WO2010002195A2 - Adhesive composition, polarizing plate, and liquid crystal display - Google Patents

Abstract

The present invention relates to an adhesive composition, to a polarizing plate, and to a liquid crystal display. According to the present invention, provided are: an adhesive composition which exhibits excellent durability and reliability under high-temperature or high-humidity conditions, exhibits improved workability related to a cutting process or a re-peeling process, and specifically effectively suppresses light leakage in a liquid crystal display; a polarizing plate containing a cured material of the adhesive composition; and a liquid crystal display.

Description

Adhesive composition, polarizer and liquid crystal display device

The present invention relates to an adhesive composition, a polarizing plate and a liquid crystal display device.

A liquid crystal display is a device that displays a screen by inserting a liquid crystal between two glass substrates. In the device, when a voltage is applied through an electrode connected to the liquid crystal, the molecular arrangement of the liquid crystal is changed, and accordingly, the transmittance of light passing through the liquid crystal is changed to display an image. Such a liquid crystal display device is a display device that is currently in the spotlight in various fields because of the advantages of low power consumption and flatness.

In order to manufacture a liquid crystal display device, a liquid crystal cell and a polarizing plate including a transparent substrate on which a liquid crystal and an electrode layer are formed are required, and an adhesive or pressure-sensitive adhesive for bonding them is required.

One of the main characteristics to be considered in the design of the liquid crystal display is the low light leakage characteristic. That is, a functional film such as a retardation plate, a wide viewing angle compensation plate, or a brightness enhancement film may be additionally attached to the polarizing plate included in the liquid crystal display device. By the way, each functional film constituting the multilayer polarizing plate is made of a material having a different molecular structure and composition, thereby exhibiting different physical properties. Accordingly, in particular, high temperature and / or high humidity conditions have a problem of poor dimensional stability depending on the difference in shrinkage and expansion behavior of the respective materials. Therefore, when the polarizing plate is fixed by an adhesive or the like, there is a problem that stress is concentrated under high temperature and / or high humidity conditions, birefringence occurs, and light leakage occurs.

Representative methods for solving such problems include a method of optimizing a design such as an adhesive for fixing a polarizing plate. For example, a method of softly designing an adhesive so as to easily deform with respect to external stress to impart stress relaxation characteristics or very hard design to suppress shrinkage of a polarizing plate according to an external environment is used.

In addition, Japanese Patent Application Laid-open No. Hei 10-279907 discloses a method of improving light leakage phenomenon by blending a relatively large molecular weight acrylic resin and a relatively small molecular weight acrylic resin to impart stress relaxation characteristics to the pressure-sensitive adhesive.

In addition, Korean Patent Laid-Open Publication No. 2003-0069461 discloses a method for compensating birefringence by blending a material exhibiting positive birefringence under a residual stress in an adhesive.

However, it is difficult to give effective light leakage suppressing ability only by controlling the stress relaxation characteristics of the pressure-sensitive adhesive. In addition, even in the case of blending a material exhibiting positive birefringence under residual stress, there is a disadvantage that essential properties such as adhesion and durability are lowered due to a decrease in compatibility with the adhesive resin.

An object of this invention is to provide an adhesive composition, a polarizing plate, and a liquid crystal display device.

The present invention provides a pressure-sensitive adhesive composition comprising an acrylic resin having a weight average molecular weight of 800,000 to 2 million, and an optically anisotropic compound present in a liquid phase at room temperature.

The present invention is another means for solving the above problems, a polarizing film or a polarizing element; And

It is provided on one side or both sides of the said polarizing film or a polarizing element, and provides the polarizing plate containing the adhesive layer containing the hardened | cured material of the adhesive composition which concerns on this invention.

The present invention provides another liquid crystal display device including a liquid crystal panel in which the polarizing plate according to the present invention is attached to one side or both sides of a liquid crystal cell.

According to the present invention, a pressure-sensitive adhesive composition exhibiting excellent durability under high temperature or high humidity conditions, and excellent workability such as cutting property and re-peelability, and which can effectively suppress light leakage phenomenon generated in a liquid crystal display device, and its hardness Provided are a polarizing plate and a liquid crystal display including a package.

The present invention, the acrylic resin having a weight average molecular weight of 800,000 to 2 million; And it relates to a pressure-sensitive adhesive composition comprising an optically anisotropic compound present in the liquid phase at room temperature.

 Hereinafter, the pressure-sensitive adhesive composition of the present invention will be described in detail.

 The acrylic resin used in the present invention is designed to have a weight average molecular weight in the range of 800,000 to 2 million. If the weight average molecular weight of the acrylic resin contained in the pressure-sensitive adhesive composition is less than 800,000, there may be a problem in durability reliability due to the decrease in cohesion force, and in excess of 2 million, the stress relaxation property is lowered and the light leakage inhibitory effect may be lowered. There is.

The specific composition of acrylic resin which can be used by this invention is not specifically limited. In the present invention, for example, (meth) acrylic acid ester monomer 90 parts by weight to 99.9 parts by weight; And 0.1 to 10 parts by weight of the crosslinkable monomer.

In addition, in this invention, acrylic resin containing an aromatic substituent can be used depending on a case. Acrylic resin containing an aromatic substituent can be manufactured by copolymerizing an aromatic ring containing monomer with the above-mentioned conventional acrylic monomer. Typically, acrylic monomers exhibit negative birefringence under residual stress, and when applied to optical parts such as polarizing plates, there is a fear of causing light leakage. The aromatic ring-containing monomer is a compound that exhibits positive birefringence under residual stress, and can be optically compensated by appropriately copolymerizing it with an acrylic monomer.

More specifically, when the acrylic resin includes an aromatic substituent, for example, 55 parts by weight to 94.9 parts by weight of (meth) acrylic acid ester monomer; 5 parts by weight to 35 parts by weight of an aromatic ring-containing monomer; And 0.1 to 10 parts by weight of the crosslinkable monomer.

The type of the (meth) acrylic acid ester monomer is not particularly limited, and alkyl (meth) acrylate can be used, for example. In this case, when the alkyl group contained in the monomer is too long, the cohesive force of the pressure-sensitive adhesive may be lowered, and the glass transition temperature (T _g ) or the adhesion may be difficult to be controlled, and thus (meth) having an alkyl group having 1 to 14 carbon atoms. Preference is given to using acrylic ester monomers. Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth ) Acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, iso Octyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate and tetradecyl (meth) acrylate. Mixtures of two or more species may be used. In the present invention, the (meth) acrylic acid ester monomer as described above is included in the monomer mixture in an amount of 90 parts by weight to 99.9 parts by weight based on the content of the crosslinkable monomer; Or it is preferably included in the monomer mixture in an amount of 55 parts by weight to 94.9 parts by weight relative to the content of the crosslinkable functional group or the aromatic ring-containing monomer. If the content of the (meth) acrylic acid ester monomer is too small, there is a risk that the balance of adhesive physical properties is lowered. If the content of the (meth) acrylic acid ester monomer is too small, the negative birefringence may be too large under residual stress, resulting in light leakage. However, the content of the (meth) acrylic acid ester monomer is only one example of the present invention, and in the present invention, whether or not an aromatic substituent is included in the polymer and its kind; Alternatively, the physical properties of the monomers can be appropriately controlled in consideration of the content of the optically anisotropic compound and the kind thereof.

On the other hand, the kind of the aromatic ring-containing monomer included in the monomer mixture of the present invention is also not particularly limited, and for example, a (meth) acrylate monomer containing an aromatic ring can be used. More specific examples of such monomers include compounds represented by the following general formula (1).

[Formula 1]

In Formula 1 R ₁ represents hydrogen or alkyl, A represents alkylene, alkenylene or alkynylene, n represents an integer of 0 to 3, Q is a single bond, -O-, -S-, alkyl Lene, alkenylene or alkynylene, and P represents an aromatic ring.

In the definition of Chemical Formula 1, "single bond" means a case where both groups of atoms are directly bonded to each other without a separate atom.

In the definition of Chemical Formula 1, R ₁ may be preferably hydrogen or alkyl having 1 to 4 carbon atoms, more preferably hydrogen, methyl or ethyl.

In addition, in the definition of Formula 1, A may be alkylene having 1 to 12, preferably 1 to 8 carbon atoms, more preferably methylene, ethylene, hexylene or octylene.

In addition, in the definition of Chemical Formula 1, alkenylene or alkynylene may be alkenylene or alkynylene having 2 to 12, preferably 2 to 8, more preferably 2 to 4 carbon atoms, specifically, ethenylene , Ethynylene, propenylene or propynylene.

In addition, in the definition of Formula 1, n is preferably an integer of 0 to 2, more preferably 0 or 1.

Also, in the definition of Chemical Formula 1, Q may preferably be a single bond, -O- or S-.

In addition, in the definition of Formula 1, P is a substituent derived from an aromatic compound, preferably an aromatic ring having 6 to 20 carbon atoms, more preferably phenyl, biphenyl, naphthyl or anthracenyl, more preferably Preferably phenyl.

In addition, in the compound of Formula 1, the aromatic ring may be optionally substituted with one or more substituents, and specific examples of the substituents may be halogen or alkyl, preferably halogen or alkyl having 1 to 12 carbon atoms, more preferably. Include, but are not limited to, chlorine, bromine, methyl, ethyl, propyl, butyl, nonyl or dodecyl.

Specific examples of the compound of Formula 1 include phenoxy ethyl (meth) acrylate, benzyl (meth) acrylate, 2-phenylthio-1-ethyl (meth) acrylate, 6- (4,6-dibro) Mo-2-isopropylphenoxy) -1-hexyl (meth) acrylate, 6- (4,6-dibromo-2-sec-butyl phenoxy) -1-hexyl (meth) acrylate, 2, 6-dibromo-4-nonylphenyl (meth) acrylate, 2,6-dibromo-4-dodecylphenyl (meth) acrylate, 2- (1-naphthyloxy) -1-ethyl (meth ) Acrylate, 2- (2-naphthyloxy) -1-ethyl (meth) acrylate, 6- (1-naphthyloxy) -1-hexyl (meth) acrylate, 6- (2-naphthyloxy A kind of) -1-hexyl (meth) acrylate, 8- (1-naphthyloxy) -1-octyl (meth) acrylate and 8- (2-naphthyloxy) -1-octyl (meth) acrylate Or a mixture of two or more kinds thereof, and preferably phenoxy ethyl (meth) acrylate and benzyl (meth) acrylate And one or more kinds of 2-phenylthio-1-ethyl acrylate, 8- (2-naphthyloxy) -1-octyl acrylate and 2- (1-naphthyloxy) -ethyl acrylate, More preferably, it may be one kind or a mixture of two or more kinds of phenoxy ethyl (meth) acrylate and benzyl (meth) acrylate.

In the present invention, the aromatic ring-containing monomer may be included in the monomer mixture in an amount of 5 parts by weight to 35 parts by weight based on the content of the (meth) acrylic acid ester monomer or the crosslinkable monomer. When the content is less than 5 parts by weight, the optical compensation effect due to the addition of the monomer may be insignificant. When the content is more than 35 parts by weight, physical properties such as adhesive properties or re-peelability may be lowered, or in some cases, optical compensation effects. May rather deteriorate. However, the content of the monomer is only one example of the present invention, and in the present invention, the content of the monomer can be appropriately controlled in consideration of the content and type of the optically anisotropic compound.

In the present invention, the crosslinkable monomer included in the monomer mixture may impart cohesive force to the pressure-sensitive adhesive by reacting with the polyfunctional crosslinking agent described below, and impart a crosslinkable functional group capable of adjusting the adhesive force, durability, and the like to the polymer. Examples of such crosslinkable monomers include hydroxy group-containing monomers, carboxyl group-containing monomers and nitrogen-containing monomers. Examples of the hydroxy group-containing monomers above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) Acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate, and examples of the carboxyl group-containing monomer are acrylic acid. , Methacrylic acid, 2- (meth) acryloyloxy acetic acid, 3- (meth) acryloyloxy propyl acid, 4- (meth) acryloyloxy butyl acid, acrylic acid duplex, itaconic acid, maleic acid and Maleic anhydride, and examples of the nitrogen-containing monomer include (meth) acrylamide, N-vinyl pyrrolidone or N-vinylcaprolactam, but are not limited thereto. In the present invention, a mixture of one or more of the above can be used.

In the present invention, the crosslinkable monomer may be included in the monomer mixture in an amount of 0.1 parts by weight to 10 parts by weight based on the content of the aforementioned (meth) acrylic acid ester monomer or an aromatic ring-containing monomer. If the content is less than 0.1 part by weight, the durability reliability of the pressure-sensitive adhesive may be lowered. If it exceeds 10 parts by weight, the adhesiveness and / or peeling force may be lowered.

In the present invention, the monomer mixture, if necessary, may further include a monomer represented by the following formula (2). Such monomers may be added for the purpose of controlling the glass transition temperature of the pressure-sensitive adhesive and providing other functionalities.

 [Formula 2]

Wherein R ₂ to R ₄ each independently represent hydrogen or alkyl, and R ₅ represents cyano; Phenyl unsubstituted or substituted with alkyl; Acetyloxy; Or COR ₆ , wherein R ₆ represents amino or glycidyloxy unsubstituted or substituted with alkyl or alkoxyalkyl.

Alkyl or alkoxy in the definition of R ₂ to R ₆ in the formula may mean alkyl or alkoxy having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 12 carbon atoms, and specifically methyl , Ethyl, methoxy, ethoxy, propoxy or butoxy.

Specific examples of the monomer of the formula (2) include nitrogen-containing monomers such as (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide or N-butoxy methyl (meth) acrylamide; Styrene-based monomers such as styrene or methyl styrene; Epoxy group-containing monomers such as glycidyl (meth) acrylate; Or carboxylic acid vinyl esters such as vinyl acetate, or the like, or two or more kinds thereof, but are not limited thereto. Such monomers may be included in the monomer mixture in an amount of 20 parts by weight or less relative to the content of the aforementioned (meth) acrylic acid ester monomer or crosslinkable monomer. When the content exceeds 20 parts by weight, there is a fear that the flexibility and peeling strength of the pressure-sensitive adhesive is lowered.

In the present invention, a method of preparing a polymer using the monomer mixture as described above is not particularly limited, and may be prepared through a general polymerization method such as solution polymerization, photopolymerization, bulk polymerization, suspension polymerization or emulsion polymerization. In the present invention, it is particularly preferable to use a solution polymerization method, and solution polymerization is preferably performed at a polymerization temperature of 50 ° C to 140 ° C by mixing an initiator in a state where each monomer is uniformly mixed. Initiators which can be used at this time include azo polymerization initiators such as azobis isobutyronitrile or azobiscyclohexane carbonitrile; And / or conventional initiators such as peroxides such as benzoyl peroxide or acetyl peroxide.

 The adhesive composition of this invention exists in a liquid state at normal temperature, and contains the compound which has optical anisotropy.

 Specifically, in the present invention, an optically anisotropic compound having a melting point below room temperature and present in a liquid phase at room temperature and including a mesogen core in a molecular structure can be used.

In the above description, "room temperature" means a temperature as it is, not a temperature rising or temperature decreasing state, for example, about 15 ° C to 30 ° C, preferably about 20 ° C to 30 ° C, and more preferably about 25 ° C. It can mean the temperature of.

 On the other hand, "mesogen" is a component that is typically included in a liquid crystal compound to form a rigid part. In the present invention, for example, a core structure in which two or more benzene rings are connected to each other. It may mean. In the above two or more benzene rings may be directly connected to each other, in some cases may be connected via another atom or group of atoms. In addition, the term benzene ring used above is a concept containing not only benzene but its derivative (s). In the present invention, the mesogen core may refer to a structure including three or more core structures preferably selected from biphenyl, toluene and benzene rings. Such a mesogen core can align the compound in a certain direction with respect to external stimuli such as shrinkage of the polarizing plate, for example, and can exhibit positive birefringence properties as a whole. Accordingly, the optically anisotropic compound according to the present invention can exhibit an effect of optically compensating negative birefringence caused by, for example, shrinkage of the polarizing plate.

 On the other hand, the said optically anisotropic compound used by this invention can also exhibit the effect of providing moderate softness | flexibility to an adhesive and having stress relaxation property in some cases.

 Usually, the optically anisotropic compound as described above has high crystallinity, poor compatibility with the polymer, and precipitates as crystals or phase separation occurs even when a very small amount is used.

 However, in the case of the present invention, as described above, using an optically anisotropic compound present in the liquid phase at room temperature, thereby solving the compatibility problem with the adhesive resin.

 On the other hand, the optically anisotropic compound of the present invention, the refractive index may be in the range of 1.49 to 1.60, preferably 1.50 to 1.55. By controlling the refractive index of the optically anisotropic compound within the above-described range, the pressure-sensitive adhesive has an excellent transmittance and has an effect of suppressing generation of haze. In the present invention, the refractive index can be measured using an Abbe refractometer, and specifically, can be measured by irradiating sodium D-ray at 25 ° C.

The specific kind of optically anisotropic compound that can be used in the present invention is not particularly limited as long as it satisfies the above-described physical properties, and may be, for example, a compound represented by the following Chemical Formula 3.

[Formula 3]

 In Chemical Formula 3,

Is

or

ego;

Is

or

Is;

Is

or

ego;

Is

or

Is;

In which Z is C-W or N;

Q ₁ to Q ₁₆ and W are each independently hydrogen, halogen, cyano, perfluoroalkyl, perfluoroalkyloxy, -R ₇ , -OR ₇ , -NHR ₇ , -N (R ₇ ) ₂ ,- C (= O) R ₇ , -SR ₇ , -SOR ₇ , -SO ₂ R ₇ , -C (= O) NR ₇ , -NR ₇ C (= O) R ₇ , -C (= O) OR ₇ , -OC (= 0) R ₇ , or -OC (= 0) OR ₇ ;

Wherein R ₇ is hydrogen, alkyl, alkenyl, alkynyl or — (R ₈ O) _q R ₉ ; Wherein R ₈ is alkylene, R ₉ is alkyl, q is an integer from 1 to 5;

l, m, n and o are each independently an integer of 0 to 2, and l + m + n + o is an integer of 2 or more;

E and F are each independently hydrogen, halogen, cyano, -R ₇ , -OR ₇ , -NHR ₇ , -N (R ₇ ) ₂ , -NCO, -NCS, -C (= O) R ₇ or- Si (R ₇ ) ₃ ;

G ₁ , G ₂ , and G ₃ are each independently a single bond, -O-, -R ₈ O-, -NR _8- , -S-, -SO-, -SO _2- , alkylene, alkenylene, Alkynylene or -UTV-; U and T are each independently a single bond, -S-, -NR _8- , -O (CH ₂ ) _p- , carbonyl or -O-, V is a single bond, -O-, carbonyl,- NR _8- , -S-,-(CH ₂ ) _p- , -O (CH ₂ ) _p- , or-(CH ₂ ) _p O-, and p is an integer from 0 to 5.

In the definition of Formula 3, alkyl or alkylene may be alkyl or alkylene having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, alkenyl, alkenylene, Alkynyl or alkynylene may be alkenyl, alkenylene, alkynyl or alkynylene having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms.

In addition, in the definition of Formula 3, alkyl, alkylene, alkenyl, alkenylene, alkynyl or alkynylene is hydroxy; Cyano; Halogen, preferably chlorine or bromine; Alkyl having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms; Alkoxy having 1 to 12, preferably 1 to 8, more preferably 1 to 4 carbon atoms; Alkynyl having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms; Or alkenyl having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 4 carbon atoms.

In addition, in the definition of Chemical Formula 3, "single bond" means a case where both groups of atoms are directly bonded to each other without a separate atom.

In addition, in the definition of Formula 3, l, m, n and o, preferably l, m and o is 1, n is 0, or l and o is 1, m and n may be 0 have.

In addition, in the definition of Formula 3, E and F may preferably be silyl substituted with hydrogen, cyano, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or alkyl group of 1 to 8 carbon atoms, and Preferably, it may be hydrogen, cyano, propyl, hexyl or hexyl dimethyl silyl.

Also, in the definition of Chemical Formula 3,

,

,

or

Is preferably

Wherein Z is CW or N, W is hydrogen, -R ₇ or -OR ₇ , and R ₇ may be alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms.

In addition, in the definition of Chemical Formula 3, G ₁ is preferably G ₁ is alkylene having 1 to 4 carbon atoms, alkenylene having 2 to 4 carbon atoms, alkynylene having 2 to 4 carbon atoms, -S-, -SO _2- , -SO-, CO-, -OC (= O)-or -C (= O) -O-, and, more preferably, G ₁ is ethenylene, propenylene, ethynylene or proti Nylene, -S-, -SO _2- , -SO-, CO-, -C (= 0) -O- or -OC (= 0),

In addition, in the definition of Formula 3, G ₂ and G ₃ is preferably each independently a single bond, alkylene having 1 to 4 carbon atoms, alkenylene having 2 to 4 carbon atoms or alkynylene having 2 to 4 carbon atoms, And more preferably each independently may be a single bond, ethenylene, propenylene, ethynylene or protinylene.

In addition, the compound of Formula 3, More preferably,

in l, m, n and o l, m and o are 1, n is 0, l and o are 1, m and n are 0,

E and F are hydrogen, cyano, ethyl, propyl, isopropyl, pentyl, hexyl, ethoxy, propoxy, pentoxy, hexyloxy, trimethyl silyl, trihexyl silyl or hexyl dimethyl silyl,

,

,

or

Is

ego,

Wherein Z is CW or N, W is hydrogen, -R ₇ or -OR ₇ ,

R ₇ is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons, and G ₁ is ethenylene, propenylene, ethynylene or protinylene, -S-, -SO _2- , -SO-, CO -, -C (= O) -O- or -OC (= O)-,

G ₂ and G ₃ may each independently be a single bond, ethenylene, propenylene, ethynylene or protinylene.

In addition, the compound of Formula 4 is more preferably,

in l, m, n and o l, m and o are 1, n is 0, l and o are 1, m and n are 0,

E and F are hydrogen, cyano, ethyl, propyl, isopropyl, pentyl, hexyl, ethoxy, propoxy, pentoxy, hexyloxy, trimethyl silyl, trihexyl silyl or hexyl dimethyl silyl,

Is

ego,

Wherein W is hydrogen, -R ₇ or -OR ₇ , R ₇ is alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms,

,

or

Each independently

or

Is,

G ₁ is preferably ethenylene, propenylene, ethynylene or protinylene, -S-, -SO _2- , -SO-, CO-, -C (= O) -O- or -OC (= O)-,

G ₂ and G ₃ may each independently be a single bond, ethenylene, propenylene, ethynylene or protinylene.

In addition, the compound of Formula 4, More preferably,

in l, m, n and o l, m and o are 1, n is 0, l and o are 1, m and n are 0,

E is hydrogen, F is hydrogen, cyano, ethyl, propyl, isopropyl, pentyl, hexyl, ethoxy, propoxy, pentoxy, hexyloxy, trimethyl silyl, trihexyl silyl or hexyl dimethyl silyl,

Is

Is,

Wherein W is hydrogen, -R ₇ or -OR ₇ , R ₇ is alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms,

,

or

Each independently

or

Is,

G ₁ is preferably ethenylene, propenylene, ethynylene or protinylene, -S-, -SO _2- , -SO-, CO-, -C (= O) -O- or -OC (= O)-,

G ₂ and G ₃ may each independently be a single bond, ethenylene, propenylene, ethynylene or protinylene.

In addition, the compound of Formula 4 is more preferably,

in l, m, n and o l, m and o are 1, n is 0, l and o are 1, m and n are 0,

E and F are hydrogen,

Is

Is,

Wherein W is hydrogen, -R ₇ or -OR ₇ , R ₇ is alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms,

,

or

Each independently

or

Is,

G ₁ is preferably ethenylene, propenylene, ethynylene or protinylene, -S-, -SO _2- , -SO-, CO-, -C (= O) -O- or -OC (= O)-,

G ₂ and G ₃ may each independently be a single bond, ethenylene, propenylene, ethynylene or protinylene.

In the present invention, the optically anisotropic compound also preferably has one or more substituents in the meta position of mesogen. The term "meta position of mesogen" as used above means at least one meta position of the benzene rings constituting the mesogen core, and preferably the meta position of the benzene ring existing at the terminal of the benzene rings constituting the mesogen core. Means. As such, when one or more substituents are included in the meta position of the mesogen, physical properties such as compatibility of the optically anisotropic compound with the adhesive resin may be further enhanced, thereby increasing the effect due to the addition of the optically anisotropic compound. You can. At this time, the kind of the substituent present in the meta position of the mesogen is not particularly limited, and may include, for example, one or more selected from the group consisting of alkyl, alkenyl and alkynyl.

In this case, in the definition of Formula 3,

end

or

In which case E is hydrogen; And / or

end

or

In which case F may be hydrogen.

In the above, Q ₁ , Q ₂ , Q ₁₄ , Q ₁₅ and W may each independently be a substituent as described above or a preferable substituent among the aforementioned substituents, and more preferably alkyl, alkenyl or alkynyl of the substituents. It may be a substituent containing.

In the present invention, one or more of the compounds represented by the following Chemical Formulas 4 to 24 may be specifically used as the optically anisotropic compound of Chemical Formula 3.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

.

 From the viewpoint of including a substituent in the meta position of the mesogen core in the specific kind of the optically anisotropic compound as described above, compounds other than Formula 22 and Formula 24 may be preferably used, but is not limited thereto.

 In the present invention, the optically anisotropic compound as described above is preferably included in an amount of 5 parts by weight to 30 parts by weight with respect to 100 parts by weight of the acrylic resin. If the content is less than 5 parts by weight, there is a fear that the optical compensation effect is lowered, if it exceeds 30 parts by weight, there is a fear that the problem of compatibility with the adhesive resin decreases.

 However, the content of the optically anisotropic compound is only one example of the present invention, in the present invention, in consideration of the type of optically anisotropic compound used, the desired optical compensation and stress relaxation effect, the content of the optically anisotropic compound It can be adjusted appropriately.

The pressure-sensitive adhesive composition of the present invention may further include 0.01 to 10 parts by weight of the crosslinking agent based on 100 parts by weight of the acrylic resin. Such a crosslinking agent may impart cohesion to the pressure-sensitive adhesive through a reaction with an acrylic resin.

The kind of specific crosslinking agent used at this time is not specifically limited, For example, general crosslinking agents, such as an isocyanate type compound, an epoxy type compound, an aziridine type compound, and a metal chelate type compound, can be used.

Specific examples of the isocyanate compound include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate and the above. One or more selected from the group consisting of reactants of any one compound with a polyol (ex. Trimethylol propane); Specific examples of the epoxy compound include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N'N'-tetraglycidyl ethylenediamine and glycerin diglycidyl ether. One or more selected from the group consisting of; Specific examples of the aziridine compound include N, N-toluene-2,4-bis (1-aziridinecarboxamide), N, N'-diphenylmethane-4,4'-bis (1-aziridinecarbox Mid), triethylene melamine, bisisoprotaloyl-1- (2-methylaziridine), and tri-1-aziridinylphosphine oxide. In addition, as a specific example of the metal chelate compound, a compound in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and / or vanadium is coordinated with acetyl acetone, ethyl acetoacetate, or the like may be used. It is not limited to this.

The crosslinking agent is preferably included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic resin described above. If the content is less than 0.01 part by weight, the cohesive force of the pressure-sensitive adhesive may be lowered. If the content is more than 10 parts by weight, the durability may be lowered such as delamination or lifting.

The pressure-sensitive adhesive composition of the present invention may further include 0.005 parts by weight to 5 middle parts of a silane coupling agent, based on 100 parts by weight of the acrylic resin, in addition to the aforementioned components. The silane coupling agent may contribute to the improvement of adhesion reliability when the pressure-sensitive adhesive is left for a long time under high temperature or high humidity conditions, and in particular, may improve the adhesion stability at the time of adhesion with the glass substrate to improve heat resistance and moisture resistance. Examples of the silane coupling agent which can be used in the present invention include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-mercapto Propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, 3 Or a mixture of one or more kinds of isocyanatepropyltriethoxysilane and γ-acetoacetatepropyltrimethoxysilane, but is not limited thereto.

The silane coupling agent is preferably included in an amount of 0.005 parts by weight to 5 parts by weight, and more preferably 0.05 part by weight to 1 part by weight based on 100 parts by weight of the acrylic resin. If the content is less than 0.005 parts by weight, the effect of increasing the adhesion may be insignificant. If the content is more than 5 parts by weight, the durability may be lowered, such as bubble or peeling phenomenon.

The pressure-sensitive adhesive composition of the present invention may further include 1 part by weight to 100 parts by weight of a tackifying resin with respect to 100 parts by weight of the acrylic resin from the viewpoint of controlling the adhesive performance. The kind of such tackifying resin is not specifically limited, For example, (hydrogenated) hydrocarbon type resin, (hydrogenated) rosin resin, (hydrogenated) rosin ester resin, (hydrogenated) terpene resin, (hydrogenated) terpene phenol resin, One kind or a mixture of two or more kinds of a polymeric rosin resin or a polymeric rosin ester resin can be used. If the content of the tackifying resin is less than 1 part by weight, the effect of addition may be insignificant. If it exceeds 100 parts by weight, the compatibility and / or cohesion improvement effect may be lowered.

The pressure-sensitive adhesive composition of the present invention may also include an initiator such as a thermal initiator or a photoinitiator in a range that does not affect the effect of the invention; Epoxy resins; Curing agent; Ultraviolet stabilizers; Antioxidants; Colorant; Adjuvant; Fillers; Antifoam; Surfactants; Photopolymerizable compounds such as polyfunctional acrylates; And one or more additives selected from the group consisting of plasticizers.

The present invention also provides a polarizing film or polarizing element; And a pressure-sensitive adhesive layer formed on one or both surfaces of the polarizing film or the polarizing element and containing a cured product of the pressure-sensitive adhesive composition according to the present invention.

 The kind of polarizing film or polarizing element which comprises the polarizing plate (or adhesive polarizing plate) of this invention is not specifically limited. In this invention, the film manufactured by extending | stretching polarizing components, such as an iodine or a dichroic dye, can be used for the film which consists of polyvinyl alcohol-type resin as said polarizing film or element, for example. As the polyvinyl alcohol-based resin, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal or saponified product of ethylene vinyl acetate copolymer may be used. In addition, the thickness of the polarizing film or element is not particularly limited, and may be formed in a conventional thickness.

 The pressure-sensitive adhesive polarizing plate of the present invention also comprises a cellulose-based film such as triacetyl cellulose on one side or both sides of the polarizing film or element; Polyester film such as polycarbonate film or polyethylene terephthalate film; Polyether sulfone-based film; And / or a protective film such as a polyethylene film, a polypropylene film, or a polyolefin film having a cyclo or norbornene structure or a polyolefin film such as an ethylene propylene copolymer. At this time, the thickness of the protective film is not particularly limited, and may be formed to a conventional thickness.

 In the present invention, the method of forming the adhesive layer on the polarizing film or the device as described above is not particularly limited, and for example, the pressure-sensitive adhesive composition or the coating liquid containing the above by the conventional means such as a bar coater on the film or device. A method of coating, drying and aging, or a method of applying the pressure-sensitive adhesive to the surface of the peelable substrate and drying it, and then transferring the adhesive layer onto a polarizing film or an element using the peelable substrate and then curing and curing may be used. have.

When the pressure-sensitive adhesive composition or the coating liquid contains a multifunctional crosslinking agent in the formation of the pressure-sensitive adhesive layer as described above, the crosslinking agent is preferably controlled from the viewpoint of uniform coating to prevent the crosslinking reaction of the functional group from proceeding when the pressure-sensitive adhesive layer is formed. Do. Accordingly, the crosslinking agent may form a crosslinked structure in the drying and aging process after the coating operation to improve cohesion, and improve adhesive properties and cuttability of the product.

 The pressure-sensitive adhesive layer forming process is also preferably carried out after sufficiently removing the bubble-inducing components such as volatile components or reaction residues in the pressure-sensitive adhesive composition or coating solution. That is, if the crosslinking density or molecular weight is too low to decrease the elastic modulus, there is a fear that small bubbles existing between the glass plate and the pressure-sensitive adhesive layer in the high temperature state become large to form scatterers therein.

 The polarizing plate of the present invention may further include at least one functional layer selected from the group consisting of a protective layer, a reflective layer, an antiglare layer, a retardation plate, a wide viewing angle compensation film, and a brightness enhancing film.

The present invention also relates to a liquid crystal display device comprising a liquid crystal panel in which the aforementioned polarizing plate according to the present invention is bonded to one side or both sides of a liquid crystal cell.

The type of liquid crystal cell constituting the liquid crystal display device of the present invention as described above is not particularly limited, such as TN (Twisted Neumatic), STN (Super Twisted Neumatic), IPS (In Plane Switching) or VA (Vertical Alignment) method It includes all common liquid crystal cells. In addition, the kind and other manufacturing method of the other structure contained in the liquid crystal display device of this invention are not specifically limited, either, The general structure of this field can be employ | adopted and used without a restriction | limiting.

Hereinafter, the present invention will be described in more detail with reference to examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited to the following examples.

Preparation Example 1 Preparation of Acrylic Resin (1)

78 parts by weight of n-butyl acrylate (n-BA), 20 parts by weight of benzyl acrylate (BzA) and 2-hydroxyethyl methacryl in a 1 L reactor equipped with a refrigeration system for easy control of nitrogen gas and refrigeration. A mixture of monomers containing 2 parts by weight of rate (2-HEMA) was added. Subsequently, 120 parts by weight of ethyl acetate (EAc) was added as a solvent, and purged with nitrogen gas for 60 minutes to remove oxygen. Thereafter, the temperature was maintained at 60 ° C, 0.03 parts by weight of azobis isobutyronitrile (AIBN) was added as an initiator, reacted for 8 hours, and diluted with ethyl acetate after the reaction was completed, and the solid content was 20% by weight. And an acrylic resin (1) having a weight average molecular weight of 1.5 million.

Preparation Examples 2 to 8: Preparation of Acrylic Resin

 An acrylic resin was manufactured in the same manner as in Preparation Example 1, except that the composition of the monomer was changed as in Table 1 below.

Table 1

Preparation Example 9 Preparation of Optically Anisotropic Compound (A)

The optically anisotropic compound (A) was prepared through the process as shown in the above scheme. Specifically, Compound (1) was dissolved in a DMF solvent, and 1.2 equivalents of Compound (2) and 1.5 equivalents of K ₂ CO ₃ were combined based on Compound (1), followed by stirring at 100 ° C. for 4 hours. . The reaction was then worked up using ether and water and purified by silica gel to give compound 3 (yield: 87%).

Thereafter, Compound (3) was dissolved in a mixed solvent of methanol and water (weight ratio: 1: 1), and NaOH 2.0 equivalent was added based on Compound (3), followed by stirring at about 80 ° C for about 1 hour. After stirring, the reaction was worked up with ether and water to give compound 4 (yield: about 95%). Thereafter, compound (4); And 1.0 equivalent of Compound 5 relative to Compound (4) was dissolved in CH ₂ Cl ₂ , 1.2 equivalents of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) and 4-dimethylaminopyridine ( DMAP) 0.1 equivalent was further mix | blended, and it stirred about 15 hours at room temperature. After stirring, the mixture was purified by silica gel to obtain an optically anisotropic compound (A) (compound (6)) in a yield of about 85%.

1 HNMR (400 MHz, CDCl 3): δ 0.85 to 1.00 (m, 6H), 1.40 (m, 4H), 1.42 to 1.60 (m, 4H), 1.80 (m, 1H), 3.98 (t, 2H), 7.22 ( dd, 1H), 7.33 (d, 2H), 7.40 (t, 1H), 7.44 (d, 1H), 7.48 (t, 2H), 7.63 (d, 2H), 7.68 (t, 2H), 7.77 (t , 1H), 7.84 (d, 1H) (Eluent = n-hexane)

Preparation Example 10 Preparation of Optically Anisotropic Compound (B)

Compound (1) was dissolved in a mixed solvent of ethanol and water (weight ratio: ethanol: water = 7: 3), and further compounded 1.0 equivalent of bromohexane and 2.2 equivalent of KOH relative to compound (1), followed by 90 ° C. Stir for about 10 hours. The ethanol was then removed via reduced pressure distillation and water was added appropriately. Thereafter, a 10% aqueous hydrochloric acid solution was added slowly to adjust the pH to about 1 to 3, and reacted to obtain Compound (2) (yield: about 90%). Compound (2) was dissolved in CH ₂ Cl ₂ and 1.0 equivalent of Compound (3) was further dissolved in Compound (2). 1.2 equivalent EDC and 0.1 equivalent DMAP were further mix | blended with respect to compound (2), and it stirred at room temperature for about 10 hours. Thereafter, the mixture was worked up with CH ₂ Cl ₂ and purified by silica gel to obtain an optically anisotropic compound (B) (compound (4)) in a yield of about 88%.

1 HNMR (400 MHz, CDCl 3): δ 0.93 (t, 3H), 1.29-1.45 (m, 4H), 1.46-1.57 (m, 2H), 1.78-1.89 (m, 2H), 4.05 (t, 2H), 7.20 (dd, 1H), 7.35 (d, 2H), 7.43 (t, 1H), 7.67 (d, 2H), 7.69-7.80 (m, 5H), 7.83 (d, 1H) (Eluent = n-hexane)

Preparation Example 11 Preparation of Optically Anisotropic Compound (C)

Compound (1) was dissolved in a mixed solvent of ethanol and water (weight ratio: ethanol: water = 7: 3), and 1.0 equivalent of Compound (5) and 2.2 equivalent KOH were combined with 1.0 equivalent of Compound (1) at 90 ° C. Stir for 10 hours. Thereafter, ethanol was removed by distillation under reduced pressure, and water was added. Subsequently, 10% aqueous hydrochloric acid solution was added slowly to adjust the pH to about 1 to 3 to prepare alkoxy benzoic acid (yield: about 90%). Subsequently, 1.0 equivalent of the prepared alkoxy benzoic acid and 1.0 equivalent of the benzoic acid (3) was dissolved in CH ₂ Cl ₂ , and 1.2 equivalents of EDC and 0.1 equivalent of DMAP were combined, followed by stirring at room temperature for about 10 hours. . Then, the mixture was worked up with CH ₂ Cl ₂ and purified by silica gel to prepare an optically anisotropic compound (C) (compound (6)) in a yield of about 85%.

1 HNMR confirmed this. 1 HNMR (400 MHz, CDCl ₃ ): δ 0.90 to 0.97 (m, 6H), 1.29 to 1.38 (m, 4H), 1.38 to 1.61 (m, 4H), 1.69 to 1.81 (m, 1H), 3.94 (dd, 2H) ), 7.21 (dd, 1H), 7.34 (d, 2H), 7.42 (t, 1H), 7.66 (d, 2H), 7.68 ~ 7.78 (m, 5H), 7.80 (d, 1H) (Eluent = n- hexane)

Preparation Example 12 Preparation of Optically Anisotropic Compound (D)

Compound (7) 1.0 equivalent to Compound 1.0 (8) was dissolved in a mixed solvent of dioxane and DMF (weight ratio: dioxane: DMF = 9: 1), Cs ₂ CO ₃ 2.0 equivalents, CuI 0.1 The equivalent and 0.1 equivalent of 1,1,1-tris (hydroxymethyl) ethane were further combined, and it stirred at 110 degreeC for about 20 hours. It was then worked up with ether and water and purified by silica gel to give compound 9 in about 90% yield.

1 HNMR (400 MHz, CDCl3): δ 0.93 (t, 3H), 1.48-1.63 (m, 2H), 2.30 (t, 3H), 7.02-7.53 (m, 6H), 7.65 (d, 2H), 7.69-7.74 (m, 4H) (Eluent = n-hexane)

Preparation Example 13 Preparation of Optically Anisotropic Compound (E)

After dissolving compound (9) in CH ₂ Cl ₂ , 2.2 equivalents of m-CPBA (m-chloroperbenzoic acid) compared to compound (9) was slowly added at 0 ° C. The mixture was stirred at room temperature for another 30 minutes, worked up, and then purified by silica gel to obtain compound (10) in about 80% yield. In addition, except that 1.0 equivalent of m-CPBA was used compared to the equivalent of compound (9), through the same procedure as above, compound (11) was prepared. 1 HNMR results of the prepared compound (11) are as follows.

1 HNMR (400 MHz, CDCl3): δ 0.93 (t, 3H), 1.48-1.63 (m, 2H), 2.30 (t, 3H), 7.18-7.22 (m, 2H), 7.63 (d, 2H), 7.65-7.70 (m, 4H), 7.99-8.05 (m, 4H) (Eluent = n-hexane)

Preparation Example 14 Preparation of Optically Anisotropic Compound (F)

Compound (12) was dissolved in butanone, and 1.2 equivalent of hexyl bromide and 1.2 equivalent of K ₂ CO ₃ were further added to 1.0 equivalent of Compound (12), followed by stirring at 80 ° C. for about 5 hours. Then work up with ether and purify with silica gel to give compound (13) in about 90% yield. Subsequently, Compound (13) is dissolved in a benzene solvent with 1.0 equivalent of Compound (14) relative to 1.0 equivalent of Compound (13), NiCl ₂ (pph ₃ ) ₂ is added as a catalyst, and the mixture is stirred at room temperature for about 2 hours. It was. Then work-up with water and ether and purification with silica gel gave compound (15) in about 70% yield.

1 HNMR confirmed this. 1 HNMR (400 MHz, CDCl 3): δ 0.98 (t, 3H), 1.30-1.45 (m, 4H), 1.45-1.59 (m, 2H), 1.80-1.89 (m, 2H), 4.05 (t, 2H), 7.21 ~ 7.60 (m, 9H), 7.87 (s, 1H), 7.92 (m, 3H) (Eluent = n-hexane)

Preparation Example 15 Preparation of Optically Anisotropic Compound (G)

Compound (16) was dissolved in THF, and 1.0 equivalent of tert-butyldimethylsilyl chloride (TBSCl) and 1.2 equivalent of imidazole were added to 1.0 equivalent of Compound (16), followed by 5 hours at 80 ° C. Stirred. The resulting salt was then filtered off and purified by silica gel to yield compound (17) in about 80% yield. Compound (17) was dissolved in butanone, and 1.2 equivalent of hexyl bromide and 1.2 equivalent of K ₂ CO ₃ were further added to 1.0 equivalent of Compound (17), followed by stirring at 80 ° C for about 10 hours. Then work up with ether and purify with silica gel. Subsequently, the purified product was dissolved in THF and deprotected by combining 1.1 equivalent of Tetra-n-butylammonium fluoride (TBAF) relative to 1.0 equivalent of the purified product. Thereafter, the mixture was stirred at room temperature for about 1 hour, worked up with ether, and then purified by silica gel to obtain compound (18). Subsequently, Compound (18) was dissolved in 1.0 equivalent of Compound (19) to 1.0 equivalent of Compound (18) and CH ₂ Cl ₂ , 1.2 equivalents of EDC and 0.1 equivalent of DMAP were combined, followed by stirring at room temperature for about 10 hours. It was. Then work up with CH ₂ Cl ₂ and purify with silica gel to give compound 20 in about 85% yield.

1 HNMR confirmed this. 1 HNMR (400 MHz, CDCl 3): δ 0.97 (t, 3H), 1.29-1.44 (m, 4H), 1.45-1.57 (m, 2H), 1.78-1.89 (m, 2H), 4.03 (t, 2H), 7.22 ~ 7.56 (m, 9H), 7.60 (d, 1H), 7.88 (d, 1H), 8.11 (d, 2H) (Eluent = n-hexane)

Preparation Example 16 Preparation of Optically Anisotropic Compound (H)

Compound (21) was dissolved in butanone, 1.2 equivalents of butyl bromide and 1.2 equivalents of K ₂ CO ₃ were combined with 1.0 equivalent of Compound (21), followed by stirring at 80 ° C for about 5 hours. Work-up with ether and water and purification with silica gel gave compound 22 in about 95% yield. Compound (22) was then dissolved in 1.0 equivalent of trimethylsilyl acetylene, 0.1 equivalent of CuI, 0.03 equivalent of PdCl ₂ (PPh ₃ ) ₂ and 4.0 equivalent of triethylamine and benzene relative to compound (22), at 60 ° C. Stir for about 10 hours. Thereafter, the mixture was worked up using ether and water, and purified by silica gel to obtain compound (23) in a yield of about 90%. Compound (23) was then mixed with 1.0 equivalent of Compound (24), 0.1 equivalent of CuI, 0.03 equivalent of PdCl ₂ (PPh ₃ ) ₂ , 6.0 equivalent of DBU (1,8-diazabicyclo [5,] relative to compound (23). 4,0] undec-7-ene) and 1.0 equivalent of H ₂ O were dissolved in benzene and stirred at 60 ° C. for 10 hours. Thereafter, the mixture was worked up using ether and water and purified by silica gel to obtain compound (25) in a yield of about 85%.

1 HNMR (400 MHz, CDCl 3): δ 1.06 (t, 3H), 1.73 to 1.92 (m, 4H), 4.07 (t, 2H), 7.17 (d, 1H), 7.22 (d, 1H), 7.25 to 7.30 (m , 3H), 7.47 (m, 3H), 7.68 (s, 1H) (Eluent = n-hexane)

Preparation Example 17 Preparation of Optically Anisotropic Compound (I)

1.2 equivalents of compound (7) were combined with a mixture of 1.0 equivalent of HPtCl ₆ · H ₂ O and 1.2 equivalents of HSiMe ₂ Cl, and stirred at 0 ° C. for 3 hours. Thereafter, the mixture was worked up using ether and water, and purified by silica gel to prepare compound (8) in a yield of about 87%. Subsequently, 1.5 equivalents of compound (8) was combined with 1.5 equivalents of n-butyllithium and 1.0 equivalent of compound (9), stirred at −78 ° C. for 6 hours, worked up with ether and water, and purified with silica gel to obtain about Compound 10 was obtained with a yield of 72%.

2 g of compound (10) were then added to 121.8 mg of 6 mol% PdCl ₂ (PPh ₃ ) ₂ , 110.2 mg of 10 mol% cuprous iodide (CuI), 5.2 ml DBU, and trimethylsilyl acetylene 413.52 Dissolve in μL and benzene (25 ml) and stir for 6 hours. Thereafter, the stirred solution was filtered through celite, distilled under reduced pressure, and then purified by silica gel to obtain compound (11) in a yield of about 80%.

1 H-NMR, (400 MHz, CDCl ₃ ): δ (ppm) 0.27 (s, 6H), 0.76 (t, 4H), 0.89 (t, 4H), 1.32 (m, 18H), 7.51 (m, 8H) ( Eluent = n-hexane)

Example 1.

 5 parts by weight of the optically anisotropic compound (A) prepared in Preparation Example was uniformly mixed with 100 parts by weight of the acrylic resin (1) prepared in Preparation Example 1, 0.1 parts by weight of tolylene diisocyanate adduct of trimethylolpropane as a crosslinking agent, and As the silane coupling agent, 0.1 part by weight of γ-glycidoxy propyl trimethoxy silane was further blended. Subsequently, the proper concentration was diluted with a solvent, and then uniformly coated and dried on a release paper to prepare an adhesive layer (thickness: 25 μm). Subsequently, the prepared pressure-sensitive adhesive layer was transferred to an iodine-based polarizing plate having a thickness of 185 μm, and aged at room temperature for 7 days to prepare an adhesive polarizing plate.

Examples 2 to 28

 Examples 2 to 28 were prepared in the same manner as in Example 1, except that compositions of acrylic resins, optically anisotropic compounds, and the like were changed as shown in Tables 2 to 5 below.

TABLE 2

TABLE 3

Table 4

Table 5

Comparative Examples 1 to 4

 Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, except that the composition of the pressure-sensitive adhesive composition was changed as in Table 6 below.

Table 6

The physical properties of the pressure-sensitive adhesive polarizers prepared in Examples and Comparative Examples were evaluated by the following methods.

1. Durability Reliability

A pressure-sensitive adhesive coated polarizer was cut to a size of 90 mm × 170 mm to prepare a sample, and the optical absorption axis was crossed on both sides of a glass substrate (110 mm × 190 mm × 0.7 mm = width × length × height). Attached. At this time, the pressure applied was about 5 Kg / cm ² , the clean room operation was performed so that bubbles and foreign matter does not occur. Thereafter, in order to evaluate the heat and moisture resistance of the specimen, the specimen was left for 1,000 hours at a temperature of 60 ° C. and a relative humidity of 90%, and then observed whether bubbles or peeling occurred. In addition, the heat resistance property was left for 1000 hours at a temperature of 80 ℃, and then observed whether the bubbles or peeling occurred in the same way. All specimens were used after being left at room temperature for 24 hours immediately before assessing the condition. Evaluation criteria are as follows.

(Circle): No bubble and peeling phenomenon in both heat and humidity conditions

(Triangle | delta): A bubble or peeling phenomenon generate | occur | produces in damp-heat or heat-resistant conditions

X: A lot of bubble or peeling phenomenon generate | occur | produces in damp-heat or heat-resistant conditions

2. Light transmission uniformity (light leakage)

Using the backlight, light uniformity was evaluated by observing whether light leaked out through the specimen in the dark room. In evaluating the uniformity of light transmission, the polarizing plate manufactured in Example or Comparative Example was cut to a size of 200 mm x 200 mm, and then crossed 90 degrees on both sides of the glass substrate (210 mm x 210 mm x 0.7 mm = width x height x height). After attaching, the specimens were used as specimens. Evaluation criteria are as follows.

⊙: Light transmission nonuniformity is not visually recognized

○: slight light transmittance nonuniformity

(Triangle | delta): Light transmissive nonuniformity exists a little.

X: A large amount of light transmitting nonuniformity exists

 The measurement results of the physical properties as described above are summarized in Tables 7 to 11 below.

TABLE 7

Table 8

Table 9

Table 10

Table 11

As can be seen from the results of Tables 7 to 11, in the embodiment according to the present invention, excellent durability and reliability at the heat and humidity conditions and heat resistance, while the effect of suppressing the light leakage phenomenon was excellent. On the other hand, in Comparative Examples 1 and 2 not according to the present invention, the durability reliability index was good, but the light transmittance uniformity index was very poor, it can be confirmed that a large amount of light leakage when applied to the actual liquid crystal display device. In addition, in the case of Comparative Examples 3 and 4, the weight average molecular weight of the acrylic resin is too low or high, and even if the optically anisotropic compound is added, the durability is high due to the lack of cohesion of the resin or the increase in the hardness of the pressure-sensitive adhesive. And it was confirmed that light transmission uniformity deteriorated.

Claims (19)

1. Acrylic resin having a weight average molecular weight of 800,000 to 2 million; And an optically anisotropic compound present in liquid phase at room temperature.
2. The pressure-sensitive adhesive composition of claim 1, wherein the acrylic resin includes an aromatic substituent.
3. The method of claim 2, wherein the acrylic resin is 55 to 94.9 parts by weight of the (meth) acrylic acid ester monomer; 5 parts by weight to 35 parts by weight of an aromatic ring-containing monomer; And 0.1 to 10 parts by weight of the crosslinkable monomer.
4. The pressure-sensitive adhesive composition of claim 3, wherein the (meth) acrylic acid ester monomer is an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms.
5. The pressure-sensitive adhesive composition of claim 3, wherein the aromatic ring-containing monomer is represented by the following Chemical Formula 1:

   [Formula 1]

   

   In Formula 1 R ₁ represents hydrogen or alkyl, A represents alkylene, alkenylene or alkynylene, n represents an integer of 0 to 3, Q is a single bond, -O-, -S-, alkyl Lene, alkenylene or alkynylene, and P represents a substituted or unsubstituted aromatic group.
6. The aromatic ring-containing monomer according to claim 5, wherein the aromatic ring-containing monomer is phenoxy ethyl (meth) acrylate, benzyl (meth) acrylate, 2-phenylthio-1-ethyl (meth) acrylate, 6- (4,6-dibro) Mo-2-isopropylphenoxy) -1-hexyl (meth) acrylate, 6- (4,6-dibromo-2-sec-butyl phenoxy) -1-hexyl (meth) acrylate, 2, 6-dibromo-4-nonylphenyl (meth) acrylate, 2,6-dibromo-4-dodecylphenyl (meth) acrylate, 2- (1-naphthyloxy) -1-ethyl (meth ) Acrylate, 2- (2-naphthyloxy) -1-ethyl (meth) acrylate, 6- (1-naphthyloxy) -1-hexyl (meth) acrylate, 6- (2-naphthyloxy ) -1-hexyl (meth) acrylate, consisting of 8- (1-naphthyloxy) -1-octyl (meth) acrylate and 8- (2-naphthyloxy) -1-octyl (meth) acrylate At least one pressure-sensitive adhesive composition selected from the group.
7. The pressure-sensitive adhesive composition of claim 3, wherein the crosslinkable monomer is a hydroxy group-containing monomer, a carboxyl group-containing monomer or a nitrogen-containing monomer.
8. The pressure-sensitive adhesive composition of claim 1, wherein the optically anisotropic compound includes a mesogen core structure in which two or more benzene rings are connected to each other.
9. The pressure-sensitive adhesive composition of claim 1, wherein the optically anisotropic compound is represented by the following Chemical Formula 3:

   [Formula 3]

   

   In Chemical Formula 3,

   

   Is

   

   or

   

   ego;

   

   Is

   

   or

   

   Is;

   

   Is

   

   or

   

   ego;

   

   Is

   

   or

   

   Is;

   In which Z is C-W or N;

   Q ₁ to Q ₁₆ and W are each independently hydrogen, halogen, cyano, perfluoroalkyl, perfluoroalkyloxy, -R ₇ , -OR ₇ , -NHR ₇ , -N (R ₇ ) ₂ ,- C (= O) R ₇ , -SR ₇ , -SOR ₇ , -SO ₂ R ₇ , -C (= O) NR ₇ , -NR ₇ C (= O) R ₇ , -C (= O) OR ₇ , -OC (= 0) R ₇ , or -OC (= 0) OR ₇ ;

   Wherein R ₇ is hydrogen, alkyl, alkenyl, alkynyl or — (R ₈ O) _q R ₉ ; Wherein R ₈ is alkylene, R ₉ is alkyl, q is an integer from 1 to 5;

   l, m, n and o are each independently an integer of 0 to 2, and l + m + n + o is an integer of 2 or more;

   E and F are each independently hydrogen, halogen, cyano, -R ₇ , -OR ₇ , -NHR ₇ , -N (R ₇ ) ₂ , -NCO, -NCS, -C (= O) R ₇ or- Si (R ₇ ) ₃ ;

   G ₁ , G ₂ , and G ₃ are each independently a single bond, -O-, -R ₈ O-, -NR _8- , -S-, -SO-, -SO _2- , alkylene, alkenylene, Alkynylene or -UTV-; U and T are each independently a single bond, -S-, -NR _8- , -O (CH ₂ ) _p- , carbonyl or -O-, V is a single bond, -O-, carbonyl,- NR _8- , -S-,-(CH ₂ ) _p- , -O (CH ₂ ) _p- , or-(CH ₂ ) _p O-, and p is an integer from 0 to 5.
10.  The pressure-sensitive adhesive composition of claim 9, wherein E and F are each independently substituted with hydrogen, cyano, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms, or alkyl group of 1 to 8 carbon atoms.
11. The method of claim 9,

    

    ,

    

    ,

    

    or

    

    Is

    

    Wherein Z is CW or N, W is hydrogen, -R ₇ or -OR ₇ , and R ₇ is an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms.
12. 10. The compound of claim 9, wherein G ₁ is alkylene having 1 to 4 carbon atoms, alkenylene having 2 to 4 carbon atoms, alkynylene having 2 to 4 carbon atoms, -S-, -SO _2- , -SO-, CO-,- OC (= O)-or -C (= O) -O-, G ₂ and G ₃ are each independently a single bond, alkylene having 1 to 4 carbon atoms, alkenylene having 2 to 4 carbon atoms or 2 to 4 carbon atoms Pressure-sensitive adhesive composition which is alkynylene.
13. 10. The compound of claim 9 wherein l, m, n and o are 1, m and o are 1, n is 0, l and o are 1, m and n are 0,

    E and F are hydrogen, cyano, ethyl, propyl, isopropyl, pentyl, hexyl, ethoxy, propoxy, pentoxy, hexyloxy, trimethyl silyl, trihexyl silyl or hexyl dimethyl silyl,

    

    ,

    

    ,

    

    or

    

    Is

    

    ego,

    Wherein Z is CW or N, W is hydrogen, -R ₇ or -OR ₇ ,

    R ₇ is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons, and G ₁ is ethenylene, propenylene, ethynylene or protinylene, -S-, -SO _2- , -SO-, CO -, -C (= O) -O- or -OC (= O)-,

    G ₂ and G ₃ are each independently a single bond, ethenylene, propenylene, ethynylene or protinylene.
14. The method of claim 9,

    

    end

    

    or

    

    And E is hydrogen;

    

    end

    

    or

    

    And F is hydrogen.
15. The pressure-sensitive adhesive composition of claim 1, wherein the optically anisotropic compound is at least one selected from the group consisting of a compound of Formula 4 to a compound of Formula 24:

    [Formula 4]

    

    [Formula 5]

    

    [Formula 6]

    

    [Formula 7]

    

    [Formula 8]

    

    [Formula 9]

    

    [Formula 10]

    

    [Formula 11]

    

    [Formula 12]

    

    [Formula 13]

    

    [Formula 14]

    

    [Formula 15]

    

    [Formula 16]

    

    [Formula 17]

    

    [Formula 18]

    

    [Formula 19]

    

    [Formula 20]

    

    [Formula 21]

    

    [Formula 22]

    

    [Formula 23]

    

    [Formula 24]

    

    .
16.  The pressure-sensitive adhesive composition of claim 1, wherein the optically anisotropic compound is included in an amount of 5 parts by weight to 30 parts by weight with respect to 100 parts by weight of the acrylic resin.
17.  The pressure-sensitive adhesive composition of claim 1, further comprising 0.01 to 10 parts by weight of a multifunctional crosslinking agent based on 100 parts by weight of the acrylic resin.
18.  Polarizing film or polarizing element; A polarizing plate formed on one side or both sides of the polarizing film or the polarizing element, the pressure-sensitive adhesive layer containing a cured product of the pressure-sensitive adhesive composition according to claim 1.
19.  The polarizing plate of claim 18, wherein the polarizing plate comprises a liquid crystal panel attached to one side or both sides of the liquid crystal cell.