KR102024260B1 - Pressure sensitive adhesive composition - Google Patents

Abstract

The present application relates to an adhesive composition, a protective film, an optical element and a display device. The pressure-sensitive adhesive composition of the present application exhibits excellent antistatic properties, exhibits appropriate low speed and high speed peeling force after the crosslinked structure is formed, and is excellent in the balance of both. Accordingly, when the pressure-sensitive adhesive composition is applied to, for example, a protective film, it exhibits an excellent protective effect and is easily peeled off at the time of high-speed peeling, which is advantageous in terms of a high-speed process, and exhibits excellent antistatic properties in the process. Can be.

Description

Adhesive composition {PRESSURE SENSITIVE ADHESIVE COMPOSITION}

The present application relates to an adhesive composition, an optical element protective film, an optical element, and a display device.

A protective film may be used to prevent dirt, such as dust, or scratches from occurring on optical elements such as polarizing plates, other plastic products, home appliances, automobiles, and the like. Protective films require proper peel force and antistatic properties.

For example, when peeling a protective film at high speed for the use of a product or the assembly of another product, it is required that the peeling force (henceforth a "high speed peeling force") is relatively low. On the other hand, the peeling force (hereinafter referred to as "low speed peeling force") at the time of peeling at a slow speed should be relatively high to show an appropriate protective function.

In addition, foreign matters such as dust may be sucked due to static electricity mainly generated when the protective film is peeled off, or, in the case of electronic products, electrostatic destruction or malfunction of the device may be caused. In particular, in recent years, as the accessories are integrated due to the spread of computers and the multifunctionality of liquid crystal TVs and mobile telephones, the problems caused by static electricity have been highlighted.

Accordingly, efforts have been made to impart an antistatic function to the pressure-sensitive adhesive contained in the protective film.

For example, in patent document 1, there exists an attempt to mix | blend an ethylene oxide modified dioctyl plasticizer with an adhesive, and to suppress generation | occurrence | production of static electricity. In addition, in patent document 2, an organic salt is added to an adhesive, and in patent document 3, a metal salt and a chelating agent are mix | blended with an adhesive. However, according to the above methods, contamination by transfer of the pressure-sensitive adhesive component to the protected product occurs, or it is difficult to suppress static electricity generated at an early stage, and the low-speed peeling force, which is particularly important for the protective function, is too low.

In particular, in recent years, a technique for imparting hydrophobicity to the surface of an optical element such as a polarizing plate has been developed, and it is becoming more difficult to secure a balance of low speed and high speed peeling force while suppressing static electricity on such a hydrophobic surface.

Japanese Laid-Open Patent Publication 1993-140519 Korean Laid-Open Patent Publication No. 2004-0030919 Korean Laid-Open Patent Publication No. 2006-0128659

The present application provides an adhesive composition, an optical element protective film, an optical element, and a display device.

Exemplary pressure-sensitive adhesive compositions include a pressure-sensitive adhesive polymer, a crosslinking agent, and a reactive polyether modified siloxane compound. The pressure-sensitive adhesive composition of the present application can be used, for example, for a surface protective film of various uses. In particular, the pressure-sensitive adhesive composition, even when applied to the protection of the hydrophobic surface can exhibit an excellent balance of low-speed and high-speed peeling force while showing excellent antistatic performance. In the present application, the term hydrophobic surface may mean a surface having a contact angle of about 90 degrees or more or 30 mN / m or less for deionized water. In the above, the contact angle can be measured by the method of using a drop shape analyzer (Drop Shape Analyzer, KRUSS DSA100) at a temperature of 23 ° C. and 60 RH% (relative humidity). May be measured by Owen-Wendt-Rabel-Kaelble method using the contact angle of deionized water and diiomethane measured by the contact angle measuring method.

In the present application, the adhesive polymer may include an alkyl (meth) acrylate, a monomer containing an alkylene oxide chain, a nitrogen-containing monomer, and a hydroxy group-containing monomer in order to express appropriate adhesion performance, antistatic performance and peeling properties. Can be used. In the present specification, that a polymer includes a compound or a monomer may mean a case where the compound or monomer is included as a polymer unit in the polymer through a polymerization reaction.

As said alkyl (meth) acrylate, the alkyl (meth) acrylate which has a C1-C14 alkyl group can be used, for example in consideration of the cohesion force, glass transition temperature, or adhesiveness of an adhesive. The alkyl group may be, for example, a straight chain or branched alkyl group. 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, isooctyl (Meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, and the like can be exemplified, and one or two or more of the above are polymerized units to the adhesive polymer. It may be included as.

As a monomer which has an alkylene oxide chain, the compound represented by following formula (1) can be illustrated, for example.

[Formula 1]

In Formula 1, Q is hydrogen or an alkyl group, U is an alkylene group, Z is hydrogen, an alkyl group or an aryl group, and m is any number, for example, a number in the range of 1-20.

When two or more [—U—O—] units are present in Formula 1, the number of carbon atoms of U in the units may be the same or different.

M in Formula 1 may be, for example, a number in the range of 1 to 16, 1 to 12, 1 to 9, or 2 to 9. Within this range, the polymerization efficiency and the crystallinity of the adhesive polymer can be maintained in an appropriate range during the production of the adhesive polymer, and appropriate conductivity can be given to the adhesive.

As used herein, unless otherwise specified, the term alkyl group may mean an alkyl group 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. The alkyl group may be linear, branched or cyclic. The alkyl group may be unsubstituted or substituted by one or more substituents.

As used herein, unless otherwise specified, the term alkylene group or alkylidene group may be an alkylene group or an alkylidene group 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. have. The alkylene group or alkylidene group may be linear, branched or cyclic. The alkylene group or alkylidene group may be substituted by one or more substituents if necessary.

In Formula 1, Q may be an alkyl group, for example, an alkyl group having 1 to 8 carbon atoms or 1 to 4 carbon atoms. When using a compound in which Q is an alkyl group, for example, when the pressure-sensitive adhesive composition is applied to a protective film or the like, it may be advantageous that the protective film is easily removed without residues or stains on the adherend.

As used herein, unless otherwise specified, the term aryl group is condensed or bonded, including a benzene ring, or two or more benzene rings connected, or two or more benzene rings sharing one or two or more carbon atoms It may mean a monovalent residue derived from a compound or a derivative thereof containing the structure. The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 22 carbon atoms, 6 to 16 carbon atoms, or 6 to 13 carbon atoms. As such an aryl group, a phenyl group, a phenylethyl group, a phenylpropyl group, benzyl group, a tolyl group, a xylyl group, a naphthyl group, etc. can be illustrated.

As a substituent which may be substituted in a specific functional group, for example, the said alkyl group, the alkylidene group, or the alkylene group in this specification, an alkyl group, an alkoxy group, an alkenyl group, an epoxy group, a cyano group, a carboxyl group, acryloyl group, meta Cryloyl group, acryloyloxy group, methacryloyloxy group or an aryl group may be exemplified, but is not limited thereto.

As the compound of the formula (1), alkoxy dialkylene glycol (meth) acrylic acid ester, alkoxy trialkylene glycol (meth) acrylic acid ester, alkoxy tetraalkylene glycol (meth) acrylic acid ester, aryloxy dialkylene glycol (meth) acrylic acid Esters, aryloxy trialkylene glycol (meth) acrylic acid esters, aryloxy tetraalkylene glycol (meth) acrylic acid esters, and polyalkylene glycol monoalkyl ether (meth) acrylic acid esters; It is not limited.

As the alkoxy, for example, alkoxy having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms or 1 to 4 carbon atoms may be exemplified, and specifically, a methoxy group or an ethoxy group may be exemplified. .

The alkylene glycol may be exemplified by alkylene glycol having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms or 1 to 4 carbon atoms, for example, ethylene glycol or propylene glycol, and the like. As the aryl oxy, aryl oxy having 6 to 24 carbon atoms or 6 to 12 carbon atoms may be exemplified, for example, phenoxy.

The kind of nitrogen-containing monomer which can be included in the adhesive polymer is not particularly limited, and for example, an amide group-containing monomer, an amino group-containing monomer, an imide group-containing monomer or a cyano group-containing monomer may be used. As said amide group-containing monomer, it is (meth) acrylamide or N, N- dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, for example. , N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N-vinylacetoamide, N, N-methylenebis (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide , N, N-dimethylaminopropylmethacrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, or (meth) acryloyl morpholine and the like can be exemplified, and as the amino group-containing monomer, aminoethyl (meth) Acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like can be exemplified, and examples of the imide group-containing monomer include N-isopropylmaleimide, N Cyclohexylmaleimide or itaciconimide It can be exemplified, and a cyano group-containing monomer include, but as acrylonitrile or methacrylonitrile, etc. The nitrile can be exemplified, without being limited thereto. N, N-dialkyl (meth) acrylamide may be selected from the above-mentioned nitrogen-containing monomers in order to secure proper physical properties, for example, conductivity, and to secure excellent peeling properties, for example, a balance between low and high speed peeling forces. Can be used as In this case, the N, N-dialkyl (meth) acrylamide may include an alkyl group 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.

The ratio of the weight ratio of the monomer of Formula 1 and the nitrogen-containing monomer in the adhesive polymer may be controlled in order to secure peeling properties, that is, excellent balance between low speed and high speed peeling force, while ensuring various physical properties such as adhesive performance. have. For example, the ratio (A / B) of the weight (A) of the monomer of Formula 1 to the weight (B) of the nitrogen-containing monomer in the adhesive polymer may be in the range of about 1.5 to 20. It is possible to provide a pressure-sensitive adhesive that exhibits an appropriate antistatic performance within the range of such a ratio, and exhibits an appropriate balance of high speed and low speed peeling force without leaving contaminants during peeling.

The adhesive polymer may also further comprise polymerized units of hydroxy group containing monomers. The monomer may provide a hydroxyl group to the adhesive polymer.

As a hydroxyl group containing monomer, the monomer represented by following formula (2) can be illustrated, for example.

[Formula 2]

In Formula (2), Q is hydrogen or an alkyl group, A and B are each independently an alkylene group, and n is any number, for example, a number from 0 to 10.

When two or more [—O—B—] units are present in Formula 2, the carbon number of B in the unit may be the same or different.

In Formula 2, A and B may be each independently a linear alkylene group.

As the compound of the formula (2), 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 the like can be exemplified, but is not limited thereto.

In one example, as the hydroxyl group-containing monomer, two kinds of monomers having different carbon numbers present in the side chain may be used.

For example, the adhesive polymer is represented by Formula 2 and is present in A and B of Formula 2 while being represented by Formula 2 and the first monomer having the number of carbons of the alkylene group in A and B of Formula 2 being in the range of 1 to 3. The number of carbons of the alkylene group to include 4 or more, 4 to 20, 4 to 16, 4 to 12, 4 to 8 or 4 to 6 may include a polymer unit of the second monomer.

As such, when calculating the number of carbons to distinguish the first and second monomers, only the number of carbons of the alkylene group formed in the straight chain form is taken into consideration. For example, the A and B substituents containing carbon are substituted. In this case, the carbon number of the substituent is not considered. Thus, through the polymerization unit of the two kinds of hydroxy monomers can be provided a pressure-sensitive adhesive excellent in particularly excellent peel force characteristics, that is, the balance of high-speed and low-speed peel force.

The ratio of the weight of the first and second monomers in the adhesive polymer may be controlled in order to secure peeling properties, that is, excellent balance between low speed and high speed peeling force, while securing various physical properties such as adhesive performance. For example, the ratio (A / B) of the weight (A) of the first monomer and the weight (B) of the second monomer in the adhesive polymer may be one or more or more than one. In another example, the ratio may be 25 or less, 20 or less, 15 or less, 10 or less, or about 8 or less. It is possible to provide a pressure-sensitive adhesive that exhibits an appropriate antistatic performance within the range of such a ratio, and exhibits an appropriate balance of high speed and low speed peeling force without leaving contaminants during peeling.

The adhesive polymer may include 40 to 94.8 parts by weight of alkyl (meth) acrylate, 0.1 to 15 parts by weight of the monomer of Chemical Formula 1, 0.1 to 5 parts by weight of the polymer unit containing nitrogen, 5 to 20 parts by weight of the first monomer, and the agent. It may comprise 0.1 to 4 parts by weight of the two monomers. Unless otherwise specified in the present specification, unit weight part may mean a ratio of weight between each component. For example, the adhesive polymer is 40 to 94.8 parts by weight of alkyl (meth) acrylate as described above, 0.1 to 15 parts by weight of the monomer of Formula 1, 0.1 to 5 parts by weight of the nitrogen-containing monomer, the first monomer 5 To include from 20 to 20 parts by weight and the second monomer of 0.1 to 5 parts by weight, the weight of the alkyl (meth) acrylate (A), the weight of the monomer of formula (B), the weight of the nitrogen-containing monomer (C ), And the ratio (A: B: C: D: E) of the weight (D) of the first monomer and the weight (E) of the second monomer is from 40 to 94.8: 0.1 to 15: 0.1 to 5: 5 to 20: 0.1 to 4 ”may mean that the adhesive polymer is formed from a mixture of monomers including the respective monomers. In the above alkyl (meth) acrylate in another example 50 to 94.8 parts by weight, 55 to 94.8 parts by weight, 60 to 94.8 parts by weight, 60 to 90 parts by weight, 60 to 85 parts by weight, 65 to 85 parts by weight or about 70 To 85 parts by weight may be included in the adhesive polymer.

In addition, the monomer of Formula 1 may be included in about 3 to 15 parts by weight, about 5 to 15 parts by weight or about 6 to 15 parts by weight. In addition, the nitrogen-containing monomer may also be included in another example of about 0.5 to 5 parts by weight.

The adhesive polymer is, if necessary, a known monomer used in the production of the adhesive polymer of the pressure-sensitive adhesive, for example, (meth) acrylic acid, 2- (meth) acryloyloxy acetic acid, 3- (meth) acryloyloxypropyl Carboxyl group-containing monomers such as acid, 4- (meth) acryloyloxy butyric acid, acrylic acid duplex, itaconic acid, maleic acid and maleic anhydride; Radical polymerizable including monomers having isocyanate groups, monomers having glycidyl groups such as glycidyl (meth) acrylate or nitrogen atoms such as (meth) acrylamide, N-vinyl pyrrolidone or N-vinyl caprolactam, etc. It may further include a radical polymerizable monomer such as a monomer or styrene. Such monomers may be polymerized to be included in the adhesive polymer, and for example, may be included in the adhesive polymer in a ratio of about 20 parts by weight or less.

The adhesive polymer is selected from the above-described monomers, and a mixture of monomers in which the selected monomers are mixed in a desired ratio is selected from solution polymerization, photo polymerization, bulk polymerization, suspension polymerization. It can be prepared by applying to a polymerization method such as (suspension polymerization) or emulsion polymerization (emulsion polymerization).

The pressure-sensitive adhesive composition may further include a crosslinking agent, which may react with the crosslinking point of the pressure-sensitive adhesive polymer to implement a crosslinking structure. The crosslinking agent may also play a role of mediating the bonding between the reactive polyether-modified siloxane compound described later and the adhesive polymer.

As a crosslinking agent, an aliphatic isocyanate crosslinking agent can be used, for example. When such a crosslinking agent implements a crosslinked structure with the adhesive polymer, that is, the adhesive polymer including two or more hydroxyl group-containing monomers, an adhesive having the necessary antistatic properties together with a suitable low speed and high speed peeling force may be realized. For example, as a crosslinking agent, the crosslinking agent containing an aliphatic cyclic isocyanate compound and / or an aliphatic acyclic isocyanate compound can be used. As used herein, the term aliphatic cyclic isocyanate compound means an isocyanate compound that includes a ring structure, but the structure does not correspond to an aromatic ring, and the aliphatic acyclic isocyanate compound is, for example, an aliphatic linear or It may mean a branched isocyanate compound. As the aliphatic cyclic isocyanate compound, for example, isocyanate compounds such as isophorone diisocyanate or methylene dicyclohexyl diisocyanate or cyclohexane diisocyanate, and the like Derivatives such as dimers or trimers, or reactants of any of the above with polyols (ex. Trimethylolpropane) may be exemplified. Examples of the aliphatic acyclic isocyanate compounds include carbon atoms such as hexamethylene diisocyanate and the like. Alkylene diisocyanate compounds having from 20 to 20, 1 to 16 carbon atoms, 1 to 12 carbon atoms, or 1 to 8 carbon atoms, derivatives thereof such as dimers or trimers, or any of the above and polyols (ex. Reactant with propane) Etc. may be exemplified, but is not limited thereto.

In the case where the aliphatic cyclic isocyanate compound and the aliphatic acyclic isocyanate compound are used together, the ratio is not particularly limited and may be appropriately selected as necessary. Typically, about 1 part by weight to about 500 parts by weight or about 20 parts by weight to about 300 parts by weight of the aliphatic acyclic isocyanate compound may be included in the crosslinking agent relative to 100 parts by weight of the aliphatic cyclic isocyanate compound. As such a crosslinking agent, that is, a crosslinking agent containing an aliphatic cyclic isocyanate compound and an aliphatic acyclic isocyanate compound may be used. Examples thereof include MHG-80B manufactured by Asahi and NZ-1 manufactured by Duranate P or BAYER. There is this.

As a crosslinking agent, if necessary further above, ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ', N'- tetraglycidyl ethylenediamine or glycerin Epoxy crosslinking agents such as diglycidyl ether and the like; N, N'-toluene-2,4-bis (1-aziridinecarboxamide), N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxamide), triethylene melamine Aziridine crosslinkers such as bisisoprotaloyl-1- (2-methylaziridine) or tri-1-aziridinylphosphineoxide, or aluminum, iron, zinc, tin, titanium, antimony, magnesium and / or vanadium A well-known crosslinking agent, such as a metal chelate crosslinking agent which is a compound in which a polyvalent metal like this is coordinated with acetyl acetone, ethyl acetoacetate, etc. can be used together.

The pressure-sensitive adhesive composition is 1 to 15 parts by weight, 2 to 15 parts by weight, 3 to 15 parts by weight, 4 to 15 parts by weight, 5 to 15 parts by weight, 5 to 14 parts by weight, 5 to 13 parts by weight based on 100 parts by weight of the adhesive polymer. And 5 to 12 parts by weight, 5 to 11 parts by weight, 5 to 10 parts by weight, or 5 to 9 parts by weight of a crosslinking agent. An appropriate crosslinked structure can be realized in this range, and the low speed and high speed peeling force of the pressure-sensitive adhesive can be adjusted to the desired range.

The pressure-sensitive adhesive composition of the present application may further include a reactive polyether modified siloxane compound. In the present application, that the polyether-modified siloxane compound is reactive means that the polyether-modified siloxane compound includes a reactive functional group, and the reactive functional group is, for example, a functional group of the aforementioned adhesive polymer, for example, It may be combined with a hydroxyl group or a carboxyl group, or the like, or may be a functional group that may be combined with a functional group of the adhesive polymer through another compound. The polyether-modified siloxane compound may play a role of imparting an antistatic ability to the pressure-sensitive adhesive, and in particular, by including the reactive functional group, maintains excellent compatibility with the adhesive polymer, thereby the pressure-sensitive adhesive during application of the surface protective film Elution to the outside of the layer or contamination of the adherend can be prevented.

Although the kind of the reactive functional group contained in the reactive polyether modified siloxane compound is not particularly limited, it needs to be selected in consideration of the possibility of bonding to the adhesive polymer. For example, the reactive polyether-modified siloxane compound may include a hydroxy group, an epoxy group or an amine group as a reactive functional group. It is preferable that the said reactive functional group exists in the terminal of the said polyether modified siloxane compound. When the reactive functional group is a hydroxy group and the adhesive polymer is a hydroxy group, the polyether modified siloxane compound may be connected to the adhesive polymer by a compound having at least two isocyanates, for example, the aliphatic isocyanate crosslinking agent described above. That is, in the above case, one isocyanate group of the crosslinking agent reacts with the hydroxyl group of the polyether modified siloxane compound to form a urethane bond, and the other isocyanate group of the crosslinking agent reacts with the hydroxyl group of the adhesive polymer to form a urethane bond. The polyether modified siloxane compound may be bonded to the adhesive polymer. Even when the reactive functional group of the polyether modified siloxane compound is another functional group such as an epoxy group or an amine group, a functional group capable of reacting with the functional group is introduced into the adhesive polymer, or a functional group capable of reacting with the functional group is introduced into the adhesive polymer. By using a compound capable of reacting with a functional group, introduction of a reactive polyether modified siloxane compound may be enabled.

Therefore, as an example, the reactive polyether modified siloxane compound has a hydroxy group as a reactive functional group, and the hydroxy group of the polyether modified siloxane compound is based on the hydroxyl group and the aliphatic isocyanate compound of the first or second monomer of the adhesive polymer. May be combined and connected.

As the reactive polyether modified siloxane compound, for example, a compound represented by the following formula (A) or (B) or a mixture of compounds thereof may be used.

[Formula 1]

[Formula B]

R ₁ to R ₁₅ in Formula A or B are each independently a hydrogen atom, an alkyl group or an alkenyl group, and Z is-(CH ₂ ) _p- (O-CH ₂ -CH ₂ ) _q- (O-CH ₂ -CH ₂ -CH ₂ ) _r -U, wherein U is a hydroxy group, an amine group or an epoxy group, p is a number in the range of 1 to 4, q + r is at least 1 number, x is a number from 1 to 10 , y is a number in the range of 1 to 10.

In Formula A or B, R ₁ to R ₁₅ may each independently be an alkyl group 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.

Also, in Formula A or B, q may be in the range of about 1 to about 30, and r may be in the range of about 1 to about 30.

The reactive polyether modified siloxane compound may have a weight average molecular weight of about 500 to 30,000. In the case of the present application, the reactive polyether-modified siloxane compound may be included in the pressure-sensitive adhesive layer in a form bonded to the adhesive polymer, thereby exhibiting excellent miscibility even in the molecular weight of the above range.

The pressure-sensitive adhesive composition is 0.01 to 5 parts by weight, 0.05 to 5 parts by weight, 0.1 to 5 parts by weight, 0.5 to 5 parts by weight, 0.5 to 4 parts by weight, 0.5 to 3 parts by weight or 0.5 to 2.5 parts by weight based on 100 parts by weight of the adhesive polymer The reactive polyether modified siloxane compound may be included. Appropriate antistatic property is secured in such a range, and the low speed and high speed peeling force of an adhesive etc. can be adjusted to a desired range.

The pressure-sensitive adhesive composition may further include a light stabilizer, for example, a light stabilizer such as a hindered amine compound. Such light stabilizers do not aggregate even when the pressure sensitive adhesive is left at high temperature, for example, so that the concentration of the antistatic agent described later in the aggregated cluster does not increase, and the alkylene oxide contained in the pressure sensitive adhesive polymer is included. The ether bond site of the chain is decomposed by heat to generate radicals, or the hydroxyl group-containing monomer can be prevented from causing a condensation reaction, thereby greatly improving the storage stability of the pressure-sensitive adhesive composition.

As an optical stabilizer, the compound represented by following formula (3) can be illustrated, for example.

[Formula 3]

In Formula 3, M ₁ to M ₅ are each independently R ¹ -N, (R ² ) (R ³ ) -C or (R ⁴ ) (R ⁵ ) -C, wherein R ¹ is a hydrogen atom, an alkyl group or alkoxy group, R ² and R ³ are each and independently selected from an alkyl group, R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group, L is an alkylene group or an alkylidene group, P is an alkyl group or a substituent of the formula (4) to be. In the above formula (3) at least one of M ₂ to M ₄ is wherein R ¹ -N, R ¹ -N of M _2, M ₃ or M _1, present immediately adjacent to M ₄ M _2, M _3, M ₄ Or M ₅ may be (R ² ) (R ³ ) -C.

[Formula 4]

In Formula 4, M ₆ to M ₁₀ are each independently R ¹ -N, (R ² ) (R ³ ) -C or (R ⁴ ) (R ⁵ ) -C, wherein R ¹ is a hydrogen atom, an alkyl group or An alkoxy group, R ² and R ³ are each independently an alkyl group, and R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group. In the above formula (4) at least one of M ₇ to M ₉ is the _{^{R 1 -N, M 7, M}} 8 or _{M M 6, M 7, M} 8, M 9 or M ₁₀ immediately adjacent to the existing ₉ is the (R ² ) (R ³ ) -C.

In Formulas 3 and 4, M ₁ to M ₁₀ are R ¹ -N, (R ² ) (R ³ ) -C or (R ⁴ ) (R ⁵ ) -C, which is nitrogen at the position of M ₁ to M ₁₀ . An atom (N) or a carbon atom (C) is present, and may refer to a form in which a substituent such as R ¹ to R ⁵ is bonded to the nitrogen atom or carbon atom.

는 상기 부호와 연결되어 있는 화학식 4의 탄소 원자가 화학식 3의 산소 원자에 결합되어 있는 것을 의미한다.In addition, the symbol in the formula

Means that the carbon atom of formula (4) linked with the above sign is bonded to the oxygen atom of formula (3).

In Formula 3, L, which is an alkylene group or an alkylidene group, may be substituted or unsubstituted if necessary. For example, L may be substituted with an aryl group, and the aryl group may be exemplified by 3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl group, but is not limited thereto. It is not.

R ¹ in Formula 3 may be, for example, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 4 to 16 carbon atoms or 4 to 12 carbon atoms. The alkyl group or alkoxy group may be linear or branched, and may be substituted by one or more substituents.

In Formula 3, R ² , R ³ and P may each independently be an alkyl group having 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear or branched, and may be substituted by one or more substituents.

In addition, in Formula 3, R ⁴ and R ⁵ may be a hydrogen atom.

In Formula 3, L may be, for example, an alkylene group having 4 to 12 carbon atoms or 6 to 10 carbon atoms, or an alkylidene group having 2 to 10 carbon atoms or 4 to 8 carbon atoms. The alkylene group or alkylidene group may be linear or branched, and may be substituted by one or more substituents.

As the compound of the formula (3), for example, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (bis (1,2,2,6,6-pentamethyl-4) -piperidyl) sebacate), methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, propanedioic acid 2-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -2-butyl-1,3-bis (1,2,2,6,6-pentamethyl- 4-piperidinyl) ester (propanedioic acid, 2-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -2-butyl-1,3-bis (1,2,2 (6,6-pentamethyl-4-piperidinyl) ester), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (bis (2,2,6,6-tetramethyl-4- piperidyl) sebacate) or bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (bis- (1-octyloxy-2,2,6,6-tetramethyl-4 -piperidinyl) sebacate) and the like can be exemplified, but is not limited thereto.

The compound of Formula 3 may be, for example, 0.01 parts by weight to 10 parts by weight, 0.05 parts by weight to 10 parts by weight, 0.05 parts by weight to 8 parts by weight, 0.05 parts by weight to 6 parts by weight, or 0.05 parts by weight based on 100 parts by weight of the adhesive polymer. It may be included in the pressure-sensitive adhesive composition in a ratio of 5 parts by weight to 5 parts by weight. Under such a ratio, generation of radicals due to decomposition of the alkylene oxide chain, condensation of hydroxy group-containing monomers, and the like can be effectively prevented, and an adhesive composition having excellent storage stability can be provided.

The pressure-sensitive adhesive composition may further include an antistatic agent. As the antistatic agent, for example, an ionic compound can be used.

As the ionic compound, for example, a metal salt can be used. The metal salt may include, for example, an alkali metal cation or an alkaline earth metal cation. As the cation, lithium ions (Li ⁺ ), sodium ions (Na ⁺ ), potassium ions (K ⁺ ), rubidium ions (Rb ⁺ ), cesium ions (Cs ⁺ ), beryllium ions (Be ²⁺ ), magnesium ions ( Mg ^{2 +} ), calcium ions (Ca ^{2 +} ), strontium ions (Sr ^{2 +} ) and barium ions (Ba ^{2 +} ), and the like, or two or more kinds thereof may be exemplified. For example, lithium ions, sodium ions, Lithium ions may be used in consideration of one or more kinds of potassium ions, magnesium ions, calcium ions and barium ions, or ionic stability and mobility.

As the anion contained in the ionic compound is _{^{PF 6 -, AsF -, NO}} 2 -, fluoride (F ^-), chloride (Cl ^-), bromide (Br ^-), iodide (I ^-), perchlorate (ClO ₄ ^-), hydroxide (OH ^-), carbonate (CO ₃ ^2-), nitrate (NO ₃ ^-), trifluoromethane sulfonate (CF ₃ SO ₃ ^-), sulfonate (SO ₄ ^-), hexafluoro phosphate (PF ₆ ^-), methyl benzene sulfonate _{(CH 3 (C 6 H 4} ) SO 3 -), p- toluenesulfonate _{(CH 3 C 6 H 4 SO} 3 -), tetraborate (B ₄ O ₇ ^2- ), carboxybenzenesulfonate (COOH (C ₆ H ₄ ) SO ₃ ⁻ ), trichloromethanesulfonate (CF ₃ SO ₂ ⁻ ), benzoate (C ₆ H ₅ COO ⁻ ), acetate ( a), a triple acetate _{^{- CH 3 COO (CF 3 COO}} -), tetrafluoroborate (BF ₄ ^-), tetra-benzyl borate _{(B (C 6 H 5)} 4 -) or tris pentafluoroethyl trifluoromethyl phosphate _{(P (C 2 F 5)} 3 F 3 -) or the like it can be illustrated.

In another example, an anion or bisfluorosulfonylimide represented by the following Chemical Formula 5 may be used as the anion.

[Formula 5]

[X (YO _m R _f ) _n ] ^-

In formula (5), X is a nitrogen atom or a carbon atom, Y is a carbon atom or a sulfur atom, R _f is a perfluoroalkyl group, m is 1 or 2, and n is 2 or 3.

In Formula 5, when Y is carbon, m is 1, when Y is sulfur, m is 2, n is 2 when X is nitrogen, and n may be 3 when X is carbon.

Anions or bis (fluorosulfonyl) imides of formula (5) exhibit high electronegativity due to perfluoroalkyl groups (R _f ) or fluorine groups, and also include unique resonance structures, forming weak bonds with cations At the same time, it has hydrophobicity. Therefore, while an ionic compound shows the outstanding compatibility with other components of compositions, such as an adhesive polymer, it can provide high antistatic property even with a small amount.

R _f in Formula 5 may be a perfluoroalkyl group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, in which case the perfluoroalkyl group is linear, branched, or cyclic. It may have a mold structure. The anion of Formula 5 may be a sulfonyl metide, sulfonylimide, carbonyl metide, or carbonyl imide anion, and specifically, tristrifluoromethanesulfonylmethide and bistrifluoromethanesulfide Ponylimide, bisperfluorobutanesulfonylimide, bispentafluoroethanesulfonylimide, tristrifluoromethanecarbonylmide, bisperfluorobutanecarbonylimide or bispentafluoroethanecarbonyl It may be a kind of imide or the like or a mixture of two or more thereof.

As the ionic compound, for example, as a cation, N-ethyl-N, N-dimethyl-N-propylammonium, N, N, N-trimethyl-N-propylammonium, N-methyl-N, N, N -Tributylammonium, N-ethyl-N, N, N-tributylammonium, N-methyl-N, N, N-trihexylammonium, N-ethyl-N, N, N-trihexylammonium, N-methyl Quaternary ammonium such as -N, N, N-trioctylammonium or N-ethyl-N, N, N-trioctylammonium, phosphonium, pyridinium, imidazolium, blood An organic salt containing pyrolidinium, piperidinium, or the like together with the anion component may be used, or the metal salt and the organic salt may be used in combination if necessary.

The content of the ionic compound in the pressure-sensitive adhesive composition is not particularly limited, for example, may be present in a ratio of 0.01 to 5 parts by weight relative to 100 parts by weight of the adhesive polymer. The ratio of the ionic compound can be changed in consideration of the desired antistatic property or compatibility between the components.

The pressure-sensitive adhesive composition may further include a silane coupling agent. Examples of the coupling agent include gamma-glycidoxypropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, gamma-glycidoxypropyl methyldiethoxy silane, gamma-glycidoxypropyl triethoxy silane , 3-mercaptopropyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma-methacryloxy propyl triethoxy silane, gamma-aminopropyl tri Methoxy silane, gamma-aminopropyl triethoxy silane, 3-isocyanato propyl triethoxy silane, gamma-acetoacetate propyl trimethoxysilane, gamma-acetoacetate propyl triethoxy silane, beta-cyanoacetyl Trimethoxy silane, beta-cyanoacetyl triethoxy silane, acetoxyaceto trimethoxy silane, and one or more kinds of the above mixtures may be used. Can be. For example, it may be appropriate to use a silane coupling agent having an acetoacetate group or a beta-cyanoacetyl group as the silane coupling agent. The silane coupling agent may be included in the pressure-sensitive adhesive composition in an amount of 0.01 to 5 parts by weight, or 0.01 to 1 part by weight based on 100 parts by weight of the adhesive polymer. Appropriate adhesive force increase effect and durability reliability can be secured in the above range.

The pressure-sensitive adhesive composition may further include a tackifier in view of control of adhesion performance. As a tackifier, hydrocarbon resin or its hydrogenated substance, rosin resin or its hydrogenated substance, rosin ester resin or its hydrogenated substance, terpene resin or its hydrogenated substance, terpene phenol resin or its hydrogenated substance, polymeric rosin resin or polymeric rosin One kind or a mixture of two or more kinds such as an ester resin can be used. A tackifier may be included in the composition in an amount of 1 to 100 parts by weight based on 100 parts by weight of the co-adhesive polymer. Suitable addition effects and compatibility and cohesion enhancement effects can be ensured in the above content range.

The pressure-sensitive adhesive composition is also a coordination compound, photoinitiator, polyfunctional acrylate, epoxy resin, crosslinking agent, UV stabilizer, antioxidant, which can form a coordination bond with the antistatic agent within a range that does not affect the effect of the application. It may further comprise one or more additives selected from the group consisting of colorants, reinforcing agents, fillers, antifoams, surfactants and plasticizers.

The pressure-sensitive adhesive composition has a low-speed peeling force of about 1 gf / 25 mm to about 10 gf / 25mm with respect to an adherend having a surface energy of 30 mN / m or less in a state where a crosslinked structure is implemented, and a high speed peeling force of 40 gf / 25mm. To 200 gf / 25mm, 40 gf / 25mm to 150 gf / 25mm or 40 gf / 25mm to 100 gf / 25mm.

As used herein, the term low speed peel force is a peel force measured at a peel angle of 180 degrees and a peel rate of 0.3 m / min, and a high speed peel force is measured at a peel angle of 180 degrees and a peel rate of 30 m / min. May be a peel force.

Specifically, each of the peeling force, the pressure-sensitive adhesive composition having a crosslinked structure is attached to the adherend having a surface energy of 30 mN / m or less, and maintained for 24 hours at a temperature of 23 ℃ and 65% relative humidity It may be measured at each peeling angle and peeling rate. The specific way of measuring each peel force is described in the following Examples. The surface energy of the adherend may be, for example, about 10 m / N / m to about 30 mN / m.

The pressure-sensitive adhesive composition may also have a ratio (H / L) of the high speed peeling force (H) to the low speed peeling force (L) of about 1 to 30, 1 to 25, 5 to 25, 10 to 25, or about 13 to 20. have.

The pressure-sensitive adhesive composition is also a peeling charge voltage generated when peeled at a peel angle of 180 degrees and a peel rate of 40 m / min from the adherend, that is, the adherend having a surface energy of 30 mN / m or less in a state where a crosslinked structure is realized. May be 0.7 kV or less. The method of measuring the peeling electrification voltage is described in the following examples.

When the low-speed peeling force, high-speed peeling force and / or peeling voltage is secured as described above, it can be easily peeled off at high speed while minimizing the occurrence of static electricity and the like while exhibiting an appropriate protection function for the adherend.

The present application also relates to an adhesive sheet. The said adhesive sheet can be a protective film, specifically, the protective film for optical elements.

For example, the adhesive sheet can be used as a protective film for optical elements, such as a polarizing plate, a polarizer, a polarizer protective film, retardation film, a viewing angle compensation film, and a brightness enhancement film. As used herein, the terms polarizer and polarizer refer to objects that are distinguished from each other. That is, the polarizer refers to the film, sheet or device itself exhibiting a polarizing function, and the polarizing plate means an optical element including other elements together with the polarizer. As other elements that may be included in the optical device together with the polarizer, a polarizer protective film or a retardation layer may be exemplified, but is not limited thereto.

The pressure-sensitive adhesive sheet may include, for example, a base film for surface protection and an adhesive layer present on one side of the base film. The pressure-sensitive adhesive layer may include, for example, a crosslinked pressure-sensitive adhesive composition, that is, a pressure-sensitive adhesive composition having a crosslinked structure as the pressure-sensitive adhesive composition.

The pressure-sensitive adhesive composition exhibits a relatively high low-speed peeling force and a relatively low high-speed peeling force after the crosslinking structure is implemented, and is excellent in balance of both peeling forces, and has excellent durability, workability, transparency, and antistatic property. Accordingly, the protective film protects the surface of optical elements such as polarizing plates, retardation plates, optical compensation films, reflective sheets, and luminance enhancing films used in various optical devices or components or display devices or components, for example, LCDs. It can be effectively used as a surface protective film for, but the above use is not limited to the protective film.

As the surface protective base film, a general film or sheet known in the art may be used. For example, polyester films such as polyethylene terephthalate or polybutylene terephthalate, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, poly (vinyl chloride) film or polyimide film Plastic films such as Such a film may consist of a single layer, or two or more layers may be laminated, and in some cases, may further include a functional layer such as an antifouling layer or an antistatic layer. In addition, from the viewpoint of improving the substrate adhesion, one or both surfaces of the substrate may be subjected to surface treatment such as primer treatment.

The thickness of the base film is not particularly limited to be appropriately selected depending on the use, and can be generally formed in a thickness of 5 μm to 500 μm or 10 μm to 100 μm.

The thickness of the pressure-sensitive adhesive layer included in the pressure-sensitive adhesive sheet is not particularly limited, and may be, for example, 2 μm to 100 μm or 5 μm to 50 μm.

The method for forming the pressure-sensitive adhesive layer is not particularly limited, and for example, the pressure-sensitive adhesive composition or a coating liquid prepared therefrom is applied to a base film or the like by a conventional means such as a bar coater, and cured, or the pressure-sensitive adhesive composition or coating liquid is once peelable. The method etc. which apply | coat to the surface of a base material, harden | cure, and transfer again to a base film can be used.

The formation process of the pressure-sensitive adhesive layer is preferably performed after sufficiently removing the bubble-inducing component such as volatile components or reaction residues in the pressure-sensitive adhesive composition or coating liquid. Accordingly, the crosslinking density or molecular weight of the pressure-sensitive adhesive is too low, the elastic modulus is lowered, the bubbles existing between the glass plate and the pressure-sensitive adhesive layer in the high temperature state is increased, it is possible to prevent the problem of forming a scattering body therein.

In addition, the method of curing the pressure-sensitive adhesive composition in the above process is also not particularly limited, and for example, the adhesive polymer and the cross-linking agent included in the composition may be subjected to an appropriate aging process or to induce activation of a photoinitiator, etc. in the interior. It may be carried out through light irradiation, for example ultraviolet light irradiation.

For example, the pressure-sensitive adhesive layer may have a gel content of about 80% to about 99%. The gel content can be calculated, for example, by the following formula (1).

[Equation 1]

Gel content = B / A × 100

In Equation 1, A represents the mass of the pressure-sensitive adhesive, B represents the dry mass of the insoluble fraction recovered after immersing the pressure-sensitive adhesive in ethyl acetate for 48 hours at room temperature.

The present application also relates to an optical device. An exemplary optical element may include an optical element and the adhesive sheet attached to a surface of the optical element. For example, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is attached to the surface of the optical element, thereby the optical element can be protected by the surface protection base film.

As an optical element contained in an optical element, a polarizer, a polarizing plate, a polarizer protective film, a retardation layer, a viewing angle compensation layer, etc. can be illustrated, for example.

As the polarizer as described above, for example, a general kind known in the art, such as a polyvinyl alcohol polarizer, may be employed without limitation.

The polarizer is a functional film or sheet capable of extracting only light vibrating in one direction from incident light while vibrating in various directions. Such a polarizer may be, for example, a form in which a dichroic dye is adsorbed in a polyvinyl alcohol-based resin film. Polyvinyl alcohol-type resin which comprises a polarizer can be obtained by gelatinizing polyvinylacetate-type resin, for example. In this case, the polyvinylacetate-based resin that can be used may include not only a single adhesive polymer of vinyl acetate, but also a co-adhesive polymer of vinyl acetate and other monomers copolymerizable with the above. Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and a mixture of one or two or more kinds of acrylamides having an ammonium group, but are not limited thereto. no. The degree of gelation of the polyvinyl alcohol-based resin is usually 85 mol% to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be further modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may also be used. In addition, the degree of polymerization of the polyvinyl alcohol-based resin may be about 1,000 to 10,000, preferably about 1,500 to 5,000.

Polyvinyl alcohol-type resin is formed into a film, and can be used as a raw film of a polarizer. The method of forming a polyvinyl alcohol-type resin into a film is not specifically limited, The general method known in this field can be used. The thickness of the raw film formed into a polyvinyl alcohol-based resin is not particularly limited, and may be appropriately controlled within, for example, 1 µm to 150 µm. In consideration of ease of stretching and the like, the thickness of the master film can be controlled to 10 ㎛ or more. The polarizer is a step of stretching (ex. Uniaxial stretching) the polyvinyl alcohol resin film as described above, a step of dyeing the polyvinyl alcohol resin film with a dichroic dye, adsorbing the dichroic dye, and a dichroic dye adsorbed. The polyvinyl alcohol-based resin film can be produced through a process of treating with a boric acid aqueous solution and a process of washing with water after treating with a boric acid aqueous solution. As the dichroic dye, iodine or a dichroic organic dye may be used.

The polarizing plate may include, for example, the polarizer; And it may include another optical film attached to one side or both sides of the polarizer. As another optical film, the above-described polarizer protective film, a retardation layer, a viewing angle compensation layer, an antiglare layer, and the like can be exemplified.

A polarizer protective film is a protective film with respect to a polarizer by the concept distinguished from the protective film containing the said adhesive layer in the above. As a polarizer protective film, For example, Cellulose-type films, such as triacetyl cellulose; Acrylic film; Polyester film such as polycarbonate film or polyethylene terephthalate film; Polyether sulfone-based film; And / or a protective film composed of a polyethylene film, a polypropylene film, or a polyolefin film having a cyclo or norbornene structure, or a polyolefin film such as ethylene propylene co-adhesive polymer. The thickness of the protective film is also not particularly limited, and may be formed to a conventional thickness.

In the optical device, a surface treatment layer may exist on the surface of the optical device protected by the protective film. For example, the surface treatment layer may have a surface energy of 30 mN / m or less. That is, a surface treatment layer having a surface energy of 30 mN / m or less is formed on the surface of the optical element protected by the protective film in the optical element, and the pressure-sensitive adhesive layer of the protective film is attached to the surface treatment layer. Can be.

The surface treatment layer may include a high hardness layer, an anti-glare layer such as an AG (anti-glare) layer or a semi-glare (SG) layer, or a low reflection layer such as an anti reflection (AR) layer or a low reflection (LR) layer. May be exemplified.

The high hardness layer may be a layer having a pencil hardness of at least 1H or at least 2H under a load of 500 g. Pencil hardness can be measured according to the ASTM D 3363 standard, for example using the pencil lead defined in KS G2603.

The high hardness layer may be, for example, a high hardness resin layer. The resin layer may include, for example, a room temperature curing type, a moisture curing type, a thermosetting type, or an active energy ray curable resin composition in a cured state. In one example, the resin layer may include a thermosetting or active energy ray-curable resin composition, or an active energy ray-curable resin composition in a cured state. In the description of the high hardness layer, the "cured state" may mean a case where the components contained in the respective resin compositions are converted into a hard state through a crosslinking reaction or a polymerization reaction. Further, in the above-mentioned room temperature curing type, moisture curing type, thermosetting type or active energy ray-curable resin composition, the cured state may be induced at room temperature or may be induced by application of heat or irradiation of active energy ray in the presence of appropriate moisture. By composition may be meant.

In this field, various resin compositions are known which can satisfy the pencil hardness in the above-mentioned range in a cured state, and the average technician can easily select a suitable resin composition.

In one example, the resin composition may include an acrylic compound, an epoxy compound, a urethane compound, a phenol compound, a polyester compound, or the like as a main material. In the above, the "compound" may be a monomeric, oligomeric or adhesive polymeric compound.

In one example, as the resin composition, an acrylic resin composition excellent in optical properties such as transparency and excellent in resistance to yellowing and the like, for example, an active energy ray-curable acrylic resin composition can be used.

The active energy ray-curable acrylic composition may include, for example, an active energy ray polymerizable adhesive polymer component and a monomer for reactive dilution.

The adhesive polymer component may include a component known in the art as a so-called active energy ray polymerizable oligomer such as urethane acrylate, epoxy acrylate, ether acrylate or ester acrylate, or a monomer such as (meth) acrylic acid ester monomer. Polymerized mixtures can be exemplified. As the (meth) acrylic acid ester monomer, alkyl (meth) acrylate, (meth) acrylate having an aromatic group, heterocyclic (meth) acrylate or alkoxy (meth) acrylate and the like can be exemplified. Various adhesive polymer components are known in the art for producing active energy ray-curable compositions, and such compounds may be selected as needed.

As the monomer for reactive dilution, which may be included in the active energy ray-curable acrylic composition, a monomer having one or two or more active energy ray-curable functional groups, for example, acryloyl group or methacryloyl group, may be exemplified. . As the monomer for reactive dilution, for example, the (meth) acrylic acid ester monomer or polyfunctional acrylate may be used.

The selection of the above components or the blending ratio of the selected components for producing the active energy ray-curable acrylic composition is not particularly limited and may be adjusted in consideration of the hardness and other physical properties of the desired resin layer.

As an anti-glare layer such as an AG layer or an SG layer, for example, a resin layer having a refractive index different from that of the resin layer may be used as the resin layer including the resin layer or the particles having the uneven surface formed thereon. Can be.

As said resin layer, the resin layer used for formation of the said high hardness layer can be used, for example. When forming an anti-glare layer, although it is not necessary to adjust the component of a resin composition so that a resin layer may show high hardness, you may form a resin layer so that a high hardness may be shown.

The method of forming the uneven surface on the resin layer is not particularly limited. For example, the resin composition may be cured in a state in which the coating layer of the resin composition is brought into contact with a mold having a desired uneven structure, or a particle having an appropriate particle size may be blended, coated and cured in the resin composition to realize the uneven structure. have.

The anti-glare layer can also be implemented using particles having a refractive index different from that of the resin layer.

In one example, the particles, for example, the difference in refractive index with the resin layer may be 0.03 or less or 0.02 to 0.2. If the difference in the refractive index is too small, it is difficult to cause haze, and if the difference is too large, scattering occurs in the resin layer to increase the haze, but a decrease in light transmittance or contrast characteristics may be induced. Consideration can be given to selecting appropriate particles.

The shape of the particles contained in the resin layer is not particularly limited, and may be, for example, spherical, elliptical, polyhedral, amorphous or other shapes. The particles may have an average diameter of 50 nm to 5,000 nm. In one example, the particle | grains in which the unevenness | corrugation is formed in the surface can be used as said particle | grain. Such particles may, for example, have an average surface roughness Rz of 10 nm to 50 nm or 20 nm to 40 nm, and / or a maximum height of irregularities formed on the surface of about 100 nm to 500 nm or 200 nm to 400 nm, and the width of the unevenness may be 400 nm to 1,200 nm or 600 nm to 1,000 nm. Such particles are excellent in compatibility with the resin layer or dispersibility therein.

As the particles, various inorganic or organic particles can be exemplified. Examples of the inorganic particles include silica, amorphous titania, amorphous zirconia, indium oxide, alumina, amorphous zinc oxide, amorphous cerium oxide, barium oxide, calcium carbonate, amorphous barium titanate or barium sulfate, and the like. Examples of the organic particles may include particles including a crosslinked or non-crosslinked material of an organic material such as an acrylic resin, a styrene resin, a urethane resin, a melamine resin, a benzoguanamine resin, an epoxy resin, or a silicone resin, but are not limited thereto. It is not.

The content of the uneven structure or the particles formed in the resin layer is not particularly limited. The shape of the uneven structure or the content of the particles, for example, in the case of the AG layer, so that the haze (haze) of the resin layer is about 5% to 15%, 7% to 13% or about 10% In the case of the SG layer, the haze may be adjusted to be about 1% to 3%. The haze may be measured according to a manufacturer's manual using a hazemeter such as Sepung's HR-100 or HM-150.

The low reflection layer, such as an AR layer or an LR layer, may be formed by coating a low refractive material. There are a variety of low refractive materials that can form a low reflection layer, all of which may be appropriately selected and used in the optical element. The low reflection layer may be formed such that the reflectance is about 1% or less through the coating of the low refractive material.

In the formation of the surface treatment layer, Korean Unexamined Patent Publication Nos. 2007-0101001, 2011-0095464, 2011-0095004, 2011-0095820, 2000-0019116, 2000-0009647, and 2000 -0018983, 2003-0068335, 2002-0066505, 2002-0008267, 2001-0111362, 2004-0083916, 2004-0085484, 2008-0005722, 2008-0063107 The materials known from Japanese Patent Application No. 2008-0101801 or 2009-0049557 may also be used.

The surface treatment layer may be formed alone or in combination of two or more thereof. As an example of the combination, the case where a high hardness layer is formed first on the surface of a base material layer and a low reflection layer is formed again on the surface can be illustrated.

The present application also relates to a display device, such as a liquid crystal display (LCD). The exemplary display device may include a liquid crystal panel, and the optical element may be attached to one side or both sides of the liquid crystal panel. The film may be attached to the liquid crystal panel using, for example, an adhesive or an adhesive. In the above, an adhesive agent or an adhesive agent is an adhesive agent or adhesive other than the adhesive agent which exists in the above-mentioned protective film.

The kind of liquid crystal panel contained in a liquid crystal display device is not specifically limited. For example, F various passive matrix systems including, but not limited to, TN (Twisted Neumatic), STN (Super Twisted Neumatic), F (ferroelectric), PD (polymer dispersed LCD), and the like; Various active matrix schemes including two terminals and three terminals; Both known liquid crystal panels, including IPS mode panels and VA mode panels, can be applied. In addition, the type of the other components included in the liquid crystal display device and the manufacturing method thereof are not particularly limited, and the general configurations in this field can be employed without limitation.

The pressure-sensitive adhesive composition of the present application exhibits excellent antistatic properties, exhibits appropriate low speed and high speed peeling force after the crosslinked structure is formed, and is excellent in the balance of both. Accordingly, when the pressure-sensitive adhesive composition is applied to, for example, a protective film, it exhibits an excellent protective effect and is easily peeled off at the time of high-speed peeling, which is advantageous in terms of a high-speed process, and exhibits excellent antistatic properties in the process. Can be.

Hereinafter, the pressure-sensitive adhesive composition will be described in more detail with reference to Examples and Comparative Examples, but the scope of the pressure-sensitive adhesive composition is not limited to the following Examples.

1. Measurement of surface resistance

The adhesive sheet of Example or Comparative Example was cut to have a width of 150 mm and a length of 50 mm, and after peeling off the release PET film at a constant speed, the pressure-sensitive adhesive layer exposed by peeling off the release PET film and the release PET film. Three locations were designated at random on the surface, and the surface resistance was measured, and the average value was obtained. In the above, the surface resistance was measured according to the manufacturer's manual using an MCP-HT 450 instrument (Mitsubishi hemical (manufactured)).

2. Measurement of low speed peeling force

The adhesive sheets prepared in Examples and Comparative Examples were subjected to high-definition anti-glare film (trade name: ALR1, LG Chemicals, surface contact angle for deionized water: 110 °, surface energy: 20 mN / m) according to JIS Z 0237. It was attached with a roller of 2 Kg. Thereafter, the film to which the adhesive sheet was attached was cut and stored for 24 hours at a temperature of 23 ° C. and a relative humidity of 65%. The foundation was 25 mm long and 100 mm long. Thereafter, the specimen was fixed to the glass substrate, and the pressure-sensitive adhesive sheet was moved in the longitudinal direction at a peel angle of 180 degrees and a peel rate of 0.3 m / min using a tensile tester (Texture Analyzer, manufactured by Stable Micro Systems Co., Ltd.) at room temperature. Peeling force was measured, peeling from an anti-glare film. Peel force was measured on two identical specimens and then the average value was employed.

3. Measurement of high speed peeling force

The pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were attached to a high-definition anti-glare film (trade name: ALR1, LG Chemical Co.) with a roller of 2 Kg according to JIS Z 0237. Thereafter, the film to which the adhesive sheet was attached was cut and stored for 24 hours at a temperature of 23 ° C. and a relative humidity of 65%. The cuttings were 25 mm long and 250 mm long. Thereafter, the specimen was fixed to the glass substrate, and the pressure-sensitive adhesive sheet in the longitudinal direction at a peel angle of 180 degrees and a peel rate of 30 m / min using a tensile tester (Texture Analyzer, manufactured by Stable Micro Systems Co., Ltd.) at room temperature. Peeling force was measured, peeling from an anti-glare film. Peel force was measured on two identical specimens and then the average value was employed.

4. Measurement of peeling electrification voltage (ESD)

The pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were cut to have a length of 220 mm and a length of 250 mm. The cut adhesive sheet was attached to a high-definition anti-glare film (brand name: ALR1, LG Chem) by the roller of 2 Kg according to JIS Z 0237. Thereafter, the pressure-sensitive adhesive sheet was peeled from the anti-glare film at a peel angle of 180 degrees and a speed of 40 m / min at a temperature of 23 ° C. and a relative humidity of 65%. The peeling was performed using a tensile tester (Texture Analyzer, manufactured by Stable Micro Systems, Inc.). The peeling electrification voltage was measured at a distance of 40 mm in the normal direction from the surface of the anti-glare film using a measuring equipment (electrostatic potential meter, KSD-200) immediately after the peeling. The peeling electrification voltage was measured twice with respect to the same specimen, and the average value thereof was obtained.

<Characteristic evaluation criteria>

A: When peeling electrification voltage is 1.0 kV or less

B: When the peeling electrification voltage is greater than 1.0 kV

5. Pollution degree evaluation

The pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were cut to have a length of 150 mm and a length of 250 mm. The cut adhesive sheet was attached to a high-definition anti-glare film (brand name: ALR1, LG Chem) by the roller of 2 Kg according to JIS Z 0237. Thereafter, a black pressure-sensitive adhesive film was attached to the surface where the pressure-sensitive adhesive sheet of the anti-glare film was not attached, and stored at room temperature for 24 hours. The adhesive sheet was then peeled off, and the anti-glare film was allowed to stand at a temperature of 60 ° C. and 90% relative humidity for 1 hour, and then, if the dirt was present in the anti-glare film in the light of the Xenon HID lamp (manufactured by Polarion). Observations and properties were evaluated according to the following criteria.

<Characteristic evaluation criteria>

A: No pollution

B: In case of contamination

Preparation Example 1 Preparation of Acrylic Adhesive Polymer (A)

86 parts by weight of 2-ethylhexyl acrylate (2-EHA) and 3 parts by weight of 2-hydroxybutyl acrylate (2-HBA) in a 3 L reactor equipped with a refrigeration device for nitrogen gas reflux and easy temperature control , 3 parts by weight of 2-hydroxyethyl acrylate (2-HEA), 1 part by weight of N, N-dimethyl acrylamide (DMAA) and polyethylene glycol monomethyl ether methacrylate (FM-401, ethylene oxide unit addition mole number) : 9 moles) 11 parts by weight (weight ratio (2-EHA: 4-HBA: 2-HEA: DMAA: FM-401) = 86: 3: 3: 1: 11), 100 parts of ethyl acetate as a solvent Poured. Nitrogen gas was then purged for 1 hour to remove oxygen and the temperature was maintained at 60 ° C. Thereafter, an appropriate amount of a reaction initiator (AIBN: azobisisobutyronitrile) and a molecular weight regulator (n-dodecyl mercaptan) was added thereto, and after reacting for about 8 hours, the reaction mixture was diluted with ethyl acetate to prepare an adhesive polymer (A). Concentration: 44% by weight, weight average molecular weight: 350,000).

Preparation Examples 2 to 11 Preparation of Adhesive Polymers (B) to (K)

An adhesive polymer was prepared in the same manner as in Preparation Example 1, except that the monomer ratio was changed as in Tables 1 and 2 when the adhesive polymer was prepared.

Production Example One 2 3 4 5 6 Adhesive polymer A B C D E F 2- EHA 82 75 73 76 78 91 4- HBA 3 3 3 3 3 3 2- HEA 3 6 15 3 3 6 DMAA One One 2 3 5 EOEOEA 15 11 FM-401 11 15 7 AIBN 185 185 185 185 185 185 n- DDM 200 200 200 200 200 200 Solid content 44 45 45 45 45 44 Viscosity 5200 5000 6500 7000 7300 4000 Content Units: Parts by weight
Solids Unit: Weight%
Viscosity Unit: cP
2- EHA : 2- Ethylhexyl Acrylate
4- HBA : 4- Hydroxybutyl Acrylate
2- HEA : 2- Hydroxyethyl Acrylate
DMAA : Dimethylacrylamide
EOEOEA 2-2- Ethoxyethoxyethyl Acrylate
FM-401: Polyethylene glycol Monomethyl ether Methacrylate (Number of Addition Moles of Ethylene Oxide Units: 9 mol)
AIBN (In ppm): Azobisisobutyronitrile
n- DDM (Unit: ppm): n- Dodecyl Mercaptan

Production Example 7 8 9 10 11 Adhesive polymer G H I J K 2- EHA 82 81 80 68 58 4- HBA 3 3 3 3 3 2- HEA 15 5 6 3 3 DMAA 15 25 EOEOEA 11 11 FM-401 11 11 AIBN 185 185 185 185 185 n- DDM 200 200 200 200 200 Solid content 45 45 44 45 45 Viscosity 4800 5300 5000 6900 11300 Content Units: Parts by weight
Solids Unit: Weight%
Viscosity Unit: cP
2- EHA : 2- Ethylhexyl Acrylate
4- HBA : 4- Hydroxybutyl Acrylate
2- HEA : 2- Hydroxyethyl Acrylate
DMAA : Dimethylacrylamide
EOEOEA 2-2- Ethoxyethoxyethyl Acrylate
FM-401: Polyethylene glycol Monomethyl ether Methacrylate (Number of Addition Moles of Ethylene Oxide Units: 9 mol)
AIBN (In ppm): Azobisisobutyronitrile
n- DDM (Unit: ppm): n- Dodecyl Mercaptan

Example  One.

Preparation of pressure-sensitive adhesive composition

6 parts by weight of a mixture of isoboron diisocyanate-based crosslinking agent and hexamethylene diisocyanate-based crosslinking agent (MHG-80B, manufactured by Asahi) and LiTFSi (lithium bis) 1 part by weight of trifluoromethanesulfonyl) imide) is uniformly blended, and 1 part by weight of OFX-0193 (Dow Corning) and 3 parts by weight of acetylacetone are further uniformly blended as a reactive polyether-modified siloxane compound, and an appropriate concentration is considered in consideration of coating properties. Dilution with to prepare a pressure-sensitive adhesive composition.

Preparation of Adhesive Sheet

The pressure-sensitive adhesive composition was coated and dried on one surface of a poly (ethylene terephthalate) PET film (thickness: 38 μm) to form a uniform coating layer having a thickness of about 20 μm. Subsequently, a release PET (poly (ethylene terephthalate)) film was laminated on the coating layer, and aged at about 50 ° C. for about 3 days to prepare an adhesive sheet (protective film).

Example  2 to 7 and Comparative example  1 to 9

The pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the composition of the pressure-sensitive adhesive composition was changed as shown in Tables 3 and 4 below.

Example One 2 3 4 5 6 7 cohesion
Polymer Kinds A A A B C D E ratio 100 100 100 100 100 100 100 Crosslinking agent ratio 6 6 6 5 7 6 6 Siloxane
compound Compound A One 4 One One One One Compound B One Li salt ratio One One One One One One One Rate unit: Parts by weight
Crosslinking agent  Kinds: Isoboron Diisocyanate Crosslinking agent  And Hexamethylene Diisocyanate Crosslinker  mixture( MHG -80B, manufactured by Asahi
Compound A: OFX -0193 (Dow Corning)
Compound B: OFX -3667 (Dow Corning)
Li Salt type: LiTFSi (lithium bis ( trifluoromethanesulfonyl ) imide )

Comparative example One 2 3 4 5 6 7 8 9 cohesion
Polymer Kinds A D F G H A I J K ratio 100 100 100 100 100 100 100 100 100 Crosslinking agent ratio 6 5 6 6 6 6 6 7 8 Siloxane
compound Compound A One One 15 One One One Compound C One Li salt ratio One One One One One One One One One Rate unit: Parts by weight
Crosslinking agent  Kinds: Isoboron Diisocyanate Crosslinking agent  And Hexamethylene Diisocyanate Crosslinker  mixture( MHG -80B, manufactured by Asahi
Compound A: OFX -0193 (Dow Corning)
Compound C: silwet  L 77 ( Momentment )
Li Salt type: LiTFSi (lithium bis ( trifluoromethanesulfonyl ) imide )

The results of evaluating the physical properties of the pressure-sensitive adhesive compositions of the respective Examples and Comparative Examples prepared above are summarized in Tables 5 and 6 below.

Example One 2 3 4 5 6 7 Surface resistance 2.4 2.2 3.1 2.2 3.6 4.0 3.3 L-peel 3.9 4.1 3.1 3.8 5.1 5.6 4.7 H-peel 61 63 50 64 82 89 93 H / L 15.6 15.4 16.1 16.8 16.1 15.9 19.8 ESD A A A A A A A Pollution A A A A A A A L-peel: Low Peel Force (Unit: gf / 25mm)
H-peel: High speed peeling force (unit: gf / 25mm)
H / L: high speed Peel force (H)  sleaze Of peeling force (L)  ratio
Surface Resistance Unit: × 10 ¹⁰  Ω / □

Comparative example One 2 3 4 5 6 7 8 9 Surface resistance 4.2 5.7 3.6 3.1 2.8 0.9 2.1 2.4 2.1 L-peel 4.5 5.4 3.3 3.9 3.2 1.3 2.2 14.4 23.6 H-peel 70 87 40 51 46 17 38 218 393 H / L 15.6 16.1 12.1 13.1 14.4 13.1 17.3 15.1 16.7 ESD B B B A B A B A A Pollution A A A B A B A A A L-peel: Low Peel Force (Unit: gf / 25mm)
H-peel: High speed peeling force (unit: gf / 25mm)
H / L: high speed Peel force (H)  sleaze Of peeling force (L)  ratio
Surface Resistance Unit: × 10 ¹⁰  Ω / □

Claims (16)

40 to 94.8 parts by weight of alkyl (meth) acrylate, 0.1 to 15 parts by weight of monomer of formula (1), 0.1 to 5 parts by weight of nitrogen-containing monomer, represented by formula (2), and alkylene groups of A and B of formula (2) 5 to 20 parts by weight of the first monomer having a number of carbons included in the range of 1 to 3 and the second monomer having the number of carbons including 4 or more of the alkylene groups of A and B represented by the formula (2) An adhesive polymer including 5 parts by weight;
1 to 15 parts by weight of an aliphatic isocyanate crosslinking agent relative to 100 parts by weight of the polymer; And
0.01 to 5 parts by weight of the reactive polyether-modified siloxane compound relative to 100 parts by weight of the polymer,
The reactive polyether-modified siloxane compound may be combined with a functional group of the adhesive polymer, or an adhesive composition having a reactive functional group that may be combined with a functional group of the adhesive polymer through another compound:
[Formula 1]

[Formula 2]

In Formulas 1 and 2, Q is hydrogen or an alkyl group, U is an alkylene group, Z is hydrogen, an alkyl group or an aryl group, m is a number in the range of 1 to 20, A and B are each independently an alkylene group, n is a number in the range of 0-10. The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive polymer comprises 60 to 85 parts by weight of alkyl (meth) acrylate. According to claim 1, wherein the adhesive polymer is a pressure-sensitive adhesive composition comprising 5 to 15 parts by weight of the monomer of the formula (1). The pressure-sensitive adhesive composition of claim 1, wherein the nitrogen-containing monomer is dialkyl (meth) acrylamide. According to claim 1, wherein the pressure-sensitive adhesive composition comprising an aliphatic isocyanate crosslinking agent 5 to 10 parts by weight relative to 100 parts by weight of the adhesive polymer. The pressure-sensitive adhesive composition of claim 1, wherein the reactive polyether-modified siloxane compound has a hydroxy group, an epoxy group, or an amine group as a reactive functional group. The reactive polyether-modified siloxane compound according to claim 1, wherein the reactive polyether-modified siloxane compound has a hydroxy group as a reactive functional group, and the hydroxy group of the polyether-modified siloxane compound is bonded via a hydroxyl group and an aliphatic isocyanate compound of the first or second monomer of the adhesive polymer. Connected pressure-sensitive adhesive composition. The pressure-sensitive adhesive composition of claim 1, wherein the reactive polyether-modified siloxane compound is represented by the following Chemical Formula A or B:
[Formula A]

[Formula B]

R ₁ to R ₁₅ in Formula A or B are each independently a hydrogen atom, an alkyl group or an alkenyl group, and Z is-(CH ₂ ) _p- (O-CH ₂ -CH ₂ ) _q- (O-CH ₂ -CH ₂ -CH ₂ ) _r -U, wherein U is a hydroxy group, an amine group or an epoxy group, p is a number in the range of 1 to 4, q + r is at least 1 number, x is a number from 1 to 10 , y is a number in the range of 1 to 10. The pressure-sensitive adhesive composition of claim 1, wherein the weight average molecular weight of the reactive polyether-modified siloxane compound is in the range of 500 to 30,000. The pressure-sensitive adhesive composition of claim 1, further comprising 0.1 to 5 parts by weight of an ionic compound relative to 100 parts by weight of the adhesive polymer. Surface protective base layer; And a pressure-sensitive adhesive layer formed on one or both surfaces of the base material layer and comprising the pressure-sensitive adhesive composition according to claim 1 in a crosslinked state. The peel force of the pressure-sensitive adhesive layer measured at a peel angle of 180 degrees and a peel rate of 0.3 m / min with respect to an adherend having a surface energy of 30 mN / m or less is in the range of 1 gf / 25mm to 10 gf / 25mm. Endogenous surface protection film. 12. The adhesive force according to claim 11, wherein the pressure-sensitive adhesive layer has a peel force of 40 gf / 25 mm to 150 gf / 25 mm measured at a peel angle of 180 degrees and a peel rate of 30 m / min for an adherend having a surface energy of 30 mN / m or less. Surface protective film in range. The optical element with which the protective film of Claim 11 is affixed on the surface so that exfoliation is possible. The optical element of Claim 14 whose surface energy of the surface with a protective film is 30 mN / m or less. A display device comprising the optical element of claim 14.