WO2015099377A1 - Composition for forming dye polarizer and dye polarizer - Google Patents

Abstract

The present invention relates to a composition for forming a dye polarizer and the dye polarizer, wherein the composition allows a dye polarizer simultaneously exhibiting excellent polarizability, heat-resistance, and dichroic ratio to be provided. The composition for forming dye polarizer includes: a solid-type anisotropic dye having a particular chemical structure; and an orientation aid having a certain chemical structure.

Description

 【Specification】

 [Name of invention]

 Dye-type polarizer forming composition and dye-type polarizer

 Technical Field

The present invention relates to a composition for forming a dye-type polarizer and a dye-type polarizer, which enables the provision of a dye-type polarizer having both excellent polarization degree, heat resistance and dichroic ratio. ^'

 [Technique to become background of invention]

 BACKGROUND ART Film polarizers, also known as sheet polarizers, are generally optical members capable of polarizing light in a specific direction and are widely used in display elements such as liquid crystal displays. For example, in the liquid crystal display device, a film polarizer is widely used to selectively transmit light in a specific direction among light incident from the backlight and light passing through the liquid crystal layer and to control polarization.

 As a polarizer in the form of a film, a polarizer using a stretched polyvinyl alcohol (PVA) film previously dyed with a dichroic dye is most widely used in the liquid crystal display device and the like.

 By the way, in the case of such a polarizer using the stretched PVA film, it exhibits poor heat resistance and moisture resistance, and optical performance may be degraded due to moisture infiltration or relaxation of the polymer. For this reason, such a polarizer is mainly contained between protective films, such as TAC, and adhere | attaches a liquid crystal display element etc. In addition, an adhesive film for adhering such a polarizer to the liquid crystal display element or the like is required, and such a polarizer may cause a polarizer thickness of about 70 to 150 μηι as a whole.

 Due to the thickness of such a polarizer, poor heat resistance and moisture resistance, it is true that the application of the polarizer using the stretched PVA film has been limited, and thus, a new use or example in which the application of the polarizer has recently been required. For example, Smarter shade

Its application was difficult for applications such as antireflection films for OLEDs.

On the other hand, in order to solve the problem of the polarizer using the stretched PVA film, a dye-type polarizer in the form of a thin film or a film including a dye layer whose main component is an oriented dichroic dye has been proposed and studied. These dye-type polarizers are separate The dichroic dye in the said dye layer is orientated using an orientation layer, and the polarization degree excellent by the dichroic dye thus oriented can be shown.

 However, these dye-type polarizers were also found to exhibit relatively poor heat resistance. For example, when exposed to a conventional dye-type polarizer at a high temperature of about 8 (rc, and tested its heat resistance, it was confirmed that the orientation of the dichroic dye and the polarization degree of the polarizer were greatly decreased. It is expected that the orientation of the dichroic dye in the layer is randomized by thermal energy.To solve this problem, an oriented liquid crystal material (liquid crystalline polymer, etc.) is added to the dye layer as a host. It has been attempted to provide a dye-type polarizer which more stabilizes the orientation of the dichroic dye and exhibits improved heat resistance, but such an attempt has also been found to be unsuccessful and shows better heat resistance, even when exposed to high temperature heat. There is a continuing need for the development of dye-type polarizers that maintain excellent dye layer orientation and high polarization. There. [Contents of the present invention;

 Problem to be solved

 The present invention provides a composition for forming a dye-type polarizer, which enables the provision of a dye-type polarizer having both excellent polarization degree, heat resistance and dichroic ratio.

In addition, the present invention is to provide a dye-type polarizer obtained by using the composition, showing excellent polarization degree, improved heat resistance and dichroic ratio. ^'

 This invention also provides the display element containing the said dye type polarizer.

 [Measures for solving the problem] The present invention is a curable anisotropic dye of the formula (1); And it provides a composition for forming a dye-type polarizer comprising an orientation aid of the formula (2), (3) or their radical polymers:

 [Formula 1]

In Chemical Formula 1, n is an integer of 2 to 5, and the repeating unit structure of-(ArN = N)-repeated two or more times may be the same or different from each other,

At least one of Q, and Q ₂ is a curable unsaturated functional group, and the rest are hydrogen, alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkylester having 1 to 20 carbon atoms, or an amine group,

A _! And A ₂ may be the same as or different from each other, and is substituted or unsubstituted arylene having 6 to 40 carbon atoms, or substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms,

Bj and B ₂ may be the same or different from each other, a simple bond,-(C = 0) 0-,-0 (C = 0)-, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or Unsubstituted arylene having 6 to 40 carbon atoms, substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, substituted or unsubstituted alkylene oxide having 1 to 20 carbon atoms, -0-, -S-, -NR, At least one selected from the group consisting of-and -PR _R is a combined divalent functional group, RP hydrogen or alkyl having 1 to 20 carbon atoms,

 [Formula 2]

Q — ^. _{j - ~~ - =: [s} ' .A Β; ί ~~~~ θ in the formula (2),

At least one of Q ₃ and Q ₄ is a curable unsaturated functional group, the remainder is hydrogen, alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkyl ester having 1 to 20 carbon atoms, -CN, -N0 ₂ , halogen, Or an amine group unsubstituted or substituted with 1 to 2 carbon atoms of 1 to 6 carbon atoms,

A ₃ and A ₄ may be the same as or different from each other, and are substituted or unsubstituted arylene having 6 to 40 carbon atoms, or substituted or unsubstituted hetero arylene having 4 to 30 carbon atoms,

B ₃ and B ₄ may be the same or different from each other, a simple bond,-(C = 0) 0-,-

0 (C = 0)-, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 40 carbon atoms, substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, substituted or An unsubstituted alkylene oxide having 1 to 20 carbon atoms, at least one selected from the group consisting of -0-, -S-, -NR _2-, and PR _2- ; R ₂ is hydrogen or alkyl of 1 to 20 carbon atoms,

 [Formula 3]

Q ₅ -B ₅ -A ₅ -B ₆ -A ₆ -B _8- Q ₆

 In Chemical Formula 2,

At least one of Q ₅ and Q ₆ is a curable bubbling functional group, and the rest are hydrogen alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aryl having 6 to 40 carbon atoms, alkoxy having 1 to 20 carbon atoms, and 1 carbon atom. It is an amine group unsubstituted or substituted with an alkyl ester of 20 to 20, CN, -N0 ₂ , halogen, ^' or alkyl having 1 to 2 carbon atoms,

A ₅ and A ₆ may be the same or different from each other, and are substituted or unsubstituted arylene having 6 to 40 carbon atoms, or substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms,

B ₅ , B ₆ and ^ can be the same or different from each other, and are a simple bond,-(C = 0) 0— _:

-0 (C = 0)-, substituted or unsubstituted C1-C20 alkylene, substituted or unsubstituted C6-C40 arylene, substituted or unsubstituted C4-C30 heteroarylene, substituted Or unsubstituted alkylene oxide having 1 to 20 carbon atoms, -0-, -S-,-

At least one member selected from the group consisting of NR ₃ -and -PR ₃ -is a combined divalent functional group,

R ₃ is hydrogen or alkyl having 1 to 20 carbon atoms. . The present invention also provides a dye-type polarizer comprising a dye layer containing a cured product of the composition for forming a dye-type polarizer.

 In addition, the present invention provides a display device including the dye-type polarizer. 【Effects of the Invention】

The composition for dye-type polarizer formation of the present invention contains a specific curable anisotropic dye and an orientation aid. The curable anisotropic dye may include a curable unsaturated functional group at its end, and may be copolymerized with an orientation aid to form a crosslinked structure by curing after orientation. Therefore, since the orientation of the anisotropic dye and the dye layer can be stabilized by such a crosslinked structure, such an orientation can be prevented from being randomized even when exposed to high temperature heat. In addition, the alignment assistant may exhibit excellent orientation, and may further improve the orientation and dichroic ratio of the dye layer as a component capable of forming a crosslinked structure in combination with the curable anisotropic dye.

 Therefore, by using the composition for forming a dye type polarizer, it is possible to maintain a high degree of orientation and polarization degree of the dye layer even when exposed to high temperature heat, as a result can provide a dye type polarizer exhibiting high polarization degree and more improved heat resistance Will be. In addition, since the alignment aid may serve as a host in the dye layer, and at the same time may further improve the orientation of the anisotropic dye, and can also act as an anisotropic dye by itself, the polarization of the dye-type polarizer is also It can be further improved. Therefore, by using the composition for forming a dye-type polarizer, it is possible to provide a dye-type polarizer having excellent physical properties such as polarization degree, transmittance, heat resistance and dichroic ratio.

 Such a dye type polarizer can replace the polarizer using a stretched PVA film that has been conventionally applied very effectively, and can exhibit excellent characteristics by overcoming the limitations of the existing dye type polarizer.

 [Specific contents to carry out invention]

 Hereinafter, a composition for forming a dye-type polarizer and a dye-type polarizer according to an embodiment of the present invention will be described in detail.

According to one embodiment of the invention, the curable anisotropic dye of the formula · 1; And an alignment aid of the following general formulas (2) and (3) or radical polymers thereof.

 In Chemical Formula 1,

n is an integer of 2 to 5, and the repeating unit structure _of- (A _r N = N) _-repeated two or more times may be the same or different from each other,

And ⁽ at least one of ¾ is a curable unsaturated functional group, the remainder is hydrogen, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkylester or amine group of 1 to 20 carbon atoms, A, and A ₂ may be the same as or different from each other, and are substituted or unsubstituted arylene having 6 to 40 carbon atoms, or substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms,

And B ₂ may be the same as or different from each other, and a simple bond,-(C = 0) 0-, -0 (C = 0)-, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted Substituted arylene having 6 to 40 carbon atoms, substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, substituted or unsubstituted alkylene oxide having 1 to 20 carbon atoms, -0-, -S-, -NR _r And -ΡΙ ^-is a divalent functional group in which at least one selected from the group consisting of, is hydrogen hydrogen or alkyl having 1 to 20 carbon atoms,

 [Formula 2]

상기 화학식 2에서，

In Chemical Formula 2,

At least one of Q ₃ and Q ₄ is a curable unsaturated functional group, the remainder is hydrogen alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkyl ester having 1 to 20 carbon atoms, —CN, —N0 ₂ , halogen, or 1 An amine group unsubstituted or substituted with 2 to 2 carbon atoms alkyl,

A ₃ and A ₄ may be the same as or different from each other, and are substituted or unsubstituted arylene having 6 to 40 carbon atoms, or substituted or unsubstituted hetero arylene having 4 to 30 carbon atoms,

B ₃ and B ₄ may be the same or different from each other, a simple bond,-(C = 0) 0-,-

0 (C = 0)-, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 40 carbon atoms, substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, substituted or Unsubstituted alkylene oxide having 1 to 20 carbon atoms, -0-, -S-,-NR ₂ -and -PR ₂ -is a divalent functional group in combination of at least one selected from the group consisting of, ¾ is hydrogen or Alkyl having 1 to 20 carbon atoms,

 [Formula 3]

Q ₅ -B ₅ -A ₅ -B ₆ -A ₆ -B _8- Q ₆

 In Chemical Formula 2,

At least one of Q ₅ and ¾ is a curable unsaturated functional group, and the other is hydrogen, Alkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 12 carbon atoms, aryl of 6 to 40 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkyl ester of 1 to 20 carbon atoms, -CN, -N0 ₂ , halogen, or 1 to 2 An amine group unsubstituted or substituted with 1 to 6 carbon atoms, and

A ₅ and A ₆ may be the same or different from each other, and are substituted or unsubstituted arylene having 6 to 40 carbon atoms, or substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms,

B ₅ , B ₆ and ¾ may be the same or different from each other, a simple bond,-(C = 0) 0- _: -0 (C = 0)-, substituted or unsubstituted alkylene having 1 to 20 carbon atoms , Substituted or unsubstituted arylene having 6 to 40 carbon atoms, substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, substituted or unsubstituted alkylene oxide having 1 to 20 carbon atoms,-O-, -S-, -At least one member selected from the group consisting of NR ₃ -and -PR ₃ -is a combined divalent functional group,

R ₃ is hydrogen or alkyl having 1 to 20 carbon atoms.

 The composition of the above-described embodiment of the general formula (1) having a structure in which a curable unsaturated functional group is introduced at both ends by irradiation with heat or UV in the structure of a non-curable azo dye applied to a conventional dichroic dye or the like. And a curable anisotropic dye and an orientation aid of the above-mentioned general formulas (2) and (3) or their radical polymers.

 More specifically, the curable anisotropic dye of Chemical Formula 1 has one or more azo groups and (hetero) arylenes connected to each other to have a functional group which can be oriented by the lower alignment layer, and together with the chemically introduced curable unsaturated functional group at the terminal. Has a structure. In addition, the alignment aid in the form of Formula 2 or the radical polymer thereof may also have a chemical structure in which an azo group and a (hetero) arylene are connected to have an oriented functional group, and a curable unsaturated functional group is introduced at an end thereof. In addition, the alignment aid in the form of the formula (3) or the radical polymer thereof may also exhibit excellent orientation including the aromatic group of (hetero) arylene, and may further enhance the orientation of the anisotropic dye and the dye layer including the same. have.

Therefore, when the dye layer of the dye-type polarizer is formed using the composition of one embodiment including these curable anisotropic dyes and an alignment aid, and after the alignment is conducted, irradiation with heat or UV, the oriented anisotropic dye ends and the alignment aid Each contained at the end Unsaturated functional groups can be cured and / or polymerized with each other to form a crosslinked structure. By the formation of such a crosslinked structure, since the orientation of the anisotropic dye and the dye layer can be stabilized, the degree to which the orientation is randomized even when exposed to high temperature heat can be greatly reduced.

 Therefore, by using the composition of this embodiment, it is possible to maintain a high degree of orientation and polarization degree of the dye layer even when exposed to high temperature heat, resulting in a dye-type polarizer exhibiting a high dichroic ratio, polarization degree and improved heat resistance Will be.

 In addition, the alignment aid may act as a host of the curable anisotropic dye in the dye layer, may further improve the orientation of the anisotropic dye, and may also act as an anisotropic dye by itself. Thus, such an orientation aid may further improve the degree of polarization of the dye-type polarizer formed from the composition of one embodiment. Therefore, by using the composition for forming a dye-type polarizer of the embodiment, it is possible to provide a dye-type polarizer having excellent physical properties such as polarization degree, transmittance, heat resistance and dichroic ratio.

 Such a dye type polarizer can replace the polarizer using a stretched PVA film that has been conventionally applied very effectively, and can exhibit excellent characteristics by overcoming the limitations of the existing dye type polarizer.

On the other hand, in each structure of the curable anisotropic dye or the orientation assistant included in the composition of the embodiment, any of the Q, to Q ₆ unsaturated functional groups known to be curable, crosslinked and / or polymerizable by heat or UV light irradiation It may be an unsaturated functional group of, representative examples of such an unsaturated functional group include a (meth) acrylate group, an epoxy group, a vinyl group or any functional group containing these at the terminal. Each of the above to Q ₆ may be independently the same or different unsaturated functional groups from each other, and may be suitably the same (meth) acrylate group or epoxy group. As a result, as appropriately cured to form a crosslinked structure, even when exposed to high temperature heat, it is possible to more stabilize the orientation of the anisotropic dye, the orientation aid and the dye layer including the same, and effectively suppress the disorder of the orientation.

Moreover, in each structure of the said curable anisotropic dye or an orientation aid, The remaining Q _{6 which} are not unsaturated functional groups are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 40 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkyl ester having 1 to 20 carbon atoms, -CN, halogen, or 1 It is appropriate that the amine group or the like is substituted or unsubstituted with alkyl having 2 to 2 carbon atoms.

In addition, the A to ₆ are each independently alkoxy having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms, halogen, -N ⁽ aryl having 6 to 40 carbon atoms unsubstituted or substituted with ¾ or alkyl ester of 1 to 6 carbon atoms Can be Ren.

In the structure of the curable anisotropic dye and the orientation aid, the specific arylene structure of these to A ₆ is included, and as the terminal Qi to Q ₆ is the functional group described above, the anisotropic dye, the orientation aid and the dye layer including the same It can be oriented more effectively by the lower orientation layer etc., and can ensure the excellent orientation of a dye layer, and the outstanding polarization degree of a dye type polarizer.

And, in the structure of the curable anisotropic dye and the orientation aid, as a divalent functional group that serves as a linker for connecting the (saturated) functional group of the terminal to the end and the linking structure of the oriented azo group and (hetero) arylene with each other. Each divalent functional group listed above may be combined, or two or more selected from them may be combined and linked divalent functional groups. In addition, although these to B ₈ may be the same as each other, in consideration of the kind of arylene or terminal functional groups to which such a linking group may be a different divalent functional group of course.

However, in terms of the electron density change or the solubility of the curable anisotropic dye or the orientation aid, the to B ₈ are each independently a simple bond,-(C = 0) 0-,-0 (C = 0)-, Substituted or unsubstituted with alkylene having 1 to 20 carbon atoms, arylene having 6 to 40 carbon atoms, alkylene oxide having 1 to 20 carbon atoms, -0- (alkylene having 1 to 20 carbon atoms)-and alkyl having 1 to 6 carbon atoms. It is appropriate to be a divalent functional group selected from the group consisting of ring amine groups.

And, ^"from the structure of the curable anisotropic dye of the formula (I), wherein n may be an integer or an integer from 2 to 4, from 2 to 5. That is, as the linking structure of the oriented azo group and (hetero) arylene is properly included, the curable anisotropic dye may exhibit excellent orientation, while the orientation of the anisotropic dye is changed by the crosslinked structure of the terminal unsaturated functional group. More effectively stabilized It becomes possible to provide the dye-type polarizer showing the excellent heat resistance. In addition, n is an integer of 2 or more, and two or more repeating unit structures of-(A! -NN)-are repeatedly included and the same unit structures may be repeated and included in anisotropic dye structure, but different from each other-(A Of course, the unit structure of _! -NN)-may be repeatedly included in the anisotropic dye structure.

In addition, in the structure of Formula 1 of the above-mentioned curable anisotropic dye or the structure of an orientation aid or a reactive mesogen described later, that each substituent is "substituted or unsubstituted" is further substituted by not only these substituents themselves but also certain substituents. It also means to be comprehensive. In the present specification, examples of the substituent which may be further substituted with each substituent include —CN, —N0 ₂ , an amine group, an alkylester, halogen, nitrile, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, halo Alkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl or siloxy and the like.

 Specific examples of the curable anisotropic dye of the above-mentioned formula (1) include compounds selected from the group consisting of the following formula la to If, but not limited to these curable anisotropic dyes falling within the scope of the formula (1) It goes without saying that the dye-type polarizer showing excellent polarization degree and heat resistance can be provided.

Formula Id

 [Formula le]

The above-mentioned curable anisotropic dye can be prepared by a method of introducing an unsaturated functional group such as a (meth) acrylate group, an epoxy group or a vinyl group to a terminal of an uncured azo dye having anisotropic or dichroic properties. However, such a manufacturing process may be in accordance with conventional reaction conditions and methods for introducing each functional group according to the type of the unsaturated functional group, and specific reaction conditions and methods are also described in the following examples, and thus, further description thereof will be omitted. Let's do it. In addition, in the composition for forming a dye-type polarizer of one embodiment, the above-mentioned curable anisotropic dye may be used by mixing one to five kinds of dyes to have an appropriate color according to the use. Anisotropic dyes of the general formula (1) are generally rod-like or rod-like similar structure, even if used in combination with each other, the dye layer comprising the same can be easily oriented according to the orientation of the underlying alignment layer, formed from the composition Dye-type polarizer can exhibit more excellent degree of polarization. On the other hand, the composition of one embodiment further comprises an orientation aid in the form of Formula 2, 3 or radical polymer thereof, the specific functional group definition in the structure of Formula 2 or 3 (ie, A ₃ to A ₆ , Β ₃ to Β ₈ , and specific examples and definitions of Q ₃ to ¾) have been described together with Chemical Formula 1, and thus, further description thereof will be omitted.

However, the alignment aid is only in the form of the monomer of Formula 2 or 3 In addition, they may be radically polymerized and included as a radical polymer in a form in which terminal unsaturated groups of formula (2) or (3) are linked to each other. Even when included in the form of such a radical polymer, the orientation of the curable anisotropic dye described above, the dichroic ratio and polarization degree of the polarizer obtained from the composition of one embodiment can be appropriately improved, and the orientation of the dye layer is more stabilized to provide heat resistance. Can be improved.

 Orientation aids in the form of such radical polymers can be obtained by using a compound of Formula 2 or 3 as a monomer and radically polymerizing it in a conventional manner, for example, about 1000 to 30000, black about 2000 to 15000, or It may have a weight average molecular weight of about 3000 to 10000.

In addition, as shown in the structure of Formula 2 or 3, the alignment aid includes an unsaturated functional group of Q ₃ to Q ₆ at least at one end, so as to properly form a cured and crosslinked structure with the above-described curable anisotropic dye. It can be exposed even if the high temperature heat stability than ^■ the orientation of the anisotropic dye and a dye-containing layer, it effectively suppress the screen orientation is such disorder.

In addition, the alignment aid may include an arylene structure of A ₃ to A ₆ may exhibit excellent orientation, further improves the orientation of the curable anisotropic dye, the dichroic ratio and polarization degree of the polarizer obtained from the composition of the embodiment You can. Moreover, the alignment aid of Formula 2 may include the same type of azo group as the curable anisotropic dye of Formula 1, and may exhibit excellent interaction therewith, thereby further improving the orientation of the anisotropic dye and the dichroic ratio and polarization degree of the polarizer. You can. In addition, by including the specific divalent functional groups of B ₃ to B ₈ described above as linkers, it is possible to appropriately control the electron density change of the orientation aid and the composition of one embodiment.

 Orientation aids of the above-mentioned formulas (II) and (3) or their radical polymers may be prepared according to methods known to those skilled in the art or may be obtained commercially, which may be obtained by conventional methods.

Specific examples of the above-described alignment aid include a compound selected from the group consisting of the following Chemical Formulas 2a to 2d and 3a to 3f, or a radical polymer obtained by using at least one thereof as a monomer, but is not limited thereto. Orienting aids falling within the category of formula (2) or (3) or their radical polymers It can be used without particular limitation, showing excellent dichroic ratio, polarization degree and heat resistance-to provide a dye type polarizer.

 Formula 2a]

화학식 2b]

Formula 2b]

[Formula 2c]

 [Formula 2d]

[Formula 3a]

[3b]

[Formula 3c]

[Formula 3d]

[

한편, 상기 일 구현예의 염료형 편광체 형성용 조성물은 상술한 경화형 이방성 염료 및 배향 보조제와 함께 반응성 메소젠을 더 포함할 수 있다. 이러한 "반웅성 메소젠 (reactive mesogen, RM)"은 이전부터 알려진 바와 같이, 분자 증에 중합, 가교 또는 경화 가능한 불포화기를 포함하여 UV 조사 등 광 조사에 의해 중합, 가교 또는 경화 가능하며， 하나 이상의 메소젠기를 포함하여 액정상 거동을 나타내는 물질을 지칭하는 것으로서, 이 또한 경화 가능한 불포화기를 갖는다. 이러한 반응성 메소젠 역시 상술한 경화형 이방성 염료 및 배향 보조제와 함께 경화되어 가교 구조를 형성할 수 있고, 이로서 상기 이방성 염료의 배향을 더욱 안정화하고 고온의 열이 가해지더라도 이러한 배향이 무질서화되는 것을 억제하여, 염료형 편광체의 편광도 및 내열성을 더욱 향상시킬 수 있다. [Formula 3f]

Meanwhile, the composition for forming a dye-type polarizer according to the embodiment may further include a reactive mesogen together with the above-described curable anisotropic dye and an orientation aid. Such "reactive mesogen" (RM), as previously known, may be polymerized, crosslinked or cured by light irradiation, including UV irradiation, including unsaturated groups that are polymerizable, crosslinked or curable in molecular buildup, As referring to a material exhibiting liquid crystal phase behavior including a mesogen group, this also has a curable unsaturated group. Such reactive mesogens may also be cured together with the above-described curable anisotropic dye and an orientation aid to form a crosslinked structure, thereby further stabilizing the orientation of the anisotropic dye and suppressing disorder of such an orientation even when high temperature heat is applied. The polarization degree and heat resistance of the dye type polarizer can be further improved.

 In addition, due to the addition of the reactive mesogen, it is possible to further improve the orientation and dichroic ratio of the anisotropic dye and the polarizer to provide a dye-type polarizer having very excellent characteristics.

As such a reactive mesogen, it is polymerized by UV irradiation including an unsaturated group. And / or curable, any material exhibiting liquid crystal phase behavior including mesogenic groups can be used without any particular limitation. However, the polarizer has excellent heat resistance by forming a crosslinked structure more effectively with the curable anisotropic dye or an orientation aid, and further improves the orientation or dichroic ratio of the curable anisotropic dye and the dye dance including the same, thereby providing a polarizer having excellent characteristics. To be obtained, a compound of formula 4 may be suitably used:

 [Formula 4]

In Formula 3, A and B are each independently arylene having 6 to 40 carbon atoms or cycloalkylene having 6 to 12 carbon atoms, black to 6 to 8 carbon atoms, R ₁₅ to R ₂ 2 are each independently hydrogen, chlorine Or halogen of fluorine, —CN, alkyl having 1 to 12 carbon atoms, aryl having 6 to 40 carbon atoms, alkoxy having 1 to 12 carbon atoms, and alkoxycarbonyl having 1 to 12 carbon atoms, and ¾ are each independently Simple bonds, -0- ， -S-, -CO-, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -C = C-，-OCH _2- Or -CH ₂ 0-, and Z ₂ are each independently a (meth) acrylate group, Ρ ,, Ρ ₂ and _, Q are each independently defined the same as A, Ei or, _Xl and x ₂ are Each independently represents an integer of 0 to 12.

 In addition, in order to achieve a more improved dichroic ratio and the like of the polarizer obtained from the composition of one embodiment, A and B in the formula (4) is phenylene, or cyclohexylene, at least one of the A and B is phenylene Is appropriate. Semi-ungsogenic mesogens comprising such compounds of formula 4 may be prepared according to methods known to those skilled in the art or may be obtained commercially.

On the other hand, a composition for one embodiment dye type polarizing element is formed with the components described _above: can further include a multi-functional binder that contains more than one curable unsaturated functional group. As the polyfunctional binder is further included, when the curing is performed after the orientation of the curable anisotropic dye described above, the unsaturated functional groups of the multifunctional binder may be cured, crosslinked or combined with the unsaturated functional groups contained in other components such as the anisotropic dye. The polymerization may be performed to form a crosslinked structure, and a crosslinked copolymer of the curable anisotropic dye, an orientation aid, optionally a reactive mesogen and a multifunctional binder, and a dye layer including the same may be formed. As a result, even when the dye layer and the dye type polarizer are exposed to high temperature heat, the orientation of the anisotropic dye can be more effectively stabilized, and a dye type polarizer having better heat resistance can be provided. Furthermore, by the addition of the multifunctional binder, the degree of curing of the dye layer and the dye-type polarizer is further increased to further improve the mechanical properties.

 As such a polyfunctional binder, the polyvalent (meth) acrylate type compound which has a bifunctional or more (meth) acrylate group can be used suitably. More specifically, examples of such a polyvalent (meth) acrylate-based compound include pentaerythryl triacrylate (pentaerythritol triacrylate), tri (2-acrylolyloxyethyl) isocinurate (tris (2-acrylolyloxyethyl) isocynurate) ,

Trimethylolpropane triacrylate and dipentaerythritol may be at least one selected from the group consisting of dipentaerythritol hexaacrylate, and two or more selected among them may be used together, of course. ᅳ

 In addition, the composition of one embodiment described above comprises about 1 to 25 parts by weight of the curable anisotropic dye, about 50 to about 95 parts by weight of the orientation aid, and about 1 to about 1 part of the reactive mesogen based on 100 parts by weight of the solids content of the total composition. And 45 parts by weight. Further, with respect to 100 parts by weight of the solid content, it may further comprise about 0 to 49 parts by weight of the multifunctional binder.

 As a result, it is possible to form a dye layer which exhibits excellent orientation and does not degrade such orientation even by high temperature heat, and furthermore, it is possible to provide a dye-type polarizer exhibiting excellent polarization and transmittance, and further improved dichroic ratio and heat resistance. Lose.

In addition, the composition of one embodiment may further include an organic solvent for dissolving or dispersing the above-described components, and optionally a thermal initiator or photoinitiator for assisting the curing of each component, such as the curable anisotropic dye It may further comprise the same initiator. As such an organic solvent, an appropriate organic solvent capable of effectively dissolving or dispersing each component such as the curable anisotropic dye and an orientation aid The solvent can be obviously selected and used by those skilled in the art, and as the thermal initiator or the photoinitiator, an initiator capable of effectively curing it can be appropriately selected and used depending on the type of the unsaturated functional group such as the curable anisotropic dye or the orientation aid. .

 Specific examples of such organic solvents include methylene chloride (MC), chloroform, cyclopentanone, and cyclonucleic acid, toluene, xylene, dioxane, N-methylpyridone (NMP), propylene glycol monomethyl ether acetate (PGMEA). ), Butyl cellosolve, ethyl cellosolve, butanol, ethanol, ethyl acetate, anisole, cyclonucleic acid, water, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), propylene glycol, acetonitrile, tetrahydro Furan (THF), diethyl ether, glycerin or 2-pyridone, and the like, and specific examples of the thermal initiator or photoinitiator include a commercially available photoinitiator such as Igacure series such as Igacure 184, 819, 907, 369, etc. are mentioned.

 On the other hand, according to another embodiment of the invention, there is provided a dye-type polarizer comprising a cured product of the above-mentioned composition for forming a dye-type polarizer.

 In one example of such a dye-type polarizer, the cured product included in the dye layer is copolymerized with a curable anisotropic dye and an orientation aid to crosslink the curable unsaturated functional groups of each component. It may include a crosslinked copolymer forming a structure, at least a portion of the curable anisotropic dye may be in an oriented state. More specifically, in the cured product, the terminally unsaturated functional groups of the curable anisotropic dye and the orientation assistant may combine with each other to form a crosslinked structure, and as a result, the crosslinked copolymer and a dye layer including the same may be formed. have.

In another example, when the dye layer of the dye-type polarizer is obtained from a composition further comprising a semi-ungogenic mesogen and / or a polyfunctional binder, together with a curable anisotropic dye and an orientation aid, The cargo may comprise a crosslinked copolymer in which a curable anisotropic dye, an orientation aid, optionally a reactive mesogen and a multifunctional binder comprising at least two curable unsaturated functional groups are copolymerized so that the curable functional groups of each component form a crosslinked structure. And at least an egg portion of the curable anisotropic dye may be in an oriented state. More specifically, in the cured product, the terminal unsaturated functional group of the curable anisotropic dye and the orientation aid, optionally the unsaturated group of the reactive mesogen and the unsaturated functional group of the multifunctional binder are cured. In the process may be bonded to each other to form a crosslinked structure, as a result can be formed the crosslinked copolymer and a dye layer including the same.

 As already clear, due to the crosslinked structure included in the crosslinked copolymer, even when exposed to high temperature heat, the orientation of the dye layer and the anisotropic dye or the like may be stabilized without disorder. Therefore, the dye-type polarizer of another embodiment exhibits improved heat resistance along with excellent polarization degree, thereby maintaining excellent polarization degree and other physical properties even when exposed to high temperature heat.

 On the other hand, in the polarizer, the dye layer may have a dichroic ratio of about 10 or more, black about 15 or more. In particular, the polarizer may exhibit more improved orientation and dichroic ratio by the addition of an orientation aid or optional reactive mesogen. In this case, the dichroic ratio may be defined as the ratio of absorbance (measured at vertical incidence) along the absorption axis and absorbance along the transmission axis. As the dye layer has excellent orientation and high dichroic ratio such as the anisotropic dye, the polarizer exhibits excellent polarization degree and can be suitably used as a polarizer for various fields or applications.

 Further, in the polarizer, the dye layer may have a thickness of about 10 / im or less, for example, about 1 to 5 thicknesses. As the dye layer and the polarizer including the same have such a thin thickness, the dye type polarizer may be more appropriately applied as an OLED antireflection film or the like, in which a stretched PVA film polarizer is difficult to apply.

 And, as will be described in more detail below, the above-described curable anisotropic dyes and the like can be oriented during the manufacturing process of the polarizer, and can be oriented in accordance with conventional orientation methods known before, for example, rubbing orientation method or photoalignment method, etc. Can be. Accordingly, the polarizer may further include an alignment layer for orienting the curable anisotropic dye under the dye layer and selectively aligning a reactive mesogen or an orientation aid together.

 According to a more suitable example, a photoalignment layer including a photoreactive polymer is further formed below the dye layer, and the photoreactive polymer is photoaligned, and then used to cure the curable anisotropic dye and optionally an orientation aid or reactive meso. Zen can be oriented.

The photo-alignment layer is a photo- semi-active polymer, for example, previously known A vinyl polymer, a norbornene-based polymer or a (meth) acrylate-based polymer having a cinnamate group, a chalcone group, an azo group or a coumarin group photoreactive group can be formed without any particular limitations. The said hardening type anisotropic dye etc. can be orientated suitably.

 However, in a specific example, the photo-alignment layer is combined with at least one photoreactor selected from the group consisting of cinnamate-based photoreactor, chalcon photoreactor, coumarin-based photoreactor and azo photoreactor to the norbornene repeating unit It is more appropriate to include norbornene-based photoreactive polymers. By applying the photoalignment layer including the photoreactive polymer, the curable anisotropic dye or the like can be more effectively oriented, and at the same time, the thermal stability and mechanical properties of the photoalignment and the dye type polarizer including the same are further improved. You can.

 However, for various photoreactive polymers including the norbornene-based photoreactive polymers, the optical alignment layer including the same, and a method of forming the same, Patent Publication No. 2012-0011796, Patent Registration No. 0982394, Patent Registration No. 1307494 and Patent Since it is disclosed in Publication No. 2012-0031882 or the like, further description thereof will be omitted.

 On the other hand, the dye-type polarizer may be a patterned dye-type polarizer having a predetermined pattern form, in this case, the dye layer is a cured product of the composition for forming a dye-type polarizer is selectively formed only in a predetermined region The remaining region may include the removed cured product pattern. As described above, the patterned polarizer is formed on the substrate by forming the dye-type polarizer forming composition on a substrate, and then selectively irradiated with heat or UV to only a portion of the region through a mask, thereby selectively selecting only the region. It can form by advancing hardening by the process. Thereafter, the composition may be removed from the remaining uncured region to easily form a patterned polarizer having a desired pattern.

 In such a patterned polarizer, the cured product pattern may be in the form of a line pattern having a predetermined pitch, line width, or the like, and the aspect ratio of the cross section in each pattern included in the cured product pattern is about 0.002 to 1 Can be

The dye-type polarized light may further include a substrate, and may have a film form in which the alignment layer, the dye layer, and the like are formed on the substrate. At this time, Cellulose-based substrates such as TAC, polyester-based substrates such as PET, acrylate-based substrates, and cyclic olefin-based substrates such as COP or COC can be used, and substrates in the form of unstretched films can be suitably used.

In addition, the above-described dye-type polarizer has a high degree of polarization of about 90 or more, and after the heat treatment for 100 hours at a silver of about 80 ^° C., the degree of polarization decrease is about 10% or less, or about 0.1 to 5% is excellent A low degree of polarization deterioration due to heat resistance and high temperature heat can be exhibited.

On the other hand, the above-described ^dye, the polarizing element comprises: forming the composition for the above-described one embodiment dye type polarizing member formed on a substrate; Orienting the curable anisotropic dye and optionally an orientation aid or reactive mesogen; And curing the composition for forming a dye-type polarizer including the oriented anisotropic dye and the like.

 That is, as in this manufacturing method, after applying the composition of the embodiment on the substrate to form a polarizer, the polarizer by a method of orienting and curing a curable anisotropic dye, which is a component of the composition, etc. It can be manufactured easily.

 In the manufacturing method, the alignment step may be performed using a rubbing orientation or photoalignment according to a conventional alignment method as described above. In a specific example, in proceeding the orientation of the curable anisotropic dye and the like through the optical alignment, an optical alignment layer including a photo-reflective polymer is further formed between the substrate and the thin film of the composition for forming a dye-type polarizer, such optical response After the photo-alignment of the polymer, it can be used to orient the curable anisotropic dye. After this orientation step, the curable anisotropic dye and orientation aid and optionally semi-ungular mesogen and / or polyfunctional binder can be cured by applying heat or by irradiation with UV or the like.

 Through the above-described method, it is possible to very easily form the dye-type polarizer in the form of a thin film using the composition of one embodiment.

Meanwhile, the above-described dye type polarizer may be included in various display devices such as a liquid crystal optical film or an OLED device, and may be applied to an antireflection film or a smarter shade of the OLED device. Hereinafter, preferred embodiments will be presented to aid in understanding the invention. However, the following examples are only to illustrate the invention, not limited to the invention only. As in the following synthesis example, a curable anisotropic dye of the formula la to If was synthesized, and these were used in the examples. In addition, in the comparative examples, known non-curable anisotropic dyes of the formulas lg and lh were used:

Formula la]

 [Formula lc]

 一 、 r

.1 f _j

 [Formula le]

[Formula If]

Synthesis Example 1 Synthesis of Curable Anisotropic Dye (Formula la)

Formaldehyde (1.2 eq) and sodium bisulfate (leg) were added to water and stirred for 1 hour. Aniline (leq) was added to this solution, and the mixture was stirred at 60 ^° C for 16 hours. After reaction, the crude product dissolved in the solvent was precipitated at a temperature below 0 ^° C., filtered, washed with ethyl acetate and dried in a vacuum oven. This produced intermediate 1.

A solution of 4-hydroxyethylaniline (leq) in DMF was mixed with sodium nitrite (1. leq) dissolved in distilled water, and IN HC1 was slowly dropped at 0 ^° C. Thereafter, the mixture was stirred for about 1 hour. The stirred solution was added dropwise to the solution of the intermediate product l (leq) and sodium acetate (3.5eq) in 40 ml distilled water. At this time, 0 ^° C. was maintained, and after the dropwise addition, the stirring was performed for about 4 hours. After stirring, the solid formed was filtered off, placed in acetone and washed. Filtration again afforded intermediate 2.

This intermediate 2 was placed in IN NaOH (8eq) solution and stirred at 70 ^° C for 16 h. The reaction solution was cooled to room temperature and then filtered again after maintaining the temperature at 0 ° C for 30 minutes. The filtered crude product was extracted with distilled water and ethyl acetate to obtain intermediate product 3.

Intermediate 3 (lg) was dissolved in propionic acid (60 ml) and DMF (20 ml) and angled to 0 ^° C. To this solution was added dropwise a solution of NaN0 ₂ (1.2eq) dissolved in water (0.5ml) and 1 hour Was stirred. Then, sulfamic acid (0.5eq) was added and stirred for 10 minutes. Ethane in which hydroxypropoxy benzene (1.5eq) was dissolved was added dropwise to the solution at 0 ^° C. and stirred for 30 minutes, followed by stirring at room temperature for 16 hours. Saturated aqueous NaHC0 ₃ solution (400 ml) was added to form a precipitate, which was filtered and washed with water. Drying in a vacuum oven gave intermediate product 4.

Intermediate 4 was dissolved in DMAc, angled to 0 ^° C., acryloyl chloride (3eq) was slowly added and stirred at room temperature for 4 hours ᅳ, diluted with diethyl ether, IN HC1 and NaHC0 ₃ aqueous solution The extract was washed with MC, extracted with MC, MC was used as a developing solution, and column chromatography was performed to prepare Chemical Formula la.

NMR (1H, CDC1 ₃ ): 2.01 (m, 2H), 2.98 (m, 2H), 3.15 (m, 6H), 5.83 (m, 2H), 6.11 (m, 2H) _: 6.35 (t, 2H), 7.62-8.10 (m, 12H)

Synthesis Example 2 Synthesis of Curable Anisotropic Dye (Formula lb)

Formaldehyde (1.2 eq) and sodium bisulfate (leg) were added to water and stirred for 1 hour. Aniline (leq) was added to this solution, and the mixture was stirred at 60 ^° C for 16 hours. After the reaction, the crude product dissolved in the solvent at 0 ^° C. or less was precipitated, filtered, washed with ethyl acetate and dried in a vacuum oven. This produced intermediate 1.

A solution of 4-hydroxyethyl-3-fluoro-aniline (leq) in DMF was mixed with sodium nitrite (1. leq) dissolved in distilled water, and IN HC1 was slowly dropped at 0 ^° C. Thereafter, the mixture was stirred for about 1 hour. The stirred solution was added dropwise to the solution of the intermediate product l (leq) and sodium acetate (3.5eq) in 40 ml distilled water. At this time, 0 ^° C. was maintained, and after the dropwise addition, the stirring was performed for about 4 hours. After stirring, the solid formed was filtered, put into acetone, and washed. Filtration again afforded intermediate 2.

This intermediate 2 was placed in IN NaOH (8eq) solution and stirred at 70 ^° C for 16 h. The reaction solution is cooled to room temperature, and then the silver is brought back to 0 ^° C.

After maintaining for 30 minutes, it was filtered. The filtered crude product was extracted with distilled water and ethyl acetate to obtain intermediate product 3. Intermediate 3 (lg) was dissolved in propionic acid (60 ml) and DMF (20 ml) and angled to 0 ^° C. In this solution NaN0 ₂ (1.2eq) dissolved in water (0.5ml). It was added dropwise and stirred for 1 hour. And sulfamic acid (0.5eq) was added and stirred for 10 minutes. This solution was added dropwise to ethanol solution in which hydroxypropoxy benzene (1.5eq) was dissolved at 0 ^° C. and stirred for 30 minutes, followed by stirring at room temperature for 16 hours. Saturated aqueous NaHC0 ₃ solution (400 ml) was added to form a precipitate, which was filtered and washed with water. Drying in a vacuum oven gave intermediate product 4.

Intermediate 4 was dissolved in DMAc, angled to 0 ^° C., acryloyl chloride (3eq) was added slowly and stirred at room temperature for 4 hours. Then, the mixture was diluted with diethyl ether, washed with IN HC1 and NaHC0 ₃ aqueous solution, extracted with MC, MC was used as a developing solution, and column chromatography was performed to prepare Chemical Formula lb.

NMR (1H, CDC1 ₃ ): 2.01 (m, 2H), 3.02-3.18 (m, 2H), 5.83 (m, 2H), 6.11 (m, 2H), 6.35 (t, 2H), 7.62-8.18 (m , 11H)

Synthesis Example 3 Synthesis of Curable Anisotropic Dye (Chemical Formula lc)

Formaldehyde (1.2 eq) and sodium bisulfate (leg) were added to water and stirred for 1 hour. Aniline (leq) was added to this solution and stirred at 60 ^° C. for 16 hours. After the reaction, the crude product dissolved in the solvent was stirred at a temperature of 0 ^° C. or lower, filtered, washed with ethyl acetate and dried in a vacuum oven. This produced intermediate 1.

A solution of 4-hydroxyethylaniline (leq) in DMF was mixed with sodium nitrite (1. leq) dissolved in distilled water, and IN HC1 was slowly dropped at 0 ^° C. Thereafter, the mixture was stirred for about 1 hour. The stirred solution was added dropwise to the solution of the intermediate product l (leq) and sodium acetate (3.5eq) in 40 ml distilled water. At this time, 0 ^° C. was maintained, and after the dropwise addition, the stirring was performed for about 4 hours. After stirring, the solid formed was filtered off, placed in acetone and washed. Filtration again afforded intermediate 2.

This intermediate 2 was placed in IN NaOH (8eq) solution and stirred at 70 ^° C for 16 h. The reaction solution is cooled to room temperature and the temperature is set back to 0 ^° C. After maintaining for 30 minutes, it was filtered. The filtered crude product was extracted with distilled water and ethyl acetate to obtain intermediate product 3.

Intermediate 3 (lg) and NaNO ₂ (1.2eq) were dissolved in DMF / water (80/20 (v / v)) and cooled to 0 ^° C. To this solution was added dropwise a solution dissolved in sulfuric acid (4.2 ml) and stirred for 1 hour. And sulfamic acid (0.3eq) was added and stirred for 10 minutes. This solution was added dropwise at 0 ^° C. to ethanol (130 ml) in which naphthylamine (leq) and saturated NaOAc (21 ml) were dissolved, and stirred for 30 minutes. Saturated NaHC0 ₃ aqueous solution (84 ml) was added thereto and stirred for 16 hours. Water (800 ml) was added to form a precipitate, filtered and washed with water. The obtained solid was dried in a vacuum oven to give intermediate product 4.

Intermediate 4 (lg) was dissolved in propionic acid (60 ml) and DMF (20 ml) and cooled to 0 ^° C. To this solution was added dropwise a solution of NaN0 ₂ (1.2eq) in water (0.5ml) and stirred for 1 hour. And sulfamic acid (0.5eq) was added and stirred for 10 minutes. This solution was added dropwise to ethanol solution in which N-phenyl-N-ethyl-ethane was dissolved in amine (1.5eq) at OT and stirred for 30 minutes, followed by stirring at room temperature for 16 hours. Saturated NaHC0 ₃ aqueous solution (400 ml) was added to form a precipitate, filtered and washed with water. Drying in a vacuum oven afforded intermediate product 5.

The intermediate product 5 was dissolved in DMAc and stirred ^at 0 ^° C., then slowly added acryloyl chloride (3eq) and stirred at room temperature for 4 hours. Then, the mixture was diluted with diethyl ether, washed with IN HC1 and NaHC0 ₃ aqueous solution, extracted with MC, MC was used as a developing solution, and subjected to column chromatography to prepare Chemical Formula lc.

NMR (1H, CDC1 ₃ ): 1.3 (q, 5H), 1.48 (s, 4H), 3.05 (d, 2), 3.55 (d, 2), 3.81 (d, 2), 4.43 (m, 4H), 5.87 (m, 2H), 6.15 (m, 2H), 6.43 (t, 2H), 6.90 (d, 2H), 7.31 (s, 2H), 7.44 (d, 2H), 7.73-8.24 (m, 14H) , 9.04 (dd, 2H)

Synthesis Example 4 Synthesis of Curable Anisotropic Dye (Formula Id)

1-naphthylamine is used instead of aniline in the synthesis of intermediate 1, 4-hydroxyethyl benzoate aniline is used in place of 4-hydroxyethylaniline in the synthesis of intermediate 2, and N-phenyl-N in the synthesis of intermediate 5 -ethyl-amine instead of N- (3- methylphenyl) - N- ethyl-ethane, except for using the ^amine, in the same manner as in synthesis example 3 Formula I d was synthesized.

NMR (1H, CDCI ₃ ): 1.22 (q, 5H), 1.45 (s, 4H), 3.10 (d, 2), 3.57 (d, 2), 3.86 (d, 2), 4.43 (m 4H), 4.8 (s, 3H), 5.87 (m, 2H), 6.18 (m, 2H), 6.49 (t, 2H), 6.92 (d, 2H), 7.22 (s, 2H), 7.44 (d, 2H), 7.65- 8.29 (m, 20H), 9.08 (dd, 2H)

Synthesis Example 5 Synthesis of Curable Anisotropic Dye (Formula l e)

2-amino-6-fluorobenzothiazole was used instead of 4-hydroxyethylaniline for the synthesis of intermediate 2, and N-phenyl _ _N _ ethyl-ethane was used instead of hydroxypropoxy benzene in the synthesis of intermediate 4. Chemical formula le was synthesized in the same manner as in Synthesis Example 1, except that used.

NMR (1H, CDCI ₃ ): 3.13 (d, 2H), 3.81 (d, 2H), 4.46 (m, 4H), 4.75 (s, 3H), 5.80 (m, 2H), 6.16 (m, 1H), 6.44 (t, 1H), 6.90 (m, 2H), 7.30-8.29 (m, 10H), 9.05 (dd, 2H)

Synthesis Example 6 Synthesis of Curable Anisotropic Dye (Formula I f)

 Formula I f was synthesized in the same manner as in Synthesis Example 1, except that 4-propyl aniline was used instead of 4-hydroxyethylaniline in the synthesis of Intermediate 2.

NMR (1H, CDCI ₃ ): 0.98 (t, 3H), 1.53 (m, 2H), 2.0 l (m, 2H), 2.49 (t, 2H), 2.98 (m, 2H), 3.15 (m, 6H) , 5.83 (m, 2H), 6.11 (m, 2H), 6.35 (t, 2H), 7.62-8.10 (m, 12H) Known compounds of the formulas 2a to 3f or radical polymers thereof-commercially available , Used as orientation aids in the following examples and comparative examples:

Formula 2a]

[화학식

[Formula 2b]

Formula

[Formula 2d]

[Formula 3a]

[Formula 3b]

[Formula 3c]

[Formula 3d]

[Formula 3e]

Example 1 Preparation of Dye Type Polarizer

Poly (cinnamate-norbornene) dissolved in cyclopentanone on a COP substrate was bar-coated and dried at 80 ^° C. Then, 30mJ of polarized light was irradiated to form a photoalignment layer. The compound of formula la (curable anisotropic dye; concentration in solution: 2 wt%;), the compound of formula 2a (orientation aid; concentration in solution: 15 wt. ⁰ /.) Dissolved in cyclopentanone on the formed photoalignment layer. , And Igacure 907 (concentration in solution: 0.7 weight ⁰ /.) Were bar-coated. Then, dried at 60 ^° C. for 2 minutes, and cured by irradiating UV of 50mJ / cm ² to prepare a dye-type polarizer.

Example 2 Preparation of Dye Type Polarizer

Compound of formula la (curable anisotropic dye; concentration in solution: 2 weight ⁰ radical polymer of the compound of formula 2c (orientation aid; Mw: 8000; concentration in solution: 15 weight ⁰ /.), And Igacure 907 (solution) increased concentration: QJ were prepared by weight _^0/0), and the composition is a dye-type polarizing element in the same manner as in example 1 except for using the.

Example 3 Preparation of Dye Type Polarizer

The compounds of the formula lb (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), the formula (2a) the compound of formula (orientation aids; solution increased concentration: 15 weight ⁰ /), and Irgacure 907 (he the solution also : A dye-type polarizer was prepared in the same manner as in Example 1 except for using a composition of 0.7 wt%). Example 4 Preparation of Dye Type Polarizer

Compounds of Formula lc (curable anisotropic dyes; a solution of concentration 2 weight _^0/0), the compound of Formula 2a (orientation aids; concentration in the solution: 15 parts by weight _^0/0), and Irgacure 907 (concentration of the solution: 0.7, except for using the composition of weight _^0/0), and is as in example 1, In the same manner, a dye-type polarizer was prepared. Example 5 Preparation of Dye Type Polarizer

The compounds of the formula ic (curable anisotropic dyes; a solution of concentration 2 weight _^0/0), the compound of Formula 2b (orientation aids; concentration in the solution: 15 parts by weight _^0/0), and Irgacure 907 (concentration of the solution: A dye-type polarizer was prepared in the same manner as in Example 1 except that the composition of 0.7 wt%) was used.

Example 6 Preparation of Dye Type Polarizer

The compound of Formula lc (curable anisotropic dyes; solution increased concentration: 2 wt. _^0/0), a radical polymer of the compound of Formula 2c (orientation aids; Mw: 8000; concentration of the solution: 15 wt%), and Irgacure 907 A dye-type polarizer was prepared in the same manner as in Example 1, except that the composition (concentration in solution: 7 weight ⁰ / ^° ) was used. Example 7 Preparation of Dye Type Polarizer

Compounds of Formula lc (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), the compounds of the radical of the formula 2d increases copolymer (orientation aids; Mw:;: 15 parts by weight _^0/0 8000 concentration in the solution), and A dye-type polarizer was prepared in the same manner as in Example 1 except that the composition of Igacure 907 (solution concentration concentration: 0.7 wt%) was used.

<Example 8> Preparation of a dye type polarizing member ^■ the compounds of Formula lc (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), the compound (alignment aids of the above formula 3a; concentration in the solution: 15 parts by weight ⁰ / ₀ ), and a dye-type polarizer was prepared in the same manner as in Example 1 except for using the composition of Igacure 907 (concentration in solution: eq 7 weight ⁰ /.).

Example 9 Preparation of Dye Type Polarizer

Formula lc compound (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), a radical polymer of the compound of Formula 3c (orientation aids; Mw: 10000; the concentration of the solution: 15 parts by weight ⁰ / o), and a divalent Thing using the composition of Cure 907 (concentration in solution: 0.7 weight ⁰ /.) Except for producing a dye-type polarizer in the same manner as in Example 1. <Example 10>: Preparation of dye type polarizer

Formula lc compound (curable anisotropic dyes; concentration in the solution: 2% by weight) a radical polymer of the compound of Formula 3d (orientation aids; Mw: 8000; concentration of the solution: 15 parts by weight _^0/0), and Irgacure 907 (solution concentration of 0.7 wt. _^0/0) was prepared in example 1 and the dye-type polarizing element in the same manner except that the composition of the.

<Example 11>: Preparation of dye type polarizer

Radical polymer of the compound of Formula 3e:; (2 parts by weight _^0/0 concentration in the solution-curing anisotropic dye) Formula lc compound of formula (orientation aids; Mw: 6000; concentration of the solution: 15 parts by weight _^0/0), and a divalent Cure 907 (concentration of the solution: 0.7 parts by weight _^0/0) was prepared in example 1 and the dye-type polarizing element in the same manner except that the composition of the. <Example 12>: Preparation of dye type polarizer

The compound of Formula Id (curable anisotropic dyes; concentration in the solution: 2 parts by weight ⁰ /), a radical increase incorporation of the compound of Formula _2c (orientation aids; Mw: 8000; concentration of the solution: 15 parts by weight _^0/0), and A dye-type polarizer was prepared in the same manner as in Example 1 except that the composition of Igacure 907 (concentration in solution: 0.7 weight ⁰ / ^° ) was used.

<Example 13>: Preparation of dye type polarizer

The compounds of the formula le (curable anisotropic dyes; concentration in the solution: 2% by weight) a radical polymer of the compound of formula 2c, (orientation aids; Mw: 8000; concentration of the solution: 15 parts by weight _^0/0), and Irgacure 907 (solution concentration of 0.7 wt. _^0/0) was prepared in example 1 and the dye-type polarizing element in the same manner except that the composition of the.

<Example 14>: Preparation of dye type polarizer

The compound of Formula If (curable anisotropic dyes; solution increased concentration: 2 wt. _^0/0), a radical polymer of the compound of Formula 2c (orientation aids; Mw: 8000; concentration of the solution: 15 parts by weight _^0/0), and a divalent Thing using the composition of Cure 907 (concentration in solution: 0.7 weight ⁰ /.) Except for producing a dye-type polarizer in the same manner as in Example 1.

<Example 15>: Preparation of dye type polarizer

Formula la compounds of (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), the compound of Formula 2a (orientation aids; concentration in the solution: 15 parts by weight _^0/0), MERCK Co. half male mesogens of RM257 ( solution of concentration: 5 wt. _^0/0), and Irgacure 907 (concentration in solution: and was prepared a dye-type polarizing element in the same manner as in example 1 except that the composition of the 1% by ^weight). <Example 16>: Preparation of dye type polarizer

Formula la compounds of (curable anisotropic dyes; a solution of concentration 2 increased _^0/0) radical polymer of the compound of Formula 2c (orientation aids; Mw:.; 8000 concentration in the solution: 15 parts by weight ⁰ /), RM257 ( A dye-type polarizer was prepared in the same manner as in Example 1 except for using the composition of Concentration in Solution: 5% by weight), and Igacure 907 (Concentration in Solution: 1% by weight).

Example 17 Preparation of Dye Type Polarizer

The compound of formula lb (curable anisotropic dye; concentration in solution: 2% by weight), the compound of formula 2a (orientation aid; concentration in solution: 15 weight ⁰ /.), RM257 (concentration in solution: 5 weight ⁰ /. ), And a dye-type polarizer was prepared in the same manner as in Example 1 except that the composition of Igacure 907 (concentration in solution: 1% by weight) was used.

<Example 18>: Preparation of dye type polarizer

Compounds of Formula lc (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), the compound of Formula 2a (orientation aids; concentration in the solution: 15 parts by weight ⁰ / ( »), RM257 (concentration in the solution: 5 parts by weight _^0/0), and Irgacure 907 (concentration in the solution: 1 was prepared in example 1 and shaped in the same manner except that the composition of the dye polarizing body weight ^_0/0).

Example 19 Preparation of Dye Type Polarizer

The compound of Formula lc (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), The compounds of Formula 2b (orientation aids; concentration in the solution: 15 parts by weight _^0/0) for using the composition of, RM257 (concentration in the solution: 5 parts by weight _^0/0), and Irgacure 907 (1 wt% solution concentration in) Except for producing a dye-type polarizer in the same manner as in Example 1. <Example 20>: Preparation of dye type polarizer

The compound of Formula lc (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), a radical polymer of the compound of Formula 2c (orientation aids; Mw: 8000; concentration of the solution: 15 parts by weight _^0/0), RM257 ( solution of concentration: 5 wt. _^0/0), and Irgacure 907 (concentration of the solution: was prepared in example 1 as a dye-type polarizing in the same manner except that the composition of the 1% increase) form.

<Example 21>: Preparation of dye type polarizer

The compound of Formula lc (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), a radical polymer of the compound of formula 2d (orientation aids; Mw:; 7000 concentration in the solution 15 increased _^0/0), RM257 ( Concentration in solution: 5 weight ⁰ /. And Irgacure 907 (solution increased concentration: 1 wt. _^0/0) was prepared in the dye type polarizing element in the same manner as in Example 1, except that the composition of the.

<Example 22>: Preparation of dye type polarizer

The compound of Formula lc (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), the compound of formula 3a (orientation aids; concentration in the solution: 15 parts by weight _^0/0), RM257 (concentration in the solution: 5 parts by weight ⁰ / ₀ ), and a dye-type polarizer was prepared in the same manner as in Example 1 except that the composition of Igacure 907 (concentration in solution: 1 weight ⁰ /.) Was used. <Example 23>: Preparation of dye type polarizer

Radical polymer of the compound of Formula 3c:; (2 parts by weight _^0/0 concentration in the solution-curing anisotropic dye) Formula lc compound of formula (orientation aids; Mw: 10000; the concentration of the solution: 15 parts by weight _^0/0), and a divalent Cure 907 (concentration in the solution: 1 weight _^0/0) was prepared in example 1 and the dye-type polarizing element in the same manner except that the composition of the. Example 24 Preparation of Dye Type Polarizer

"Compound of Formula lc (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0) radical polymer of Formula 3d compound (orientation aids; Mw: 8000; solution in concentration: 15 wt. _^0/0), RM257 (concentration of the solution: 5 parts by weight _^0/0): was prepared in example 1 and the dye-type polarizing element in the same manner except that the composition of, and Irgacure 907 (1 increased _^0/0 concentration in the solution).

Example 25 Preparation of Dye Type Polarizer

Radical polymer of the compound of Formula 3e:; (2 parts by weight _^0/0 concentration in the solution-curing anisotropic dye) Formula lc compound of formula (orientation aids; Mw:. 6000; solution in concentration: 15 weight ⁰ /), and teeth Cure 907 (concentration in the solution: 1 weight _^0/0) was prepared in example 1 and the dye-type polarizing element in the same manner except that the composition of the.

<Example 26>: Preparation of dye type polarizer

Radical polymer of the compound of Formula 2c:; (2 parts by weight _^0/0 concentration in the solution-curing anisotropic dye), the formula (Id) compounds of the (orientation aids; Mw: 8000; solution in concentration: 15 wt. _^0/0), and a divalent Cure 907 (solution increased concentration: 1 wt. _^0/0) was prepared in the dye type polarizing element in the same manner as in example 1, except that the composition of the. <Example 27>: Preparation of dye type polarizer

The compounds of formula le (curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0), a radical polymer of the compound of Formula 2c (orientation aids; Mw: 8000; concentration of the solution: 15 parts by weight ⁰ / o), RM257 ( Concentration in solution: 5% by weight), and Igacure 907 (concentration in solution: 1% by weight) in the same manner as in Example 1 except that the composition was used. Polarizer was prepared.

<Example 28>: Preparation of dye type polarizer

. Radical polymer of the compound of Formula 2c:; (2 parts by weight _^0/0 solution of the concentration of curable anisotropic dye) the compound of formula If (orientation aids; Mw:. 8000; concentration of the solution: 15 parts by weight ⁰ /), and teeth Using a composition of Cure 907 (concentration in solution: 1% by weight) Except for producing a dye-type polarizer in the same manner as in Example 1.

<Comparative Example 1>: Production of Dye Type Polarizer

The compound of Formula lg (conventional non-curable anisotropic dyes; solution increased concentration: 2 increased ⁰ /), a radical polymer of the compound of Formula 2c (orientation aids; Mw:;: 15 parts by weight _^0/0 8000 concentration in the solution) , and Irgacure 907 (concentration of the solution: 0.7 parts by weight _^0/0) was prepared in example 1 and the dye-type polarizing element in the same manner except that the composition of the.

<Comparative Example 2>: Preparation of Dye-Type Polarizer

The compounds of the formula lh (conventional non-curable anisotropic dyes; concentration in the solution: 2 parts by weight _^0/0) radical polymer of the Formula 2c compounds (orientation aids; Mw:;: 15 parts by weight ^0/8000 concentration in the solution.) , And a dye-type polarizer was prepared in the same manner as in Example 1, except that the composition of Igacure 907 (concentration in solution: 7 wt% in solution) was used. <Comparative Example 3>: Production of Dye Type Polarizer

The compound of Formula lg (conventional non-curable anisotropic dyes; solution increased concentration: 2 wt. _^0/0) radical polymer of the compound of Formula 2c (orientation aids; Mw: 8000; solution of concentration 15% by weight) and divalent Cure 907 (concentration in the solution: 1 weight _^0/0) was prepared in example 1 and the dye-type polarizing element in the same manner except that the composition of the.

 '

 Comparative Example 4 Preparation of Dye Type Polarizer

The compounds of the formula lh (conventional non-curable anisotropic dyes; a solution concentration: 2 wt. _^0/0), a radical polymer of the compound of Formula 2c (orientation aids; Mw:;: 15 parts by weight _^0/0 8000 concentration in the solution) And a dye-type polarizer was prepared in the same manner as in Example 1 except that the composition of Igacure 907 (concentration in solution: 1 weight ⁰ /.) Was used.

<Comparative Example 5>: Production of Dye Type Polarizer

Carried out without the use of the alignment aids of the composition of Example 1, formula la compound (curable anisotropic dyes; concentration in the solution: 2 parts by weight ⁰ /), and Irgacure 907 (a solution of concentration 0.7 wt _^0/0), the composition of the In the same manner as in Example 1 except that used Dye type polarizer was prepared.

<Comparative Example 6>: Preparation of Dye Type Polarizer

Compound of formula la (curable anisotropic dye; concentration in solution: 2 weight ⁰ /.), RM257 (concentration in solution: 5 weight ⁰ / (»), and igacure, without using an orientation aid in the composition of Example 15 A dye-type polarizer was prepared in the same manner as in Example 15 except that the composition of 907 (concentration in solution: 1 weight ⁰ / ^° ) was used.

<Experimental Example 1>: Dichroic ratio (DR) and heat resistance evaluation of dye type polarizer The dichroic ratio (measured at the wavelength of 380 to 780 nm to obtain an average value) was measured using a Jasco Polarimeter, and heat resistance evaluation was performed. After the heat treatment for 100 hours in an oven at 80 ^° C, the degree of dichroic ratio decrease compared to the dichroic ratio before the heat treatment was summarized in Table 1 below.

 TABLE 1

 Dichroic ratio 80 ° C 100 hours heat treatment Dichroic ratio Decreasing rate (%) Dichroic ratio

Example 1 9.2 8.5 7.6 Example 2 1 1.8 10.9 7.6 Example 3 8.4 8.0 4.8 Example 4 13.9 13.8 0.7 Example 5 13.5 13.1 3.0 Example 6 15.1 14.6 3.3 Example 7 14.9 14.5 2.7 Example 8 9.6 9.4 2.1 Implementation Example 9 14.1 13.2 6.4 Example 10 14.6 14.3 2.0 Example 11 15.1 14.2 6.0 Example 12 13.8 13.4 2.9 Example 13 7.7 7.1 7.8 Example 14 9.8 9.7 1.0 Example 15 9.4 9.2 2.1 Example 16 1 1.5 1 1.6 0 Example 17 7.5 7.3 2.7 Example 18 13.5 13.5 0 Example 19 13.0 12.8 1.5 Example 20 14.1 14.2 0 Example 21 15.0 14.6 2.7 Example 22 9.0 9.2 0 Example 23 14.5 14.4 0.7 Example 24 14.0 14.0 0 Example 25 15.0 14.7 0.7 Example 26 13.2 13.1 0.8 Example 27 9.5 9.4 1.0 Example 28 9.4 9.5 0 Comparative Example 1 8.2 3.7 54.9 Comparative Example 2 7.4 3.2 56.8 Comparative Example 3 8.5 5.6 34.1 Comparative Example 4 7.6 5.8 23.7 Comparative Example 5 8.5 4.7 44.7 Comparative Example 6 6.1 3.5 42.6 Referring to Table 1, the dye-type polarizer of the Example exhibits excellent dichroic ratio and excellent properties as the polarizer, After the heat treatment, the dichroic ratio and the degree of decrease in polarization degree were minimized, indicating that the heat resistance and durability were excellent.

Claims

【Patent Claims】 【Claim 1】 A curable anisotropic dye of the following formula (1); and A composition for forming a dye-type polarizer comprising an orientation aid of the following formulas 2 and 3 or radical polymers thereof:

In Formula 1, n is an integer from 2 to 5, and the repeating unit structures of -(A N=N)- repeated two or more times may be the same or different from each other, And at least one of Q ₂ is a curable unsaturated functional group, and the remainder are hydrogen, alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, alkyl ester or amine group with 1 to 20 carbon atoms, A! and A ₂ may be the same or different from each other and are substituted or unsubstituted arylene having 6 to /40 carbon atoms, or substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, B, and B ₂ may be the same or different from each other, and may be a simple bond, -(C=0)0-, -0(C=Q)-, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted Or unsubstituted arylene having 6 to 40 carbon atoms, substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, substituted or unsubstituted alkylene oxide having 1 to 20 carbon atoms, -0-, -S-, -NR and -ρ - is a divalent functional group combining one or more types selected from the group consisting of, !^ is hydrogen or alkyl having 1 to 20 carbon atoms [Formula 2] In Formula 2, At least one of Q ₃ and Q 4 is a curable unsaturated functional group, and the remainder is hydrogen, alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, alkyl ester with 1 to 20 carbon atoms, -CN, -N0 ₂ , halogen, or 1 to 2 amine groups substituted or unsubstituted with alkyls having 1 to 6 carbon atoms, A ₃ and A 4 may be the same or different from each other and are substituted or unsubstituted arylene having 6 to 40 carbon atoms, or substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, B ₃ and B ₄ may be the same or different from each other, a simple bond, -(C=0)0-, -0(C=0)-, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted Or unsubstituted arylene having 6 to 40 carbon atoms, substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, substituted or unsubstituted alkylene oxide having 1 to 20 carbon atoms, -0-, -S-, -NR ₂ - and -PR ₂ - is a divalent functional group combining one or more types selected from the group consisting of, R ₂ is hydrogen or alkyl having 1 to 20 carbon atoms, [Formula 3] Q ₅ - B ₅ - A ₅ - B ₆ - A ₆ - B ₈ -Q ₆ In Formula 2, At least one of Q ₅ and Q ₆ is a curable unsaturated functional group, and the others are hydrogen, alkyl with 1 to 20 carbon atoms, cycloalkyl with 3 to 12 carbon atoms, aryl with 6 to 40 carbon atoms, alkoxy with 1 to 20 carbon atoms, and carbon atoms. It is an amine group substituted or unsubstituted with 1 to 20 alkyl esters, -CN, -N0 ₂ , halogen, or 1 to 2 alkyls with 1 to 6 carbon atoms, A ₅ and A ₆ may be the same or different from each other and are substituted or unsubstituted arylene having 6 to 40 carbon atoms, or substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, B ₅ , B ₆ and 8 ₈ may be the same or different from each other, a simple bond, -(C=0)0-, -0(C=0)-, substituted or unsubstituted alkyl having 1 to 20 carbon atoms lene, substituted or unsubstituted arylene having 6 to 40 carbon atoms, substituted or unsubstituted heteroarylene having 4 to 30 carbon atoms, substituted or unsubstituted alkylene oxide having 1 to 20 carbon atoms, -0-, -S- , -NR ₃ - and -PR ₃ - is a divalent functional group combining one or more types selected from the group consisting of, and R ₃ is hydrogen or alkyl having 1 to 20 carbon atoms. 【Claim 2】 The method of claim 1, wherein the unsaturated functional groups of Q to Q ₆ are each independently a curable unsaturated group having a (meth)acrylate group, an epoxy group, or a vinyl group at the terminal. A composition for forming a functional dye-type polarizer. 【Claim 3】 The method of claim 1, wherein the remainder of the unsaturated functional group to Q ₆ are each independently hydrogen, alkyl with 1 to 20 carbon atoms, aryl with 6 to 40 carbon atoms, alkoxy with 1 to 20 carbon atoms, alkyl ester with 1 to 20 carbon atoms, A composition for forming a dye-type polarizer that is an amine group substituted or unsubstituted with -CN, halogen, or 1 to 2 alkyls having 1 to 6 carbon atoms. 【Claim 4】 The method of claim 1, wherein A, to A ₆ are each independently substituted or unsubstituted with alkoxy having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms, halogen, -N0 ₂ or alkyl ester having 1 to 6 carbon atoms. A composition for forming a dye-type polarizer containing 6 to 40 arylene. 【Claim 5】 The method of claim 1, wherein B ₈ is each independently a simple bond, (C=0)0-, -0(C=0)-, alkylene having 1 to 20 carbon atoms, arylene having 6 to 40 carbon atoms, A dye-type polarizer that is a divalent functional group selected from the group consisting of alkylene oxide having 1 to 20 carbon atoms, -0- (alkylene having 1 to 20 carbon atoms) -, and amine group unsubstituted or substituted with alkyl having 1 to 6 carbon atoms. Composition for forming. 【Claim 6】 The composition for forming a dye-type polarizer according to claim 1, further comprising a reactive mesogen ^: 【Claim 7】 The composition for forming a dye-type polarizer according to claim 6, wherein the semi-male mesogen includes a compound of the following formula (4): [Formula 4]

In Formula 4 above, A and B are each independently arylene having 6 to 40 carbon atoms or cycloalkylene having 6 to 12 carbon atoms, R ₁₅ to R ₂₂ are each independently selected from the group consisting of hydrogen, halogen, -CN, alkyl with 1 to 12 carbon atoms, aryl with 6 to 40 carbon atoms, alkoxy with 1 to 12 carbon atoms, and alkoxycarbonyl with 1 to 12 carbon atoms. is selected, E, and are each independently a simple bond, -0-, -S-, -CO-, -COO-, -OCO-, - CH=CH-COO-, -OCO-CH=CH-, -C=C -, -OCH ₂ - or -C¾0-, Zi and Z ₂ are each independently a (meth)acrylate group, P _h P ₂ and Q are each independently defined equal to Α, Ε, or ^' , X, and x ₂ are each independently integers from 0 to 12. . 【Claim 8】 The dye according to claim 6, comprising 1 to 25 parts by weight of a curable anisotropic dye, 50 to 95 parts by weight of an orientation aid, and 1 to 45 parts by weight of a reactive mesogen, based on 100 parts by weight of solid content of the entire composition. Composition for forming a polarizer. 【Claim 9】 A dye-type polarizer comprising a dye layer containing a cured product of the composition for forming a dye-type polarizer according to any one of claims 1 to 8. 【Claim 10】 The method of claim 9, wherein the cured product includes a cross-linked copolymer in which a curable anisotropic dye and an orientation aid are copolymerized to form a cross-linked structure of the curable unsaturated functional groups of each component, and at least a portion of the curable anisotropic dye is oriented. A dye-type polarizer. 【Claim 11】 The method of claim 9, wherein the cured product comprises a cross-linked copolymer in which a curable anisotropic dye, an orientation aid, and a reactive mesogen are copolymerized to form a cross-linked structure in which the curable functional groups of each component are copolymerized, Hardened type. A dye-type polarizer in which at least a portion of the anisotropic dye is oriented. 【Claim 12】 [Me] The dye-type polarizer according to item 9, wherein the dye layer has a dichroic ratio of 10 or more. 【Claim 13】 The dye-type polarizer according to claim 9, wherein the dye layer has a thickness of 1 to 10 m. [Claim 14] The dye-type polarizer according to claim 9, further comprising an orientation element that orients the curable anisotropic dye below the dye layer. 【Claim 15】 The method of claim 14, wherein the orientation layer is a norbornene-based repeating unit in which one or more photoreactive groups selected from the group consisting of a cinnamate-based photoreactive group, a chalcone-based photoreactive group, a coumarin-based photoreactive group, and an azo-based photoreactive group are combined. A dye-type polarizer that is a photo-alignment layer containing a nene-based photoreactive polymer. 【Claim 16】 The dye-type polarizer according to claim 9, which has a polarization degree of 90 or more and a rate of decrease in polarization degree of 10% or less after heat treatment at a temperature of 80 ^° C for 48 hours. 【Claim 17】 The dye-type polarizer according to claim 9, further comprising a substrate and having a film form. 【Claim 18】 A display device comprising the dye-type polarizer of claim 9.