KR20180029668A - Crosslinkable composition - Google Patents

Abstract

The present invention relates to a crosslinkable composition, comprising: block copolymers; and an isocyanate crosslinking agent. The crosslinkable composition of the present application is able to form an adhesive excellent in durability, stress relaxation, and re-workability. Furthermore, when the crosslinkable composition is used additionally, for instance, a coating process can be efficiently carried out even when a coating solid content is maintained at a high level such that productivity is excellent and the adhesive excellent in uniformity of thickness can be formed. The crosslinkable composition can be used for an optical film such as, for example, a polarizing plate.

Description

Crosslinkable composition [0002]

This application relates to crosslinkable compositions and uses thereof.

The crosslinkable composition can be applied to various applications. For example, the crosslinkable composition can be used for forming a pressure-sensitive adhesive or an adhesive. Such a pressure-sensitive adhesive or adhesive can be used for bonding a display panel and an optical film or a conductive film to each other in a display device such as an LCD (Liquid Crystal Display Device), an OLED (Organic Light Emitting Display) or a PDP Purpose or the like.

The main physical properties required in the composition to be applied to the above applications are cohesive force, adhesive force, reworkability, low light leakage property and stress relaxation property, and in Patent Documents 1 to 3, the crosslinking property Compositions have been proposed.

As various display devices have become thinner in recent years, components applied to a display device, for example, a glass substrate, a conductive film, and other optical films tend to be thin, too. The problem caused by the bending which has not been caused is increasing.

Patent Document 1: Korean Patent No. 1023839 Patent Document 2: Korean Patent No. 1171976 Patent Document 3: Korean Patent No. 1171977

The present application relates to crosslinkable compositions and uses thereof. The present application provides a crosslinkable composition capable of forming a layer having desired properties such as cohesive force, adhesive force, reworkability, low light leakage property and stress relaxation property, and at the same time having a superior bending inhibiting ability, particularly a bending inhibiting ability at high temperature .

The term crosslinkable composition means a composition comprising a component capable of forming a crosslinked structure. In the above, the crosslinking structure may mean a chemical crosslinking structure or a physical crosslinking. The crosslinkable composition of the present application comprises a block copolymer capable of forming physical crosslinking itself by so-called phase separation or self-assembling property and, when necessary, introducing a crosslinkable functional group capable of chemical crosslinking into the block copolymer , A physical crosslinking structure and a chemical crosslinking structure can be simultaneously formed.

Such a crosslinkable composition may be, for example, a pressure-sensitive adhesive composition or an adhesive composition. In the above, the pressure-sensitive adhesive composition or the adhesive composition may mean a composition containing a crosslinked structure or a composition capable of exhibiting the properties of the pressure-sensitive adhesive or adhesive before the crosslinked structure is formed.

When the crosslinkable composition is used as a pressure-sensitive adhesive composition or an adhesive composition, the crosslinkable composition may be included as a main component of the pressure-sensitive adhesive or the adhesive composition. As used herein, the inclusion of a component as a major component in a subject means that the ingredient is present in the subject in an amount of at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt% 75% by weight or more, 80% by weight or more, 85% by weight or more, or 90% by weight or more. The upper limit of the content in the object of the component contained in the main component is not particularly limited and may be, for example, about 100% by weight. Also, in the present application, when referring to the content of the components in a composition, the content thereof is based on the solids content of the composition.

Exemplary crosslinkable compositions may include block copolymers. As used herein, the term " block copolymer " may refer to a copolymer comprising blocks of different polymerized monomers. The crosslinkable composition may contain the block copolymer as a main component. As used herein, the fact that the crosslinkable composition includes a block copolymer as a base polymer may mean that the crosslinkable composition contains the block copolymer as a main component. Accordingly, the crosslinkable composition may contain at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt% Or more, 85 wt% or more, or 90 wt% or more, and the upper limit of the ratio may be about 100 wt%. The weight% is based on the weight of the solid content of the crosslinkable composition.

In one example, the block copolymer may include a first block having a glass transition temperature of 40 ° C or higher and a second block having a glass transition temperature of 0 ° C or lower. As used herein, the "glass transition temperature of a given block" of a block copolymer may mean a glass transition temperature measured from a polymer formed only of the monomers contained in the block or a glass transition temperature calculated on the basis of the monomers. In one example, the glass transition temperature of the first block may be at least 50 ° C, at least 60 ° C, at least 65 ° C, or at least 70 ° C. The upper limit of the glass transition temperature of the first block is not particularly limited. For example, the glass transition temperature may be 150 占 폚 or lower, 140 占 폚 or lower, 130 占 폚 or lower, or 120 占 폚 or lower. In the above, the glass transition temperature of the second block may be -10 ° C or lower, -20 ° C or lower, -30 ° C or lower, -35 ° C or -40 ° C or lower. The lower limit of the glass transition temperature of the second block is not particularly limited. For example, the glass transition temperature of the second block may be -80 占 폚 or higher, -70 占 폚 or higher, -60 占 폚 or higher, or -55 占 폚 Or more. The block copolymer containing at least two kinds of the above-mentioned two blocks can form a proper type of phase separation structure. Such a block copolymer exhibits an appropriate cohesive force in accordance with a change in temperature, so that the layer of the crosslinkable composition exhibits excellent stress relaxation and flexibility while maintaining excellent properties such as durability reliability, light-shielding property and reworkability, And the like.

The first block in the block copolymer may have a Number Average Molecular Weight (Mn) of, for example, from 2,500 to 150,000. The number average molecular weight of the first block may mean, for example, the number average molecular weight of the polymer produced by polymerizing only the monomer forming the first block. The number average molecular weight referred to in the present specification can be measured by, for example, a method as shown in the examples using GPC (Gel Permeation Chromatograph). The number average molecular weight of the first block may be 5,000 or more, 7,000 or more, 9,000 or more, 10,000 or more, 15,000 or more, 20,000 or more, 25,000 or more, or 30,000 or more. The number average molecular weight of the first block may be about 130,000 or less, about 110,000 or less, about 100,000 or less, about 90,000 or less, about 80,000 or about 70,000 or about 65,000 or less.

The block copolymer may have a number average molecular weight 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 100,000, at least 150,000, or at least about 200,000. The number average molecular weight of the block copolymer may also be about 280,000 or less, about 260,000 or less, or about 250,000 or less in another example.

The block copolymer may have a molecular weight distribution (PDI; Mw / Mn), that is, a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) within a range of 1.0 to 4.0. The molecular weight distribution may be about 1.2 or more, about 1.4 or more, or about 1.5 or more in another example. In addition, the molecular weight distribution may be about 3.5 or less, about 3 or less, or about 2.5 or less in another example.

The above-mentioned physical properties can be maintained more excellent by controlling the molecular weight characteristics as described above.

In one example, the block copolymer may be a crosslinkable copolymer having a crosslinkable functional group. Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, an isocyanate group and a glycidyl group, and for example, a hydroxy group can be used.

In the case of containing a crosslinkable functional group, the functional group may be included in, for example, a second block having a low glass transition temperature. In one example, the first block having a high glass transition temperature may not contain a crosslinkable functional group, and the second block may contain a crosslinkable functional group. When a crosslinkable functional group is included in the second block, a block copolymer capable of forming physical crosslinking by phase separation itself has a crosslinking point at a soft part, thereby forming a chemical crosslinking structure and maintaining the above properties .

The kind of the monomer forming the first block and the second block in the block copolymer is not particularly limited as long as the glass transition temperature as described above can be ensured by the combination of the respective monomers.

In one example, the first block may comprise polymerized units derived from (meth) acrylic acid ester monomers. As used herein, the fact that a monomer is contained in a polymer or a block in a polymerized unit may mean that the monomer undergoes a polymerization reaction to form a skeleton of the polymer or block, for example, a main chain or a side chain. As the (meth) acrylic acid ester monomer, for example, alkyl (meth) acrylate may be used. In one example, considering the control of cohesion, glass transition temperature and tackiness, alkyl (meth) acrylates having an alkyl group of 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 Methacrylate may be used. Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (Meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate and lauryl (meth) acrylate. Can be selected and used. As the monomer forming the first block in consideration of the ease of controlling the glass transition temperature and the like, though not particularly limited, methacrylic acid ester monomers such as alkyl methacrylates, specifically those having a carbon number of 1 An alkyl methacrylate having an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 16 carbon atoms, a carbon number of 1 to 12, a carbon number of 1 to 8, or a carbon number of 1 to 4 can be used.

For example, the first block may include the alkyl methacrylate as a main component. Accordingly, the alkyl methacrylate may be at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, or at least 75 wt%, based on the weight of the total monomer units forming the first block At least 80 wt%, at least 85 wt%, or at least 90 wt% of the first block may be included in the first block, and the upper limit of the ratio may be about 100 wt%.

In the block copolymer, the second block may also comprise polymerized units derived from (meth) acrylic acid ester monomers. As the monomer forming the second block in consideration of the ease of controlling the glass transition temperature and the like, there may be mentioned acrylic acid ester monomers such as alkyl acrylate, specifically having 1 to 20 carbon atoms, Alkyl acrylates having 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms and 1 to 4 carbon atoms can be used.

For example, the second block may contain the alkyl acrylate as a main component. Accordingly, the alkyl acrylate may comprise at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, based on the weight of the total monomer units forming the second block % Or more, 80 wt% or more, 85 wt% or more, or 90 wt% or more, and the upper limit of the ratio may be about 100 wt%.

The second block of the block copolymer may further include, for example, a copolymerizable monomer having a crosslinkable functional group. For example, the second block may contain 90 to 99.9 parts by weight of the (meth) acrylic acid ester monomer and polymerized units derived from 0.1 to 10 parts by weight of a copolymerizable monomer having a crosslinkable functional group . In the present specification, the unit weight portion may mean the ratio of the weight between each component. For example, as described above, the second block includes 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 (A: B) based on the weight of the (meth) acrylic acid ester monomer (A) forming the polymerized unit of the second block and the copolymerizable monomer (B) having a crosslinkable functional group is 90 to 99.9: 0.1 to 10, respectively.

Examples of the copolymerizable monomer having a crosslinkable functional group include a copolymerizable monomer having a moiety copolymerizable with other monomers contained in the block copolymer such as the above (meth) acrylic acid ester monomer and having a crosslinkable functional group, For example, a monomer having a hydroxyl group or the like can be used. In the production of pressure-sensitive adhesives, a variety of copolymerizable monomers having the above-mentioned crosslinkable functional groups are known, and all of these monomers can be used in the polymer. Examples of the copolymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylate or 2-hydroxypropyleneglycol (meth) acrylate such as hydroxyalkyl (meth) acrylate or 8-hydroxyoctyl (Meth) acrylate, and the like can be used, but the present invention is not limited thereto. Hydroxyalkyl acrylate or hydroxyalkylene glycol acrylate among the above monomers may be used in consideration of reactivity with other monomers forming the second block and easiness of controlling the glass transition temperature and the like. no.

The first block and / or the second block may further comprise any other comonomer, if necessary, for example, for controlling the glass transition temperature and the like, and the monomer may be included as polymerized units have. Examples of the comonomer include (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-vinylpyrrolidone, Nitrogen-containing monomers such as lactam and the like; (Meth) acrylic acid esters, alkoxy alkylene glycol (meth) acrylic acid esters, alkoxy alkylene glycol (meth) acrylic acid esters, alkoxy alkylene glycol (Meth) acrylic acid esters, phenoxy alkylene glycol (meth) acrylic acid esters, phenoxy alkylene glycol (meth) acrylic acid esters, phenoxy trialkylene glycol Alkylene oxide group-containing monomers such as polyalkylene glycol (meth) acrylic acid esters and the like; Styrene-based monomers such as styrene or methylstyrene; Glycidyl group-containing monomers such as glycidyl (meth) acrylate; And carboxylic acid vinyl esters such as vinyl acetate, but are not limited thereto. These comonomers may be included in the polymer by selecting one kind or more than two types as appropriate according to need. Such comonomers may be included in the block copolymer, for example, in a proportion of 20 parts by weight or less, or 0.1 part by weight to 15 parts by weight, based on the weight of the other monomers in each block.

The block copolymer may include, for example, 10 parts by weight to 50 parts by weight of the first block and 50 parts by weight to 90 parts by weight of the second block. The ratio of the weight between the first block and the second block can be adjusted as described above to provide the crosslinkable composition and the pressure-sensitive adhesive excellent in physical properties. In another example, the block copolymer may comprise from 5 to 45 parts by weight of the first block and from 55 to 95 parts by weight of the second block or from 5 to 45 parts by weight of the first block and from 60 to 60 parts by weight of the second block, 95 parts by weight.

In another example, the ratio of the second block based on the total content of the first and second blocks included in the block copolymer may be about 50 wt% to 90 wt%. The proportion may be at least about 55% by weight or at least about 60% by weight in other examples.

In one example, the block copolymer may be a diblock copolymer comprising the first and second blocks, i.e. a block copolymer comprising only two blocks of the first and second blocks . By using the diblock copolymer, the durability of the pressure-sensitive adhesive, the stress relaxation property, and the reworkability can be maintained more excellent.

The method for producing the block copolymer is not particularly limited and can be produced in a usual manner. The block polymer is polymerized by, for example, an LRP (Living Radical Polymerization) method. Examples of the block polymer include an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator to produce an alkali metal or alkaline earth metal Anion polymerization which is synthesized in the presence of an inorganic acid salt such as a salt, an anionic polymerization method in which an organic alkali metal compound is used as a polymerization initiator and synthesized in the presence of an organoaluminum compound, an atomic transfer radical polymerization (ATRP), Atomic Transfer Radical Polymerization (ATRP), ICAR (Initiators), which conducts polymerization under an organic or inorganic reducing agent that generates electrons using an atom transfer radical polymerization agent as a polymerization initiator for continuous activator regeneration) Atom Transfer Radical Polymerization (ATRP) (RAFT) using a reversible addition-cleavage chain transfer agent using a reducing agent addition-cleavage chain transfer agent, or a method using an organic tellurium compound as an initiator. Among these methods, an appropriate method can be selected and applied.

The crosslinkable composition may further comprise a crosslinking agent capable of crosslinking the block copolymer. As the crosslinking agent, a crosslinking agent having at least two functional groups capable of reacting with the crosslinkable functional group contained in the block copolymer may be used. As such a crosslinking agent, an isocyanate crosslinking agent may be used.

In the present application, in order to impart optimum flexibility to the crosslinked structure formed by the block copolymer and improve the fin characteristics, (B) a polyfunctional isocyanate crosslinking agent having no polyalkylene oxide chain; And (C) a polyfunctional isocyanate crosslinking agent having a polyalkylene oxide chain can be applied. The crosslinking agent (C) may be bifunctional. The above-mentioned multi-functional or bifunctional functional group means a case where the cross-linking agent has two or more isocyanate groups or a case where two or more isocyanate groups are present. The isocyanate crosslinking agent (B) is, for example, an isocyanate crosslinking agent having two or more, two to ten, two to nine, two to eight, two to seven, two to six, two To 5, or from 3 to 5 carbon atoms.

Examples of the isocyanate crosslinking agent (B) include diisocyanates such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoboron diisocyanate, tetramethylxylene diisocyanate and naphthalene diisocyanate Or a compound obtained by reacting the diisocyanate compound with a polyol can be used. As the polyol, for example, trimethylolpropane and the like can be used. For example, various isocyanate crosslinking agents as described above are known in the field of the production of pressure-sensitive adhesives.

As the (C) isocyanate crosslinking agent, for example, a compound represented by the following formula (1) can be used.

[Chemical Formula 1]

In the general formula (1), A is an alkylene group or an alkylidene group having 1 to 4 carbon atoms, Ar ₁ and Ar ₂ are aryl groups substituted with one isocyanate group, L ₁ and L ₂ are linkers, and n ranges from 2 to 60 Lt; / RTI >

As the alkylene group or alkylidene group of A in the above formula, an ethylene group or a propylene group can be exemplified.

On the other hand, the aryl group of Ar ₁ and Ar ₂ includes a structure in which one benzene ring structure, two or more benzene rings are linked together by sharing one or two carbon atoms, or is linked by any linker A monovalent residue derived from a compound or a derivative thereof. Such an aryl group may be, for example, an aryl group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms unless otherwise specified. Examples of the aryl group include, but are not limited to, a phenyl group or a benzyl group.

In formula (1), the aryl groups of Ar ₁ and Ar ₂ may be the same or different from each other and are each substituted with one isocyanate group. The aryl group may contain a substituent other than the isocyanate group. Examples of other substituents which may be contained in this case include, but are not limited to, alkyl groups 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. For example, when the aryl group of Ar ₁ and Ar ₂ is a phenyl group, the isocyanate group may be substituted with an ortho, meta, or para position based on the moiety linked to L ₁ or L _2. .

The linker represented by L ₁ or L ₂ which may be the same or different from each other may be an oxygen atom, a sulfur atom, -NR ₁ -, -S (═O) ₂ -, a carbonyl group, an alkylene group, , alkynylene _{group, -C (= O) -X 1} -, -X 1 -C (= O) -, -NR 1 -C (= O) -X 1 - or -X ₁ -C (= O) -NR < ₁ > - can be illustrated. R ₁ may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and X ₁ may be an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group or an alkynylene group.

The alkyl group or alkoxy group in the above may be exemplified by a linear, branched or cyclic alkyl or 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, Substituted or unsubstituted.

Examples of the alkylene group include straight chain, branched chain or cyclic alkylene groups 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, It may be in an unsubstituted state.

Examples of the alkenylene group, alkynylene group, alkenyl group or alkynyl group in the above include straight, branched or cyclic alkyl groups having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms An alkenylene group, an alkynylene group, an alkenyl group or an alkynyl group, which may be substituted or unsubstituted.

The range of the aryl group in the above can be similarly applied except for the portion in which the range of the aryl group of Ar1 and Ar2 described above is substituted with an isocyanate group.

In the above formula (1), n may be in the range of 2 to 60 or 10 to 60, and specifically in a range that satisfies the number average molecular weight described later.

As the (C) isocyanate crosslinking agent, the number average molecular weight may be within the range of about 500 to 10,000. In another example, the number average molecular weight may be at least about 700, at least about 900, at least about 1,100, at least about 1,300, at least about 1,500, at least about 1,700, or at least about 1,900. In another example, the number average molecular weight may be about 9,000 or less, about 8,000 or less, about 7,000 or less, about 6,000 or less, about 5,000 or less, about 4,000 or less or about 3,000 or less. Within this range, the effect of addition of the crosslinking agent (C) can be more excellent.

The crosslinkable composition may contain the isocyanate crosslinking agent (B) in a proportion of 0.01 to 2 parts by weight based on 100 parts by weight of the block copolymer. The proportion of (B) isocyanate crosslinker may be at least about 0.03 part by weight, at least about 0.05 part by weight, or at least about 0.06 part by weight in another example.

The crosslinkable composition may contain the isocyanate crosslinking agent (C) in a proportion of 0.01 to 5 parts by weight based on 100 parts by weight of the block copolymer. In another embodiment, the ratio of (C) isocyanate crosslinking agent may be about 0.03 parts by weight or more, about 0.05 parts by weight or more, about 0.06 parts by weight or more, about 0.08 parts by weight or more, about 0.1 parts by weight or more, or about 0.15 parts by weight or more. About 4 parts by weight or less, about 3.5 parts by weight or less, about 3 parts by weight or less, about 2.5 parts by weight or less, about 2 parts by weight or less, about 1.5 parts by weight or less, or about 1 part by weight Parts by weight.

The ratio of the cross-linking agents (B) and (C) can be adjusted to maximize the desired effect.

For example, the ratio of the cross-linking agent of (B) and (C) can be adjusted so that K in the following formula 1 falls within the range of 0.5 to 100.

[Equation 1]

K = C / B

In the formula (1), B is a weight part of the (A) block copolymer of the crosslinking agent (B), and C is a weight part of 100 weight parts of the (A) block copolymer of the crosslinking agent (C).

K in the above formula 1 may be 0.7 or more, 0.9 or more, 1.1 or more, 1.3 or more, 1.5 or more, or about 1.65 or more in other examples. In another example, K may be 80 or less, 60 or less, 40 or less, 30 or less, 10 or less, 9 or less or 8 or less.

In the calculation of the above formula (1), for example, in the case where two or more crosslinking agents corresponding to the crosslinking agent (B) are present in the composition or two or more crosslinking agents corresponding to the crosslinking agent (C) The substituted B and C are the total weight of the crosslinking agent.

In another example, the ratio of the cross-linking agent of (B) and (C) can be adjusted so that M in the following formula (2) becomes 0.01 or more.

[Equation 2]

M = (42 x B _NCO x B) / B _MW + (84 x C) / C _Mn

(B) is 100 parts by weight of the (A) block copolymer of the crosslinking agent (B), and C is a part by weight of 100 parts by weight of the (A) block copolymer of the crosslinking agent (C) _NCO is the number of isocyanate groups in the crosslinking agent (B), B _MW is the molecular weight of the crosslinking agent (B), and C _Mn is the number average molecular weight of the crosslinking agent (C).

In the calculation of the above formula (2), for example, in the case where two or more crosslinking agents corresponding to the crosslinking agent (B) are present in the composition, (42 x B _NCO x B) / B _MW is calculated separately for each of the crosslinking agents And introduced into equation (2). In the calculation of the formula (2), (84 占 C) / C _Mn is calculated separately for each of the crosslinking agents and introduced into the formula (2) even when two or more crosslinking agents corresponding to the crosslinking agent (C)

M in the formula 2 may be about 0.015 or more, or about 0.018 or more, or about 0.02 or more in other examples. In another example, M is about 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, 1 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less, 0.09 or less, 0.08 or less, 0.07 or less, 0.06 or less, 0.05 or less, 0.04 or less or 0.035 or less.

Within the above range, the desired physical properties can be secured for the crosslinkable composition.

The crosslinkable composition may further include a polyfunctional epoxy compound or a polyfunctional aziridine compound as a component that ensures interlayer adhesion when the crosslinkable composition is applied to various laminated structures.

Such compounds include, for example, ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidylethylenediamine or glycerine diglyme Epoxy compounds such as cyydyl ether; Or N, N'-diphenylmethane-4,4'-bis (1-aziridine carboxamide), triethylene Aziridine compounds such as melamine, bisisoproparyl-1- (2-methyl aziridine), or tri-1-aziridinyl phosphine oxide, and the like, but are not limited thereto.

The crosslinkable composition may contain the epoxy or aziridine compound in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the block copolymer, but this may be controlled in consideration of the desired effect.

The crosslinkable composition may further comprise an ionic compound. As the ionic compound, for example, a metal salt or an ionic liquid can be applied. The above ionic liquid means an ionic compound present in a liquid state at room temperature.

As the metal salt in the above, for example, a salt containing an alkali metal cation or an alkaline earth metal cation can be used. Cations, the lithium ions (Li ^+), sodium ion (Na ^+), potassium ion (K ^+), rubidium ions (Rb ^+), cesium ion (Cs ^+), beryllium ion (Be ^{2 +),} magnesium ion ( Mg ^{2 +),} calcium ions (Ca ^{2 +),} strontium ion (Sr ^{2 +)} and barium ion (Ba ^{2 +)} there is iljong or two kinds or more of the like can be illustrated, for example, a lithium ion, a sodium ion, Potassium ion, magnesium ion, calcium ion and barium ion, or ion 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 ^-), 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 -),} carboxymethyl sulfonate _{(COOH (C 6 H 4)} SO 3 -), sulfonate as a triple (CF ₃ SO ₂ ^-), benzo carbonate ^{_{(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 ^- ), and the like.

In another example, the anion may be an anion or bifluorosulfonylimide represented by the following formula (2), or the like.

(2)

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

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.

When Y is carbon in Formula (2), m is 1, and when Y is sulfur, m is 2, n is 2 when X is nitrogen, and n is 3 when X is carbon.

The anion or bis (fluorosulfonyl) imide of formula (2) exhibits a high electronegativity due to the perfluoroalkyl group (R _f ) or the fluorine group and also forms a weak bond with the cation, including a unique resonance structure And at the same time has hydrophobicity. Therefore, the ionic compound exhibits excellent compatibility with other components of the composition such as a polymer, and can give a high antistatic property even in a small amount.

R _f in Formula 2 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, wherein the perfluoroalkyl group may be a straight chain, And may have a cyclic structure. The anion of the formula (2) may be a sulfonylimide-based, sulfonylimide-based, carbonylimide-based or carbonylimide-based anion. Specific examples thereof include tris trifluoromethanesulfonylmethide, bistrifluoromethanesulfonyl A perfluorobutanesulfonylimide, bispentafluoroethanesulfonylimide, tris trifluoromethanecarbonylmide, bis perfluorobutanecarbonylimide or bispentafluoroethanecarbonyl, bispentafluoroethanesulfonylimide, bis Imide, etc., or a mixture of two or more species.

Examples of the ionic liquid include, for example, N-ethyl-N, N-dimethyl-N-propylammonium, N, N, N-trimethyl- N, N, N-trihexylammonium, N-methyl-N, N, N-trihexylammonium, N-ethyl- Quaternary ammonium such as N, N, N-trioctylammonium or N-ethyl-N, N, N-trioctylammonium, phosphonium, pyridinium, imidazolium, An organic salt containing pyrolidinium or piperidinium together with the anion component may be used.

The crosslinkable composition may simultaneously contain the metal salt and the ionic liquid if necessary.

The content of the ionic compound in the crosslinkable composition is not particularly limited and may be, for example, 0.01 to 15 parts by weight relative to 100 parts by weight of the block copolymer. The ratio of the ionic compound can be changed in consideration of the desired antistatic property and compatibility between the components.

The crosslinkable composition may further include a silane coupling agent. As the silane coupling agent, for example, a silane coupling agent having a beta-cyano group or an acetoacetyl group can be used. Such a silane coupling agent can be used, for example, so that a pressure-sensitive adhesive formed by a copolymer having a low molecular weight can exhibit excellent adhesion and adhesion stability, and can maintain excellent durability reliability under heat and moisture and heat have.

As the silane coupling agent having a beta-cyano group or an acetoacetyl group, for example, a compound represented by the following formula (3) or (4) can be used.

(3)

(R ¹ ) _n Si (R ² ) _(4-n)

[Chemical Formula 4]

(R ³ ) _n Si (R ² ) _(4-n)

In Formula 3, or 4, R ¹ is a beta-cyano-acetyl or beta-and cyano-acetyl group, R ³ is acetonitrile, and an acetyl group or an acetoacetyl group, R ² is an alkoxy group, n is 1 to 3 ≪ / RTI >

In the general formula (3) or (4), 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 the general formula (3) or (4), 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, Can be.

In Formula 3 or 4, n may be, for example, 1 to 3, 1 to 2, or 1.

Examples of the compound represented by the general formula (3) or (4) include acetoacetylpropyltrimethoxysilane, acetoacetylpropyltriethoxysilane, beta-cyanoacetylpropyltrimethoxysilane or beta-cyanoacetylpropyltriethoxysilane , But are not limited thereto.

In the crosslinkable composition, the silane coupling agent may be contained 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 block copolymer, and the desired properties may be effectively imparted to the pressure-sensitive adhesive within this range .

The crosslinkable composition may further comprise a tackifier as necessary. Examples of the tackifier include a hydrocarbon resin or hydrogenated product thereof, a rosin resin or hydrogenated product thereof, a rosin ester resin or hydrogenated product thereof, a terpene resin or hydrogenated product thereof, a terpene phenol resin or hydrogenated product thereof, Polymerized rosin ester resin, and the like, or a mixture of two or more of them may be used, but the present invention is not limited thereto. The tackifier may be contained in the crosslinkable composition in an amount of 100 parts by weight or less based on 100 parts by weight of the block copolymer.

The crosslinkable composition may further include, if necessary, at least one additive selected from the group consisting of an epoxy resin, a curing agent, a UV stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, a defoamer, a surfactant and a plasticizer.

The crosslinkable composition may be used as a pressure-sensitive adhesive composition for a protective film. In the use of each of the crosslinkable compositions mentioned below, the pressure-sensitive adhesive composition may contain the crosslinkable composition as a main component based on the solid content. The protective film can be used, for example, for protecting the surface of various optical films.

The crosslinkable composition may also be used as a pressure-sensitive adhesive composition for a conductive film.

The crosslinkable composition may be a pressure-sensitive adhesive composition for an optical film. The pressure-sensitive adhesive composition for an optical film can be produced by, for example, laminating an optical film 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, And can be used for adhering to an adherend. In one example, the crosslinkable composition is a pressure-sensitive adhesive composition for a polarizing plate, and can be used for adhering a polarizing film to a liquid crystal panel.

The present application is also directed to a pressure-sensitive adhesive optical laminate. Exemplary optical stacks include optical films; And 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 adhering the optical film to another optical film such as a liquid crystal panel of a LCD device or a touch panel. The pressure-sensitive adhesive layer may include the cross-linkable composition of the present invention described above. The crosslinkable composition may be included in the pressure-sensitive adhesive layer in a state of realizing a crosslinked structure. The crosslinkable composition may be included as a main component of the pressure-sensitive adhesive composition. Examples of the optical film include a polarizing film, a retardation film, a brightness enhancement film, a conductive film, or a laminate in which two or more of the above are laminated.

The present application also relates to an adhesive polarizing plate. The polarizing plate may have, for example, a structure in which the optical film is a polarizing film in the adhesive optical laminate.

The kind of the polarizing film included in the polarizing plate is not particularly limited, and for example, general types known in the art such as a polyvinyl alcohol polarizing film and the like can be employed without limitation.

A polarizing film is a functional film capable of extracting only light vibrating in one direction from incident light while vibrating in various directions. Such a polarizing film may be, for example, a form in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film. The polyvinyl alcohol-based resin constituting the polarizing film can be obtained by, for example, gelling a polyvinyl acetate-based resin.

In this case, the polyvinyl acetate-based resin that can be used may include not only homopolymers of vinyl acetate but also copolymers of vinyl acetate and other monomers copolymerizable therewith. Examples of the monomer copolymerizable with vinyl acetate include monomers such as unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group, or a mixture of two or more thereof. no.

The degree of gelation of the polyvinyl alcohol-based resin may be generally from 85 mol% to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be further modified. For example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. 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 polarizing film is obtained by stretching a polyvinyl alcohol-based resin film as described above, for example, a process of uniaxially or biaxially stretching, a process of dyeing a polyvinyl alcohol-based resin film with a dichroic dye and adsorbing the dichroic dye, A process of treating a polyvinyl alcohol resin film adsorbed with a coloring pigment with an aqueous solution of boric acid and a process of washing with an aqueous solution of boric acid after washing.

As the dichroic dye, iodine or dichroic organic dyes may be used.

The polarizing plate may further include a protective film attached to one side or both sides of the polarizing film. In this case, the pressure sensitive adhesive layer may be formed on one side of the protective film. The kind of the protective film is not particularly limited and includes, for example, a cellulose-based film such as TAC (triacetyl cellulose); Polycarbonate film or PET (poly (ethylene terephthalate)); Polyethersulfone-based films; Or a polyolefin film produced by using a polyethylene film, a polypropylene film, a resin having a cyclo or norbornene structure, or an ethylene-propylene copolymer, or the like, or a film having a laminate structure of two or more layers. Particularly, it is more effective in improving heat resistance durability when PET-based, polyolefin-based film and acrylic-based film having good moisture barrier properties are applied.

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

The method for forming the pressure-sensitive adhesive layer on the polarizing plate or the optical film as described above is not particularly limited, and for example, a method of directly coating the crosslinkable composition on a polarizing plate or an optical film and curing the crosslinked structure Or a method of forming a crosslinked structure by coating and curing the crosslinkable composition on the release treated surface of a release film and then transferring the crosslinked structure onto a polarizing plate or an optical film.

The method for coating the crosslinkable composition is not particularly limited, and for example, a method of applying the crosslinkable composition by a conventional means such as a bar coater may be used.

The multifunctional crosslinking agent contained in the crosslinkable composition during the coating process is preferably controlled in such a manner that the crosslinking reaction of the functional groups is not proceeded from the viewpoint of performing a uniform coating process so that the crosslinking agent is cured and hardened The crosslinking structure is formed to improve the cohesive force of the pressure-sensitive adhesive, and the adhesive property and cuttability can be improved.

The coating process is also preferably performed after sufficiently removing the bubble-inducing component such as volatile components or reaction residues in the crosslinkable composition, so that the crosslinking density or the molecular weight of the pressure-sensitive adhesive is too low to lower the elastic modulus, It is possible to prevent the problem that the bubbles existing between the glass plate and the adhesive layer become large to form a scattering body therein.

The method of curing the crosslinkable composition by subsequent curing of the above-mentioned coating is not particularly limited. For example, the coating layer may be appropriately adjusted so that a cross-linking reaction of the block copolymer contained in the coating layer and the multi- A method in which the temperature is maintained at a predetermined temperature, or the like.

In one mode of the adhesive optical film, the pressure-sensitive adhesive layer may be provided on the optical film through the undercoating layer. As the undercoat layer, a known undercoat layer can be applied, for example, a undercoat layer including a polymer can be applied. In the case where the undercoating layer is applied, the pressure-sensitive adhesive of the above-mentioned type including the mixture of the cross-linking agents (B) and (C) may be applied as the pressure-sensitive adhesive, and an adhesive containing only the cross- It can also be applied.

As such a primer layer, for example, a polymer having a primary amino group at the terminal may be used. Examples of such a polymer include a polymer derived from a poly (meth) acrylic acid ester or a polyethylene imine material having a primary amino group at the terminal thereof Can be used.

The undercoat layer may further comprise, if necessary, from 0.01 to 500 parts by weight of an antioxidant relative to 100 parts by weight of the polymer. As such an antioxidant, at least one selected from known types such as phenol-based, phosphorus-based, sulfur-based and amine-based antioxidants can be used.

Such a primer layer can be formed in a known manner, and can be formed, for example, by applying a primer layer-forming coating composition to a known coating method such as a coating method, a dipping method, or a spraying method.

The present application is also directed to a display device, e.g., an LCD device.

An exemplary display device may include a liquid crystal panel and the polarizing plate or optical laminate attached to one or both sides of the liquid crystal panel. The polarizing plate or the optical laminate may be attached to the liquid crystal panel by the above-described pressure-sensitive adhesive.

Examples of the liquid crystal panel in the apparatus include passive matrix type panels such as TN (twisted nematic) type, STN (super twisted nematic) type, F (ferroelectic) type or PD (polymer dispersed) type; An active matrix type panel such as a two terminal or a three terminal; A known panel such as an in-plane switching (IPS) panel and a vertical alignment (VA) panel may be used.

Other types of liquid crystal display devices, such as a color filter substrate or an array substrate, are not particularly limited, and configurations known in the art can be employed without limitation.

The present invention provides crosslinkable compositions and uses thereof. Specifically, the present application discloses a crosslinkable composition capable of forming a layer having excellent warpage suppressing ability, particularly a warpage suppressing ability at a high temperature, while securing required physical properties such as cohesive force, adhesive force, reworkability, low light leakage property and stress relaxation property Can be provided. The crosslinkable composition can be used for an optical film or a conductive film such as a polarizing plate.

The crosslinkable composition will be described in detail in the following examples and comparative examples, but the range of the crosslinkable composition is not limited by the following examples.

1. Evaluation of molecular weight

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

<Measurement Conditions>

Measuring instrument: Agilent GPC (Agilent 1200 series, U.S.)

Column: Two PL Mixed B connections

Column temperature: 40 ° C

Eluent: THF (Tetrahydrofuran)

Flow rate: 1.0 mL / min

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

2. Evaluation of durability

The polarizing plates prepared in Examples and Comparative Examples were cut to have a width of about 180 mm and a length of about 220 mm to prepare specimens, and the specimens were attached to glass to prepare samples. The applied pressure was about 5 Kg / cm ² at the time of attachment, and the work was performed in a clean room to prevent the inflow of foreign matter or bubbles. The damp heat resistance was evaluated by observing the occurrence of bubbles and peeling after the sample was left at 60 ° C and 90% relative humidity for 1,000 hours. The durability was evaluated by maintaining the sample at 80 ° C for 1,000 hours The occurrence of bubbles and peeling was observed and evaluated according to the following criteria.

The wet heat resistance and the heat resistance durability were evaluated after each sample after being left under the above conditions was maintained at room temperature for 24 hours.

<Evaluation Criteria>

A: No bubbles and peeling occurred

B: Bubbles and / or slight peeling occurred

C: large amount of bubbles and / or peeling occurred

3. Estimation of glass transition temperature

The glass transition temperature (Tg) of each block or the like of the block copolymer was calculated according to the following equation.

<Formula>

1 / Tg =? Wn / Tn

In the above formula, Wn represents the weight fraction of the monomer used in each block and the like, and Tn represents the glass transition temperature which appears when the monomer used forms a homopolymer.

That is, in the above formula, the value obtained by dividing the weight fraction of the used monomer by the glass transition temperature (Wn / Tn) obtained when the monomer is formed into the homopolymer is calculated for each monomer on the right side to be.

4. Measuring the fin distance

The polarizing plates prepared in Examples and Comparative Examples were cut to have a width of about 35 mm and a length of about 400 mm and were laminated to a laminar alkali glass (width: 40 mm, length: 410 mm, thickness: To prepare a sample. Subsequently, the sample was held for 72 hours under constant temperature and humidity conditions of 25 DEG C and 50% relative humidity, and then left in an oven at 60 DEG C for 70 hours, and the fin distance was measured. The fin distance was the height of the sample on a flat bottom, with one end in contact with the floor and the other end at the bottom.

Production Example 1. Preparation of block copolymer (A)

0.1 g of EBiB (ethyl 2-bromoisobutyrate) and 14.2 g of methyl methacrylate (MMA) were mixed in 6.2 g of ethyl acetate (EAc). The flask containing the mixture was sealed with a rubber membrane, purged with nitrogen at about 25 캜 for about 30 minutes and stirred, and dissolved oxygen was removed through bubbling. Then 0.002 g of CuBr ₂ , 0.005 g of tris (2-pyridylmethyl) amine, and 0.017 g of V-65 (2,2'-azobis (2,4-dimethyl valeronitrile) And the reaction was initiated by immersing in a reaction tank at about 67 ° C (polymerization of the first block). A mixture of 155 g of butyl acrylate (BA) previously bubbled with nitrogen, 0.8 g of hydroxybutyl acrylate (HBA) and 250 g of ethyl acetate (EAc) at the time when the conversion of methyl methacrylate was about 75% Was added in the presence of nitrogen. Then, 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 carried out (polymerization of the second block). When the conversion of the monomer (BA) reaches 80% or more, the reaction mixture is exposed to oxygen, diluted with an appropriate solvent, and the reaction is terminated to prepare a block copolymer (in the above process, V- The reaction mixture was appropriately divided until the end of the reaction.

Production Examples 2 to 4. Preparation of Block Copolymers (A2 to A4)

Except that the raw materials and additives used in the polymerization of the first block were adjusted as shown in Table 1 and the kinds of raw materials and additives used in the polymerization of the second block were adjusted as shown in Table 2 A block copolymer was prepared in the same manner as in Preparation Example 1.

Block copolymer A1 A2 A3 A4
1st
block MMA ratio 100 80 60 70 BMA ratio 0 20 40 30 Tg (占 폚) 110 90 72 80 Mn (x 10000) 3.8 4.3 4.9 5.8 PDI 1.27 1.34 1.38 1.41 Second
block BA ratio 99.5 97 94 95 HBA ratio 0.5 3 6 5 Tg (占 폚) -47 -46.2 -47.5 -47 block
Public
coalescence Mn (x 10000) 20.6 22.3 24.1 20.4 PDI 1.7 1.8 2.1 2.1 First block: second block (weight ratio) 10.5: 89.5 10.1: 89.9 11.2: 88.8 34.7: 65.3 Ratio Units: parts by weight
BA: butyl acrylate (homopolymer Tg: about -45 ° C)
HBA: 4-hydroxybutyl acrylate (homopolymer Tg: about -80 ° C)
MMA: methyl methacrylate (homopolymer Tg: about 110 ° C)
BMA: butyl methacrylate (homopolymer Tg: about 27 ° C)
Tg: glass transition temperature
Mn: number average molecular weight
PDI: molecular weight distribution

Production Example 5. Preparation of random copolymer (B)

10 parts by weight of methyl methacrylate (MMA), 87.3 parts by weight of n-butyl acrylate, and 2.7 parts by weight of 4-hydroxybutyl acrylate were charged into a 1 L reactor equipped with a cooling device to easily regulate the temperature and nitrogen gas was refluxed , N-dodecyl mercaptan as a molecular weight regulator was added in an amount of 300 ppm, and 120 parts by weight of ethyl acetate was added as a solvent. Subsequently, nitrogen gas was purged for about 60 minutes to remove oxygen, and 0.1 part by weight of AIBN (azobisisobutyronitrile) as a reaction initiator was added while maintaining the temperature at 60 DEG C, and the mixture was reacted for about 8 hours to prepare a random copolymer. The number average molecular weight (Mn) of the prepared random copolymer (B) was about 93,000, and the molecular weight distribution (PDI) was about 4.6.

Example 1

Preparation of coating solution (crosslinkable composition)

A polyfunctional isocyanate crosslinking agent (Coronate L, number of isocyanate groups (B _NCO ): 3, molecular weight (B _MW ): about 741 g / mol, manufactured by NPU, Japan) was added to 100 parts by weight of the solid content of the block copolymer , 0.18 part by weight of a bifunctional isocyanate crosslinking agent having a polypropylene glycol unit (Sigma Aldrich, CAS No. 9057-91-4, number average molecular weight (Mn, C _Mn ): about 2300) and DBTDL (Dibutyltin dilaurate) , And ethyl acetate as a solvent were mixed to adjust the coating solids to about 30% by weight to prepare a coating solution (crosslinkable composition).

Production of adhesive polarizer

The prepared coating solution was coated on a release-treated surface of a poly (ethylene terephthalate) (MRF-38, manufactured by Mitsubishi) having a thickness of 38 탆 and subjected to release treatment so that the thickness after drying was about 23 탆, For about 3 minutes. After drying, a WV liquid crystal layer of a polarizing plate (TAC / PVA / TAC laminated structure: TAC = triacetyl cellulose, PVA = polyvinyl alcohol polarizing film) coated with a WV (Wide View) liquid crystal layer on one side was laminated on the above- The formed coating layer was laminated to prepare a pressure-sensitive polarizer.

Examples 1 and 7 and Comparative Examples 1 to 7

A crosslinkable composition (coating liquid) and a pressure-sensitive polarizing plate were prepared in the same manner as in Example 1, except that components and ratios were controlled as shown in Table 2 or 3 in the preparation of the crosslinkable composition (coating liquid).

Example One 2 3 4 5 6 7 polymer Kinds A1 A1 A1 A1 A2 A3 A4 content 100 100 100 100 100 100 100 Crosslinking agent (B) content 0.1 0.08 0.08 0.15 0.1 0.1 0.1 Cross-linking agent (C) content 0.18 0.26 0.56 0.26 0.18 0.18 0.18 M in equation 2 0.024 0.023 0.034 0.035 0.024 0.024 0.024 K of Equation 1 1.8 3.25 7 1.73 1.8 1.8 1.8 DBTDL content 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Content Unit: parts by weight
Crosslinking agent (B): Coronate L, manufactured by Japan NPU
Crosslinking agent (C): Tolylene 2,4-diisocyanate terminated poly (propylene glycol) (number average molecular weight: 2,300, Sigma Aldrich, CAS No. 9057-91-4)
DBTDL: dibutyltin dilaurate

Comparative Example One 2 3 polymer Kinds B B B content 100 100 100 Crosslinking agent (B) content 0.01 0.1 4 Cross-linking agent (C) content 0.01 0.18 0.01 M in equation 2 0.002 0.024 0.681 K of Equation 1 One 1.8 0.003 DBTDL content 0.1 0.1 0.1 Content Unit: parts by weight
Crosslinking agent (B): Coronate L, manufactured by Japan NPU
Crosslinking agent (C): Tolylene 2,4-diisocyanate terminated poly (propylene glycol) (number average molecular weight: 2,300, Sigma Aldrich, CAS No. 9057-91-4)
DBTDL: dibutyltin dilaurate

The physical property evaluation results of the above-mentioned Examples and Comparative Examples are shown in Tables 4 and 5 below.

Example One 2 3 4 5 6 7 Heat resistance durability A A A A A A A Wet heat resistance A A A A A A A Fringe distance (mm) 8 7 9 8 8 7 8

Comparative Example One 2 3 Heat resistance durability C B A Wet heat resistance C A A Fringe distance (mm) 5 18 24

Claims (13)

(A) a block copolymer having a first block having a glass transition temperature of 40 ° C or higher and a second block having a glass transition temperature of 0 ° C or lower; (B) a multifunctional isocyanate crosslinking agent having no polyalkylene oxide chain; And (C) a bifunctional isocyanate crosslinking agent having a polyalkylene oxide chain,
K in the following formula (1) is in the range of 0.5 to 100,
Wherein M in the following formula (2) is not less than 0.01:
[Equation 1]
K = C / B
[Equation 2]
M = (42 x B _NCO x B) / B _MW + (84 x C) / C _Mn
In formulas (1) and (2), B is the weight part of the (A) block copolymer of the crosslinking agent (B) and C is the weight part of the crosslinking agent (C) , B _NCO is the number of isocyanate groups in the crosslinking agent (B), B _MW is the molecular weight of the crosslinking agent (B), and C _Mn is the number average molecular weight of the crosslinking agent (C). The crosslinkable composition according to claim 1, wherein the block copolymer is a crosslinkable copolymer containing a crosslinkable functional group in the second block. The polyfunctional isocyanate crosslinking agent according to claim 1, wherein the polyfunctional isocyanate crosslinking agent (B) is at least one selected from the group consisting of tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoboron diisocyanate, tetramethylxylene diisocyanate and naphthalene diisocyanate Or a reaction product of at least one isocyanate compound selected from the above group and a polyol. 2. The crosslinkable composition according to claim 1, wherein the isocyanate crosslinking agent (C)
[Chemical Formula 1]

In the general formula (1), A is an alkylene group or an alkylidene group having 1 to 4 carbon atoms, Ar ₁ and Ar ₂ are aryl groups substituted with one isocyanate group, L ₁ and L ₂ are linkers, and n ranges from 2 to 60 Lt; / RTI &gt; The crosslinkable composition according to claim 1, wherein the isocyanate crosslinking agent (B) is contained in a proportion of 0.01 to 2 parts by weight based on 100 parts by weight of the block copolymer. The crosslinkable composition according to claim 1, wherein the (C) isocyanate crosslinking agent is contained in a proportion of 0.01 to 5 parts by weight based on 100 parts by weight of the block copolymer. The crosslinkable composition according to claim 1, further comprising a polyfunctional epoxy compound or a polyfunctional aziridine compound. The crosslinkable composition of claim 1, further comprising an ionic compound. 9. The crosslinkable composition according to claim 8, wherein the ionic compound comprises a metal salt and an ionic liquid. Optical film; And a pressure-sensitive adhesive layer which is present on one side or both sides of the optical film and which comprises the crosslinkable composition of claim 1 which is crosslinked. Polarizing film; And a pressure-sensitive adhesive layer which is present on one side or both sides of the polarizing film and which comprises the crosslinkable composition of claim 1 which is crosslinked. A pressure-sensitive adhesive optical film in which a pressure-sensitive adhesive layer is provided on an optical film through a primer layer,
Wherein the undercoat layer comprises a polymer,
Wherein the pressure-sensitive adhesive layer comprises a block copolymer having a first block having a glass transition temperature of 40 캜 or higher and a second block having a glass transition temperature of 0 캜 or lower; And a polyfunctional isocyanate crosslinking agent having a polyalkylene oxide chain. A display panel; And the adhesive type optical laminate of claim 10 or the adhesive type polarizing plate of claim 11 attached to one surface or both surfaces of the display panel.