WO2016099149A1 - Adhesive composition - Google Patents

Abstract

The present application may provide an adhesive composition, which has excellent durability in a high-temperature or high-humidity condition, which exhibits excellent adhesion with an optical film, and which thus can form an adhesive having excellent cutting property, re-workability, etc. In addition, the present application may provide an adhesive composition that can form an adhesive, which can effectively suppress bending even when applied to a thin substrate, such as a glass substrate having a very small thickness, which requires a minimized time for stabilization of physical properties, and which can prevent degradation of the secured physical properties as time elapses, an adhesion-type optical member formed using the adhesive composition, an optical laminate, and a display device.

Description

Pressure-sensitive adhesive composition

This application is filed with Korean Patent Application No. 2014-0181434, filed December 16, 2014, Korean Patent Application No. 2014-0187438, filed December 23, 2014, and Korean Patent Application No. 2015, filed December 15, 2015. Claiming the benefit of priority based on -0179554, all contents disclosed in the documents of the relevant Korean patent application are included as part of this specification.

The present application relates to an adhesive composition, an optical laminate, a polarizing plate, and a display device.

In the implementation of the display device, a so-called adhesive or adhesive is used. For example, a liquid crystal display (LCD) device includes a liquid crystal panel that is a display panel and an optical film, and an adhesive or an adhesive may be used when attaching the optical film to a liquid crystal panel or laminating optical films. As an optical film, there exist a polarizing film, retardation film, a brightness improving film, etc., The said adhesive or adhesive agent can be used in order to laminate | stack between such optical films, or to attach an optical film to adherends, such as a liquid crystal panel.

The main required physical properties of the pressure-sensitive adhesive or adhesive for optical films include cohesion, adhesion, reworkability, low light leakage characteristics, and stress relaxation. In patent documents 1-3, the adhesive for achieving the said physical property is proposed.

Recently, as a display panel, a panel to which a substrate having a very thin thickness is applied is sometimes used, and it is an important problem to prevent warpage of the panel after adhesion to an adhesive or an adhesive applied to such a panel. In addition, the pressure-sensitive adhesive or adhesive for an optical film is basically required to ensure durability at high temperature and / or high humidity conditions, and in some cases it may also be required to ensure an appropriate antistatic performance.

Moreover, adhesiveness with an optical film is calculated | required by the adhesive or adhesive agent for optical films. In the case where the adhesion with the optical film is insufficient, the adhesive or the adhesive may come out during cutting of the film, which not only causes contamination of other optical films or display panels, but also the edges when the optical film is attached. There is a problem that sufficient adhesion is not secured at the portion. In addition, when the adhesiveness is insufficient, the adhesive or the like may remain in the adherend when reworking, ie, peeling the optical film once attached again, may cause various problems.

[Preceding technical literature]

[Patent Documents]

Patent Document 1: Republic of Korea Patent No. 1023839

Patent Document 2: Republic of Korea Patent No. 1171976

Patent Document 3: Republic of Korea Patent No. 1171977

One object of the present application is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive optical member that is excellent in durability at high temperature or high humidity conditions, and has excellent adhesiveness with an optical film and is excellent in cutting properties and reworkability. . The present application can also effectively suppress warpage even when applied to thin substrates such as glass substrates of very thin thickness, minimize the time required for stabilization of physical properties, and prevent the deterioration of the secured physical properties over time. It is also an object of the present invention to provide an adhesive composition capable of forming an adhesive. Another object of the present application is to provide a pressure-sensitive adhesive optical member, an optical laminate, and a display device formed using the pressure-sensitive adhesive composition as described above.

Exemplary pressure-sensitive adhesive composition may include (A) block copolymer as one component. As used herein, the term “block copolymer” may refer to a copolymer comprising blocks of different polymerized monomers.

The block copolymer may include a first block having a glass transition temperature of 50 ° C. or more and a second block having a glass transition temperature of −10 ° C. or less. In the present specification, the "glass transition temperature of a predetermined block" of a block copolymer may mean a glass transition temperature calculated by monomers forming the block. In one example, the glass transition temperature of the first block may be 60 ° C. or more, 65 ° C. or more, 70 ° C. or more, 75 ° C. or more, 80 ° C. or more, 85 ° C. or more, 90 ° C. or more, or 95 ° C. or more. The upper limit of the glass transition temperature of the first block is not particularly limited, but for example, the glass transition temperature may be about 150 ° C. or less, 140 ° C. or less, 130 ° C. or less or 120 ° C. or less. In addition, the glass transition temperature of the second block may be -20 ° C or less, -30 ° C or less, -35 ° C or less, or -40 ° C or less. The lower limit of the glass transition temperature of the second block is not particularly limited, but for example, the glass transition temperature may be about -80 ° C or higher, -70 ° C or higher, -60 ° C or higher, or about -55 ° C or higher. . The block copolymer including at least two kinds of the blocks may form, for example, a fine phase separation structure in the pressure-sensitive adhesive. Such a block copolymer can form an adhesive which exhibits appropriate cohesive force and stress relaxation property according to temperature change and maintains excellent physical properties required for optical films, such as durability reliability, light leakage preventing property and reworkability.

In the block copolymer, the first block may have, for example, a number average molecular weight (Mn) in a range of 2,500 to 150,000. The number average molecular weight of the first block means, for example, the number average molecular weight of a polymer prepared by polymerizing only the monomers forming the first block, or the block copolymer is prepared by the first block acting as a macro initiator. If so, it may mean the number average molecular weight of the macroinitiator. The number average molecular weight referred to in the present specification can be measured by, for example, the method shown in the Examples by using GPC (Gel Permeation Chromatograph). In another example, the number average molecular weight of the first block may be about 100,000 or less, about 90,000 or less, about 80,000 or less, about 70,000 or less, about 60,000 or less, about 50,000 or less, about 40,000 or less, or about 35,000 or less. Further, in another example, the number average molecular weight of the first block may be about 5,000 or more, about 10,000 or more, about 15,000 or more, about 20,000 or more, or about 25,000 or more.

The block copolymer may have a number average molecular weight in the range of 50,000 to 300,000. The number average molecular weight of the block copolymer may in another example be at least 90,000, at least about 100,000, at least about 150,000 or at least about 200,000. The number average molecular weight may be about 250,000 or less in another example. The block copolymer has a molecular weight distribution (PDI; Mw / Mn), that is, a ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) in the range of 1.0 to 3.5 or in the range of about 1.4 to 2.0. There may be. The molecular weight characteristics can be adjusted as described above to provide a pressure-sensitive adhesive composition or pressure-sensitive adhesive.

In one example, the block copolymer may be a crosslinkable copolymer having a crosslinkable functional group. As a crosslinkable functional group, a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, etc. can be illustrated, For example, a hydroxyl group can be used.

When including a crosslinkable functional group, the functional group may be included in, for example, either one of the first or second blocks, or both the first and second blocks. In one example, the crosslinkable functional group may be included in the second block having a low glass transition temperature. In this case, the first block may not include a crosslinkable functional group, and only the second block may include a crosslinkable functional group. When the cross-linkable functional group is included in the second block, it exhibits an appropriate cohesion force and stress relaxation property according to the temperature change, thereby forming an adhesive that maintains excellent physical properties required for optical films such as durability, light leakage prevention properties, and reworkability. can do.

The type of monomers forming the first block and the second block in the block copolymer is not particularly limited as long as the glass transition temperature is secured by the combination of the monomers.

In one example, the first block may comprise polymerized units derived from (meth) acrylic acid ester monomers. In the present specification, that the monomer is included in the polymer or the block as a polymerized unit may mean that the monomer forms a backbone, for example, a main chain or a side chain of the polymer or block through a polymerization reaction. As said (meth) acrylic acid ester monomer, an alkyl (meth) acrylate can be used, for example. In one example, in consideration of the cohesion, glass transition temperature and adhesion control, etc., alkyl having 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 ( Meta) acrylates can be used. 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 Bornyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and lauryl (meth) acrylate, and the like, and the glass transition temperature of one or more of the above is ensured. It can be selected to use. Although not particularly limited, the monomer forming the first block in consideration of the ease of glass transition temperature control and the like is a methacrylic acid ester monomer, for example, 1 to 20 carbon atoms, 1 to 16 carbon atoms Alkyl methacrylate having an alkyl group having 1 to 12, 1 to 8 carbon atoms or 1 to 4 carbon atoms can be used.

The second block of the block copolymer comprises, for example, polymerized units derived from 90 to 99.9 parts by weight of the (meth) acrylic acid ester monomer and 0.1 to 10 parts by weight of the copolymerizable monomer having a crosslinkable functional group. can do. In the present specification, the unit weight part may mean a ratio of weights between components. For example, as described above, the second block may include polymerized units derived from 90 to 99.9 parts by weight of the (meth) acrylic acid ester monomer and 0.1 to 10 parts by weight of the copolymerizable monomer having a crosslinkable functional group. And the ratio (A: B) based on the weight of the (meth) acrylic acid ester monomer (A) and the copolymerizable monomer (B) having a crosslinkable functional group forming the polymerized unit of the second block is from 90 to 99.9: It may mean the case of 0.1 to 10.

As the (meth) acrylic acid ester monomer forming the second block, it is possible to secure the glass transition temperature in the above-described range through copolymerization with the copolymerizable monomer among the monomers that may be included in the first block. Kinds of monomers can be selected and used. Although not particularly limited, the (meth) acrylic acid ester monomer forming the second block in consideration of the ease of glass transition temperature control, etc., is an acrylic acid ester monomer, for example, 1 to 20 carbon atoms among the monomers described above. Alkyl acrylates having an alkyl group having 1 to 16, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms can be used.

As a copolymerizable monomer which has a crosslinkable functional group, for example, it has a site | part which can be copolymerized with the other monomer contained in a block copolymer like the said (meth) acrylic acid ester monomer, and also the above-mentioned crosslinkable functional group, an example For example, the monomer which has a hydroxyl group etc. can be used. Copolymerizable monomers having such crosslinkable functional groups are variously known in the field of pressure-sensitive adhesives, and all of these monomers may be used in the polymer. For example, as a copolymerizable monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxy Hydroxyalkyl (meth) acrylates such as hexyl (meth) acrylate or 8-hydroxyoctyl (meth) acrylate, or 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) Hydroxyalkylene glycol (meth) acrylates such as acrylate may be used, but is not limited thereto. In consideration of the reactivity with other monomers forming the second block, the ease of controlling the glass transition temperature, etc., hydroxyalkyl acrylate or hydroxyalkylene glycol acrylate may be used among the above monomers. no.

The first block and / or the second block may further comprise other optional comonomers, if necessary, for example, for the control of the glass transition temperature, and the monomers may be included as polymerized units. have. As said comonomer, it is (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-butoxy methyl (meth) acrylamide, N-vinyl pyrrolidone, or N-vinyl capro Nitrogen-containing monomers such as lactams and the like; Alkoxy alkylene glycol (meth) acrylic acid ester, alkoxy dialkylene glycol (meth) acrylic acid ester, alkoxy trialkylene glycol (meth) acrylic acid ester, alkoxy tetraalkylene glycol (meth) acrylic acid ester, alkoxy polyethylene glycol (meth) acrylic acid Esters, phenoxy alkylene glycol (meth) acrylic acid esters, phenoxy dialkylene glycol (meth) acrylic acid esters, phenoxy trialkylene glycol (meth) acrylic acid esters, phenoxy tetraalkylene glycol (meth) acrylic acid esters or phenoxy Alkylene oxide group-containing monomers such as polyalkylene glycol (meth) acrylic acid ester and the like; Styrene-based monomers such as styrene or methyl styrene; Glycidyl group-containing monomers such as glycidyl (meth) acrylate; Or carboxylic acid vinyl esters such as vinyl acetate, but are not limited thereto. Such comonomers may be included in the polymer by selecting one or more kinds thereof as necessary. Such comonomers may be included in the block copolymer, for example, in a ratio of 20 parts by weight or less, or 0.1 to 15 parts by weight, relative to the weight of other monomers in each block.

The block copolymer may include, for example, 5 parts by weight to 50 parts by weight of the first block and 50 parts by weight to 95 parts by weight of the second block. By adjusting the ratio of the weight between the first block and the second block as described above, it is possible to provide the pressure-sensitive adhesive composition and pressure-sensitive adhesive of excellent physical properties. In another example, the block copolymer may include 5 parts by weight to 45 parts by weight of the first block and 55 parts by weight to 95 parts by weight of the second block, or 5 parts by weight to 45 parts by weight of the first block and 60 parts by weight of the second block. 95 parts by weight may be included.

In another example, the block copolymer may comprise at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75% or at least about 80% of the second block by weight. It may include more. The first block may be included in a proportion of about 99% or less and about 95% or more by weight. In this state, the second block may be included in a ratio of about 5 to 100 parts by weight with respect to 100 parts by weight of the first block. The second block is about 90 parts by weight, about 80 parts by weight, about 70 parts by weight, about 60 parts by weight, about 50 parts by weight, about 40 parts by weight or less, about 100 parts by weight of the first block. 30 parts by weight or less, about 20 parts by weight or less, or about 15 parts by weight or less.

In one example, the block copolymer may be a diblock copolymer including the first and second blocks, that is, a block copolymer including only two blocks of the first and second blocks. . By using a diblock copolymer, the durability, stress relaxation property, and reworkability of an adhesive can be maintained more excellently.

The method for producing the block copolymer is not particularly limited and can be prepared in a conventional manner. The block polymer may be polymerized by, for example, a Living Radical Polymerization (LRP) method, for example, an organic rare earth metal complex may be used as a polymerization initiator, or an organic alkali metal compound may be used as a polymerization initiator. Anion polymerization method synthesized in the presence of an inorganic acid salt such as a salt, anion polymerization method synthesized in the presence of an organoaluminum compound using an organoalkali metal compound as a polymerization initiator, atom transfer radical polymerization using an atom transfer radical polymerizer as a polymerization controller Method (ATRP), activators regenerated by electron transfer (ARRP), which uses an atomic transfer radical polymerizer as a polymerization control agent and performs polymerization under an organic or inorganic reducing agent that generates electrons for continuous activator regeneration Atomic radical polymerization (ATRP), inorganic Reducing agent A reversible addition-cracking chain transfer polymerization method using a reversible addition-cracking chain transfer agent (RAFT) or a method using an organic tellurium compound as an initiator, etc., and an appropriate method can be selected and applied from these methods.

The pressure-sensitive adhesive composition may further include a crosslinking agent (B) capable of crosslinking the block copolymer as an additional component. As a crosslinking agent, the crosslinking agent which has at least two functional groups which can react with the crosslinkable functional group contained in the said block copolymer can be used. As such a crosslinking agent, an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent or a metal chelate crosslinking agent can be exemplified. For example, when (A) block copolymer contains a hydroxyl group as a crosslinkable functional group, a polyfunctional isocyanate compound can be used as a crosslinking agent normally. In the present application, the polyfunctional isocyanate compound includes two or more isocyanate groups, for example, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 It may mean a compound containing about 5 to 5 or about 2 to 4.

As the polyfunctional isocyanate compound which can be used as the crosslinking agent, for example, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, tetramethylxylene diisocyanate or naphthalene diisocyanate Diisocyanate compounds such as; Or a compound obtained by reacting one or more of the diisocyanate compounds with a polyol, but is not limited thereto. As a polyol which can be used above, trimethylol propane etc. can be illustrated.

One or more kinds of crosslinking agents may be used in the pressure-sensitive adhesive composition, but a crosslinking agent that may be used is not limited thereto.

For example, the multifunctional crosslinking agent may be included in the pressure-sensitive adhesive composition in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the block copolymer. In another example, the crosslinking agent may be included in a ratio of 0.03 parts by weight or more or 0.05 parts by weight or more. In addition, the crosslinking agent may be included in another proportion of 8 parts by weight or less, 6 parts by weight or less, 4 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less. It is possible to maintain excellent gel fraction, cohesion, adhesion and durability of the pressure-sensitive adhesive in the range as described above.

The pressure-sensitive adhesive composition may further include (C) a polyfunctional epoxy compound or a polyfunctional aziridine compound as an additional component. As used herein, the term polyfunctional epoxy compound refers to two or more epoxy groups, for example, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 It can mean a compound containing from about 5 to about 5 or 2 to 4, the term multifunctional aziridine compound is at least two, for example, 2 to 10, 2 to 9, It may mean a compound containing 2 to 8, 2 to 7, 2 to 6, 2 to 5 or about 2 to 4. By further including the above compounds, an adhesive excellent in interfacial adhesion to a member such as an optical film can be formed.

The term epoxy group in the present application may refer to a cyclic ether having three ring constituent atoms or a monovalent moiety derived from a compound containing the cyclic ether, unless otherwise specified. Examples of the epoxy group include glycidyl group, epoxyalkyl group, glycidoxyalkyl group or alicyclic epoxy group. In the above, the alicyclic epoxy group may mean a monovalent moiety derived from a compound containing an aliphatic hydrocarbon ring structure, wherein the two carbon atoms forming the aliphatic hydrocarbon ring also include an epoxy group. As the alicyclic epoxy group, an alicyclic epoxy group having 6 to 12 carbon atoms can be exemplified, for example, a 3,4-epoxycyclohexylethyl group or the like can be exemplified. In addition, the term aziridine group is a heterocycle-type functional group including three ring-constituting atoms, and may mean a functional group including one amine group and two methylene bridges or a derivative derived from the functional group.

(C) component can contribute especially to improving adhesiveness between an adhesive and an optical film. For example, when the pressure-sensitive adhesive is formed on an optical film into which a functional group such as a hydroxyl group or a carboxyl group is introduced, as described below, the optical film is formed by various chemical or physical interactions of the component (C) with the functional group on the optical film. The adhesion between the adhesive and the adhesive may increase.

Examples of the polyfunctional epoxy compound (C) include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidyl ethylenediamine and glycerin One or more selected from the group consisting of diglycidyl ether can be exemplified, and as the polyfunctional aziridine compound, N, N'-toluene-2,4-bis (1-aziridinecarboxamide), N, N '-Diphenylmethane-4,4'-bis (1-aziridinecarboxamide), triethylene melamine, bisisoprotaloyl-1- (2-methylaziridine) and tri-1-aziridinylforce Pinoxide and the like can be exemplified, but is not limited thereto.

Component (C) may be included in the pressure-sensitive adhesive composition in a ratio of 0.1 to 10 parts by weight based on 100 parts by weight of the block copolymer (A). Component (C) may, in another example, be included at least 0.3 parts by weight relative to 100 parts by weight of component (A). In addition, component (C) may be included in an amount of 8 parts by weight, 6 parts by weight or 4 parts by weight or less based on 100 parts by weight of component (A). Within such a range, while ensuring proper adhesion with the optical film, other physical properties required for the pressure-sensitive adhesive can also be stably maintained.

The pressure-sensitive adhesive composition may further include one or more compounds selected from the group consisting of (D) an imidazole compound, a phosphine compound, an amine compound, a phenol compound, and an acid anhydride. Such a compound may promote physical or chemical interaction of the pressure-sensitive adhesive composition or the pressure-sensitive adhesive on the optical film surface to further enhance the adhesion to the surface and shorten the time required for securing the adhesion.

As an imidazole compound, a phosphine compound, an amine compound, a phenol compound, etc. which can be applied as a component (D), the following compounds can be used, for example.

That is, the compound represented by following formula (1) can be used as an imidazole compound.

[Formula 1]

R 1 to R 4 in Formula 1 are each independently hydrogen, an alkyl group, or an aryl group.

As the alkyl group in Formula 1, 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 may be exemplified, and the alkyl group may be linear, branched or cyclic. It may be optionally substituted with one or more substituents.

In Formula 1, an aryl group having 6 to 30 carbon atoms, 6 to 24 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms may be exemplified, and such an aryl group may be optionally substituted with one or more substituents.

As the compound of Formula 1, a compound in which R1 is hydrogen or an alkyl group, R2 to R4 are each independently hydrogen, an alkyl group or an aryl group, and at least R4 and / or R3 is an alkyl group or an aryl group can be used.

Such compounds include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, and 2-phenyl. Midazole or 2-phenyl-4-methylimidazole and the like can be exemplified, but is not limited thereto.

As a phosphine compound, the compound represented by following formula (2) can be used, for example.

[Formula 2]

R 5 to R 7 in Formula 2 are each independently hydrogen, an alkyl group, or an aryl group.

The definition of an alkyl group or an aryl group in the formula (2) is the same as in the case of formula (1).

Examples of the compound represented by the formula (2) include triphenylphosphine, tributylphosphine, tri (p-methphenyl) phosphine or tri (nonylphenyl) phosphine, and the like.

As an amine compound, the compound represented by following formula (3) or (4) can be used, for example.

[Formula 3]

In Formula 3, L1 and L2 are alkylene groups.

[Formula 4]

In formula (4), R8 to R10 are each independently hydrogen, an alkyl group, an aryl group, an arylalkyl group, or a hydroxyalkyl group.

The definition of an alkyl group or an aryl group in the formula (3) or 4 is the same as in the case of formula (1).

In addition, in the general formula (3), as the alkylene group, an alkylene 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 may be exemplified. It may be chain or cyclic, and may be optionally substituted with one or more substituents.

As the compound represented by the formula (3) or (4), 1,8-diazabicyclo [5.6.0] unde-7-ene, benzyl dimethylamine or triethanolamine and the like can be exemplified, but is not limited thereto.

As the phenolic compound, for example, a compound represented by the following formula (5) may be used.

[Formula 5]

In formula (5), R11 to R15 are each independently hydrogen, an alkyl group, an aminoalkyl group, an alkylaminoalkyl group or a dialkylaminoalkyl group.

The definition of the alkyl group or aryl group in the formula (5) is the same as in the case of formula (1).

As the compound of Formula 5, for example, R11 to R15 are each independently hydrogen, an alkyl group, an aminoalkyl group, an alkylaminoalkyl group or a dialkylaminoalkyl group, and at least one of R11 to R15 is an aminoalkyl group, an alkylaminoalkyl group or a di Compounds that are alkylaminoalkyl groups can be exemplified.

Examples of such a compound include, but are not limited to, 2- (dimethylaminomethyl) phenol.

In addition, maleic anhydride or tetrahydrophthalic anhydride may be used as the acid anhydride-based compound, but is not limited thereto.

Component (D) may be included in the pressure-sensitive adhesive composition in a ratio of 0.001 to 5 parts by weight based on 100 parts by weight of the block copolymer (A). Component (D) may be included in another example at least 0.005 parts by weight relative to 100 parts by weight of component (A), in another example at most 4 parts by weight, at most 3 parts by weight, at most 2 parts by weight or It may be included in a ratio of 1 part by weight or less. Within this range, the desired adhesion and the like can be secured, and other physical properties can be maintained stably.

The pressure-sensitive adhesive composition may include a tin compound as an additional component. Such a tin-based compound may allow the crosslinked pressure-sensitive adhesive to exhibit excellent interfacial adhesion with the optical film while the pressure-sensitive adhesive effectively crosslinks through interaction with the component (D).

As the tin-based compound, an organic tin compound may be used, for example, dialkyl tin oxide, a fatty acid salt of dialkyl tin or a fatty acid salt of stannous tin, and the like, and specifically, a dialkyl tin oxide or Dialkyl tin dilaurate and the like can be used. In the kind of the tin compound, alkyl may be linear, branched or cyclic alkyl 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 tin-based compound may be included in the pressure-sensitive adhesive composition in a ratio of 0.001 to 5 parts by weight based on 100 parts by weight of the (A) block copolymer. The tin compound may, in another example, be included in an amount of at least 0.005 parts by weight based on 100 parts by weight of component (A), and in another example, 4 parts by weight, 3 parts by weight, 2 parts by weight or less, based on 100 parts by weight of component (A) or It may be included in a ratio of 1 part by weight or less. Within this range, the desired crosslinking degree, adhesion, etc. can be secured, and other physical properties can be stably maintained.

The pressure-sensitive adhesive composition may include an ionic compound as an additional component. As the ionic compound, an inorganic salt or an ionic liquid can be used. From the viewpoint of securing the above-described interfacial adhesion or the like and causing no curing retardation phenomenon, it was confirmed that the ionic liquid can bring a beneficial effect over the inorganic salt. In the present application, the term ionic liquid may mean an ionic compound present in a liquid state at room temperature. In the above, the room temperature is a natural temperature that is not heated or reduced, and may mean a temperature of about 10 ° C to 30 ° C, about 15 ° C to 30 ° C, about 20 ° C to 30 ° C, about 25 ° C, or about 23 ° C. Can be.

The ionic compound may be included in the pressure-sensitive adhesive composition so that the pressure-sensitive adhesive may have appropriate antistatic properties.

When an inorganic salt is applied as an ionic compound, the salt containing an alkali metal cation or alkaline earth metal cation can be used as said inorganic salt. Such cations include lithium ions (Li ⁺ ), sodium ions (Na ⁺ ), potassium ions (K ⁺ ), rubidium ions (Rb ⁺ ), cesium ions (Cs ⁺ ), beryllium ions (Be ^{2 +} ), magnesium ions (Mg ^{2 +),} calcium ion (Ca ^2+), strontium ion (Sr ^{2 +)} and barium ion (Ba ^{+ 2)} there is a iljong or different than, such as may be illustrated, for example, a lithium ion, a sodium ion Lithium ions may be used in consideration of one kind or two or more kinds of potassium ions, magnesium ions, calcium ions and barium ions, or ion stability and mobility.

In addition, as said ionic liquid, the compound which has onium salt containing nitrogen, sulfur, or phosphorus as a cation component can be used. Such cations include N-ethyl-N, N-dimethyl-N-propylammonium, N, N, N-trimethyl-N-propylammonium, N-methyl-N, N, N-tributylammonium and N-ethyl -N, N, N-tributylammonium, N-methyl-N, N, N-trihexylammonium, N-ethyl-N, N, N-trihexylammonium, N-methyl-N, N, N-tri Quaternary ammonium compounds such as octyl ammonium or N-ethyl-N, N, N-trioctyl ammonium, phosphonium or derivatives thereof, such as tetraalkyl phosphonium, pyridinium or derivatives thereof, tetrahydropyri Dinium or a derivative thereof, dihydropyridinium or a derivative thereof, imidazolium or a derivative thereof, a compound containing a pyrroline skeleton or a derivative thereof, a compound containing a pyrrole skeleton or a derivative thereof, 1-ethyl-3- Imidazolinium or derivatives thereof, such as methylimidazolinium, pyrazolnium or derivatives thereof, trialkylsulfonium or derivatives thereof, 1-methyl-1-propyl Raleigh blood such as pyridinium Raleigh pyridinium and the like can be piperidinium (piperidinium) or a derivative thereof, such as illustrated (pyrolidinium) or a derivative thereof or a 1-methyl-1-propyl piperidinium. In the present application, a compound containing a cation in which the alkyl group included in the cation is substituted with an alkoxy group, a hydroxy group, an alkynyl group, an epoxy group, or the like among the aforementioned cations may be used.

In one example, as the cation of the ionic liquid, a cation represented by Chemical Formula A may be applied.

[Formula A]

R 1 to R 4 in formula (A) each independently represent hydrogen, alkyl, alkoxy, alkenyl or alkynyl.

Alkyl or alkoxy in formula (A) may be alkyl or alkoxy having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms. In addition, the alkyl or alkoxy may be linear, branched or cyclic alkyl or alkoxy, and may be optionally substituted with one or more substituents.

Alkenyl or alkynyl in Formula A may be alkenyl or alkynyl having 2 to 20 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. In addition, the alkenyl or alkynyl may be linear, branched or cyclic alkenyl or alkynyl, and may be optionally substituted with one or more substituents.

When alkyl, alkoxy, alkenyl or alkynyl in the definition of Formula A is substituted with one or more substituents, examples of substituents include hydroxy, alkyl, alkoxy, alkenyl, alkynyl, cyano, thiol, amino, aryl or Heteroaryl, and the like, but is not limited thereto.

In one example, R 1 to R 4 of Formula A may each independently be alkyl, for example, straight or branched alkyl of 1 to 12 carbon atoms. R 1 to R 4 in Formula (A) each independently represent linear or branched alkyl having 1 to 12 carbon atoms, but R 1 to R 4 may not correspond to alkyl having the same carbon number at the same time. In such a case, the case where R1 to R4 are all alkyl groups having the same carbon number is excluded in the range of the formula (A). When R1 to R4 are all alkyl having the same carbon number, there is a high probability that the compound exists in the solid phase at room temperature.

In Formula A, R1 may be alkyl having 1 to 3 carbon atoms, and R2 to R4 may be each independently alkyl having 4 to 20 carbon atoms, 4 to 15 carbon atoms, or 4 to 10 carbon atoms. By using such a cation, an adhesive having excellent optical properties, adhesive properties, workability, and antistatic property can be provided, adhesion to the substrate can be increased, and the time required for stabilization of physical properties such as curing can be further shortened. have.

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 ^-), hexafluorophosphate (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, as the anion, an anion represented by the following formula (B) or bisfluorosulfonylimide may be used.

[Formula B]

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

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

In Formula B, 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 B 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 a polymer, it can provide high antistatic property even with a small amount.

R _f of Formula B 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 the formula (B) may be a sulfonyl metide, sulfonylimide, carbonyl metide, or carbonyl imide anion, and specifically, tristrifluoromethanesulfonylmethide and bistrifluoromethanesulphate 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.

The ionic compound is present in the pressure-sensitive adhesive composition in a ratio of 0.01 to 15 parts by weight, 0.01 to 10 parts by weight, 0.01 to 5 parts by weight, 0.1 to 5 parts by weight or 0.5 to 5 parts by weight with respect to 100 parts by weight of the block copolymer (A). Can be. While the desired antistatic property is secured under such a ratio, other required physical properties such as adhesion with the optical film can be stably maintained.

The pressure-sensitive adhesive composition may further include a silane coupling agent. As a silane coupling agent, the silane coupling agent which has a beta-cyano group or an acetoacetyl group can be used, for example. Such a silane coupling agent may, for example, allow the pressure-sensitive adhesive formed by a low molecular weight copolymer to exhibit excellent adhesion and adhesion stability, and also to maintain excellent durability and the like in heat and moisture resistant conditions. have.

As a silane coupling agent which has a beta-cyano group or an acetoacetyl group, the compound represented by following formula (5) or 6 can be used, for example.

[Formula 5]

(R1) _n Si (R2) _(4-n)

[Formula 6]

(R3) _n Si (R2) _(4-n)

In formula (5) or (6), R1 is a beta-cyanoacetyl group or a beta-cyanoacetylalkyl group, R3 is an acetoacetyl group or an acetoacetylalkyl group, R2 is an alkoxy group, n is a number from 1 to 3.

In Formula 5 or 6, the alkyl group may 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, and the alkyl group may be linear, branched or cyclic. have.

In Formula 5 or 6, the alkoxy group may be an alkoxy 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, and the alkoxy group may be linear, branched or cyclic. have.

N in Formula 5 or 6 may be, for example, 1 to 3, 1 to 2 or 1.

As the compound of the formula (5) or (6), for example, acetoacetylpropyl trimethoxy silane, acetoacetylpropyl triethoxy silane, beta-cyanoacetylpropyl trimethoxy silane or beta-cyanoacetylpropyl triethoxy silane Etc. may be illustrated, but is not limited thereto.

In the pressure-sensitive adhesive composition, the silane coupling agent may be included in an amount of 0.01 parts by weight to 5 parts by weight or 0.01 parts by weight to 1 parts by weight with respect to 100 parts by weight of the (A) block copolymer. Can be.

An adhesive composition may further contain a tackifier as needed. As the tackifier, for example, a hydrocarbon resin or a hydrogenated substance thereof, a rosin resin or a hydrogenated substance thereof, a rosin ester resin or a hydrogenated substance thereof, a terpene resin or a hydrogenated substance thereof, a terpene phenol resin or a hydrogenated substance thereof, a polymerized rosin resin or One kind or a mixture of two or more kinds such as a polymerized rosin ester resin may be used, but is not limited thereto. The tackifier may be included in the pressure-sensitive adhesive composition in an amount of 100 parts by weight or less based on 100 parts by weight of the block copolymer.

The pressure-sensitive adhesive composition may further further comprise one or more additives selected from the group consisting of epoxy resins, curing agents, ultraviolet stabilizers, antioxidants, colorants, reinforcing agents, fillers, defoamers, surfactants and plasticizers, if desired.

The pressure-sensitive adhesive composition may have a gel fraction of 80% by weight or less after implementing the crosslinked structure. The gel fraction can be calculated by the following general formula (1).

[Formula 1]

Gel fraction (%) = B / A × 100

In Formula 1, A is the mass of the pressure-sensitive adhesive composition embodying a crosslinked structure, B is 72 hours in ethyl acetate at room temperature in a state that the pressure-sensitive adhesive composition of mass A in a mesh of 200 mesh size The dry mass of the insoluble fraction collected after deposition is shown.

By maintaining the gel fraction at 80% by weight or less, excellent workability, durability, and reworkability can be maintained. The lower limit of the gel fraction of the pressure-sensitive adhesive composition is not particularly limited, and may be, for example, 0 wt%. However, the gel fraction of 0 wt% does not mean that the crosslinking did not proceed at all in the pressure-sensitive adhesive composition. For example, in the pressure-sensitive adhesive composition having a gel fraction of 0% by weight, the pressure-sensitive adhesive composition or crosslinking did not proceed at all, but the degree of crosslinking was low, so that the gel could not be maintained in the 200-mesh network. Leakage may also be included.

The pressure-sensitive adhesive composition may be a pressure-sensitive adhesive composition for an optical film. The pressure-sensitive adhesive composition for an optical film may, for example, laminate optical films such as a polarizing film, a retardation film, an anti-glare film, a wide viewing angle compensation film, or a brightness enhancement film to each other, or the optical film or a laminate thereof such as a liquid crystal panel or the like. It can be used for attachment to adherends. In one example, the pressure-sensitive adhesive composition, as a pressure-sensitive adhesive composition for a polarizing plate, may be an pressure-sensitive adhesive composition used for attaching the polarizing film to the liquid crystal panel.

The present application also relates to an adhesive optical member, for example, an adhesive polarizing plate. An exemplary optical member includes an optical film; And it may include a pressure-sensitive adhesive layer formed on one side or both sides of the optical film. The pressure-sensitive adhesive layer may be, for example, a pressure-sensitive adhesive layer for attaching the optical film to a liquid crystal panel or the like of another LCD device or another optical film. In addition, the pressure-sensitive adhesive layer may include the pressure-sensitive adhesive composition of the present application described above. The pressure-sensitive adhesive composition may be included in the pressure-sensitive adhesive layer in a state of implementing a crosslinked structure. As the optical film in the above, a polarizer, a polarizing plate, a retardation film, a brightness enhancing film, or the like, or a laminate in which two or more kinds are stacked in the above may be exemplified. In the present application, the term polarizer and the polarizing plate is a concept that is distinguished from each other, for example, the polarizer means a layer itself exhibiting a polarizing function such as a polyvinyl alcohol film described later, and the polarizing plate includes such a polarizer together with other elements. It may mean a laminate.

Between the optical film and the pressure-sensitive adhesive layer in the optical member, for example, a functional group capable of interacting with the pressure-sensitive adhesive layer as a functional group capable of interacting with the pressure-sensitive adhesive layer, such as a hydroxyl group, an amino group, a carboxyl group, a urethane bond or a urea bond, etc. This may be introduced. Such functional groups may enhance the adhesion between the optical film and the pressure-sensitive adhesive layer through physical or chemical interactions with the polyfunctional isocyanate compound, the polyfunctional epoxy compound, or the polyfunctional aziridine compound present in the pressure-sensitive adhesive layer. The functional group may be introduced by employing an optical film formed of a polymer having such a functional group in a molecule, or by an easy adhesion treatment such as corona discharge or plasma treatment. In the present application, the surface of the optical film into which the above functional groups are introduced or a portion of the optical film subjected to the corona discharge or the plasma treatment may be referred to as an easy adhesion layer.

The corona or plasma treatment conditions performed to introduce such functional groups are not particularly limited, and methods known in the art may be appropriately employed and applied.

The present application also relates to a pressure-sensitive adhesive polarizing plate. The polarizing plate may have, for example, a structure in which the optical film is a polarizer in the adhesive optical member.

The kind of polarizer contained in a polarizing plate is not specifically limited, For example, the general kind known in this field, such as a polyvinyl alcohol-type polarizer, can be employ | adopted without a restriction | limiting.

The polarizer is a functional film 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 resin which can be used may include not only a homopolymer of vinyl acetate but also a copolymer 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 may be about 85 mol% to 100 mol% or 98 mol% or more. The polyvinyl alcohol-based resin may be further modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. In addition, the degree of polymerization of the polyvinyl alcohol-based resin may be about 1,000 to 10,000 or about 1,500 to 5,000.

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 further include a protective film attached to one side or both sides of the polarizer, in which case, the pressure-sensitive adhesive layer may be formed on one side of the protective film. The type of protective film is not particularly limited, and includes, for example, a cellulose film such as triacetyl cellulose (TAC); Polyester film such as polycarbonate film or PET (poly (ethylene terephthalet)); Polyether sulfone-based film; Alternatively, a film having a laminated structure of one layer or two or more layers, such as a polyethylene film, a polypropylene film or a polyolefin-based film produced using a resin having a cyclo or norbornene structure, an ethylene-propylene copolymer, or the like can be used.

The polarizing plate may further include one or more functional layers 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.

In the pressure-sensitive adhesive polarizing plate, there may be a treatment layer between the polarizer and the pressure-sensitive adhesive layer. The easy adhesion layer may be a layer formed by the hydroxy group, amino group, carboxyl group, urethane bond, urea bond, or the like present on the surface of the other functional layer such as the polarizer or a protective film formed on one surface of the polarizer, or the like. It may be a layer formed by performing corona discharge or plasma treatment on the surface of the polarizer or another functional layer.

In the present application, the method of forming the pressure-sensitive adhesive layer on the polarizing plate or the optical film as described above is not particularly limited. For example, the pressure-sensitive adhesive composition may be directly coated on the polarizing plate or the optical film and cured to realize a crosslinked structure. Alternatively, after the pressure-sensitive adhesive composition is coated and cured on the release treatment surface of the release film to form a crosslinked structure, a method of transferring it to a polarizing plate or an optical film may be used.

The method of coating the pressure-sensitive adhesive composition in the above is not particularly limited, and for example, a method of applying the pressure-sensitive adhesive composition by a conventional means such as a bar coater may be used.

In the coating process, the multifunctional crosslinking agent included in the pressure-sensitive adhesive composition is preferably controlled from the crosslinking reaction of the functional group from the viewpoint of performing a uniform coating process, whereby the crosslinking agent crosslinks in the curing and aging process after the coating operation. By forming a structure, the cohesive force of the pressure-sensitive adhesive may be improved, and adhesive properties and cuttability may be improved.

The coating 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, so that the crosslinking density or molecular weight of the pressure-sensitive adhesive is too low to lower the elastic modulus, at a high temperature Bubbles existing between the glass plate and the adhesive layer may be increased to prevent a problem of forming scatterers therein.

The method of implementing the crosslinking structure by curing the pressure-sensitive adhesive composition subsequent to the coating is also not particularly limited. For example, the coating layer may have an appropriate temperature such that a crosslinking reaction between the block copolymer contained in the coating layer and the multifunctional crosslinking agent may be caused. This can be done in such a way as to maintain.

If necessary, before forming the pressure-sensitive adhesive layer, a process of forming an easy adhesion layer on the surface on which the pressure-sensitive adhesive layer is formed may be performed, for example, corona discharge or plasma treatment.

The present application also provides a thin glass substrate; The optical laminated body containing the said adhesive optical member or polarizing plate adhering to the said glass substrate. The polarizing plate or the optical member may be attached to the glass substrate by the adhesive described above. The pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition of the present application can exhibit excellent adhesion with the substrate as described above, and can also effectively suppress warpage even when applied to a thin substrate. The glass substrate may have a thickness of, for example, about 1 mm or less, about 0.9 mm or less, or about 0.8 mm or less. The lower limit of the thickness of the glass substrate is not particularly limited and may be, for example, about 0.1 mm or more, about 0.3 mm or more, or about 0.5 mm or more.

The present application also relates to a display device, for example an LCD device. The display device may include the above-described adhesive optical member or polarizing plate. For example, if the display device is an LCD device, the device may include a liquid crystal panel and the polarizing plate or optical member attached to one side or both sides of the liquid crystal panel. The polarizing plate or the optical member may be attached to the liquid crystal panel by the adhesive described above.

The liquid crystal panel in the apparatus may be, for example, a passive matrix panel such as twisted nematic (TN) type, super twisted nematic (STN) type, ferroelectic (F) type or polymer dispersed (PD) type; Active matrix panels such as two-terminal or three-terminal; All known panels, such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.

Further, other configurations of the liquid crystal display device, for example, upper and lower substrates such as a color filter substrate or an array substrate, are not particularly limited, and a configuration known in the art may be employed without limitation.

In the present application, it is possible to provide a pressure-sensitive adhesive composition which is excellent in durability at high temperature or high humidity conditions, and excellent in adhesion with an optical film, and capable of forming a pressure-sensitive adhesive excellent in cutting properties and reworkability. In addition, in the present application, even when applied to a thin substrate such as a very thin glass substrate, it is possible to effectively suppress the warp, to minimize the time required for stabilization of physical properties, and to prevent the deterioration of the secured physical properties over time. The adhesive composition which can form the adhesive which can be formed, the adhesive optical member formed using the above-mentioned adhesive composition, an optical laminated body, and a display apparatus can be provided.

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

1. Molecular weight evaluation

The number average molecular weight (Mn) and the molecular weight distribution (PDI) were measured under the following conditions using GPC (Gel Permeation Chromatography), and in the preparation of the calibration curve, the measurement results were converted using standard polystyrene of Agilent system.

<Measurement conditions>

Meter: Agilent GPC (Agilent 1200 series, U.S.)

Column: Connect 2 PL Mixed B

Column temperature: 40 ℃

Eluent: THF (Tetrahydrofuran)

Flow rate: 1.0 mL / min

Concentration: ~ 1 mg / mL (100 μL injection)

2. Glass Adhesion Measurement

The adhesive polarizing plate of the Example or the comparative example was cut | disconnected so that it might be 25 mm in width, and 100 mm in length, and the sample was produced, and after peeling a release sheet (release PET film), it adhered to the alkali free glass using a laminator. It was then stored for 24 hours in constant temperature and humidity conditions (23 ° C., 50% relative humidity). Then, the peel force was evaluated using a physical property analyzer (texture analyzer, stable microsystem) while peeling the adhesive polarizing plate from the alkali-free glass at room temperature at a peel rate of 0.3 m / min and a peel angle of 180 degrees.

3. Evaluation of adhesive / substrate adhesion

After the formation of the pressure-sensitive adhesive layer in the process of manufacturing the pressure-sensitive adhesive polarizing plate of the Examples or Comparative Examples, the polarizing plates that have elapsed by the time described in the following evaluation criteria, respectively, was cut to have a width of 7 cm and a length of 10 cm, and a release sheet (release PET film) After removing, the adhesive tape (measuring adhesive tape) for measuring adhesive peeling with a laminator is affixed with an adhesive area of 5 cm in width and 10 cm in length. Thereafter, the resultant was maintained at constant temperature and humidity conditions (25 ° C., 50% relative humidity) for 5 minutes, and the residual amount of the adhesive remaining on the surface of the polarizing plate substrate was checked while removing the attached adhesive tape. A grating is displayed in the longitudinal direction of the polarizing plate, and visually observed and confirmed based on the amount of the adhesive remaining in the grating.

<Evaluation Criteria>

A: Within 1 day after coating, 90% or more of the adhesive remains

B: Within 2 days after coating, 90% or more of the adhesive remains

C: Within 3 days after coating, more than 90% of the adhesive remains

D: After 4 days after coating, the adhesive remains at least 90%

4. Evaluation of Surface Resistance of Adhesive Layer

The adhesive polarizing plate of Example or Comparative Example was cut to have a width of 50 mm and a length of 50 mm to prepare a specimen, and after removing the release PET adhered to the adhesive layer of the specimen, the surface resistance was measured. Surface resistance was measured according to the manufacturer's manual using an MCP-HT 450 instrument (manufactured by Mitsubishi Chemical, Japan). The specimens were maintained at 23 ° C. and 50% relative humidity for 24 hours before the release sheet (release PET film) was removed from the polarizer and measured after applying a voltage of 500 volts (V) for 1 minute.

Preparation Example 1 Preparation of Acrylic Block Copolymer (A1)

0.1 g EBiB (ethyl 2-bromoisobutyrate) and 28.4 g methyl methacrylate (MMA) were mixed in 12.4 g ethyl acetate (EAc). The flask containing the mixture was sealed with a rubber membrane, purged with nitrogen at about 25 ° C. for about 30 minutes, and dissolved oxygen was removed by bubbling. Then, 0.002 g of CuBr2, 0.005 g of tris (2-pyridylmethyl) amine) and 0.017 g of V-65 (2,2'-azobis (2,4-dimethyl valeronitrile)) were added to the oxygen-free mixture. The reaction was initiated by immersing in a reactor at about 67 ° C. (polymerization of the first block). A mixture of 310 g of butyl acrylate (BA), 1.6 g of hydroxybutyl acrylate (HBA) and 500 g of ethyl acetate (EAc) previously bubbled with nitrogen at a time when the conversion rate of methyl methacrylate is about 75% Was added in the presence of nitrogen. Thereafter, 0.006 g of CuBr2, 0.012 g of TPMA, and 0.05 g of V-65 were added to the reaction flask, and a chain extension reaction was performed (polymerization of the second block). Block copolymers were prepared by exposing the reaction mixture to oxygen and terminating the reaction by dilution in an appropriate solvent when the conversion of monomers (BA) reached 80% or more (in the process V-65 takes into account its half-life). Appropriately divided to the end of the reaction).

Preparation Examples 2 and 3. Preparation of Acrylic Block Copolymers (A2) and (A3)

A block copolymer as shown in Table 1 was prepared in the same manner as in Preparation Example 1, except that the kind of the raw material (monomer, etc.) used in the polymerization of the block copolymer and the polymerization conditions were adjusted.

Production Example One 2 3 4 5 6 A1 B1 A2 A3 B2 B3 First block MMA Rate 100 100 80 60 60 70 BMA Ratio 0 0 20 40 40 30 Tg 110 110 90 72 72 80 Mn (× 10000) 2.9 1.9 3.2 1.7 2.9 3.8 PDI 1.37 1.27 1.44 1.32 1.38 1.41 2nd block BA ratio 99 99.5 97 95 94 95 HBA Ratio One 0.5 3 5 6 5 Tg -47 -47 -46.2 -47 -47.5 -47 Block copolymer Mn (× 10000) 23.7 10.6 27.3 10.4 14.1 10.4 PDI 2.8 1.7 3.1 2.2 2.1 2.1 Weight ratio 10.1: 89.9 10.5: 89.5 10:90 10.5: 98.5 11.2: 88.8 34.7: 65.3 Ratio Unit: parts by weight Tg: glass transition temperature (unit: ℃) Mn: number average molecular weight PDI: molecular weight distribution MMA: methyl methacrylate (monopolymer Tg: about 110 ° C) BMA: butyl methacrylate (monopolymer Tg: about 20 (Degree C) BA: butyl acrylate (monopolymer Tg: about -45 deg. C) HBA: 4-hydroxybutyl acrylate (monopolymer Tg: about -80 deg. C) Weight ratio: Weight ratio of the first block and the second block (first block: agent 2 blocks)

Example 1.

Preparation of pressure-sensitive adhesive composition (coating liquid)

0.1 weight part of a crosslinking agent (Coronate LS, Nippon Polyurethane) with respect to 100 weight part of block copolymers (A1) in the manufacture example 1, a polyfunctional epoxy compound (N, N, N ', N'- tetraglycidyl ethylenediamine) 0.5 parts by weight, ionic liquid (FC-4400, 3M) 1.0 part by weight, 2-methylimidazole (Acros) 0.01 part by weight, DBTDL (Dibutyltin dilaurate, Alfa Aesar) 0.01 part by weight and beta-cyanoacetyl 0.4 parts by weight of a silane coupling agent having a group (AD M-812, LG Chem) was mixed, and ethyl acetate was mixed as a solvent to adjust the coating solid content to about 10 to 13 wt% to prepare a coating solution (adhesive composition).

Preparation of Adhesion Polarizer

The prepared pressure-sensitive adhesive composition was coated on a release treated surface of a poly (ethylene terephthalate) PET (MRF-38, manufactured by Mitsubishi Corporation) having a thickness of about 38 μm after the release treatment as a release sheet, so as to have a thickness of about 25 μm, The pressure-sensitive adhesive layer was formed by maintaining in an oven at 110 ° C. for about 3 minutes. The formed pressure-sensitive adhesive layer was laminated on one surface of the protective film (TAC film) of the iodine-based polarizing plate to produce a pressure-sensitive adhesive polarizing plate (structure of the adhesive polarizing plate: laminated structure of release PET / adhesive layer / TAC / PVA / TAC: TAC = tree Acetyl cellulose, PVA = polyvinyl alcohol polarizing film).

Examples 2-4 and Comparative Examples 1-5

An adhesive composition (coating liquid) and a pressure-sensitive adhesive polarizing plate were manufactured in the same manner as in Example 1 except that the composition was changed as described in Table 2 or 3 in the process of preparing the pressure-sensitive adhesive composition.

Example One 2 3 4 5 6 7 Block copolymer type A1 A2 A2 A3 B1 B2 B3 NCO Ratio 0.1 0.1 0.1 0.45 0.1 0.07 0.2 Epoxy Ratio 0.5 0.5 0.05 0.5 Aziridine Ratio 1.5 1.5 1.5 Ionic liquid ratio One 3.5 One One Metal salt ratio One One One Substance 1 Ratio 0.01 0.05 0.05 0.05 Substance 2 Ratio 0.01 0.01 0.01 Substance 3 Ratio 0.01 0.01 0.01 0.01 0.1 0.1 0.1 SCA Ratio 0.4 0.4 0.4 0.4 0.2 0.2 0.2 Percentage Unit: 100 parts by weight of the block copolymer NCO: Coronate LS (Nippon Polyurethane) Epoxy: N, N, N'.N'-tetraglycidyl ethylenediamineAziridine: triethylene melamine Metal salt: LiTFSi: lithium bis (trifluoromethanesulfonyl imide) ion Sexual liquid: FC-4400 (3M) Metal salt: HQ-115A (3M) Material 1: 2-methyl imidazole (Acros) Substance 2: 2-ethyl-4-methyl imidazole (TCI) Substance 3: Dibutyltin dilaurate (Alfa Aesar) SCA: Silane Coupling Agent: AD-M812 (LG Chemical)

Comparative example One 2 3 Block copolymer type A1 A2 A3 NCO Ratio 0.1 0.1 0.45 Epoxy ratio 0.5 0.5 Aziridine Ratio Ionic liquid ratio One One Metal salt ratio One Substance 1 Ratio 0.01 Substance 3 Ratio 0.01 0.01 0.01 SCA Ratio 0.4 0.4 0.4 Ratio unit: 100 parts by weight of the block copolymer parts by weight NCO: Coronate LS (Nippon Polyurethane) Epoxy: N, N, N'.N'-tetraglycidyl ethylenediamineAziridine: triethylene melamineionic liquid: FC-4400 (3M) Metal salt : HQ-115A (3M) Substance 1: 2-methyl imidazole (Acros) Substance 2: 2-ethyl-4-methyl imidazole (TCI) Substance 3: Dibutyltin dilaurate (Alfa Aesar) SCA: Silane coupling agent: AD-M812 ( LG Chem)

Physical properties measured for the Examples and Comparative Examples are shown in Table 4 below.

Adhesive force (gf / 25mm) Interface adhesion Surface resistance (× 10 ¹¹ Ω / □) Example One 450 A 2.3 2 360 A 1.4 3 460 A 4.2 4 210 A 3.1 5 310 B 0.1 6 300 B 0.1 7 200 B 0.1 Comparative example One 430 D 2.3 2 480 D 3.6 3 230 C 4.5

In the present application, it is possible to provide a pressure-sensitive adhesive composition which is excellent in durability at high temperature or high humidity conditions, and excellent in adhesion with an optical film, and capable of forming a pressure-sensitive adhesive excellent in cutting properties and reworkability. In addition, in the present application, even when applied to a thin substrate such as a very thin glass substrate, it is possible to effectively suppress the warp, to minimize the time required for stabilization of physical properties, and to prevent the deterioration of the secured physical properties over time. The adhesive composition which can form the adhesive which can be formed, the adhesive optical member formed using the above-mentioned adhesive composition, an optical laminated body, and a display apparatus can be provided.

Claims (19)

(A) a block copolymer having a first block having a glass transition temperature of 50 ° C. or more and a second block having a glass transition temperature of −10 ° C. or less, wherein a hydroxyl group is present in the first or second block; (B) polyfunctional isocyanate compounds; (C) a polyfunctional epoxy compound or a polyfunctional aziridine compound; And (D) An adhesive composition comprising at least one compound selected from the group consisting of an imidazole compound, a phosphine compound, an amine compound and a phenol compound. The pressure-sensitive adhesive composition of claim 1, wherein the hydroxyl group of the block copolymer (A) is present only in the second block. The pressure-sensitive adhesive composition of claim 1, wherein the polyfunctional isocyanate compound (B) is contained in a ratio of 0.1 to 10 parts by weight based on 100 parts by weight of the (A) block copolymer. The polyfunctional epoxy compound according to claim 1, wherein the polyfunctional epoxy compound is ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidyl ethylene At least one selected from the group consisting of diamine and glycerin diglycidyl ether, and the polyfunctional aziridine compound is N, N'-toluene-2,4-bis (1-aziridinecarboxamide), N, N'- Diphenylmethane-4,4'-bis (1-aziridinecarboxamide), triethylene melamine, bisisoprotaloyl-1- (2-methylaziridine) and tri-1-aziridinylphosphineoxy At least one pressure-sensitive adhesive composition selected from the group consisting of. The pressure-sensitive adhesive composition of claim 1, wherein (C) the polyfunctional epoxy compound or the polyfunctional aziridine compound is contained in a ratio of 0.01 to 10 parts by weight based on 100 parts by weight of the (A) block copolymer. The pressure-sensitive adhesive composition of claim 1, wherein the imidazole compound is a compound represented by the following Chemical Formula 1: [Formula 1]

R 1 to R 4 in Formula 1 are each independently hydrogen, an alkyl group, or an aryl group. The pressure-sensitive adhesive composition of claim 1, wherein the phosphine compound is a compound represented by the following Chemical Formula 2: [Formula 2]

R 5 to R 7 in Formula 2 are each independently hydrogen, an alkyl group, or an aryl group. The pressure-sensitive adhesive composition of claim 1, wherein the amine compound is a compound represented by the following Chemical Formula 3 or 4: [Formula 3]

L1 and L2 in formula (3) are alkylene groups: [Formula 4]

In formula (4), R8 to R10 are each independently hydrogen, an alkyl group, an aryl group, an arylalkyl group, or a hydroxyalkyl group. The pressure-sensitive adhesive composition of claim 1, wherein the phenolic compound is a compound represented by the following Chemical Formula 5: [Formula 5]

In formula (5), R11 to R15 are each independently hydrogen, an alkyl group, an aminoalkyl group, an alkylaminoalkyl group or a dialkylaminoalkyl group. The pressure-sensitive adhesive composition of claim 1, wherein the compound (D) is included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the (A) block copolymer. The pressure-sensitive adhesive composition of claim 1, further comprising an ionic liquid. The pressure-sensitive adhesive composition of claim 11, wherein the ionic liquid is contained in a ratio of 0.01 to 15 parts by weight with respect to 100 parts by weight of the (A) block copolymer. The pressure-sensitive adhesive composition of claim 1, further comprising a tin compound. Optical film; And a pressure-sensitive adhesive layer formed on one or both surfaces of the optical film and comprising the cross-linked pressure-sensitive adhesive composition of claim 1. The adhesive optical member according to claim 14, wherein an easy adhesion treatment layer is present between the optical film and the adhesive layer. Polarizer; And a pressure-sensitive adhesive layer formed on one or both surfaces of the polarizer and comprising the cross-linked pressure-sensitive adhesive composition of claim 1. The pressure-sensitive adhesive polarizing plate according to claim 16, wherein an easy adhesion treatment layer exists between the polarizer and the pressure-sensitive adhesive layer. A glass substrate having a thickness of 1 mm or less; The optical laminated body containing the adhesive optical member of Claim 14 or the adhesive polarizing plate of Claim 16 attached to the said glass substrate by the adhesive layer. A display device comprising the adhesive optical member of claim 14 or the adhesive polarizing plate of claim 16.