KR20160074286A

KR20160074286A - Optical film having reverse wavelength dispersion and display device comprising same

Info

Publication number: KR20160074286A
Application number: KR1020140183428A
Authority: KR
Inventors: 문정욱; 김정우; 황승연; 전성호; 최대승
Original assignee: 주식회사 엘지화학
Priority date: 2014-12-18
Filing date: 2014-12-18
Publication date: 2016-06-28

Abstract

The present invention relates to an optical film having reverse wavelength dispersion and a display device comprising the same. The optical film according to the present invention can have stable reverse wavelength dispersion while having a small thickness, and thus is suitable to be used as a λ/2 wave plate, a λ/4 wave plate, a protective film, an anti-reflection film, and the like in a display device using liquid crystals or OLEDs.

Description

TECHNICAL FIELD [0001] The present invention relates to an optical film having an inverse wavelength dispersion and a display device including the optical film. [0002]

The present invention relates to an optical film comprising a polymer of a cyclic olefin compound and having an inverse wavelength dispersion, and a display device comprising the same.

A phase retarder is a type of optical element that changes the polarization state of light passing through it. It is also called a wave plate. When the electromagnetic wave passes through the phase retarder, the polarization direction (electric field vector direction) becomes the sum of two components (normal and extraordinary rays) parallel or perpendicular to the optical axis, and the vector sum of the two components depends on the birefringence and thickness of the phase retarder So that the polarization direction after passing is different. At this time, changing the polarization direction of light by 90 degrees is called a quarter-wave plate (λ / 4), and a 180 ° change is called a half-wave plate (λ / 2).

At this time, the retardation value of the phase retarder depends on the wavelength, and the wavelength dispersion of the retardation value is classified into normal wavelength dispersion, flat wavelength dispersion, and reverse wavelength dispersion.

Among them, a phase retarder exhibiting reverse wavelength dispersion is most useful because it has a predetermined retardation (? / 4,? / 2, etc.) in a wide wavelength band, and most phase retarders formed of a conventional resin film exhibit a constant wavelength dispersion .

Various studies have been conducted to solve such problems. For example, Japanese Patent Application Laid-Open No. 1998-068816, Japanese Laid-Open Patent Publication No. 1998-090521, Japanese Laid-Open Patent Application No. 1999-052131, 002841 discloses a layered phase retarder in which a plurality of optically anisotropic layers are laminated. However, a laminate type phase retarder having a structure in which a plurality of optically anisotropic layers are stacked has a disadvantage in that productivity is deteriorated and manufacturing cost is high, since complicated procedures for arranging a plurality of films are required while controlling optical orientation in manufacturing.

On the other hand, Japanese Patent Application Laid-Open No. 2002-221622 discloses a method of manufacturing a wide-band? / 4 wave plate including only one phase retarder by inducing inverse wavelength dispersion through stretching of a film. It is not suitable for a liquid crystal display device which is required to have a thin layer.

Japanese Patent Application Laid-Open No. 2002-267838 discloses a method of using a liquid crystal composition comprising a rod-shaped liquid crystal compound and a non-liquid crystalline substance oriented vertically to the long axis of the compound, for the purpose of producing a thin-film broadband wave plate . However, in the case of the above composition, reverse wavelength dispersion is not induced when the mixing ratio of the non-liquid crystal material is low, and when the mixing ratio is high, the liquid crystal properties of the composition itself are lost.

Accordingly, it is desired to develop a broadband phase retarder having a stable inverse wavelength dispersion and a thin thickness. Particularly, there is an urgent need to study a polymer that can produce such a compensation film by a more simplified method.

The present invention is to provide an optical film which can exhibit a reverse wavelength dispersion with a thin thickness.

The present invention also provides a display device comprising the optical film.

According to the present invention, there is provided a polymer comprising a polymer containing a repeating unit derived from the polymerization of a cyclic olefin compound represented by the following formula (1)

There is provided an optical film satisfying the following relational formula I and relational expression II:

[Chemical Formula 1]

In Formula 1,

p is an integer of 0 to 4,

At least one of R ¹ , R ² , R ³ , and R ⁴ is a group represented by the following formula (2)

Any one of R ¹ and R ² and any one of R ³ and R ⁴ may be bonded together to form a benzene group, a naphthalene group, an anthracene group, an indene group, a tetrahydronaphthalene group, an indane group, an indole group or a phthalimide group To form an aryl group,

And R ¹ , R ² , R ³ , or R ⁴ except for forming the aryl group are the same or different from each other and each independently hydrogen; halogen; A substituted or unsubstituted C1 to C20 linear or branched alkyl; Substituted or unsubstituted C2-C20 linear or branched alkenyl; A substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

(2)

In Formula 2,

D is a single bond or a divalent linking group,

m is an integer of 0 to 10,

G is an aryl group which is a benzene group, a naphthalene group, an anthracene group, an indene group, a tetrahydronaphthalene group, an indane group, an indole group, or a phthalimide group;

[Relation I]

? N (450 nm) /? N (550 nm) < 1.0

[Relation Formula II]

? N (650 nm) /? N (550 nm)> 1.0

In the above relational expressions I and II,? N (?) Means the specific refractive index at the wavelength?.

According to the present invention, the polymer may comprise a repeating unit of the following formula (3a) or a repeating unit of the following formula (3b):

[Chemical Formula 3] (3b)

In the above formulas (3a) and (3b)

n is independently from 50 to 5,000,

p, R ¹ , R ² , R ³ , and R ⁴ are each as defined in formula (1).

On the other hand, according to the present invention, the polymer may contain a repeating unit derived from the copolymerization of the compound represented by the formula (1) and the compound represented by the following formula (4)

[Chemical Formula 4]

In Formula 4,

r is an integer of 0 to 4,

R ⁵ to R ⁸ are the same or different from each other, and each independently hydrogen; halogen; A substituted or unsubstituted C1 to C20 linear or branched alkyl; Substituted or unsubstituted C2-C20 linear or branched alkenyl; A substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

When R ⁵ to R ⁸ are not hydrogen, halogen or a polar functional group, at least one combination of R ⁵ and R ⁶ , R ⁷ and R ⁸ is connected to each other to form an alkylidene group having 1 to 10 carbon atoms Or R ⁵ or R ⁶ may be bonded to any one of R ⁷ and R ⁸ to form a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms.

According to the present invention, the polymer may have a weight average molecular weight of 10,000 to 5,000,000.

According to the present invention, there is provided a display device including the optical film.

The optical film according to the present invention can exhibit a stable inverse wavelength dispersion with a thin thickness and is suitable as a? / 2 wavelength plate, a? / 4 wavelength plate, a protective film, an antireflection film, etc. of a display using a liquid crystal or OLED Lt; / RTI >

Hereinafter, the optical film according to the embodiment of the present invention will be described in detail.

The 'specific birefringent index' refers to a retardation value at a wavelength (λ) of transmitted light that passes through an optically anisotropic material, unless otherwise explicitly stated throughout the present specification, and Δn ( lt; / RTI >

And, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. And, the singular forms used herein include plural forms unless the phrases expressly have the opposite meaning.

Also, as used herein, the term " comprises " embodies specific features, regions, integers, steps, operations, elements or components, and does not exclude the presence of other specified features, regions, integers, steps, operations, elements, It does not.

On the other hand, as a result of continuous research by the present inventors, it has been found that when a polymer containing a repeating unit derived from the polymerization of a cyclic olefin compound represented by the following formula (1) is used as a resin for an optical film, it exhibits a stable inverse wavelength dispersion Respectively.

According to this embodiment of the present invention,

1. A polymer composition comprising a polymer containing a repeating unit derived from polymerization of a cyclic olefin compound represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

p is an integer of 0 to 4,

Any one of R ¹ and R ² and any one of R ³ and R ⁴ may be bonded to each other to form a benzene group, a naphthalene group, an anthracene group, an indene group, An aryl group which is a tetrahydronaphthalene group, an indane group, an indole group, or a phthalimide group is formed,

(2)

In Formula 2,

D is a single bond or a divalent linking group,

m is an integer of 0 to 10,

G is a benzene group, a naphthalene group, an anthracene group, an indene group, a tetrahydronaphthalene group, an indane group, an indole group, group, or a phthalimide group;

[Relation I]

? N (450 nm) /? N (550 nm) < 1.0

[Relation Formula II]

? N (650 nm) /? N (550 nm)> 1.0

According to an embodiment of the present invention, the compound represented by Formula 1 may be a benzene group, a naphthalene group, an anthracene group, an indene group, a tetrahydronaphthalene group At least one aryl group selected from the group consisting of an indole group, an indole group, and a phthalimide group is bonded to a linker (-D- (CH ₂ ) _m -) By cyclic olefins (

). &Lt; / RTI > The compound represented by Formula 1 may be a compound in which the aryl group is directly linked to the cyclic olefin without the linker.

Generally, cyclic olefins exhibit positive birefringence. However, polymers having repeating units derived from addition polymerization or ring-opening polymerization of the compound represented by the above formula (1) have a structure in which the fluorene-derived groups are vertically erected when they are stretched, Thereby providing an optical film that exhibits high transmittance.

According to an embodiment of the present invention, at least one of R ¹ , R ² , R ³ , and R ⁴ in Formula 1 may be a group represented by the following Formula 2, preferably R ¹ , R ² , R ³ , And R < ⁴ > may be the group represented by the formula (2).

(2)

In the general formula ( ₂ ), -D- (CH ₂ ) _m - represents a cyclic olefin of the general formula

) And G which is an aryl group.

In the linker, D is a single bond or a divalent linking group.

Wherein the divalent linking group is selected from the group consisting of -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, , -NR-CO-NR-, -O (CH ₂ ) _x -, - (CH ₂ ) _x O-, -CH═CHCH ₂ O-, -OCH ₂ CH═CH-, - (CH ₂ ) _x COO _{-, -OCO (CH 2) x} -, - (CH 2) x OCO-O-, -OCO-O- (CH 2) x -, -SCH 2 -, -CH 2 S-, -CF 2 O _{-, -OCF 2 -, -CF 2} S-, -SCF 2 -, - (CH 2) x -, -CF 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CF 2 -, -CH = - CH = -, -C = C-, -CH = N-, -N = CH-, or -N = N-; Each R is independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and x may independently be an integer of 1 to 8.

In Formula 2, G is a group selected from the group consisting of a benzene group, a naphthalene group, an anthracene group, an indene group, a tetrahydronaphthalene group, an indane group, An indole group, and an aryl group such as a phthalimide group. Preferably, G is selected from the group consisting of phenyl, naphthyl, anthracenyl, indenyl, tetrahydronaphthyl, indanyl, indolyl, Or phthalimidyl.

In Formula 2, m is an integer of 0 to 10. When m is 0, the G in the formula (2) is connected by the D. When m is an integer of 1 to 10, that is, an alkylene group having 1 to 10 carbon atoms, the alkylene group may be linear or branched. The at least one hydrogen contained in the alkylene group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or a cyano group. Wherein said substitution can be a single substitution or a multiple substitution of two or more. Also, at least one -CH ₂ - group constituting the alkylene group may be substituted with -S- or -O-.

According to an embodiment of the present invention, any one of R ¹ and R ² and any one of R ³ and R ⁴ may be bonded to each other to form a benzene group, a naphthalene group, an anthracene group, an indene group, a tetrahydronaphthalene group , An indane group, an indole group, or an aryl group, which is a phthalimide group.

That is, when any one of R ¹ and R ² and either R ³ or R ⁴ is linked to form the aryl group in Formula 1, the aryl group may be bonded to the cyclic olefin (

) Directly connected without the linker. As a non-limiting example,

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And the like.

R ¹ , R ² , R ³ , or R ⁴ , which are the same as or different from each other except for forming the aryl group, are each independently hydrogen; halogen; A substituted or unsubstituted C1 to C20 linear or branched alkyl; Substituted or unsubstituted C2-C20 linear or branched alkenyl; A substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron.

When R ¹ , R ² , R ³ , and R ⁴ are not hydrogen, halogen, or a polar functional group, one or more combinations selected from the group consisting of R ¹ and R ² , R ³ and R ⁴ are connected to each other form an alkylidene group having 1 to 10 carbon atoms, or R ¹ or R ² is R ³ and R ⁴ are connected with any one of an aromatic ring having a carbon number of 4 to 12, saturated or unsaturated aliphatic ring, or a 6 to 24 carbon atoms .

Specifically, a polar functional group that includes at least one or more polar functional groups that can be substituted for R ¹ , R ² , R ³ , and R ⁴ , that is, oxygen, nitrogen, phosphorus, sulfur, &Lt; / RTI > and the like. However, it may be various polar functional groups including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon or boron.

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In the polar functional group,

m is independently an integer of 1 to 10,

L ¹ is a substituted or unsubstituted, linear or branched alkylene having 1 to 20 carbon atoms; A substituted or unsubstituted linear or branched alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted C2-C20 linear or branched alkynylene; A substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted carbonyloxysylene having 1 to 20 carbon atoms; Or a substituted or unsubstituted alkoxysilene having 1 to 20 carbon atoms,

L ² , L ³ and L ⁴ are each independently hydrogen; halogen; A substituted or unsubstituted C1 to C20 linear or branched alkyl; Substituted or unsubstituted C2-C20 linear or branched alkenyl; A substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; A substituted or unsubstituted C1-C20 alkoxy; And substituted or unsubstituted carbonyloxy of 1 to 20 carbon atoms.

The substituted or unsubstituted aryl of 6 to 40 carbon atoms which may be substituted on R ¹ , R ² , R ³ , or R ⁴ of Formula 1; Or a heteroaryl group having 6 to 40 carbon atoms including a heteroatom of Group 14, Group 15 or Group 16 may be selected from the group consisting of the following functional groups and may be variously substituted with aryl or heteroaryl:

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In this functional group, E ¹ to E ⁹ are the same or different from each other and each independently represents hydrogen, substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, Or unsubstituted aryloxy having 6 to 30 carbon atoms, and substituted or unsubstituted aryl having 6 to 40 carbon atoms.

On the other hand, in the structure of the above-mentioned cyclic olefin compound, the definition of each substituent will be specifically described as follows:

First, "alkyl" means a linear or branched saturated monovalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. The alkyl group is not only unsubstituted but can also be referred to as being further substituted by a certain substituent group described later. Examples of alkyl groups include methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert- butyl, pentyl, hexyl, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, Dichloromethyl, trichloromethyl, iodomethyl, bromomethyl and the like.

"Alkenyl" means a linear or branched monovalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms, comprising at least one carbon-carbon double bond . The alkenyl group may be bonded through a carbon atom containing a carbon-carbon double bond or through a saturated carbon atom. The alkenyl group is not only unsubstituted, but may also be referred to as being further substituted by a certain substituent group described later. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl and dodecenyl.

"Cycloalkyl" means a saturated or unsaturated nonaromatic monovalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, inclusive of those further substituted by certain substituents described below, can do. Cyclopentyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbonyl (i.e., bicyclo [ 1] hept-5-enyl).

"Aryl" means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 40, preferably 6 to 12, ring atoms, which is further substituted by a certain substituent group . Examples of the aryl group include phenyl, naphthalenyl and fluorenyl.

"Alkoxyaryl" means that at least one hydrogen atom of the above-defined aryl group is substituted with an alkoxy group. Examples of alkoxyaryl groups include methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentoxyphenyl, hexoxyphenyl, heptoxy, octoxy, noxy, methoxybiphenyl, methoxynaphthalenyl, Methoxyfluorenyl, methoxyanthracenyl and the like.

The term "aralkyl" means that at least one hydrogen atom of the above-defined alkyl group is substituted with an aryl group, and those further substituted by a certain substituent group described later may be collectively referred to. Examples thereof include benzyl, benzhydryl and trityl.

"Alkynyl" refers to a linear or branched monovalent hydrocarbon moiety of 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 6 carbon atoms, including one or more carbon-carbon triple bonds. do. Alkynyl groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. The alkynyl group may be further encompassed by a substituent which is further substituted by a certain substituent group described later. For example, ethynyl, propynyl and the like.

"Alkylene" means a linear or branched, saturated divalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. The alkylene group may be referred to as being further substituted by a certain substituent group described later. Examples of the alkylene group include methylene, ethylene, propylene, butylene, hexylene and the like.

"Alkenylene" refers to a linear or branched divalent hydrocarbon moiety of from 2 to 20, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms comprising at least one carbon-carbon double bond do. The alkenylene group may be bonded through a carbon atom containing a carbon-carbon double bond and / or through a saturated carbon atom. The alkenylene group may be referred to as being further substituted by a certain substituent group described later.

Means a saturated or unsaturated nonaromatic bivalent monocyclic, bicyclic, or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, inclusive of which is further substituted by a given substituent group . Examples thereof include cyclopropylene and cyclobutylene.

"Arylene" means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 20, preferably 6 to 12, ring atoms, which is further substituted by a constant substituent group It can be referred to collectively. The aromatic moiety contains only carbon atoms. Examples of the arylene group include phenylene and the like.

The term "aralkylene" means a divalent moiety in which at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group, which may be further encompassed by a substituent which is further substituted by a certain substituent group described later. For example, benzylene and the like.

"Alkynylene" refers to a linear or branched divalent hydrocarbon moiety of from 2 to 20 carbon atoms, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms comprising at least one carbon-carbon triple bond do. The alkynylene group may be bonded through a carbon atom containing a carbon-carbon triple bond or through a saturated carbon atom. The alkynylene group may be referred to collectively as being further substituted by a certain substituent group described later. For example, ethynylene or propynylene.

The substitution of the substituents described above with "substituted or unsubstituted" means that not only each of the substituents themselves but also those further substituted by a certain substituent are included. In the present specification, examples of substituents which can be further substituted for each substituent, unless otherwise defined, include halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, Is selected from the group consisting of oxygen, nitrogen, phosphorus, silicon, or boron, such as, for example, alkyl, alkenyl, "And the like.

According to one embodiment, the polymer may include a repeating unit represented by the following formula (3a) or a repeating unit represented by the following formula (3b) according to the polymerization reaction of the cyclic olefin compound of the formula (1)

[Chemical Formula 3] (3b)

In the above formulas (3a) and (3b)

n is independently from 50 to 5,000,

p, R ¹ , R ² , R ³ , and R ⁴ are each as defined in formula (1).

Among them, the repeating unit of formula (3a) may be formed by the addition polymerization of the compound of formula (1). As an example, the addition polymerization can be carried out in the presence of a catalyst composition comprising a cocatalyst and a precatalyst comprising a Group 10 transition metal.

At this time, the addition polymerization reaction may be carried out at a temperature of 10 ° C to 200 ° C. When the reaction temperature is lower than 10 ° C, the polymerization activity may be lowered, and when it is higher than 200 ° C, the catalyst may be decomposed.

The cocatalyst may further include a first cocatalyst to provide a Lewis base capable of weakly coordinating with the metal of the precatalyst; And a second co-catalyst to provide a compound comprising a Group 15 electron donor ligand. Preferably, the cocatalyst can be a catalyst mixture comprising a first co-catalyst providing the Lewis base and, optionally, a second co-catalyst comprising a neutral 15 group electron donor ligand.

At this time, the catalyst mixture may contain 1 to 1,000 moles of the first co-catalyst per 1 mole of the catalyst, and 1 to 1,000 moles of the second co-catalyst. If the content of the first catalyst or the second catalyst is excessively small, the catalyst may not be activated properly. On the contrary, if the content of the first catalyst or the second catalyst is excessively large, the catalyst activity may be lowered.

As the precatalyst including the Group 10 transition metal, it is easily separated by the first co-catalyst providing Lewis base and easily participates in the Lewis acid-base reaction so that the central transition metal can be converted into the catalytically active species. A compound having a Lewis base functional group which is released from the metal can be used. For example [(Allyl) Pd (Cl) ] 2 (Allylpalladiumchloride dimer), (CH 3 CO 2) 2 Pd [Palladium (Ⅱ) acetate], [CH 3 COCH = C (O-) CH 3] 2 Pd [Palladium ( ⅱ) acetylacetonate], NiBr (NP (CH 3) 3) 4, [PdCl (NB) O (CH 3)] there are _two and more.

In addition, as the first co-catalyst which provides a Lewis base capable of weakly coordinating with the metal of the precatalyst, it readily reacts with the Lewis base to form vacancies of the transition metal, and in order to stabilize the transition metal thus produced, A compound capable of weakly coordinating with the metal compound or a compound providing the same can be used. Borates such as borane or dimethylanilinium tetrakis (pentafluorophenyl) borate such as B (C ₆ F ₅ ) ₃ , methylaluminoxane (MAO) or Al (C ₂ H ₅₎ ) ₃ , or a transition metal halide such as AgSbF ₆ .

As the second cocatalyst for providing the compound containing the neutral 15 group electron donating ligand, alkylphosphine, cycloalkylphosphine or phenylphosphine may be used.

The first co-catalyst and the second co-catalyst may be used separately, but these two co-catalysts may be used as a compound for activating the catalyst by making one salt. For example, a compound prepared by ion-binding an alkylphosphine and a borane or a borate compound or the like may be used.

Through the above-described method, the repeating unit of the formula (3a) and the polymer of one embodiment containing the same can be prepared. In addition, in the case where the polymer further contains an olefin-based repeating unit, a cyclic olefin-based repeating unit, or an acrylate-based repeating unit, these repeating units are formed by a conventional production method of each repeating unit, To obtain the polymer by copolymerization with the repeating unit of formula (3a).

Meanwhile, the repeating unit of formula (3b) may be formed by ring-opening polymerization of the compound of formula (1).

The ring-opening polymerization may be carried out in the presence of a catalyst composition comprising a cocatalyst and a precatalyst comprising a transition metal of Group 4, Group 6, or Group 8.

In another alternative, the polymer comprising the recurring units of formula (3b) can be prepared by reacting norbornene methanol or the like in the presence of a catalyst composition comprising a precatalyst comprising a transition metal of Group 4, Group 6, or Group 8, (Alkyl) ol as a monomer to form a ring-opening polymer having a pentane ring, and then introducing a linker and a group derived from the fluorene to the ring-opening polymer. At this time, the introduction of the fluorene group can be carried out by a condensation reaction of the ring-opening polymer with a carboxylic acid compound or an acyl chloride compound having a fluorene group.

In the above ring-opening polymerization, when hydrogen is added to the double bond in the norbornene ring contained in the monomer such as the above-mentioned formula (1), the ring opening can proceed and, at the same time, the polymerization proceeds to form a repeating unit represented by the above- A reactive polymer may be prepared. Or the polymerization and the ring opening may be progressed sequentially to produce the photoreactive polymer.

The ring-opening polymerization can be carried out in the presence of a catalyst comprising a transition metal of Group 4 (e.g., Ti, Zr, Hf), Group 6 (e.g. Mo, W) or Group 8 (e.g. Ru, Os) In the presence of a catalyst mixture comprising a cocatalyst providing a Lewis base capable of weakly coordinating with the catalyst and optionally a neutral Group 15 and Group 16 activator capable of promoting the activity of the precatalyst metal, . Also, in the presence of such a catalyst mixture, 1 to 100 mol% of a linear alkene such as 1-alkene or 2-alkene, which can control the molecular weight, is added in an amount of 1 to 100 mol% . A catalyst containing a transition metal of Group 4 (for example, Ti, Zr) or Group 8 to Group 10 (for example, Ru, Ni, Pd) is added to the monomer in an amount of 1 to 30 wt% The reaction of hydrogenating the double bond in the norbornene ring at the temperature can be carried out.

When the reaction temperature is too low, the polymerization activity is lowered. When the reaction temperature is too high, the catalyst is decomposed. In addition, when the hydrogenation reaction temperature is too low, the activity of the hydrogenation reaction is lowered, and when the hydrogenation reaction temperature is too high, the catalyst is decomposed.

The catalyst mixture may comprise one or more elements selected from the group consisting of Group 1 (e.g., Ti, Zr, Hf), Group 6 (e.g., Mo, W), or Group 8 1 to 100,000 moles of a cocatalyst providing a Lewis base capable of weakly coordinating with the metal of the catalyst and optionally an activator comprising neutral elements of group 15 and group 16 capable of promoting the activity of the catalytic metal and 1 to 100 moles of activator per mole of the catalyst.

When the content of the cocatalyst is less than 1 mol, there is a problem that the catalyst is not activated, and when it is more than 100,000 mol, the catalyst activity is lowered. The activating agent may not be required depending on the kind of the catalyst. When the content of the activating agent is less than 1 mol, there is a problem that the catalyst is not activated, while when it is more than 100 mol, the molecular weight is lowered.

When the content of the catalyst containing a transition metal of Group 4 (e.g., Ti, Zr) or Group 8 to Group 10 (e.g. Ru, Ni, Pd) used in the hydrogenation reaction is less than 1 wt% And when it is more than 30% by weight, there is a problem that the polymer is discolored, which is not preferable.

The procatalyst comprising the transition metal of Group 4 (e.g. Ti, Zr, Hf), Group 6 (e.g. Mo, W) or Group 8 (e.g. Ru, Os) Such as TiCl ₄ , WCl ₆ , MoCl ₅ , RuCl ₃ , and ZrCl ₄ , which are readily involved in the Lewis acid-base reaction and have functional groups that break away from the center metal, Metal compounds.

The cocatalyst providing the Lewis base capable of weakly coordinating with the metal of the precatalyst may be borane or borate such as B (C ₆ F ₅ ) ₃ , methylaluminoxane (MAO) or Al (C ₂ H ₅ ) ₃ , Al (CH ₃ ) Cl ₂ , alkylaluminum halides, and aluminum halides. Alternatively, substituents such as lithium, magnesium, germanium, lead, zinc, tin and silicon may be used instead of aluminum. As such, it is a compound which forms a transition metal easily by easily reacting with a Lewis base and weakly binds to a transition metal compound in order to stabilize the transition metal thus produced, or a compound providing the same.

An activator for polymerization may be added, but it may not be necessary depending on the kind of the catalyst. Activators comprising neutral elements of group 15 and group 16 that can enhance the activity of the precatalyst metal include water, methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethyl mercaptan ), 2-chloroethanol, trimethylamine, triethylamine, pyridine, ethylene oxide, benzoyl peroxide, t-butyl peroxide and the like.

Catalysts comprising Group 4 (e.g., Ti, Zr) or transition metals of Group 8 to Group 10 (such as Ru, Ni, Pd) used in the hydrogenation reaction may be in a homogeneous form Or the metal catalyst complex is supported on a particulate support. The particulate support is preferably silica, titania, silica / chromia, silica / chromia / titania, silica / alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite.

Through the above-described method, the repeating unit of the formula (3b) and the polymer of one embodiment containing it can be produced. When the above-mentioned photoreactive polymer further contains an olefin-based repeating unit, a cyclic olefin-based repeating unit, or an acrylate-based repeating unit, these repeating units may be formed by a usual production method of each repeating unit, To obtain a photoreactive polymer by copolymerization with the repeating unit of formula (3b).

According to another embodiment, the polymer may be a copolymer of the compound of Formula 1 and a cyclic olefin compound having a different structure.

For example, the polymer may contain repeating units derived from copolymerization of the compound represented by Formula 1 and the compound represented by Formula 4 below:

[Chemical Formula 4]

In Formula 4,

r is an integer of 0 to 4,

According to one embodiment, the copolymer may comprise repeating units of formula (3a) or repeating units of formula (3b); And a repeating unit of the following formula (5a) or a repeating unit of the following formula (5b):

[Chemical Formula 5a] [Chemical Formula 5b]

In the above general formulas (5a) and (5b)

n is independently from 50 to 5,000,

^{r, R 5, R 6,} R 7, and R ⁸ are as defined in formula (4), respectively.

Preferably, the copolymer may include a repeating unit of the formula (3a) and a repeating unit of the formula (5a) by addition polymerization of the compound represented by the formula (1) and the compound represented by the formula (4). The copolymer may contain repeating units of the formula (3b) and repeating units of the formula (5b) by ring-opening polymerization of the compound represented by the formula (1) and the compound represented by the formula (4).

Herein, the polar functional group, aryl, heteroaryl, and the like which may be substituted for R ⁵ to R ⁸ in the general formulas (4), (5a) and (5b) are described in detail in the above-mentioned formula (1).

On the other hand, the copolymer may contain a repeating unit derived from polymerization of 1 to 99% by weight of the compound represented by the formula (1) and 1 to 99% by weight of the compound represented by the formula (4). That is, in order to ensure a more stable reverse wavelength dispersion, the compound represented by Formula 1 is contained in an amount of 1 wt% or more, or 10 wt% or more, or 20 to 99 wt%, or 20 to 90 wt% It is advantageous. In addition to the compound of Formula 1, the compound of Formula 4 may be used for the purpose of improving photo-alignment properties or mechanical properties. Here, the content of the compound of formula (4) may be determined in consideration of the reverse wavelength dispersion property of the compound of formula (1).

On the other hand, the homopolymer of the compound represented by Formula 1 or the copolymer of the compound represented by Formula 1 and the compound represented by Formula 4 may be 10,000 to 5,000,000, or 50,000 to 2,500,000, or 100,000 to 1,000,000, or 200,000 to 500,000 Having a weight-average molecular weight of not less than 20,000 can be advantageous for securing processability, heat resistance, and the like.

An optical film comprising a polymer as described above may exhibit a stable inverse wavelength dispersion and preferably satisfy the following relational formulas I and II:

[Relation I]

? N (450 nm) /? N (550 nm) < 1.0

[Relation Formula II]

? N (650 nm) /? N (550 nm)> 1.0

Particularly, in satisfying the above relational formulas I and II, the optical film of one embodiment has a difference in Δn (450 nm) and Δn (650 nm) of not less than 0.1, preferably not less than 0.15, Lt; / RTI > Namely, even if any optical film satisfies the above-described relations, when the difference between the values of DELTA n (450 nm) and DELTA n (650 nm) is less than 0.1, sufficient inverse wavelength dispersion can not be exhibited and the? / 2 wavelength plate, And the like.

As such, the optical film according to one embodiment can be suitably used for a lambda / 2 wave plate, a lambda / 4 wave plate, a protective film, an antireflection film or the like of a display device using a liquid crystal or an OLED due to its excellent reverse wavelength dispersion property . Particularly, in a display device using an OLED, glare occurs due to reflection by a transistor when external light is applied, and the optical film of the above embodiment can be suitably used as a reverse wavelength dispersive film for preventing this.

On the other hand, the optical film may be produced by a conventional method except that the optical film contains a copolymer of the cyclic olefin compound represented by Formula 1 or a copolymer of the cyclic olefin compound represented by Formula 1 and Formula 3 .

For example, the optical film may be formed by dissolving the polymer or copolymer in an organic solvent to prepare a coating composition, coating the coating composition on the substrate, and stretching the resulting film.

For example, a coating solution is prepared by mixing 1 to 60% by weight of the polymer or copolymer with the remaining amount of an organic solvent, and the coated solution is coated on a substrate such as a metal, glass or the like polished in a mirror-finished state using a knife coater or a bar coater An optical film can be produced by casting, drying the solvent, and stretching. At this time, the drying temperature of the organic solvent may be appropriately selected depending on the kind of the solvent used. It is preferable that the surface temperature of the substrate is maintained at room temperature or lower.

Examples of the organic solvent include toluene, anisole, chlorobenzene, dichloroethane, cyclohexane, cyclopentane, propylene glycol methyl ether acetate, and the like. The above-mentioned photoreactive polymer exhibits excellent solubility for various organic solvents, so that various organic solvents can be used without limitation.

According to another embodiment of the present invention, there is provided a display device including the optical film. Such a display device may be a liquid crystal display device in which the optical film is included for orientation of a liquid crystal, a stereoscopic image display device in which the optical film is incorporated in a liquid crystal retardation film for realizing a stereoscopic image, or the like. However, since the configuration of these display devices is the same as that of a conventional display device except that the above-mentioned polymer and optical film are included, a further detailed description thereof will be omitted.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

Synthetic example 1: Synthesis of cyclic olefin compounds

In a high pressure reactor by cracking of dicyclopentadiene (DCPD) (1R, 4S ) -bicyclo [2.2.1] the hept-2-ene (2,3- dihydro-1 H -inden-2-yl) methyl acrylate and Diels -alde reaction to obtain the compound 1.

Specifically, 100 g of dicyclopentadiene (DCPD), 404 g of (2,3-dihydro-1H-inden-2-yl) methyl acrylate and 0.0004 g of hydroquinone were placed in a high pressure reactor and stirred at 180 ° C. for 4 hours . After the reaction, distillation yielded about 202 g of Compound 1 (yield: about 50%).

The NMR spectrum of the obtained compound 1 is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 7.26 (2H, dd), 7.06 (2H, dd), 6.05 (2H, dd), 4.36 (2H, dd), 3.69 (1H, s) , 2.73 (6H, m), 2.37 (1H, dd), 1.99 (2H, m), 1.75-1.50

Synthetic example 2: Synthesis of cyclic olefin compound

In the high-pressure reactor, (1R, 4S) -bicyclo [2.2.1] hept-2-ene by dicyclopentadiene (DCPD) cracking was reacted with benzyl acrylate with Diels-alder to obtain Compound 2.

Specifically, 100 g of dicyclopentadiene (DCPD), 456 g of benzyl acrylate, and 0.0004 g of hydroquinone were placed in a high-pressure reactor and stirred at 180 ° C for 4 hours. After the reaction, distillation yielded about 282 g of Compound 2 (yield: about 62%).

The NMR spectrum of the obtained compound 2 is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 7.32 (5H, dd), 6.05 (2H, dd), 5.34 (2H, s), 3.69 (1H, dd), 2.37 (1H, dd) , 2.27 (1H, dd), 1.99 (1H, dd), 1.75-1.50 (3H, m)

Synthetic example 3: Synthesis of cyclic olefin compounds

In a high-pressure reactor, (1R, 4S) -bicyclo [2.2.1] hept-2-ene was reacted with methyl acrylate and Diels-alder by dicyclopentadiene (DCPD)

Specifically, 100 g of dicyclopentadiene (DCPD), 162.8 g of methyl acrylate, and 0.0004 g of hydroquinone were placed in a high-pressure reactor and stirred at 180 ° C. for 4 hours. After the reaction, distillation yielded about 80 g of compound 2 (yield: about 69%).

The NMR spectrum of the obtained compound 3 is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 6.05 (2H, dd), 3.77 (1H, dd), 3.68 (3H, s), 2.37 (1H, dd), 2.27 (1H, dd) , 1.99 (1H, dd), 1.75-1.50 (3H, m)

Synthetic example 4: Synthesis of cyclic olefin compounds

In the high-pressure reactor, (1R, 4S) -bicyclo [2.2.1] hept-2-ene by dicyclopentadiene (DCPD) cracking was reacted with butyl acrylate with Diels-alder to obtain compound 4.

Specifically, 100 g of dicyclopentadiene (DCPD), 232.2 g of butyl acrylate and 0.0004 g of hydroquinone were placed in a high-pressure reactor and stirred at 180 ° C for 4 hours. After the reaction, distillation yielded about 120 g of Compound 4 (yield: about 62%).

The NMR spectrum of the obtained compound 4 is as follows.

¹ H NMR (CDCl _3, standard TMS) δ (ppm): 6.05 (2H, dd), 4.08 (2H, dd), 3.77 (1H, dd), 2.37 (1H, dd), 2.27 (1H, dd) , 1.99 (1H, dd), 1.75-1.45 (7H, m), 0.90 (3H, t)

Example 1: Synthesis of polymer

Compound 1 (100 g) according to Synthesis Example 1 was dissolved in toluene (300 ml) and stirred for 30 minutes under a nitrogen atmosphere. The temperature was raised to 105 캜, and dichloromethane was added thereto, in which palladium acetate trimer (0.0140 g) and tricyclohexylphosphinium tetrakis (pentafluorophenyl) borate (0.1203 g) were dissolved. This was reacted with stirring at 105 DEG C for 18 hours. After the reaction, the temperature was lowered to room temperature, and polymer precipitation was obtained using ethanol. The precipitate was recovered as a filter and dried in a vacuum oven at 90 DEG C for 24 hours to obtain a polymer (yield = 64%, Mw = 151,000, PDI = 2.11).

Example 2: Synthesis of polymer

Compound 2 (100 g) according to Synthesis Example 2 was dissolved in toluene (300 ml) and stirred for 30 minutes under a nitrogen atmosphere. The temperature was raised to 105 캜, and dichloromethane was added thereto, in which palladium acetate trimer (0.0140 g) and tricyclohexylphosphinium tetrakis (pentafluorophenyl) borate (0.1203 g) were dissolved. This was reacted with stirring at 105 DEG C for 18 hours. After the reaction, the temperature was lowered to room temperature, and polymer precipitation was obtained using ethanol. The precipitate was recovered as a filter and dried in a vacuum oven at 90 DEG C for 24 hours to obtain a polymer (yield = 45%, Mw = 214,000, PDI = 2.20).

Example 3: Synthesis of polymer

A copolymer was obtained in the same manner as in Example 1 except that a mixture of the compound 1 (10 g) and the compound 3 (90 g) in Synthesis Example 3 was used instead of the compound 1 as the monomer compound (Yield = 80%, Mw = 314,000, PDI = 2.07).

Example 4: Synthesis of polymer

A copolymer was obtained in the same manner as in Example 1 except that a mixture of the compound 1 (10 g) and the compound 4 (90 g) according to Synthesis Example 4 was used instead of the compound 1 as the monomer compound (Yield = 71%, Mw = 274,000, PDI = 2.23).

Control Example : Synthesis of polymer

A polymer was obtained (yield = 90%, Mw = 357,000, PDI = 1.74) in the same manner as in Example 1, except that Compound 3 (100 g) was used instead of Compound 1 as the monomer compound.

Manufacturing example 1 to 4: Preparation of optical film

Each of the polymers according to Examples 1 to 4 was dissolved in methylene chloride to a solids content of 20% by weight. Then, this solution was filtered using a filter having a pore size of 0.45 mu m to prepare a coating solution.

The coating solution was cast on a glass substrate using a knife coater, dried at room temperature for 1 hour, and then dried at 100 DEG C under nitrogen atmosphere for 1 hour. After drying, the film was immersed in water for 30 seconds, and then the film on the glass substrate was peeled off to obtain a transparent film having a uniform thickness of less than 2% in thickness, which was stretched to obtain an optical film.

compare Manufacturing example : Manufacture of Optical Film

An optical film was obtained in the same manner as in the above production example, except that the polymer according to the control example was used in place of the polymer of the example.

Experimental Example : Phase difference Measure value

For each of the optical films obtained through the production examples, the retardation value was measured using Axoscan (manufactured by Axomatrix). At this time, the thickness of the optical film was measured independently, and the retardation value (? N d) was determined from the obtained value.

Δn DELTA n (450 nm) /
DELTA n (550 nm) DELTA n (650 nm) /
DELTA n (550 nm) 450 nm 550 nm 650 nm Production Example 1 0.95 1.01 1.04 0.94 1.03 Production Example 2 0.96 1.00 1.08 0.96 1.08 Production Example 3 0.96 1.01 1.05 0.95 1.04 Production Example 4 0.98 1.00 1.03 0.98 1.03 Comparative Manufacturing Example 1.01 1.00 0.99 1.01 0.99

As can be seen from the above Table 1, it was confirmed that the optical films according to Production Examples 1 to 4 satisfied the conditions according to the relational expressions I and II and exhibited stable inverse wavelength dispersion.

Claims

1. A polymer composition comprising a polymer containing a repeating unit derived from polymerization of a cyclic olefin compound represented by the following formula (1)
An optical film satisfying the following relational formula I and relational expression II:
[Chemical Formula 1]

In Formula 1,
p is an integer of 0 to 4,
At least one of R ¹ , R ² , R ³ , and R ⁴ is a group represented by the following formula (2)
Any one of R ¹ and R ² and any one of R ³ and R ⁴ may be bonded together to form a benzene group, a naphthalene group, an anthracene group, an indene group, a tetrahydronaphthalene group, an indane group, an indole group or a phthalimide group To form an aryl group,
And R ¹ , R ² , R ³ , or R ⁴ , except for forming the aryl group, are the same or different from each other and each independently hydrogen; halogen; A substituted or unsubstituted C1 to C20 linear or branched alkyl; Substituted or unsubstituted C2-C20 linear or branched alkenyl; A substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
(2)

In Formula 2,
D is a single bond or a divalent linking group,
m is an integer of 0 to 10,
G is an aryl group which is a benzene group, a naphthalene group, an anthracene group, an indene group, a tetrahydronaphthalene group, an indane group, an indole group, or a phthalimide group;
[Relation I]
? N (450 nm) /? N (550 nm) < 1.0
[Relation Formula II]
? N (650 nm) /? N (550 nm)> 1.0
In the above relational expressions I and II,? N (?) Means the specific refractive index at the wavelength?.

The method according to claim 1,
The bivalent linking group is selected from the group consisting of -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO- NR-CO-NR-, -O ( CH 2) x -, - (CH 2) x O-, -CH = CHCH 2 O-, -OCH 2 CH = CH-, - (CH 2) x COO-, _{-OCO (CH 2) x -,} - (CH 2) x OCO-O-, -OCO-O- (CH 2) x -, -SCH 2 -, -CH 2 S-, -CF 2 O-, _{-OCF 2 -, -CF 2 S-,} -SCF 2 -, - (CH 2) x -, -CF 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CF 2 -, -CH = CH- , -C = C-, -CH = N-, -N = CH-, or -N = N-; Each R is independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and x is independently an integer of 1 to 8.

The method according to claim 1,
Wherein the polymer comprises a repeating unit represented by the following formula (3a) or a repeating unit represented by the following formula (3b):
[Formula 3]

In the above formulas (3a) and (3b)
n is independently from 50 to 5,000,
p, R ¹ , R ² , R ³ , and R ⁴ are each as defined in formula (1).

The method according to claim 1,
Wherein the polymer contains a repeating unit derived from the copolymerization of the compound represented by the formula (1) and the compound represented by the following formula (4)
[Chemical Formula 4]

In Formula 4,
r is an integer of 0 to 4,
R ⁵ to R ⁸ are the same or different from each other, and each independently hydrogen; halogen; A substituted or unsubstituted C1 to C20 linear or branched alkyl; Substituted or unsubstituted C2-C20 linear or branched alkenyl; A substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
When R ⁵ to R ⁸ are not hydrogen, halogen or a polar functional group, at least one combination of R ⁵ and R ⁶ , R ⁷ and R ⁸ is connected to each other to form an alkylidene group having 1 to 10 carbon atoms Or R ⁵ or R ⁶ may be bonded to any one of R ⁷ and R ⁸ to form a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms.

5. The method of claim 4,
Wherein the polymer is a repeating unit represented by the following formula (3a) or a repeating unit represented by the following formula (3b); And a repeating unit of the following formula (5a) or a repeating unit of the following formula (5b):
[Formula 3]

In the above formulas (3a) and (3b)
n is independently from 50 to 5,000,
p, R ¹ , R ² , R ³ , and R ⁴ are each as defined in Formula 1;
[Chemical Formula 5a] [Chemical Formula 5b]

In the above general formulas (5a) and (5b)
n is independently from 50 to 5,000,
^{r, R 5, R 6,} R 7, and R ⁸ are as defined in formula (4), respectively.

5. The method of claim 4,
Wherein the polymer contains from 1 to 99% by weight of the compound represented by the formula (1) and from 1 to 99% by weight of the compound represented by the formula (4).

The method according to claim 1,
Wherein the polymer has a weight average molecular weight of 10,000 to 5,000,000.

A display device comprising the optical film according to claim 1.