KR101205476B1 - Maleimide compound having photoreactive group and photoreactive polymer - Google Patents

Abstract

The present invention relates to novel maleimide-based compounds that can be used as photoreactive compounds or to the preparation of various photoreactive polymers and to photoreactive polymers that exhibit good photoreactivity. The maleimide compound has a structure in which a specific photoreactor is bonded to a maleimide structure.

Description

MALEIMIDE COMPOUND HAVING PHOTOREACTIVE GROUP AND PHOTOREACTIVE POLYMER}

The present invention relates to novel maleimide compounds and photoreactive polymers having photoreactive groups. More specifically, the present invention relates to maleimide compounds and photoreactive polymers exhibiting excellent photoreactivity, which may be used as photoreactive compounds or used in the preparation of various photoreactive polymers.

Maleimide is used as a starting material for various organic synthesis reactions, such as the Michael addition or the Diels-Aldar reaction. In addition, since it is highly reactive with hydroxy (-OH), amine (-NR ₃ ), or sulfur (-S), and can form stable CO, CN, CS bonds, it is not only a precursor of a compound but also a monomer of a polymer. It is used a lot.

For example, the maleimide is not only used as a monomer of the polyimide-based polymer, but also serves to enhance the hardness or viscoelasticity of the polymer by binding to various polymers as a cross-linker. And because of its unique affinity, it can also be used for protein separation.

On the other hand, various photoreactive compounds or polymers are used in various optical applications, such as photoresist, and these applications are increasingly wider and require photoreactive polymers having various characteristics. However, the development of various photoreactive polymers and the like has not yet been made properly, and even so far, even known photoreactive polymers often have poor thermal stability or insufficient photoreactivity.

For this reason, the development of the photoreactive polymer etc. which have the outstanding photoreactivity and thermal stability, show various characteristics, and is applicable to various optical application fields is calculated | required.

Accordingly, the present invention provides a maleimide compound that can be used as a photoreactive compound or used in the preparation of various photoreactive polymers as it has excellent photoreactivity.

The present invention also provides a photoreactive polymer which can be prepared from the maleimide compound and exhibit excellent photoreactivity.

The present invention provides a maleimide compound having a photoreactor represented by the following formula (1):

[Formula 1]

In Formula 1, S ₁ is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted aralkylene having 7 to 15 carbon atoms; Substituted or unsubstituted alkynylene having 2 to 20 carbon atoms; And heteroalkylene having 6 to 20 carbon atoms including hetero group 14, 15 or 16 hetero atoms in the carbon chain,

A is a photoreactor of Formula 1a or 1b,

[Formula 1a]

[Chemical Formula 1b]

In the above general formulas (1a) and (1b)

B is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Carbonyl; Carboxy; ester; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; And substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms,

X is oxygen or sulfur,

P is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted aralkylene having 7 to 15 carbon atoms; Substituted or unsubstituted alkynylene having 2 to 20 carbon atoms; And substituted or unsubstituted cyclic alkylene having 4 to 8 carbon atoms,

R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are the same as or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted cyclic alkyl having 4 to 8 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted C6-C40 aryl; Heteroaryl having 6 to 40 carbon atoms, including group 14, 15 or 16 hetero elements; Substituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms; And a polar functional group containing at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron.

In addition, the present invention provides a photoreactive polymer comprising a repeating unit represented by the following formula (2):

[Formula 2]

In Formula 2, n is 50 to 5000, and S ₁ and A are as defined for Formula 1.

The maleimide-based compound of the present invention exhibits excellent photoreactivity and can be used as a photoreactive compound by itself or in the preparation of various photoreactive polymers that can be applied to various optical applications. The photoreactive polymer obtained therefrom exhibits excellent photoreactivity and thermal stability, and thus can be preferably applied to optical applications.

Hereinafter, the maleimide compound and the photoreactive polymer according to the embodiment of the present invention will be described in detail.

According to one embodiment of the invention, a maleimide compound having a photoreactor represented by the following Chemical Formula 1 is provided:

[Formula 1]

In Formula 1, S ₁ is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted aralkylene having 7 to 15 carbon atoms; Substituted or unsubstituted alkynylene having 2 to 20 carbon atoms; And heteroalkylene having 6 to 20 carbon atoms including hetero group 14, 15 or 16 hetero atoms in the carbon chain,

A is a photoreactor of Formula 1a or 1b,

[Formula 1a]

[Chemical Formula 1b]

In the above general formulas (1a) and (1b)

B is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Carbonyl; Carboxy; ester; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; And substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms,

X is oxygen or sulfur,

P is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted aralkylene having 7 to 15 carbon atoms; Substituted or unsubstituted alkynylene having 2 to 20 carbon atoms; And substituted or unsubstituted cyclic alkylene having 4 to 8 carbon atoms,

R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are the same as or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted cyclic alkyl having 4 to 8 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted C6-C40 aryl; Heteroaryl having 6 to 40 carbon atoms, including group 14, 15 or 16 hetero elements; Substituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms; And a polar functional group containing at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron.

The compound of one embodiment has a predetermined photoreactor (Formula 1a or 1b), such as a cinnamate structure, a Whamcon structure or a coumarin structure, in a maleimide structure that can be used as a precursor of various compounds or a monomer of a polymer. The reactor was introduced. Due to the chemical structure into which the photoreactor is introduced, the maleimide compound may be used as a photoreactive compound by itself.

In addition, various compounds or polymers may be prepared from the maleimide compound due to the characteristics of the maleimide structure that may be used as a precursor, and the compound or polymer thus prepared may also exhibit excellent photoreactivity due to the photoreactor. Therefore, it becomes possible to manufacture various photoreactive polymers applicable to various optical applications using the maleimide compound.

For example, various photoreactive polymers may be obtained by applying various polymerization methods to the maleimide compound. More specifically, since the maleimide structure can be used as a monomer of the polyimide, not only can a photoreactive polyimide be obtained from the maleimide-based compound, but also a copolymer with a monomer such as a polymer or an acrylate through radical polymerization. You can also get Since these polymers or copolymers can exhibit various structures and properties and have photoreactors, they can be widely applied to various optical applications such as photoresist.

On the other hand, the maleimide structure is basically transparent, so that UV absorption occurs well in the low wavelength range. Therefore, when the photoreaction is included here and the photoreaction is developed, all the irradiated light can participate in the photoreaction without light loss. As a result, the light efficiency is increased, so that the light reaction occurs quickly even in a small amount of light. Therefore, the said maleimide type compound, the photoreactive polymer obtained from this, etc. can exhibit the further outstanding photoreactivity. For example, the light efficiency and photoreactivity may be further increased by introducing a substituent into a maleimide structure in which UV absorption occurs at 200 nm or less, mainly a light absorption and photoreaction at 250 nm or more, as a substituent.

In addition, due to the properties of the maleimide structure, the maleimide compound and the photoreactive polymer obtained therefrom can exhibit excellent thermal stability. More specifically, the maleimide compound and the photoreactive polymer may exhibit excellent orientation even when high temperature thermal stress is applied. As a result, the maleimide compound and the photoreactive polymer may have excellent thermal stability as compared to the photoreactive polymer having an acrylic or vinyl backbone. Can be represented.

As a result, the above-described maleimide-based compound may not only be used as a photoreactive compound by showing excellent photoreactivity and thermal stability in itself, but also various photoreactive polymers having various structures and properties may be prepared using the same. In addition, these photoreactive polymers may also exhibit excellent thermal stability and photoreactivity, and thus may be suitably applied to various optical applications.

Hereinafter, the maleimide compound will be described in more detail.

In the maleimide compound, a polar functional group which may be substituted for R 10 to R 14, that is, a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron may be formed of the functional groups listed below. It may be selected from the group, in addition to a variety of polar functional groups containing one or more selected from oxygen, nitrogen, phosphorus, sulfur, silicon or boron:

-R ₅ OR ₆ , -OR ₆ , -OC (O) OR ₆ , -R ₅ OC (O) OR ₆ , -C (O) OR ₆ , -R ₅ C (O) OR _6, -C (O ) R ₆ , -R ₅ C (O) R ₆ , -OC (O) R ₆ , -R ₅ OC (O) R ₆ ,-(R ₅ O) _r -OR ₆ ,-(OR ₅ ) _r- OR ₆ , -C (O) -OC (O) R ₆ , -R ₅ C (O) -OC (O) R ₆ , -SR ₆ , -R ₅ SR ₆ , -SSR ₆ , -R ₅ SSR ₆ , -S (= O) R ₆ , -R ₅ S (= O) R ₆ , -R ₅ C (= S) R _6- , -R ₅ C (= S) SR ₆ , -R ₅ SO ₃ R ₆ , -SO ₃ R ₆ , -R ₅ N = C = S, -N = C = S, -NCO, -R ₅ -NCO, -CN, -R ₅ CN, -NNC (= S) R ₆ , -R ₅ NNC (= S) R ₆ , -NO ₂ , -R ₅ NO ₂ ,

Each independently in the functional group, r is an integer of 1 to 10, R ₅ is substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted alkynylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted carbonyloxyylene having 1 to 20 carbon atoms; Or substituted or unsubstituted alkoxylene having 1 to 20 carbon atoms,

R ₆ , R ₇ , and R ₈ are hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; And substituted or unsubstituted carbonyloxy having 1 to 20 carbon atoms.

Further, in the maleimide compound, the substituted or unsubstituted aryl having 6 to 40 carbon atoms; Or a hetero aryl having 6 to 40 carbon atoms including a hetero element of Group 14, 15 or 16 may be selected from the group consisting of the functional groups listed below, and in addition, may be various aryls or hetero aryls:

In these functional groups, the R _'10 to R' ₁₈ are the same or different, with the remainder having 1 to 20 carbon atoms each independently a linear or branched alkyl, substituted or unsubstituted substituted or unsubstituted C1 to C20 each other Alkoxy, substituted 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 above-described structure of the maleimide compound, the definition of each substituent in detail as follows:

Firstly, "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 may encompass not only unsubstituted but also further substituted by a certain substituent described below. 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.

“Heteroalkyl” means a linear or branched hydrocarbon moiety comprising a group 14, 15 or 16 hetero element, such as oxygen, sulfur or nitrogen, in the carbon chain constituting the alkyl as defined above. Such heteroalkyls may comprise 6 to 20, preferably 6 to 10 carbon atoms. Examples of heteroalkyl include dialkyl ether or dialkyl thioether.

By "alkenyl" is meant 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. . Alkenyl groups may be bonded through a carbon atom comprising a carbon-carbon double bond or through a saturated carbon atom. Alkenyl groups may be broadly referred to as unsubstituted as well as those further substituted by the following substituents. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl, dodecenyl, and the like.

"Cycloalkyl" refers to a saturated or unsaturated non-aromatic monovalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, which also includes those further substituted by certain substituents described below. can do. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, isobornyl, norbornyl (ie, bicyclo [2 , 2,1] hept-5-enyl).

“Aryl” means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having from 6 to 40, preferably from 6 to 12 ring atoms, encompassing those further substituted by certain substituents described below. May be referred to. Examples of the aryl group include phenyl, naphthalenyl, fluorenyl and the like.

"Alkoxyaryl" means that at least one hydrogen atom of the aryl group defined above is substituted with an alkoxy group. Examples of the alkoxyaryl group are methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentoxyphenyl, hexoxyphenyl, heptoxy, octoxy, nanoxy, methoxybiphenyl, methoxynaphthalenyl, Methoxy fluorenyl, methoxy anthracenyl, and the like.

“Aralkyl” means that at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group, and may be referred to as being further substituted by a specific substituent described below. For example, benzyl, benzhydryl, trityl, etc. are mentioned.

By "alkynyl" is meant a linear or branched monovalent hydrocarbon moiety of from 2 to 20 carbon atoms, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms containing at least one carbon-carbon triple bond do. Alkynyl groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynyl groups may also be referred to collectively further substituted by certain substituents described below. For example, ethynyl, propynyl, etc. are mentioned.

"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 can also be referred to collectively further substituted by certain substituents described below. Examples of the alkylene group include methylene, ethylene, propylene, butylene, hexylene and the like.

＂Heteroalkylene＂ is a linear or branched divalent hydrocarbon moiety comprising a group 14, 15 or 16 hetero element, such as oxygen, sulfur or nitrogen, in the carbon chain constituting the alkylene as defined above Means. Such heteroalkylenes may comprise 6 to 20, preferably 6 to 10 carbon atoms.

“Alkenylene” means a linear or branched divalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms containing at least one carbon-carbon double bond. do. Alkenylene groups may be bonded through a carbon atom comprising a carbon-carbon double bond and / or through a saturated carbon atom. Alkenylene group can also refer to what is further substituted by the specific substituent mentioned later.

“Cycloalkylene” refers to a saturated or unsaturated non-aromatic divalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, including those further substituted by certain substituents described below. May be referred to. For example, cyclopropylene, cyclobutylene, etc. are mentioned.

“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 the following substituents It may be referred to inclusively. The aromatic moiety contains only carbon atoms. Phenylene etc. are mentioned as an example of an arylene group.

“Aralkylene” means a divalent moiety in which at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group, and may be referred to as a whole further substituted by a specific substituent described below. For example, benzylene etc. can be mentioned.

By "alkynylene" it is meant a linear or branched divalent hydrocarbon moiety of 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 6, carbon atoms containing at least one carbon-carbon triple bond do. Alkynylene groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynylene groups can also be referred to collectively further substituted by certain substituents described below. For example, ethynylene, propynylene, etc. are mentioned.

Substituted or unsubstituted substituents described above encompass not only each of these substituents themselves, but also those further substituted by constant substituents. In the present specification, examples of the substituent which may be further substituted with each substituent include halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, Alkoxy, haloalcohol, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, siloxy or polar functional groups including oxygen, nitrogen, phosphorus, sulfur, silicon or boron as previously described Etc. can be mentioned.

The above-mentioned maleimide compound may be prepared according to a conventional method of introducing predetermined substituents, more specifically, photoreactors of Formulas 1a and 1b into maleimide, and various methods known to prepare other maleimide structures. It can be prepared as. For example, a compound such as N-ethanol maleimide having alkylol introduced into maleimide and an acyl chloride-based compound having a photoreactive group, for example, cinnamoyl chloride or coumarin acyl chloride, are substituted with cinnamate. The maleimide compound can be produced by introducing a photoreactive group such as a group or a coumarin group. In addition, the above-described maleimide compound may be prepared by introducing the photoreactor in various ways according to the structure and type of the other photoreactor.

On the other hand, according to another embodiment of the invention, there is provided a photoreactive polymer comprising a repeating unit represented by the following formula (2):

[Formula 2]

In Formula 2, n is 50 to 5000, and S ₁ and A are as defined for Formula 1.

Such photoreactive polymers include repeating units derived from the above-described maleimide-based compounds, and may exhibit excellent photoreactivity and thermal stability depending on the synergism of the maleimide structure and a predetermined photoreactor, and are preferable for optical applications. Can be applied.

Since the definition of each substituent bonded to the photoreactive polymer has already been described in detail with respect to Formula 1, further description thereof will be omitted.

The photoreactive polymer may include only one or more repeating units selected from the group consisting of repeating units represented by Formula 2, but may also be a copolymer further comprising other types of repeating units. Examples of such repeating units include any olefinic repeating unit, acrylate repeating unit, or cyclic olefinic repeating unit, etc., to which cinnamate-based, coumarin-based, chalcone-based or azo-based photoreactors are bonded or unbonded. Can be. Examples of such repeating units are disclosed in patent publication no. 2010-0021751 and the like.

More specifically, the photoreactive polymer may be a copolymer further comprising an acrylate-based repeating unit of Formula 3 together with the repeating unit of Formula 2:

(3)

In Formula 3, m is 50 to 5000, Ra is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, Rb is hydrogen or an alkyl group having 1 to 20 carbon atoms.

However, the photoreactive polymer is a repeating unit of Formula 2 in an amount of about 50 mol% or more, specifically about 50 to 100 mol%, preferably about 70 mol% or more, so that excellent properties according to Chemical Formula 2 are not impaired. It may include.

In addition, the photoreactive polymer may be prepared by a method such as radical addition polymerization of the maleimide compound of one embodiment, and when further comprising other repeating units, a monomer corresponding thereto may be added together with the maleimide compound. It can be prepared in the form of a copolymer by polymerization. For example, when the photoreactive polymer is in the form of a copolymer including the repeating units of Formulas 2 and 3, together with the maleimide compound, methyl methacrylate, methyl acrylate, butyl acrylate or isobonyl An acrylate monomer such as acrylate may be copolymerized to prepare a photoreactive polymer in the form of the copolymer. In particular, in the case of copolymerizing such an acrylate monomer, the radical addition polymerization proceeds more preferably with respect to the maleimide compound, so that the photoreactive polymer may be prepared in a higher yield. In this case, the radical addition polymerization may be performed using a conventional radical initiator such as AIBN.

In addition, the repeating unit of Formula 2 constituting the photoreactive polymer may have a polymerization degree of about 50 to 5,000, preferably a polymerization degree of about 100 to 4000, and more preferably about 1000 to 3000. In addition, the photoreactive polymer may have a weight average molecular weight of 10000 to 1000000, preferably 20000 to 500000. Accordingly, the photoreactive polymer may be suitably included in the coating composition for forming the alignment film to exhibit excellent coatability, but the alignment film formed therefrom may exhibit excellent liquid crystal alignment.

The photoreactive polymer described above may exhibit excellent photoreactivity and thermal stability that can be suitably used in various optical applications such as photoresist, and may exhibit various properties depending on the structure of the polymer or copolymer including the repeating unit. . Therefore, it can be preferably used for various light applications.

The photoreactive polymers described above may exhibit photoreactivity under exposure of polarized light having a wavelength of about 250 to 450 nm, for example, of polarized light having a wavelength of about 250 to 400 nm, more specifically, a wavelength of about 280 to 350 nm. It can exhibit excellent photoreactivity under exposure. In particular, by selecting and adjusting the type of photoreactor of Formula 1a or 1b, it can exhibit excellent photoreactivity with respect to light over a wide wavelength band and light polarized in various directions.

On the other hand, according to another embodiment of the invention, there is provided an alignment film comprising the photoreactive polymer described above. Such an alignment layer may include not only a thin film but also an alignment film in a film form. According to another embodiment of the invention, there is provided a liquid crystal retardation film comprising such an alignment film and a liquid crystal layer on the alignment film.

Such an alignment film and a liquid crystal retardation film may be manufactured using constituents and manufacturing methods known in the art, except for including the photoreactive polymer described above as a photoalignment polymer.

For example, the alignment layer may be formed by mixing the photoreactive polymer, the binder resin and the photoinitiator and dissolving it in an organic solvent to obtain a coating composition, then coating the coating composition on a substrate and performing UV curing.

At this time, the binder resin may be an acrylate resin, and more specifically, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, tris (2-acryloyloxy Ethyl) isocyanurate and the like can be used.

In addition, as the photoinitiator, a conventional photoinitiator known to be usable for the alignment layer may be used without particular limitation. For example, photoinitiators known under the trade names Irgacure 907 and 819 may be used.

As the organic solvent, toluene, anisole, chlorobenzene, dichloroethane, cyclohexane, cyclopentane, propylene glycol methyl ether acetate, and the like can be used. Since the photoreactive polymer described above exhibits excellent solubility in various organic solvents, various organic solvents may be used without particular limitation.

In the coating composition, the solid content concentration including the photoreactive polymer, the binder resin and the photoinitiator may be 1 to 15% by weight, and in order to cast the alignment layer into a film, 10 to 15% by weight is preferable, and a thin film form In order to form, 1 to 5% by weight is preferable.

The alignment film thus formed may be formed on the substrate, and may be formed under the liquid crystal to align it. In this case, the substrate may be a glass substrate, a substrate containing a cyclic polymer such as COP or COC, a substrate containing an acrylic polymer or a substrate containing a cellulose polymer such as TAC, and the like, and the coating composition After coating on the substrate by various methods such as spin coating, blade coating, and the like, the alignment layer may be formed by UV curing.

Photo-alignment may occur by UV curing. In this step, alignment may be performed by irradiating polarized UV in a wavelength range of about 150 to 450 nm. In this case, the intensity of the exposure may be about 50 mJ / cm 2 to 10 J / cm 2, preferably about 500 mJ / cm 2 to 5 J / cm 2.

The UV is a polarizing device using a substrate coated with a dielectric anisotropic substance on the surface of a transparent substrate such as quartz glass, soda lime glass, soda lime free glass, ② polarizing plate finely deposited aluminum or metal wire, or ③ quartz Polarized UV selected from polarized UV may be applied by passing or reflecting through a Brewster polarizer or the like due to reflection of glass.

As for the substrate temperature at the time of irradiating the said UV, normal temperature is preferable. However, in some cases, UV may be irradiated in a heated state within a temperature range of 100 ° C or lower. It is preferable that the film thickness of the final coating film formed by the above series of processes is 30-1000 nm.

An alignment film is formed by the method mentioned above, a liquid crystal layer is formed on it, and a liquid crystal phase difference film can be manufactured in accordance with a conventional method. As the alignment layer includes the photoreactive polymer, the alignment layer may exhibit excellent photoreactivity and orientation, and thus, an effective photoalignment may be progressed.

The above-described alignment film or liquid crystal retardation film may be applied to an optical film or an optical filter for implementing a stereoscopic image.

Accordingly, according to another embodiment of the present invention, a display device including the alignment layer is provided. The display device may be a liquid crystal display device in which the alignment layer is included for alignment of liquid crystals, or a stereoscopic image display device in which the alignment layer is included in an optical film or a filter for realizing a stereoscopic image. However, since the configuration of these display elements includes the photoreactive polymer and the alignment layer described above, since the structure of the display device is the same as that of a conventional device, detailed description thereof will be omitted.

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.

In addition, all operations dealing with air or water sensitive compounds in the following examples were carried out using the standard Schlenk technique or dry box technique. Nuclear magnetic resonance (NMR) spectra were obtained using a Bruker 300 spectrometer, where ¹ H NMR was measured at 300 MHz and ¹³ C NMR at 75 MHz, respectively. The molecular weight and molecular weight distribution of the ring-opening hydrogenated polymer were measured using gel permeation chromatography (GPC), in which polystyrene samples were used as standard.

Toluene was purified by distillation in potassium / benzophenone and dichloromethane was distilled and purified in CaH ₂ .

Preparation Example 1:

Furan (92.5 g, 1.36 mol) and maleic anhydride (100 g, 1.01 mol) were added to EA (125 ml) and stirred at room temperature for about 24 hours. Filtration gave Compound 1 of the following scheme and dried in a vacuum oven. Dried compound 1 (28 g, 0.17 mol) was added to ethanol (50 ml), and ethanol amine (11 g, 1.03 equiv) dissolved in 15 ml ethanol was added dropwise. After stirring under reflux at 85 ° C. for 4 hours, the reaction mixture was cooled to room temperature and sonicated to obtain Compound 2 in a crystalline solid state. Formula 2 (25 g) was dissolved in toluene, stirred under reflux for 16 hours, cooled to 0 ° C., and recrystallization was performed. Thereafter, the mixture was washed with petroleum ether to obtain compound 3. Total yield 38%.

NMR (DMSO-d6, ppm) 2.77 (2H, t), 3.61 (2H, t), 6.83 (2H, d)

Example 1:

Compound 3 (10 g, 71 mmol) obtained in Production Example 1 and cinnamoyl chloride (1 equivalent) obtained by chlorination with SOCl ₃ were added to toluene (100 g), and triethylamine (2 equivalent) was added dropwise thereto at 90 ° C. It was stirred at reflux for 16 hours. Thereafter, the salt was removed by filtration and the solvent was evaporated. Subsequently, EA / water was added and extracted to prepare compound 4 of the following reaction scheme which is a maleimide compound having a photoreactive group. Yield 44%.

NMR (CDCl ₃ , ppm) 2.86 (2H, t), 3.65 (2H, t), 6.35 (1H, dd), 6.83 (2H, d), 6.95 (2H, d), 7.53 (2H, d), 7.70 (1H, dd), 7.81 (1H, m)

Compound 4

Example 2:

Compound 3 (10 g, 71 mmol) obtained in Production Example 1 and 4-methoxy-cinnamoyl chloride (1 equivalent) obtained by chlorination with SOCl ₃ were added to toluene (100 g), and triethylamine (2 equivalent) was added dropwise. After stirring at reflux for 16 hours at 90 ℃. Thereafter, the salt was removed by filtration and the solvent was evaporated. Subsequently, EA / water was added and extracted to prepare compound 5 of the following reaction scheme which is a maleimide compound having a photoreactive group. Yield 57%.

NMR (CDCl ₃ , ppm) 2.86 (2H, t), 3.65 (2H, t), 4.33 (3H, s), 6.35 (1H, dd), 6.85 (4H, m), 7.41 (2H, d), 7.67 (1H, dd)

Compound 5

Example 3:

Compound 3 (10 g, 71 mmol) obtained in Production Example 1 and 4-fluoro-cinnamoyl chloride (1 equivalent) obtained by chlorination with SOCl ₃ were added to toluene (100 g), and triethylamine (2 equivalent) was added dropwise. After stirring at reflux for 16 hours at 90 ℃. Thereafter, the salt was removed by filtration and the solvent was evaporated. Subsequently, EA / water was added and extracted to prepare compound 6 of the following reaction formula which is a maleimide compound having a photoreactive group. Yield: 41%.

NMR (CDCl ₃ , ppm) 2.86 (2H, t), 3.65 (2H, t), 6.36 (1H, dd), 6.93 (4H, m), 7.70 (1H, m), 7.87 (2H, d)

Compound 6

Example 4:

Compound 3 (10 g, 71 mmol) obtained in Production Example 1 and 3-fluoro-cinnamoyl chloride (1 equivalent) obtained by chlorination with SOCl ₃ were added to toluene (100 g), and triethylamine (2 equivalent) was added dropwise. After stirring at reflux for 16 hours at 90 ℃. Thereafter, the salt was removed by filtration and the solvent was evaporated. Subsequently, EA / water was added and extracted to prepare compound 7 of the following reaction formula which is a maleimide compound having a photoreactive group. Yield 32%.

NMR (CDCl ₃ , ppm) 2.86 (2H, t), 3.65 (2H, t), 6.36 (1H, dd), 6.84 (2H, d), 7.17-7.75 (4H, m), 7.81 (1H, m) , 7.83 (2H, d)

Compound 7

Example 5:

Compound 3 (10 g, 71 mmol) obtained in Production Example 1 and 4-phenoxy-cinnamoyl chloride (1 equivalent) obtained by chlorination with SOCl ₃ were added to toluene (100 g), and triethylamine (2 equivalent) was added dropwise. After stirring at reflux for 16 hours at 90 ℃. Thereafter, the salt was removed by filtration and the solvent was evaporated. Subsequently, EA / water was added and extracted to prepare compound 8 of the following reaction formula which is a maleimide compound having a photoreactive group. Yield 32%.

NMR (CDCl ₃ , ppm) 2.86 (2H, t), 3.65 (2H, t), 6.84 (2H, d), 7.17 ~ 7.35 (4H, m), 7.81 (1H, m), 7.83 (2H, d)

Compound 8

Example 6:

Compound 4 (10 g, 37 mmol), methylmethacrylate (1 equiv) and AIBN (1 mol%) prepared in Example 1 were added to toluene and stirred at 70 ° C. for 24 hours. After the reaction, the polymer solution was added dropwise to ethanol to obtain a precipitate. And, dried in a vacuum oven to prepare a photoreactive polymer. (Mw = 32000, PDI = 2.13, yield = 61%).

Example 7:

Compound 5 (10 g, 33 mmol), methylmethacrylate (1 equiv) and AIBN (1 mol%) prepared in Example 2 were added to toluene and stirred at 70 ° C. for 24 hours. After the reaction, the polymer solution was added dropwise to ethanol to obtain a precipitate. And, dried in a vacuum oven to prepare a photoreactive polymer. (Mw = 50000, PDI = 4.10, yield = 54%).

Example 8:

Compound 6 (10 g, 34 mmol), methylmethacrylate (1 equiv) and AIBN (1 mol%) prepared in Example 3 were added to toluene and stirred at 70 ° C. for 24 hours. After the reaction, the polymer solution was added dropwise to ethanol to obtain a precipitate. And, dried in a vacuum oven to prepare a photoreactive polymer. (Mw = 25000, PDI = 2.57, yield = 36%).

Example 9:

Compound 7 (10 g, 34 mmol), methylmethacrylate (1 equiv) and AIBN (1 mol%) prepared in Example 4 were added to toluene and stirred at 70 ° C. for 24 hours. After the reaction, the polymer solution was added dropwise to ethanol to obtain a precipitate. And, dried in a vacuum oven to prepare a photoreactive polymer. (Mw = 37000, PDI = 2.93, yield = 40%).

Example 10:

Compound 8 (10 g, 28 mmol), methylmethacrylate (1 equiv) and AIBN (1 mol%) prepared in Example 5 were added to toluene and stirred at 70 ° C. for 24 hours. After the reaction, the polymer solution was added dropwise to ethanol to obtain a precipitate. And, dried in a vacuum oven to prepare a photoreactive polymer. (Mw = 33000, PDI = 3.51, yield = 47%).

Test Example 1 Preparation of Liquid Crystal Film and Evaluation of Physical Properties

The photoreactive polymers prepared in Examples 6 to 10 were dissolved in toluene at a concentration of 2 to 3% by weight, and the solution was dropped on a glass substrate or a polymer film (cycloolefin-based stretched film of COC or COP or TAC film). Stirred and bar-coated and dried at 60 ° C. for 2 minutes. After drying, the degree of coating was evaluated by observing the degree to which a uniform coating film was formed on the substrate or the film. The degree of coating property was represented by an integer of 1 to 5, the closer to 5 was evaluated as a coating film having a uniform thickness on the substrate or film.

On the other hand, the coating film was irradiated with ultraviolet (UV) light of 200mJ / cm ² to proceed with curing to form an orientation film. The liquid crystal for A-plate was coated on the thus formed alignment film, and dried at 60 ° C. for 2 minutes to irradiate 50 mJ / cm ² ultraviolet rays to cure the liquid crystal. And the film was put between the polarizing plates, and the degree of orientation was confirmed. The degree of orientation was also represented by an integer of 1 to 5, and closer to 5 was evaluated as having excellent orientation.

In addition, after forming the alignment film, the thermal stress was applied at 100 ℃ for 10 hours, the temperature was lowered again, and the liquid crystal coating, drying and liquid crystal curing was carried out in the same manner as in the evaluation of the orientation. Then, the orientation after thermal stress addition was confirmed by the method similar to the orientation evaluation method mentioned above. The orientation after such thermal stress addition was also represented by an integer of 1 to 5, and closer to 5 was evaluated as showing excellent thermal stability due to excellent orientation after thermal stress addition.

Each property evaluation result described above is shown in Table 1 below.

Polymer used Coating Orientation Thermal Stability (Orientation after Thermal Stress Applied) Example 6 5 4.5 4 Example 7 5 5 5 Example 8 5 5 5 Example 9 5 5 5 Example 10 5 4.5 4

Referring to Table 1, it was confirmed that the photoreactive polymers of the examples were included in the alignment film to exhibit excellent orientation, as well as to exhibit excellent coating properties enabling the formation of uniform coating films on various substrates. In addition, it was confirmed that the photoreactive polymer maintains excellent orientation even after thermal stress is added, and exhibits excellent thermal stability. The excellent thermal stability of such photoreactive polymers appears to be due to the presence of maleimide backbones, which have been shown to exhibit superior thermal stability over previous photoreactive polymers having backbones such as acrylic or vinyl based.

Claims (11)

Maleimide compounds having a photoreactor represented by the following formula (1):
[Formula 1]

In Formula 1, S ₁ is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted aralkylene having 7 to 15 carbon atoms; Substituted or unsubstituted alkynylene having 2 to 20 carbon atoms; And heteroalkylene having 6 to 20 carbon atoms including hetero group 14, 15 or 16 hetero atoms in the carbon chain,
A is a photoreactor of Formula 1a or 1b,
[Formula 1a]

[Chemical Formula 1b]

In the above general formulas (1a) and (1b)
B is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Carbonyl; Carboxy; ester; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; And substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms,
X is oxygen or sulfur,
P is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted aralkylene having 7 to 15 carbon atoms; Substituted or unsubstituted alkynylene having 2 to 20 carbon atoms; And substituted or unsubstituted cyclic alkylene having 4 to 8 carbon atoms,
R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are the same as or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted cyclic alkyl having 4 to 8 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted C6-C40 aryl; Heteroaryl having 6 to 40 carbon atoms, including group 14, 15 or 16 hetero elements; Substituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms; And a polar functional group containing at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron.
The maleimide compound according to claim 1, wherein the polar functional group containing at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron is selected from the group consisting of the functional groups listed below:
-R ₅ OR ₆ , -OR ₆ , -OC (O) OR ₆ , -R ₅ OC (O) OR ₆ , -C (O) OR ₆ , -R ₅ C (O) OR _6, -C (O ) R ₆ , -R ₅ C (O) R ₆ , -OC (O) R ₆ , -R ₅ OC (O) R ₆ ,-(R ₅ O) _r -OR ₆ ,-(OR ₅ ) _r- OR ₆ , -C (O) -OC (O) R ₆ , -R ₅ C (O) -OC (O) R ₆ , -SR ₆ , -R ₅ SR ₆ , -SSR ₆ , -R ₅ SSR ₆ , -S (= O) R ₆ , -R ₅ S (= O) R ₆ , -R ₅ C (= S) R _6- , -R ₅ C (= S) SR ₆ , -R ₅ SO ₃ R ₆ , -SO ₃ R ₆ , -R ₅ N = C = S, -N = C = S, -NCO, -R ₅ -NCO, -CN, -R ₅ CN, -NNC (= S) R ₆ , -R ₅ NNC (= S) R ₆ , -NO ₂ , -R ₅ NO ₂ ,

Each independently in the functional group, r is an integer of 1 to 10, R ₅ is substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted alkynylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted carbonyloxyylene having 1 to 20 carbon atoms; Or substituted or unsubstituted alkoxylene having 1 to 20 carbon atoms,
R ₆ , R ₇ , and R ₈ are hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; And substituted or unsubstituted carbonyloxy having 1 to 20 carbon atoms.
The compound of claim 1, wherein the substituted or unsubstituted aryl having 6 to 40 carbon atoms; Or a hetero aryl having 6 to 40 carbon atoms including a group 14, 15 or 16 hetero element is selected from the group consisting of the functional groups listed below:

In these functional groups, R _'10 to R' ₁₈ are the same or different and each independently represents alkoxy, optionally substituted substituted or unsubstituted C1 to C20 linear or branched alkyl, substituted or unsubstituted C1 to C20 of each other Or unsubstituted aryloxy having 6 to 30 carbon atoms, and substituted or unsubstituted aryl having 6 to 40 carbon atoms.
A photoreactive polymer comprising a repeating unit represented by the following formula (2):
(2)

In Formula 2, S ₁ is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted aralkylene having 7 to 15 carbon atoms; Substituted or unsubstituted alkynylene having 2 to 20 carbon atoms; And heteroalkylene having 6 to 20 carbon atoms including hetero group 14, 15 or 16 hetero atoms in the carbon chain,
n is 50 to 5000,
A is a photoreactor of Formula 1a or 1b,
[Formula 1a]

[Chemical Formula 1b]

In the above general formulas (1a) and (1b)
B is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Carbonyl; Carboxy; ester; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; And substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms,
X is oxygen or sulfur,
P is a simple bond; Substituted or unsubstituted alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted aralkylene having 7 to 15 carbon atoms; Substituted or unsubstituted alkynylene having 2 to 20 carbon atoms; And substituted or unsubstituted cyclic alkylene having 4 to 8 carbon atoms,
R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are the same as or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted cyclic alkyl having 4 to 8 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted C6-C40 aryl; It is selected from the group consisting of heteroaryl having 6 to 40 carbon atoms containing a hetero element of Group 14, 15 or 16, and substituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms.
The light according to claim 4, further comprising an olefinic repeating unit, an acrylate repeating unit, or a cyclic olefin repeating unit, wherein the cinnamate-based, coumarin-based, chalcone-based or azo-based photoreactor is bonded or unbonded. Reactive polymers.
The photoreactive polymer of claim 5, further comprising an acrylate-based repeating unit represented by Formula 3 below:
(3)

In Formula 3, m is 50 to 5000, Ra is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, Rb is hydrogen or an alkyl group having 1 to 20 carbon atoms.
5. The photoreactive polymer of claim 4 having a weight average molecular weight of 10000 to 1000000.
The photoreactive polymer of claim 1, wherein the photoreactive polymer exhibits photoreactivity under exposure of polarized light having a wavelength of 250 to 450 nm.
An alignment film comprising the photoreactive polymer of any one of claims 4 to 8.
A liquid crystal retardation film comprising the alignment film of claim 9 and a liquid crystal layer on the alignment film.
A display element comprising the alignment layer of claim 9.