the present invention, the styrene mixture comprises the styrene compound represented by Formula 6, the primary amine, and the reaction catalyst in a molar ratio of 1: 2 to 3: 2 to 2.5, preferably 1: 2 to 2.5 : It can be included in a molar ratio of 2 to 2.3.

Here, if the amount of the primary amine used is less than 2 molar ratio with respect to 1 molar ratio of the styrene compound represented by Chemical Formula 6, the yield of the aminocarbonyl styrene compound as a reaction product may decrease, and there is no increase in the yield even when used in excess of 3 molar ratio. However, since unreacted residues increase, it is recommended to use within the above range.

Meanwhile, in the present invention, prior to the step of preparing the styrene compound represented by Formula 6, a Fischer ester reaction of a compound represented by Formula 4 and an alcohol having 1 to 10 carbon atoms was carried out. Preparing a halogenbenzene compound; may further include. At this time, the yield of the halogenbenzene compound is very high, 95% or more, preferably 98% or more.

[Formula 4]

In Formula 4, X is -F, -Br or -Cl, preferably -Br.

In addition, the manufacturing method of the present invention described above may further include washing and filtering.

Through the above preparation step, the final product, the compound represented by Chemical Formula 3 (aminocarbonylstyrene compound), can be obtained in a yield of 90% or more, preferably in a high yield of 92%.

In addition, the aminocarbonyl styrene compound represented by Formula 3 of the present invention can be prepared with high productivity through other methods as follows in addition to the method described above, and the aminocarbonyl styrene compound of the present invention is as shown in Scheme 3 below. It can be manufactured through a process.

[Scheme 3]

In Formula 4, X is -F, -Br, or -Cl, preferably -Br, and in Formula 3-1, R ² is the same as R ^{2 in} Formula 3 above. In addition, R ² in Formula 3, Formula 7 and Formula 8 is the same as described above.

If the step (1) of preparing the aminocarbonylstyrene compound represented by Formula 3 according to Scheme 3 will be described in detail, the compound represented by Formula 4 below, SOCl ₂ , pyridine, the following Formula 7 or Formula 8 The primary amine, DMAP (4-Dimethylaminopyridine), and methylene chloride are mixed and then subjected to an amidation reaction at 70° C. to 90° C. to prepare a halogenbenzene compound represented by Formula 3-1 below (1 -2-1); And performing a Suzuki coupling reaction with the halogen benzene compound at 60°C to 100°C to prepare a compound represented by the following Chemical Formula 3 (1-2-2); through a process including Aminocarbonylstyrene can be prepared.

In the step (1-2-1) of preparing the halogenbenzene compound represented by Chemical Formula 3-1, a single halogenbenzene compound represented by Chemical Formula 3-1 is obtained by performing an amidation reaction in one step as described above in terms of productivity improvement. It can be prepared by a process, and further, by reacting a compound represented by the following formula 1 with SOCl ₂ to replace the -OH group of the carboxylic acid of the compound represented by formula 4 with -Cl, the reaction product thereof is pyridine, the following formula 7 Alternatively, a primary amine represented by Formula 8, DMAP (4-Dimethylaminopyridine), and methylene chloride were mixed, and then an amidation reaction was performed at 70° C. to 90° C. to prepare a halogenbenzene compound represented by the following Formula 3-1. By doing so, the yield can also be improved a little more.

In the step (1-2-1) of preparing a halogenbenzene compound represented by Formula 3-1, the compound represented by Formula 4, SOCl ₂ , primary amine, DMAP, and methylene chloride are 1: 8 to 10: 2.5 to 3.5: 0.01 to 0.1: 3.5 to 5 molar ratio, preferably 1: 8.5 to 9.5: 2.8 to 3.2: 0.02 to 0.5: 4 to 4.5 molar ratio.

Here, when SOCl ₂ is less than 8 molar ratio with respect to 1 molar ratio of the compound represented by Chemical Formula 4, there may be a problem of inferior reactivity. It is good to do.

And, with respect to the 1 molar ratio of the compound represented by Chemical Formula 4, if the primary amine is less than 2.5 molar ratio, the yield of the halogenbenzene compound represented by Chemical Formula 3-1 may decrease, and even if it is used in excess of 3.5 molar ratio, there is no increase in the yield. It is economical.

In addition, as the DMAP serves as a catalyst in the present invention, there may be a problem of lengthening the reaction time when used in a molar ratio of less than 0.01 molar ratio with respect to 1 molar ratio of the compound represented by Formula 4, and even if used in excess of 0.1 molar ratio, the yield is increased. Therefore, it is recommended to use within the above range.

The amidation reaction is preferably carried out under 50°C to 100°C, preferably 70°C to 90°C. If it is carried out at less than 50°C, the yield of the halogenbenzene compound represented by Formula 3-1 as the reaction product may decrease. There is no increase in yield even if it is used in excess of 100°C, so it is good to perform it within the above temperature range.

In the following step (1-2-2) of preparing a compound represented by Formula 3, the compound represented by Formula 3 is a halogenbenzene compound represented by Formula 3-1, vinyl borate, palladium (Pd ) A catalyst, cesium carbonate (Cs ₂ CO ₃ ) and potassium carbonate (K ₂ CO ₃ ) selected from at least one salt (base) and a polar solvent of a halogen benzene mixture in a 60 ℃ ~ 100 ℃ atmosphere under the Suzuki coupling reaction It can be manufactured.

Here, the Suzuki coupling reaction is good to be carried out under 60 ℃ ~ 100 ℃, preferably under 70 ℃ ~ 90 ℃, more preferably under 75 ℃ ~ 85 ℃, the reaction yield will fall when performed at less than 60 ℃ In addition, even if it is used in excess of 100°C, there is no increase in yield, so it is preferable to perform it within the above temperature range.

The halogen-benzene mixture is 1 selected from the halogenbenzene compound represented by Formula 3-1, vinyl borate, palladium (Pd) catalyst, cesium carbonate (Cs ₂ CO ₃ ) and potassium carbonate (K ₂ CO ₃ ). 1: 1.5 ~ 3: 0.05 ~ 0.2: 2.5 ~ 4: 3 ~ 6 molar ratio, preferably 1: 1.5 ~ 2.5: 0.08 ~ 0.15: 3 ~ 5 molar ratio of more than a kind of salt (base) and a polar solvent It can be characterized.

Here, if the molar ratio of the halogenbenzene compound and the vinyl borate is less than 1: 1.5, the yield of the styrene compound may decrease, and even if the molar ratio of the vinyl borate exceeds 1: 3, there is no effect of increasing the yield, so that the molar ratio within the above range is used. It is good.

In addition, when the molar ratio of the halogenbenzene compound and the palladium catalyst is less than 1:0.05, the reaction temperature proposed by the present invention must be increased, and in this case, there may be a problem of lowering productivity, and the palladium catalyst is used in a 1:0.2 molar ratio. Even if it is used in excess, it is uneconomical because there is no further effect of increasing the yield.

In addition, the cesium carbonate (Cs ₂ CO ₃ ) and/or potassium carbonate (K ₂ CO ₃ ) serves as a base in the present invention, and when the molar ratio of the halogenbenzene compound and the salt is less than 1: 2.5, There may be a problem of this dropping, and if it is used in excess of 1:4, there is no increase in the yield, so it is better to perform it within the above temperature range.

In addition, the solvent is a polar solvent containing at least one selected from tetrahydrofuran (THF), water (H ₂ O), dimethylformamide (DMF), toluene and isopropyl alcohol (i-PrOH) Can be used, and it is preferable from the viewpoint of a smooth reaction to use in a 3 to 6 molar ratio with respect to 1 mol of the halogenbenzene compound.

The manufacturing method of the present invention described above may further include washing and filtering.

Through the above preparation step, the final product, the compound represented by Chemical Formula 3 (aminocarbonylstyrene compound), can be obtained in a yield of 90% or more, preferably in a high yield of 92%.

Next, a step (2) of radical polymerization of aminocarbonyl styrene represented by Chemical Formula 3 under a radical initiator will be described.

The radical polymerization may be carried out in a nitrogen atmosphere at 50°C to 100°C with a radical initiator of the aminocarbonyl styrene represented by Formula 3 above. And the radical initiator may be a general radical initiator used in the art, preferably AIBN (Azobisisobutyronitrile), benzoyl peroxide, and a radical initiator containing at least one selected from Irgacure 651, Irgacure 907, Irgacure 184. I can.

After preparing the compound represented by Chemical Formula 1 by the method described above, the polarizing film of the present invention prepared using a polarizing film composition containing the same, the polarizing film was measured according to the spectrophotometer (Minolta, CM 3500d) method. At the time, the transmittance is 42% to 50%, and when measured based on the retardation film optical material inspection equipment, the polarization degree is 92 to 99%, preferably the transmittance is 43% to 49% and the polarization degree is 94% to 99%. It can have very good transparency and polarization.

In addition, the polarizing film of the present invention has a glass transition temperature (Tg) of 200°C to 350°C, preferably 220°C to 300°C, and may exhibit excellent polarization characteristics when extruded at high temperature. In addition, since a side chain liquid crystalline polymer is used, it is effective to increase the degree of orientation by adjusting to an orientation structure of a nematic or smectic structure.

Such, the polarizing film of the present invention can be applied in various forms, for example, a dye-based polarizing film, an iodine-based polarizing film, a retardation polarizing film, a transflective polarizing film, a highly reflective transflective film, a surface anti-reflective film, LC It can be applied and used as a film such as a (Liquid crystal) film or a reflective polarizing film.

Hereinafter, the present invention will be described in more detail based on examples. However, the scope of the present invention is not limited by the following examples.

[ Example ]

Preparation example One : Of aminocarbonylstyrene Produce

(1) 2- Bromo Of dimethyl terephthalate Produce

2-Bromo dimethyl terephthalic acid (204 mmol), methanol (MeOH) 0.4M and sulfuric acid (H ₂ SO ₄ ) were added to and mixed in a round flask, followed by refluxing for 5 hours.

Next, the reaction solution was filtered and washed to obtain a reaction product in a yield of 98%, and the reaction product was 2-bromo dimethyl terephthalate represented by the following formula (9) through ¹ H-NMR measurement. It was confirmed, and the results are shown below.

¹ H NMR (400 MHz , CDCl ₃ , δ, ppm ,): 3.97 (d, 6H, -OCH3), 7.83 (d, 1H, Ar-H), 8.02 (d, 1H, Ar-H), 8.33 ( s, 1H, Ar-H).

[Formula 9]

(2) 2-vinyl Of dimethyl terephthalate Produce

In a round flask, the 2-bromo dimethyl terephthalate 28.4 mmol, vinyl borate 56.8 mmol, Pd catalyst (Pd cat) 2.84 mmol, cesium carbonate (Cs ₂ CO ₃ ) 85.2 mmol and dimethylformamide (DMF ) 0.1M was added and stirred for mixing, and then reacted at 80°C for 6 hours, and the reaction solution was filtered and washed to obtain a reaction product in 95% yield.

^{Through 1} H-NMR measurement, it was confirmed that the reaction product was 2-Vinyl dimethyl terephthalate represented by the following Chemical Formula 9-1, and the results are shown below.

¹ H NMR (400 MHz , CDCl ₃ , δ, ppm ,): 3.97 (d, 6H, -OCH ₃ ), 5.44 (d, 1H, =CH ₂ ), 5.79 (d, 1H, =CH ₂ ), 6.92 (q, 1H, -CH=), 7.92-7.99 (m, 2H, Ar-H), 8.27 (s, 1H, Ar-H).

[Chemical Formula 9-1]

(3) 2,5-bis[(4- Methoxyphenyl ) Aminocarbonyl ]Production of styrene

The 2-vinyldimethylterephthalate 10mmol, trimethylaluminuim 22.0mmol, p-anisidine 22.0mmol and toluene 1.0M were added to a round flask, mixed, and then refluxed at 80°C for 6 hours. Then, the reaction solution was filtered and washed to obtain a reaction product in 92.7% yield.

^{1 Through} H-NMR and C NMR measurement, the reaction product is 2,5-bis[(4-methoxyphenyl)aminocarbonyl]styrene (2,5-Bis[(4-methoxyphenyl) represented by the following formula 9-2. ) aminocarbonyl] styrene), and the results are shown below.

¹ H NMR (400 MHz , DMSO - d6 , δ, ppm ,): 3.75 (d, 6H, -OCH ₃ ), 5.43 (d, 1H,=CH ₂ ), 5.97 (d, 1H, =CH ₂ ), 6.92(d, 4H, Ar-H), 7.01(q, 1H,-CH=), 7.59~7.70(m, 5H, Ar-H), 7.94(d, 1H, Ar-H), 8.25(s, 1H, Ar-H), 10.15 (s, 1H, -NH-), 10.21 (s, 1H, -NH-). MS (EI): m/z 402.

C NMR ( Calcd for C ₂₄ H ₂₂ N ₂ O ₄ ): C, 71.63; H, 5.51; N, 6.96. Found: C, 71.08; H, 5.45; N, 6.75.

[Chemical Formula 9-2]

Preparation example 2 : Of aminocarbonylstyrene Produce

(1) 2- Bromo - Of bis(4-methoxyphenyl)terephthalamide Produce

2-Bromo dimethyl terephthalic acid (2-Bromo terephthalic acid) 26 mmol, thionyl chloride (thionyl chloride, SOCl ₂ ) 0.25 M was added to a round flask, followed by mixing at 50 ℃ and reacted for 6 hours. Next, 130 mmol of pyridine, 1.3 mmol of 4-Dimethylaminopyridine (DMAP), 78 mmol of p-anisidine, and 0.1 M of methylene chloride were added thereto, followed by stirring at 50° C. and 6 hours. During the amidation reaction was carried out. Next, the reaction solution was filtered and washed to obtain a reaction product in a yield of 95.3%.

¹ H-NMR measurement confirmed that the reaction product was 2-bromo-bis (4-methoxyphenyl) terephthalamide (2-Bromo-bis (4-methoxyphenyl) terephthalamide) represented by the following formula 9-3, The results are shown below and in FIG. 4.

¹ H NMR (400 MHz , DMSO - d6 , δ, ppm ,): 3.74 (d, 6H, -OCH ₃ ), 6.92 (d, 4H, Ar-H), 7.61 to 7.70 (m, 5H, Ar-H ), 8.03 (d, 1H, Ar-H), 8.26 (s, 1H, Ar-H), 10.15 (s, 1H, -NH-), 10.21 (s, 1H, -NH-).

[Formula 9-3]

(2) 2,5-bis[(4- Methoxyphenyl ) Aminocarbonyl ]Production of styrene

In a round flask, the 2-bromo-bis (4-methoxyphenyl) terephthalamide 28.4 mmol, vinyl borate 56.8 mmol, Pd catalyst (Pd cat.) 2.84 mmol, cesium carbonate (Cs ₂ CO ₃ ) 85.2 After adding and stirring 0.1M of mmol and dimethylformamide (DMF) and mixing, the mixture was reacted at 80° C. for 6 hours, and the reaction solution was filtered and washed to obtain a reaction product in a yield of 95.1%.

^{Through 1} H-NMR and C NMR measurement, it was confirmed that the reaction product was 2,5-bis[(4-methoxyphenyl)aminocarbonyl]styrene represented by the following formula 9-2, and the results are shown below. .

¹ H NMR (400 MHz , DMSO - d6 , δ, ppm ,): 3.75 (d, 6H, -OCH ₃ ), 5.43 (d, 1H,=CH ₂ ), 5.97 (d, 1H, =CH ₂ ), 6.92(d, 4H, Ar-H), 7.01(q, 1H,-CH=),7.59~7.70(m, 5H, Ar-H), 7.94(d, 1H, Ar-H), 8.25(s, 1H, Ar-H), 10.15 (s, 1H, -NH-), 10.21 (s, 1H, -NH-). MS (EI): m/z 402.

C NMR ( Calcd for C ₂₄ H ₂₂ N ₂ O ₄ ): C, 71.63; H, 5.51; N, 6.96. Found: C, 71.08; H, 5.45; N, 6.75.

[Chemical Formula 9-2]

Preparation example 3: Of aminocarbonylstyrene Produce

(1) 2- Bromo - Of bis(4-methoxyphenyl)terephthalamide Produce

A halogenbenzene compound was prepared in the same manner as in (1) of Preparation Example 2, but 2-bromo-bis(3-methoxyphenyl) represented by the following 9-4 using m-assidine instead of p-anisidine. ) Terephthalamide (2-Bromo-bis(3-methoxyphenyl) terephthalamide) was prepared (yield 93.5%), and the NMR measurement results are shown below.

¹ H NMR (400 MHz , DMSO - d6 , δ, ppm ,): 3.83 (d, 6H, -OCH ₃ ), 7.36 (s, 2H, Ar-H), 6.73 to 7.40 (m, 6H, Ar-H ), 8.10 (d, 1H, Ar-H), 8.15 (s, 1H, Ar-H), 8.40 (s, 1H, -Ar-H), 9.15 (s, 1H, -NH-).

[Formula 9-4]

(2) 2,5-bis[(3- Methoxyphenyl ) Aminocarbonyl ]Production of styrene

An aminocarbonylstyrene compound was prepared in the same manner as in (2) of Preparation Example 2, but instead of 2-bromo-bis(4-methoxyphenyl)terephthalamide, the 2-bromo-bis(3-methoxyphenyl) ) Using terephthalamide, 2,5-bis[(3-methoxyphenyl)aminocarbonyl]styrene represented by the following 9-5 was prepared (yield 95.9%), and the NMR measurement results are shown below.

¹ H NMR (400 MHz , DMSO - d6 , δ, ppm ,): 3.74 (d, 6H, -OCH ₃ ), 5.41 (d, 1H, CH ₂ =CH-), 6.07 (d, 1H, CH ₂ = CH-), 6.14 (m, 2H, Ar-H), 6.60 (m, 2H, Ar-H), 7.00 (s, 1H, CH ₂ =CH-), 7.21~7.29 (m, 5H, Ar-H ), 7.48 (d, 1H, Ar-H), 7.95 (d, 1H, Ar-H), 8.29 (s, 1H, -Ar-H), 10.15 (s, 2H, -NH-).

[Chemical Formula 9-5]

Preparation example 4 to 8 and Preparation Comparative Example One

An aminocarbonylstyrene compound was prepared in the same manner as in Preparation Example 1, but Preparation Examples 4 to 8 and Comparative Preparation Example 1 were carried out by preparing compounds as shown in Table 1 below.

division yield division Chemical formula R ⁵ Preparation Example 1 Formula 9-6 -OCH ₃ 92.7% Preparation Example 2 Formula 9-6 -OCH ₃ 95.1% Preparation Example 3 Formula 9-7 -OCH ₃ 95.9% Preparation Example 4 Formula 9-6 -OC ₄ H ₉ 94.3% Preparation Example 5 Formula 9-6 -OC ₈ H ₁₇ 93.8% Preparation Example 6 Formula 9-6 -OC ₁₂ H ₂₅ 90.5% Preparation Example 7 Formula 9-6 -CN 94.8% Preparation Example 8 Formula 9-7 -CN 96.2% Comparative Preparation Example 1 Formula 9-7 -OC ₁₈ H ₃₇ 87.3%

[화학식 9-7]

[Formula 9-6]

[Chemical Formula 9-7]

Example 1: Preparation of polarizing film

(One)The aminocarbonyl styrene prepared in Preparation Example 1, 2,5-bis[(4-methoxyphenyl)aminocarbonyl]styrene, was reacted with 25M AIBN (Azobisisobutyronitrile) 10 mol%, 75° C. under nitrogen conditions for 48 hours. An amideside chain liquid crystalline polymer (SC-LCP) represented by Formula 1-1 was prepared (yield 93.2%).

[Formula 1-1]

In Formula 1-1, R ¹ is -0CH ₃ and n is a rational number that satisfies the weight average molecular weight of 137,500.

(2) Next, with respect to 100 parts by weight of polyethersulfone (PES) as a polymer resin, 4 parts by weight of a polarizing dichroic dye, which is SC-LCP represented by Formula 1-1, was mixed to prepare a mixture.

Next, after the mixture was extruded through a T-die, the extruded molding was stretched at a stretching temperature of 240° C. at 5 times the stretching ratio to prepare a polarizing film having an average thickness of 60 μm.

Example 2

(1) 2,5-bis[(3-methoxyphenyl)aminocarbonyl]styrene prepared in Preparation Example 3 was reacted with 25M AIBN (Azobisisobutyronitrile) 10 mol%, 75° C. under nitrogen conditions for 48 hours Thus, an amideside chain liquid crystalline polymer represented by the following Formula 1-2 was prepared (yield 92.5%), and the NMR measurement results are shown below.

¹ H NMR (400 MHz , DMSO - d6 , δ, ppm ,): 5.41 (d, 1H, CH ₂ =CH-), 6.07 (d, 1H, CH2=CH-), 6.14 (m, 2H, Ar- H), 6.60 (m, 2H, Ar-H), 7.00 (s, 1H, CH ₂ =CH-), 7.21 to 7.29 (m, 5H, Ar-H), 7.48 (d, 1H, Ar-H) , 7.95 (d, 1H, Ar-H), 8.29 (s, 1H, -Ar-H), 10.15 (s, 2H, -NH-).

[Formula 1-2]

In Formula 1-2, R ⁵ is -0CH ₃ and n is a rational number satisfying a weight average molecular weight of 125,680.

(2) Next, a polarizing film was prepared in the same manner as in Example 1, but as a polarizing dichroic dye, a polarizing film was prepared using a liquid crystalline polymer with an amide side chain represented by the following Formula 1-2.

Example 3 to 7 and Comparative example One

(1) As shown in Table 2, SC-LCP was prepared in the same manner as in Example 1, except that Preparation Examples 4 to 8 and Comparative Preparation Example 1 were used instead of Preparation Example 1.

division yield Chemical formula Example 1 Formula 1-1 -OCH ₃ 93.2% Example 2 Formula 1-2 -OCH ₃ 92.5% Example 3 Formula 1-1 -OC ₄ H ₉ 92.1% Example 4 Formula 1-1 -OC ₈ H ₁₇ 91.5% Example 5 Formula 1-1 -OC ₁₂ H ₂₅ 90.3% Example 6 Formula 1-1 -CN 94.0% Example 7 Formula 1-2 -CN 93.1% Comparative Example 1 Formula 1-1 -OC ₁₈ H ₃₇ 85.2%

[화학식 1-2]

[Formula 1-1]

[Formula 1-2]

(2) Next, using the SC-LCP prepared in Examples 3 to 7 and Comparative Example 1 as a polarizing dichroic dye, polarizing films were each prepared in the same manner as in Example 1.

Experimental example 1: physical property measurement evaluation

Glass transition temperature (Tg), thermal decomposition temperature (Td), transmittance (%), and polarization degree (%) of the polarizing films prepared in Examples 1 to 7 and Comparative Example 1 were measured as follows, and the results were It is shown in Table 3 below.

(One) Thermal property evaluation

Evaluation was performed by measuring 5% weight loss (Td's) through TGA (thermogravimetric analysis) measurement and glass transition temperature (Tg) through differential scanning calorimeter (DSC), and DSC analysis conditions were 7 mg sample weight and scan speed. It was 10°C/min.

And, the Tg measurement graph for the polarizing film of Example 6 is shown in FIG. 1, and it can be seen that the glass transition temperature is 294°C, which is very high.

(2) Transmittance measurement method

The transmittance of the polarizing film was measured using a spectrophotometer (Minolta, CM 3500d).

(3) How to measure the degree of polarization

The polarization degree of the polarizing film was measured using a retardation film optical material inspection equipment.

(4) Polarization structure measurement method

Using a polarizing microscope (Motic, BA300pol), the polarization structure of nematic or smectic structure was measured.

division Glass transition temperature
(Tg, ℃) Pyrolysis temperature
(Td, ℃) Polarization structure
(S/N) Example 1 245 360 S Example 2 232 347 S Example 3 264 384 N Example 4 256 373 N Example 5 250 366 N Example 6 294 396 S Example 7 278 387 S Comparative Example 1 263 371 N S:smetic structure, N:nematic structure

Looking at the experimental results in Table 3, it was confirmed that the polarizing film of the present invention not only has excellent thermal properties, but also that the liquid crystal polymer, which is a polyethylene (PE)-based side chain, has nematic or smectic structure alignment. In particular, looking at FIG. 2 in which the polarization structure of Example 1 is measured, it can be confirmed that it has a smectic structure through the measurement with a polarization microscope.

Manufacturing example 1: Preparation of polarizing film

Using the amideside chain liquid crystalline polymer (SC-LCP) represented by Chemical Formula 1-1 prepared in (1) of Example 1, a polarizing film was prepared in the following manner.

Based on 100 parts by weight of polyethersulfone (PES) as a polymer resin, as a polarizing dichroic dye, 2 parts by weight of SC-LCP represented by the following formula 1-1 and as a dichroic auxiliary dye, the following formulas 10-1 and the following A mixture was prepared by mixing 3 parts by weight of the dichroic auxiliary dye represented by Formula 17-1 at a weight ratio of 1:1.

Next, after the mixture was extruded through a T-die, the extruded molding was stretched at a stretching temperature of 240° C. at 5 times the stretching ratio to prepare a polarizing film having an average thickness of 50 μm.

[Formula 10-1]

In Formula 10-1, R ¹ is a methyl group.

[Chemical Formula 17-1]

In Formula 17-1, R ¹ Is an n-butyl group.

Manufacturing example 2 ~ Manufacturing example 10

(1) A polarizing film was prepared in the same manner as in Preparation Example 1, but as a dichroic auxiliary dye, 3 parts by weight of a mixture of the following Formula 11-1 and Formula 17-1 in a weight ratio of 1:1 was used. Preparation Example 2 was carried out.

(2) In addition, a polarizing film was prepared in the same manner as in Preparation Example 1, but as a dichroic auxiliary dye, the following Formula 11-1, the following Formula 12, and the Formula 17-1 were mixed in a weight ratio of 1:1:1 Preparation Example 3 was carried out using a mixture of 2 parts by weight.

(3) In addition, a polarizing film was prepared in the same manner as in Preparation Example 1, but prepared using a mixture of 2 parts by weight of the following formula 11-1 and the following formula 12 in a weight ratio of 1:1 as a dichroic auxiliary dye Example 4 was carried out.

(4) In addition, polyethylene terephthalate (PET) was used as the polymer resin, and a polarizing film was prepared in the same manner as in Preparation Example 1, but as a dichroic auxiliary dye, the following Formula 14-1 and the following Formula 16 were 1: Preparation Example 5 was carried out using a mixture of 2 parts by weight mixed at a weight ratio of 1.

(5) In addition, a polarizing film was prepared in the same manner as in Preparation Example 1, but as a dichroic auxiliary dye, a mixture of 2 parts by weight of the following Formula 14-1 and Formula 17-1 in a weight ratio of 1:1 was used. Then, Preparation Example 6 was carried out.

(6) In addition, a polarizing film was prepared in the same manner as in Preparation Example 1, but polyethylene terephthalate (PET) was used as the polymer resin, and the following Formula 13-1 and the following Formula 19 were 1:1 as a dichroic auxiliary dye. Preparation Example 7 was carried out using a mixture of 2 parts by weight mixed at a weight ratio of the furnace.

(7) In addition, a polarizing film was prepared in the same manner as in Preparation Example 1, but using a mixture of 2 parts by weight of the formula 10-1 and the following formula 11-1 in a weight ratio of 1:1 as a dichroic auxiliary dye Preparation Example 8 was carried out.

(8) In addition, polyethylene terephthalate (PET) was used as a polymer resin, and a polarizing film was prepared in the same manner as in Preparation Example 1, but the above formula 10-1 and the following formula 18 were 1:1 as a dichroic auxiliary dye. Preparation Example 9 was carried out using a mixture of 2 parts by weight mixed at a ratio by weight of the furnace.

(9) In addition, a polarizing film was prepared in the same manner as in Preparation Example 1, but as a dichroic auxiliary dye, a mixture of 2 parts by weight of the formula 10-1 and the following formula 14-1 was mixed in a weight ratio of 1:1. Preparation Example 10 was carried out.

[Chemical Formula 11-1]

In Formula 11-1, R ¹ is -SO ₃ H, R ² , R ³ , R ⁴ and R ⁵ are -H, R ⁶ and R ⁹ are a phenyl group, R ⁷ And R ⁸ is -H.

[Formula 12]

[Chemical Formula 13-1]

In Formula 13-1, R ¹ And R ² is an n-butyl group.

[Formula 14-1]

In Formula 14-1, R ¹ And R ² is an n-butyl group.

[Formula 16]

[Chemical Formula 17-1]

In Formula 17-1, R ¹ silver It is an n-butyl group.

[Formula 18]

[Formula 19]

Comparative example One

After purchasing a commercially available PVA-I2 polarizing film, it was stretched and dyed with an iodine solution to prepare a polarizing film. At this time, the iodine solution was prepared including 3 parts by weight based on 100 parts by weight of the polarizing film.

Comparative example 2

It was carried out in the same manner as in Preparation Example 1, but as a dichroic auxiliary dye, the formula 10-1, the formula 12, the formula 14-1, and the formula 17-1 were 6 in a weight ratio of 1:1:1:1 Comparative Example 2 was carried out using parts by weight.

Comparative example 3

Comparative Example 3 was carried out using polyethylene terephthalate (PET) as a polymer resin, and 8 parts by weight of a mixture of Formula 12 and Formula 17-1 in a weight ratio of 1:1 as a dichroic auxiliary dye. .

Comparative example 4

Comparative Example 4 was carried out using polyethylene terephthalate (PET) as a polymer resin, and 8 parts by weight of a mixture of Formula 11-1 and Formula 17-1 in a weight ratio of 1:1.

Experimental example 2: Measurement of transmittance and polarization

The transmittance and polarization degree of the polarizing film prepared in Preparation Example were measured in the same manner as in Experimental Example 1, and the results are shown in Table 4 below.

division Transmittance
(%) Polarization degree
(%) Manufacturing Example 1 46.3 98.0 Manufacturing Example 2 42.3 96.3 Manufacturing Example 3 44.1 97.3 Manufacturing Example 4 42.9 95.1 Manufacturing Example 5 42.4 96.7 Manufacturing Example 6 42.2 95.4 Manufacturing Example 7 46.9 97.2 Manufacturing Example 8 47.1 94.9 Manufacturing Example 9 46.0 95.3 Manufacturing Example 10 43.7 97.9 Comparative Example 1 42.1 94.3 Comparative Example 2 36.0 91.2 Comparative Example 3 37.8 89.4 Comparative Example 4 39.0 92.7

Looking at the experimental results in Table 3, it can be seen that in the case of the polarizing film of the present invention of Preparation Examples 1 to 10, the transmittance is about 42% to 48%, and the polarization degree has very good transmittance and polarization degree of about 94.5 to 99%. there was.

In addition, when comparing the experimental results of Table 3 with the measurement results of transmittance and polarization of Example 1 of Table 2, by additionally using a dichroic auxiliary dye, the nematic or spicy of the liquid crystal polymer, which is a PE-based side, It was confirmed that the orientation of the metic structure has the effect of increasing the transmittance and polarization degree together with the auxiliary dye.

However, Comparative Example 1, which is a conventional polarizing film, had a transmittance of 42.1% and a polarization degree of 94.3%, which was excellent, but the transmittance and polarization degree were somewhat insufficient than those of Preparation Examples 1 to 10.

In addition, in the case of Comparative Preparation Example 2 to Comparative Preparation Example 4 in which the dichroic auxiliary dye was used in excess of 5 parts by weight, the transmittance was greatly decreased, and the polarization degree was also rather poor as compared to Preparation Examples 1 to 10.

Through the above Examples and Experimental Examples, it was confirmed that a polarizing film prepared with a polarizing dichroic dye containing an amide side chain liquid crystalline polymer (SC-LCP) has excellent transmittance and polarization.

Claims (15)

delete Polymer resin;
A polarizing dichroic dye containing a compound represented by the following formula (2) or a compound represented by the following formula (2-1); And
Including; a dichroic auxiliary dye containing at least one selected from the compounds represented by the following Formulas 10 to 19,
Including 1 to 10 parts by weight of the polarizing dichroic dye based on 100 parts by weight of the polymer resin,
Polarizing film, characterized in that the transmittance is 42% to 50%;
[Formula 2]

In Formula 2, R ¹ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, an alkoxyl group having 1 to 15 carbon atoms, -CN or -(Ph-CN), and n is a weight average molecular weight of 30,000 to 210,000. Is a rational number,
[Formula 2-1]

In Formula 2-1, R ¹ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, an alkoxyl group having 1 to 15 carbon atoms, -CN or -(Ph-CN), and n is a weight average molecular weight of 30,000 to 210,000 Is a rational number that satisfies
[Formula 10]

In Formula 10, R ¹ is a C 1 alkyl group,
[Formula 11]

In Formula 11, R ¹ is -H, a C1 to C5 alkyl group, -SO ₃ H, -CHO, a C1 to C5 alkoxy or aryl group, and R ² , R ³ , R ⁴ and R ⁵ are each independently As being, -H, C1 ~ C5 alkyl group or isopropyl group, R ⁶ and R ⁹ are each independently, C1 ~ C5 alkyl group, phenyl group, halogen group or isopropyl group, R ⁷ and R ⁸ are each As independent, it is a hydrogen atom or a C1 ~ C5 alkyl group,
[Formula 12]

[Formula 13]

In Formula 13, R ¹ and R ² are each independently a C1 ~ C5 alkyl group or -SO ₃ H,
[Formula 14]

In Formula 14, R ¹ and R ² are each independently a C1 ~ C5 alkyl group or -SO ₃ H,
[Formula 15]

In Formula 15, R ¹ is a C1 ~ C5 alkyl group or -SO ₃ H,
[Formula 16]

[Formula 17]

In Formula 17, R ¹ is a C1 to C5 alkyl group or -SO ₃ H.
[Formula 18]

[Formula 19]

The polarizing film of claim 2, wherein the polarizing dichroic dye has a glass transition temperature (Tg) of 200°C to 350°C.
The method of claim 2, wherein the polymer resin is polycarbonate (PC), polyethylene terephthalate (PET), cycloolefin copolymer (COC), cycloolefin polymer (COP), triacetylcellulose (TAC), polyethersulfone (PES). ) And a polarizing film comprising at least one selected from polyetherimide (PEI).
delete delete The polarizing film of claim 2, wherein the polarizing film has an average thickness of 10 μm to 100 μm.
The polarizing film according to claim 2, wherein the polarizing film further comprises a transparent protective film on one side or both sides.
The method of claim 8, wherein the transparent protective film comprises at least one selected from polycarbonate, polyethylene terephthalate, cycloolefin copolymer, cycloolefin polymer, triacetylcellulose, polyethersulfone, and polyetherimide. Polarizing film.
The polarizing film according to any one of claims 2 to 4 and 7, wherein the transmittance is 42% to 50%, and the polarization degree is 92 to 99%.
The method of claim 10, wherein the polarizing film is a dye-based polarizing film, an iodine-based polarizing film, a retardation polarizing film, a transflective polarizing film, a highly reflective transflective film, a surface antireflection film, a liquid crystal (LC) film or a reflective polarizing film Polarizing film, characterized in that the film is one type selected from the film.
delete Preparing a mixed solution by mixing a polymer resin and a polarizing dichroic dye containing a compound represented by the following Formula 2 or a compound represented by the following Formula 2-1;
An extrusion step of extruding the mixed solution into a film; And
Including; a stretching step of stretching the extruded film,
The compound represented by Formula 2 or the compound represented by Formula 2-1
Preparing a compound represented by the following Chemical Formula 3; And
A method for producing a polarizing film, characterized in that it is prepared by performing a process including; radical polymerization of a compound represented by the following formula (3) under a radical initiator;
[Formula 2]

In Formula 2, R ¹ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, an alkoxyl group having 1 to 15 carbon atoms, -CN or -(Ph-CN), and n is a weight average molecular weight of 30,000 to 210,000. Is a rational number,
[Formula 2-1]

In Formula 2-1, R ¹ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, an alkoxyl group having 1 to 15 carbon atoms, -CN or -(Ph-CN), and n is a weight average molecular weight of 30,000 to 210,000 Is a rational number that satisfies
[Formula 3]

In Formula 3, R ² is

or

And R ⁴ is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN).
The method of claim 13, wherein the compound represented by Formula 3 is
A step of preparing a styrene compound represented by the following Formula 6 by performing a Suzuki coupling reaction on a halogenbenzene mixture containing a halogenbenzene compound represented by the following Formula 5 under 60°C to 100°C; And
Performing an amidation reaction on a styrene mixture containing a styrene compound represented by Formula 6, a primary amine represented by Formula 8 below, a reaction catalyst, and an organic solvent;
A method of manufacturing a polarizing film, characterized in that it is manufactured, including;
[Formula 5]

[Formula 6]

In Formulas 5 and 6, X is F-, Br- or Cl-, and R ⁵ is an alkyl group having 1 to 10 carbon atoms,
[Formula 8]

R ⁴ in Formula 8 is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN).
The method of claim 13, wherein the compound represented by Formula 3 is
A compound represented by the following Formula 4, SOCl ₂ , pyridine, a primary amine represented by the following Formula 8, DMAP (4-Dimethylaminopyridine) and methylene chloride were mixed, and then an amidation reaction was performed at 70° C. to 90° C. Preparing a halogenbenzene compound represented by the following formula 3-1; And
Performing a Suzuki coupling reaction with the halogen benzene compound under 60°C to 100°C;
A method of manufacturing a polarizing film, characterized in that it is manufactured by performing a process including a;
[Formula 3-1]

In Formula 3-1, R ² is

And R ⁴ in Formula 3-1 is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN),
[Formula 4]

In Formula 4, X is -F, -Br or -Cl,
[Formula 8]

R ⁴ in Formula 8 is a phenyl group, an alkylphenyl group, a biphenyl group, an alkylbiphenyl group, -CN or -(Ph-CN).

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