TWI691568B - Adhesive composition, adhesive layer, optical member and image display device including thereof - Google Patents

Abstract

An adhesive composition, an adhesive layer, an optical member using the same, and an image display device using the same. The adhesive composition includes 100 parts by weight of an adhesive resin (A), and 0.1 parts by weight to 20 parts by weight of a silicone alkoxy oligomer (B) having an epoxy equivalent weight of 100 g/mol to 2000 g/mol and containing 5 wt% to 60 wt% of an alkoxy group, wherein the adhesive resin (A) includes at least one selected from the group consisting of an acrylic adhesive resin (A1), a urethane adhesive resin (A2) and a polyester adhesive resin (A3) prepared through polymerization of monomers not containing a carboxyl group.

Description

Next composition, next layer, optical member and shadow containing it Image display device

The present invention relates to an adhesive composition, an adhesive layer, an optical film, and a display device.

The liquid crystal panel of the liquid crystal display has optical members such as a polarizing plate containing a polarizer, an optical film for improving display quality, and the like. Such an optical member is attached to the liquid crystal panel via an adhesive.

For example, the optical member may be attached to the liquid crystal panel through an adhesive film in which an adhesive is deposited on one surface of the adhesive film in an adhesive layer. Such adhesive films are easy to handle and can be manufactured without the process of drying adhesives. In addition, when bonding failure (such as wrong bonding position or intrusion of foreign substances into the bonding interface) occurs during the bonding of the optical member containing the adhesive film to the liquid crystal display, the optical member can be bonded again after the optical member is peeled off the liquid crystal panel To the LCD panel. Through this process, it is possible to reduce the occurrence of failures and reuse expensive liquid crystal cells.

Recently, the demand for thin liquid crystal displays has increased in the art and such thin liquid crystal displays employ thin liquid crystal panels or thin optical members in order to obtain additional thickness reduction. However, since such a thin liquid crystal panel or thin optical member employs a glass substrate subjected to chemical etching or has a thin thickness, the use of a typical adhesive aimed at improving durability may cause the thin liquid crystal display to split or crack.

Therefore, an adhesive used for a thin liquid crystal panel or a thin optical member needs to have re-peelability (also referred to as reworkability) to prevent the formation of residues of the adhesive while allowing easy separation of the adhesive. In addition, the adhesive needs to have a certain degree of adhesion durability that can prevent the occurrence of failures (such as peeling or detachment in durability tests that are typically performed in the form of environmental durability tests through heating and humidification).

Therefore, although the adhesive used for the liquid crystal display needs to have both reworkability and adhesion durability, it is difficult for the typical technology to achieve this requirement.

For example, a polymer-type silane coupling agent that contains an acrylic polymer and has a siloxane main chain as the main chain and contains alkoxy groups, epoxy groups, and polyether groups in the side chain is known in the art. Pressure-sensitive adhesive composition (refer to Patent Document 1); pressure-sensitive adhesive composition containing acrylic polymer and silicon oligomer (refer to Patent Document 2 to Patent Document 4); and acrylic copolymer and silane coupling agent containing carboxyl group Pressure sensitive adhesive composition (refer to Patent Document 5 and Patent Document 6). However, these subsequent compositions of Patent Literature 1 to Patent Literature 6 are insufficient to ensure the reworkability and adhesion durability required for thin image display devices and thin optical members. (Prior Art Literature) (Patent Literature 1) JP H07-331206 A (Patent Literature 2) JP 2006-316256 A (Patent Literature 3) JP 2010-007044 A (Patent Literature 4) JP 2012-012537 A (Patent Literature 5) WO 2012/26456 A (Patent Literature 6) JP 2008-176173 A

【technical problem】

An aspect of the present invention is to provide an adhesive composition suitable for a thin image display device and a thin optical member while ensuring reworkability for ensuring easy peelability of the adhesive film and according to the heat and increase in the bonding state Wet durability test durability.

Another aspect of the present invention is to provide an adhesive layer formed of the adhesive composition as described above, an optical member containing the adhesive layer (such as an adhesive polarizer), and an image display device using the optical member. 【Technical Solution】

An embodiment of the present invention relates to an adhesive composition containing: 100 parts by weight of the adhesive resin (A); and 0.1 parts by weight to 20 parts by weight having an epoxy equivalent weight of 100 g/mol to 2000 g/mol and containing 5% by weight (wt%) to 60% by weight of alkoxy silicone alkoxy oligomer (B), wherein the adhesive resin (A) contains at least one selected from the group consisting of Who: Acrylic adhesive resin (A1), urethane adhesive resin (A2) and polyester adhesive resin (A3) are prepared by polymerization of monomers that do not contain carboxyl groups.

Another embodiment of the present invention relates to an adhesive layer formed of the adhesive composition as described above.

Yet another embodiment of the present invention relates to an optical member containing an optical film and an adhesive layer formed on at least one surface of the optical film.

Yet another embodiment of the present invention relates to an image display device containing at least one optical member as described above. 【Favourable Effects】

Embodiments of the present invention provide an adhesive composition suitable for a thin image display device and a thin optical member while ensuring reworkability for ensuring easy peelability of the adhesive film and according to the heating and humidification in the bonded state Durability of durability test.

Hereinafter, embodiments of the present invention will be described in detail. Next composition

An embodiment of the present invention relates to an adhesive composition containing: 100 parts by weight of an adhesive resin (A); and 0.1 to 20 parts by weight of an epoxy equivalent having an amount of 100 g/mol to 2000 g/mol and A silicone alkoxy oligomer (B) containing 5% by weight (wt%) to 60% by weight of alkoxy groups, wherein the adhesive resin (A) contains at least one selected from the group consisting of the following One: acrylic adhesive resin (A1), urethane adhesive resin (A2) and polyester adhesive resin (A3), which are prepared by polymerization of monomers that do not contain carboxyl groups. In the case of such characteristics, the subsequent composition can ensure a high level of reworkability and durability, thereby achieving advantageous characteristics of the liquid crystal display.

As used herein, the term "(meth)acrylate" generally refers to acrylate and methacrylate. In addition, (meth)-containing compounds, such as (meth)acrylic acid, also broadly refer to compounds having (meth) and compounds not containing (meth). For example, "(meth)acryloyl" includes acryloyl and methacryloyl. In addition, the term "(meth)acrylate" includes acrylate and methacrylate. The term "(meth)acrylic acid" includes acrylic acid and methacrylic acid.

As used herein, the term "resin" generally refers to oligomers, polymers, copolymers, and the like prepared by the polymerization of unit monomers. <Adhesive resin (A)>

Although the mechanism that can solve the problems of the present invention is evaluated as follows, it should be understood that the present invention is not limited thereto.

According to an embodiment of the present invention, then the resin (A) may not contain carboxyl groups or may contain a minimum amount of carboxyl groups. As used herein, the expression "adhesive resin (A) contains the least amount of carboxyl groups" means that the adhesive resin does not contain any carboxyl groups or only contains carboxyl groups in the form of terminal groups.

The adhesive resin (A) containing the least amount of carboxyl groups prevents the alkoxy groups of the silicone alkoxy oligomer (B) described below from reacting with the carboxyl groups at the side chain of the silicone alkoxy oligomer (B) Silanol groups are generated. Therefore, the adhesive resin (A) containing the least amount of carboxyl groups provides the effect of preventing the reduction of the amount of alkoxy groups that contribute to the improvement of reworkability due to modification to silanol groups. Therefore, the adhesive resin (A) provides the effect of preventing deterioration of the reworkability of the adhesive layer. In addition, the resin (A) prevents the amount of silanol groups having high reactivity from increasing, thereby preventing the reworkability from being deteriorated by the coupling reaction of the silanol groups on the surface of the glass contained in the liquid crystal display. In addition, the subsequent resin (A) is advantageous when applied to a liquid crystal display having an IPS panel that is vulnerable to acidic components of carboxyl groups.

In other words, the adhesive resin (A) according to the embodiment of the present invention is prepared to reduce the amount of carboxyl groups as much as possible (to minimize the amount of carboxyl groups). Here, the expression "to reduce the amount of carboxyl groups as much as possible" means that the adhesive resin is prepared so that the carboxyl groups are present in the form of terminal groups of the adhesive resin (A) (if present) or no carboxyl groups are present in the adhesive resin (A).

In one embodiment, the adhesive resin (A) may be composed of at least two substances selected from the group consisting of: acrylic adhesive resin (A1), urethane adhesive resin (A2), polyester adhesive Resin (A3) and combinations thereof are prepared by polymerization of monomers that do not contain carboxyl groups. In this embodiment, it is possible to minimize the amount of carboxyl groups contained in the subsequent resin (A). Therefore, the adhesive resin (A) can significantly improve the reworkability of the adhesive layer as compared with a resin containing a large amount of carboxyl groups.

In one embodiment, the resin (A) may then have a weight average molecular weight of 20,000 to 2,500,000.

For example, when the acrylic adhesive resin (A1) is used, the adhesive resin (A) may have a weight average molecular weight of 300,000 to 2,500,000 or 500,000 to 2,200,000. Within this range, the adhesive resin (A) can improve the durability of the adhesive layer.

For example, when the urethane adhesive resin (A2) and the polyester adhesive resin (A3) are used, the adhesive resin (A) may have a weight average molecular weight of 20,000 to 100,000 or 30,000 to 60,000. Within this range, the adhesive resin (A) can improve the durability of the adhesive layer.

Herein, the weight average molecular weight can be measured by the method described in the examples described below.

In one embodiment, the resin (A) may then have a viscosity of, for example, 100 mPa·s to 100,000 mPa·s, 300 mPa·s to 50,000 mPa·s, or 500 mPa·s to 30,000 mPa·s. Within this range, the subsequent resin (A) can provide a smooth coating layer after coating the subsequent composition while ensuring the thickness uniformity of the coating layer.

In one embodiment, the resin (A) may then contain hydroxyl groups. In this embodiment, the adhesive resin (A) can improve the durability of the adhesive layer. When using a hydroxyl-containing adhesive resin (A), especially with an isocyanate-based crosslinking agent, the adhesive resin (A) can further improve the durability of the adhesive layer by forming a network structure by crosslinking between the hydroxyl group and the isocyanate compound Sex. [Acrylic Adhesive (A1)]

The acrylic adhesive resin (A1) is a carboxyl-free monomer and can be prepared using a carboxyl-free monomer known in the art, but is not limited to a specific monomer. Specifically, the acrylic adhesive resin (A1) can be prepared by polymerizing the main chain (meth)acrylic monomer and the side chain monomer. (Main chain monomer)

The (meth)acrylic monomer used for the preparation of the acrylic adhesive resin (A1) may include alkyl (meth)acrylate, alkoxy (meth)acrylate, aryloxy (meth)acrylate, ( Aryl methacrylate and acrylate (meth)acrylate. These can be used alone or in combination thereof.

Specifically, the (meth)acrylic acid alkyl ester may be a (meth)acrylic acid ester containing a C ₁ to C ₂₀ alkyl group. Examples of the alkyl (meth)acrylate may include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylic acid Isobutyl ester, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate , Isononyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like.

Specifically, the alkoxy (meth)acrylate may be a (meth)acrylate containing a C ₁ to C ₂₀ alkylalkoxy group. Examples of the alkoxy (meth)acrylate may include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and the like.

Specifically, the aryloxy (meth)acrylate may be a (meth)acrylate containing C ₁ to C ₂₀ aryloxy. The aryloxy (meth)acrylate may include, for example, phenoxyethyl (meth)acrylate and the like. In addition, the aryl (meth)acrylate containing aromatic groups and heterocyclic groups disclosed in paragraphs "0036" to "0037" of Japanese Patent Publication No. 2010-275524 A can also be used as (meth) Acrylic monomer. These (meth)acrylic monomers can be used alone or in combination.

Specifically, the acyl (meth)acrylate may be a (meth)acrylate containing a C ₁ to C ₂₀ acyl group. Specifically, such an acyl (meth)acrylate may be a (meth)acrylate containing a C ₁ to C ₁₀ unsaturated acyl group, for example a (meth)acrylic group containing an average carbon number of 3 to 9 (a Radical) acrylate. According to this embodiment, the adhesive resin can further improve the heating durability and moisture-heat durability of the adhesive layer. (Side chain monomer)

Examples of the side chain monomer used in the preparation of the acrylic adhesive resin (A1) may include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,6-hexanediol Mono(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate Ester, trimethylolethane di(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-benzene (meth)acrylate Oxypropyl, 4-hydroxycyclohexyl (meth)acrylate, N-2-hydroxyethyl (meth)acrylamide, cyclohexane dimethanol monoacrylate and the like. In addition, the monomer that provides the side chain may include a compound containing (meth)acrylic acid and a glycidyl group (such as alkyl glycidyl ether, aryl glycidyl ether, glycidyl (meth)acrylate, and the like) And vinyl compounds (such as vinylpyridine, styrene or the like) by addition reaction. These can be used alone or in combination thereof.

Specifically, when a monomer having at least one hydroxyl group is used, the hydroxyl group may be provided to the subsequent resin (A). In this embodiment, the adhesive can further improve the durability of the adhesive layer. Examples of the monomer having at least one hydroxyl group may include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-2-hydroxyethyl (meth)acrylamide, and cyclohexyl Alkyl dimethanol monoacrylate. In one embodiment, at least one of 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and N-2-hydroxyethyl (meth)acrylamide may be used. In this embodiment, the adhesive resin exhibits excellent cross-linking activity and compatibility with other resins contained in the adhesive composition, thereby further improving durability. (Preparation of acrylic adhesive resin (A1))

The acrylic adhesive resin (A1) can be prepared by any typical method known in the art using a polymerization initiator (such as solution polymerization, emulsion polymerization, suspension polymerization, inverse suspension polymerization, film polymerization, and spray polymerization). Polymerization control can be performed by thermal insulation polymerization, temperature controlled polymerization, or isothermal polymerization. In addition to using a polymerization initiator to initiate polymerization, irradiation, electromagnetic radiation, and UV radiation may be performed to initiate polymerization. In these methods, solution polymerization using a polymerization initiator can be used because this method can easily adjust the molecular weight while reducing impurities. After adding 0.01 parts by weight to 0.50 parts by weight of the polymerization initiator based on 100 parts by weight of the original monomer (main chain monomer and side chain monomer), for example, ethyl acetate, toluene or methyl ethyl ketone can be used as The solvent performs solution polymerization under a nitrogen atmosphere at a reaction temperature of, for example, 60°C to 90°C for 3 hours to 10 hours.

The polymerization initiator may include, for example, an azo compound such as azobisisobutyronitrile (AIBN), 2-2′-azobis(2-methylbutyronitrile), azobiscyanovaleric acid, and the like; Organic peroxides, such as third butyl peroxypivalate, third butyl peroxybenzoate, third butyl peroxy-2-ethylhexanoate, di-third butyl peroxide Compounds, cumene hydroperoxide, benzoyl peroxide, tert-butyl hydroperoxide and the like; and inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate And its analogs. These starters can be used alone or in combination.

In the preparation of the acrylic adhesive resin (A1), the main chain monomer and the side chain monomer may be present in a weight ratio of, for example, 99.99:0.01 to 80:20 or 99.9:0.1 to 90:10. Within this range, the acrylic adhesive resin (A1) can exhibit further improved adhesion. [Urethane adhesive resin (A2)]

The urethane adhesive resin (A2) can be prepared by the reaction of polyester polyol and/or polyether polyol and an isocyanate compound. (Polyester polyol)

Any polyester polyol known in the art can be used without limitation as the polyester polyol used in the preparation of the urethane adhesive resin (A2). For example, the polyester polyol used in the preparation of the urethane-adhesive resin (A2) can be prepared from an acid component (such as polycarboxylic acid) and a diol component or a polyol component.

The acid component may include, for example, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and the like.

The glycol component may include, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dihydroxy Methylpentane, polyethylene oxide glycol, polypropylene oxide glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol, and the like.

The polyol component may include, for example, glycerin, trimethylolpropane, pentaerythritol, and the like.

In addition, polyester multi-components obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), poly(valerolactone) and the like can also be used alcohol.

In the polyester polyol prepared as above, the polyester polyol having two or three functional groups can further improve the adhesive strength of the urethane adhesive resin (A2).

In addition, any polyester polyol selected from a polyester polyol having a low molecular weight and a polyester polyol having a high molecular weight can be used to prepare a urethane adhesive resin without being limited to a specific number average molecular weight ( A2). Specifically, in consideration of the number of its functional groups, the polyester polyol used in the urethane adhesive resin (A2) may have a number average molecular weight of 1,000 to 5,000. Such polyester polyols can improve the cohesion of the urethane adhesive resin (A2) while reducing its gelation by maintaining suitable reactivity. More specifically, the polyester polyol used in the urethane-adhesive resin (A2) may have a number average molecular weight of 1,000 to 3,500. In this case, the polyester polyol can improve the cohesion of the urethane adhesive resin (A2) while reducing gelation by maintaining suitable reactivity.

In addition, if necessary, the polyester polyol used in the preparation of the urethane-adhesive resin (A2) may additionally use diols (such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylene Ethyl pentanediol, glycerol, trimethylolpropane, pentaerythritol and the like) and polyamines (such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, xylylene Diamines and their analogues). (Polyether polyol)

Any polyether polyol known in the art can be used without limitation as the polyether polyol used in the preparation of the urethane adhesive resin (A2). For example, polyalkylene glycol adducts (molecular weight 100 to 5,500) of polyols can be used. Polyols may contain, for example, aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol (butanediol), neopentyl glycol, and the like; triols such as glycerol, Trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3 ,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4 ,5-pentanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerol, pentaglycerin (pentaglycerin), 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolpropane and the like; tetrahydric alcohols such as erythritol, pentaerythritol, 1,2,3,4-pentaerythritol, 2,3,4, 5-Hexaerythritol, 1,2,3,5-pentaerythritol, and 1,3,4,5-hexanetetraol; pentavalent alcohols, such as forsythol, arabitol, xylitol, and the like Hexahydric alcohols, such as sorbitol, mannitol, iditol, and the like.

Among them, dihydric to tetrahydric alcohols such as propylene glycol, 1,4-butanediol, and glycerin can be used. In this case, it is possible to achieve suitable control of the reactivity of the polyether polyol used in the preparation of the urethane adhesive resin (A2).

Polyether polyols having two or three functional groups and prepared from any of the polyols described above can be used to prepare the urethane adhesive resin (A2). Such polyether polyols provide advantages in controlling the reactivity in the preparation of the urethane adhesive resin (A2).

In addition, any polyether polyol selected from polyether polyols having a low molecular weight and polyether polyols having a high molecular weight can be used to prepare urethane adhesive resins without being limited to a specific number average molecular weight ( A2). Specifically, in consideration of the number of its functional groups, the polyether polyol used in the urethane-adhesive resin (A2) may have a number average molecular weight of 1,000 to 5,000. Such polyether polyols can improve the cohesion of the urethane adhesive resin (A2) while reducing its gelation by maintaining suitable reactivity. More specifically, the polyether polyol used in the urethane adhesive resin (A2) may have a number average molecular weight of 1,000 to 3,500. In this case, the polyether polyol can improve the cohesion of the urethane adhesive resin (A2) while reducing gelation by maintaining suitable reactivity. (Isocyanate compound)

Any isocyanate compound selected from aromatic polyisocyanate, aliphatic polyisocyanate, any aromatic aliphatic polyisocyanate, alicyclic polyisocyanate, and the like known in the art may be used as the amine acid without limitation. The isocyanate compound used in the preparation of the ester adhesive resin (A2). Examples of the aromatic polyisocyanate may include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate , 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dimethoxy Aniline diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, and the like. Examples of the aliphatic polyisocyanate may include trimethylene diisocyanate, tetraisocyanate Methylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, Dodecyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like. Examples of aromatic aliphatic polyisocyanates may include ω,ω'-diisocyanate-1,3- Xylene, ω,ω'-diisocyanate-1,4-xylene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1, 3-tetramethylxylylene diisocyanate and the like. Examples of alicyclic polyisocyanates may include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane Diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4 , 4'-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane and the like.

Among the aforementioned isocyanate compounds, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) The crosslinking characteristics of the adhesive resin (A) can be further improved. (Preparation of Urethane Adhesive Resin (A2))

As described above, the urethane adhesive resin (A2) according to the present invention can be prepared by reacting polyester polyol and/or polyether polyol with an isocyanate compound. For example, the urethane adhesive resin (A2) can be prepared by reacting polyester polyol, polyether polyol, and isocyanate compound.

When polyester polyol and polyether polyol are used together, the molar ratio of polyester polyol to polyether polyol (polyester polyol: polyether polyol) may be, for example, 10:90 to 90:10, or 30:70 to 70:30. Within this range, the urethane adhesive resin (A2) can exhibit further improved compatibility.

Based on 100 parts by weight of the total polyol component (for example, if polyester polyol and polyether polyol are used together, the total polyol component means the sum of polyester polyol and polyether polyol), the isocyanate compound can be For example, 1 to 30 parts by weight, or 3 to 20 parts by weight is used. Within this range, the isocyanate compound can be substantially completely reacted and the hydroxyl group can remain in the molecule of the carbamate-based adhesive resin. Therefore, the hydroxyl group can form a network structure with the isocyanate-based crosslinking agent, thereby further improving the durability of the adhesive layer.

Any catalyst known in the art can be used to prepare the urethane adhesive resin (A2). Examples of the catalyst may include tertiary amine compounds, organometallic compounds (such as tin compounds and non-tin compounds), and the like.

Examples of tertiary amine compounds may include triethylamine, triethylenediamine, 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU), and the like.

Examples of tin compounds may include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, sulfide Dibutyltin, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethanol, tributyltin ethanol, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate, and Its analogs.

Examples of non-tin compounds may include titanium compounds, such as dibutyl titanium dichloride, tetrabutyl titanate, and titanium tributoxide; lead compounds, such as lead oleate, 2-ethylhexanoic acid Lead, lead benzoate and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc Compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium compounds such as zirconium naphthenate, and the like.

These catalysts can be used alone or in combination.

In one embodiment, when polyester polyol and polyether polyol are used together, two or more catalysts may be used together. The use of two or more catalysts allows easy control of the difference in reaction rate between polyols.

The combination of the two catalysts may include tertiary amine/organometallic catalysts, tin/non-tin catalysts, and non-tin/non-tin catalysts, but is not limited thereto. In one embodiment, a non-tin-based/non-tin-based catalyst combination may be used, such as a combination of lead 2-ethylhexanoate and lead naphthenate. Specifically, in terms of parts by weight, the weight ratio of lead 2-ethylhexanoate to lead naphthenate may be less than 1 (that is, the amount of lead 2-ethylhexanoate is less than the amount of lead naphthenate), For example, 0.2 to 0.8:1. Within this range, it is possible to more easily control the difference in reaction rate between polyols.

The catalyst can be used in an amount of 0.01 parts by weight to 1.0 parts by weight based on 100 parts by weight of polyol and isocyanate compound.

In the preparation of the urethane adhesive resin (A2), any solvent known in the art may be used without limitation. Examples of the solvent may include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, and the like. In some embodiments, the solvent can be ignored depending on the polyol or isocyanate compound.

The urethane adhesive resin (A2) can be prepared at a reaction temperature of 100°C or lower, for example, 85°C to 95°C. Within this range, the reaction temperature is advantageous in controlling the reaction rate or cross-linked structure of the carbamate-adhesive resin, so that the carbamate-adhesive resin (A2) having a predetermined molecular weight and the desired chemical structure can be easily prepared .

In addition, the reaction may be carried out until the remaining isocyanate groups disappear while checking the remaining amount via, for example, an infrared spectrophotometer (IR), but is not limited to a specific reaction time. [Polyester adhesive resin (A3)]

The polyester adhesive resin (A3) can be prepared by esterification using a polyol component and a carboxylic acid component.

In the preparation of the polyester adhesive resin (A3), any polyol component known in the art may be used without limitation. For example, the polyol component may include linear aliphatic diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Diol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; and aliphatic diols with hydrocarbon side chains, such as neopentyl glycol, 2-methyl-1 ,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol , 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,3,5-tri Methyl-1,3-pentanediol, 2-methyl-1,6-hexanediol, and the like. These can be used alone or in combination thereof. In some embodiments, the polyol component may include C ₂ to C ₆ linear aliphatic diols, specifically, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, or have C An aliphatic diol with ₁ to ₄ C ₄ hydrocarbon side chains. Specifically, when neopentyl glycol is used as a polyol component, it is possible to ensure a good balance between the initial adhesive force, mechanical strength, and heat resistance of the adhesive composition.

In addition, in the preparation of the polyester adhesive resin (A3), the polyol component may optionally contain a small amount of polyether diol or ternary or higher polyol. Examples of polyether diols or ternary or higher polyols are disclosed in, for example, paragraphs "0039" to "0040" of Japanese Patent Laid-Open Publication No. 2007-0045913A.

In the preparation of the polyester adhesive resin (A3), any carboxylic acid component known in the art can be used without limitation. For example, the carboxylic acid component may include aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and p-oxygen Benzoic acid; saturated dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and aliphatic dicarboxylic acids, including decane dicarboxylic acid, octadecane dicarboxylic acid and Analogs; saturated dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, hexahydrophthalic acid, and dimerization acid. These can be used alone or in combination thereof.

In the preparation of polyester adhesive resin (A3), the carboxylic acid component may contain a small amount of ternary or more ternary carboxylic acids as needed, such as trimellitic acid, trimesic acid, pyromellitic acid, 1,2 , 4-butane tricarboxylic acid and 1,2,5-hexane tricarboxylic acid. Among them, when the aromatic dicarboxylic acid, specifically terephthalic acid or isophthalic acid, or the aliphatic dicarboxylic acid having a carbon number of 6 to 12 (including the carbon in the carboxyl group), specifically sebacic acid When used as a carboxylic acid component, it is possible to ensure a good balance between the initial adhesive force, mechanical strength, and heat resistance of the adhesive composition. (Preparation of polyester adhesive resin (A3))

In the preparation of the polyester adhesive resin (A3), in consideration of the balance between the polyol component and the carboxylic acid component, the polyol component may be mixed in an amount of 1 equivalent or more per equivalent of the carboxylic acid component. For example, the polyol component may be mixed in an amount of 1.2 to 2.0 equivalents per equivalent of the carboxylic acid component. Within this range, the carboxylic acid component can be completely reacted in the polyester adhesive resin (A3) to ensure reworkability while allowing hydroxyl groups to remain in the polyester adhesive resin (A3) to improve the durability of the adhesive layer.

In the preparation of the polyester adhesive resin (A3), any catalyst known in the art can be used. Examples of the catalyst may include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; antimony-based catalysts such as antimony trioxide; germanium-based catalysts such as germanium oxide; zinc acetate; manganese acetate; dibutyltin oxide , And its analogs. These can be used alone or in combination thereof.

In the preparation of the polyester adhesive resin (A3), based on 100 parts by weight of the total polymerization component (the total amount of the polyol component and the carboxylic acid component), the catalyst used for the esterification may be 0.01 parts by weight to 1.0 parts by weight The amount used. Within this range, it is possible to achieve sufficient esterification while reducing the reaction rate and reducing side reactions.

In the preparation of the polyester adhesive resin (A3), any solvent known in the art can be used without limitation. Examples of the solvent may include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, and the like. In some embodiments, the solvent may be omitted depending on the type of polyol or carboxylic acid component used in the preparation of the polyester-adhesive resin (A3), or the solvent may be added in order to adjust the concentration.

The polyester adhesive resin (A3) can be prepared at a reaction temperature of, for example, 100°C to 400°C, 120°C to 300°C, or 150°C to 280°C.

In the preparation of polyester adhesive resin (A3), the reaction pressure is slowly reduced from normal pressure. The preparation of the polyester adhesive resin (A3) can be carried out in the reaction system under a pressure of, for example, 10 Pa to 1000 Pa. At this time, the decompression can be performed through several stages over time.

The reaction time can be appropriately determined depending on the type of polyol or carboxylic acid component, the reduced pressure conditions, and the like. For example, the polyester-adhesive resin (A3) can be obtained by reacting for 0.5 hour to 20 hours or 1 hour to 10 hours. <Silicone alkoxy oligomer (B)>

Silicone alkoxy oligomers are low-molecular-weight silicone resins with a polyorganosiloxane main chain, in which the molecular ends or side chains are blocked by alkoxy silane groups.

The silicone alkoxy oligomer (B) may contain at least one organic substituent selected from the group consisting of a methyl group, a phenyl group, an epoxy group, a mercapto group, an amine group, a methacryloyl group, and an acryloyl group. In one embodiment, the silicone alkoxy oligomer (B) may contain at least one of a methyl group and an epoxy group.

In addition, the silicone alkoxy oligomer (B) may contain methoxy and/or ethoxy as alkoxy.

Further, in some embodiments, the alkoxy group may be present in the silicone alkoxy oligomer (B in an amount of, for example, 5 to 60% by weight, 10 to 55% by weight, or 15 to 50% by weight) )in. Within this range, when the silicone alkoxy oligomer (B) is used together with the acrylic adhesive resin (A1) as the adhesive resin (A), the adhesive composition can ensure processability and reworkability. In addition, when the urethane adhesive resin (A2) or the polyester adhesive resin (A3) is used as the adhesive resin (A) together with the silicone alkoxy oligomer (B), the silicone alkoxy oligomer The substance (B) may contain a certain amount of alkoxy groups within the above range, but is not limited thereto.

As for the silicone alkoxy oligomer (B), any silicone alkoxy oligomer obtained through synthesis or from a commercially available product can be used without limitation, as long as the silicone alkoxy oligomer can satisfy the ring Requirements for oxygen equivalent and alkoxy groups in the above range.

The silicone alkoxy oligomer (B) can be prepared by hydrolyzing or condensing a silane coupling agent having an epoxy group and an alkoxy group and an alkoxy silane in the presence of an acid or the like.

Examples of the silane coupling agent having an epoxy group and an alkoxy group used in the preparation of the silicone alkoxy oligomer (B) may include 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3- Glycidoxypropyltriethoxysilane, but not limited thereto.

Examples of the alkoxysilane used in the preparation of the silicone alkoxy oligomer (B) may include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyl Triethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxy Silane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and trifluoropropyltrimethoxysilane, but not limited thereto.

In order to meet the required conditions for the epoxy equivalent and the amount of alkoxy groups in the preparation of the silicone alkoxy oligomer (B), the silane coupling agent and alkoxy groups having epoxy groups and alkoxy groups can be suitably adjusted The mixing ratio of silane (for example, molar ratio).

In addition, in the preparation of the silicone alkoxy oligomer (B), any known solvent such as methanol or ethanol can be suitably used.

In the preparation of silicone alkoxy oligomer (B), the reaction temperature can be adjusted depending on the raw materials. For example, the silicone alkoxy oligomer (B) can be prepared by reaction at room temperature. In addition, the reaction time can also be adjusted in the range of, for example, 0.5 hours to 5 hours depending on the raw materials.

Examples of commercially available products of silicone alkoxy oligomers (B) satisfying the required conditions of epoxy equivalent and alkoxy groups may include X-41-1053 (having an epoxy equivalent of 830 g/mol and Contains 50% by weight of alkoxy groups, X-41-1059A (with an epoxy equivalent of 350 g/mol and contains 42% by weight of alkoxy groups), and X-41-1056 (with an epoxy of 280 g/mol Equivalent and contains 27% by weight of alkoxy groups) (all can be purchased from Shin-Etsu Chemical Co. Ltd.).

The silicone alkoxy oligomer (B) may have an epoxy equivalent weight of, for example, 100 g/mol to 2,000 g/mol. For example, the silicone alkoxy oligomer (B) may have an epoxy equivalent weight of 200 g/mol to 1,500 g/mol, or 250 g/mol to 1,200 g/mol. Within this range, the adhesive composition can ensure a high level of reworkability and durability of the adhesive layer.

In one embodiment, when an acrylic adhesive resin (A1) is used as the adhesive resin (A), despite its improved durability, the silicone alkoxy oligomer (B) having an epoxy equivalent of less than 100 g/mol The reworkability improvement of the following composition cannot be achieved. On the other hand, despite its improved reworkability, the silicone alkoxy oligomer (B) having an epoxy equivalent of more than 2,000 g/mol adversely affects the durability of the subsequent composition.

When the urethane adhesive resin (A2) or the polyester adhesive resin (A3) is used as the adhesive resin (A) together with the silicone alkoxy oligomer (B), it can be used without limitation Any silicone alkoxy oligomer (B) within the epoxy equivalent range.

The silicone alkoxy oligomer (B) may have a number average molecular weight of, for example, 200 to 50,000, 300 to 10,000, or 500 to 5,000. Within this range, the silicone alkoxy oligomer (B) is advantageously used to prepare a durable and reprocessable adhesive composition. Here, the number average molecular weight can be measured by the method set forth in the examples described below.

In the adhesive composition, the silicone alkoxy oligomer (B) may be present in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the adhesive resin (A). If the amount of the silicone alkoxy oligomer (B) is less than 0.1 parts by weight, then the composition cannot ensure reworkability. If the amount of the silicone alkoxy oligomer (B) is greater than 20 parts by weight, when applied to a polarizing plate and the like, the composition may then exhibit deterioration in durability under moist heat conditions, thereby deteriorating the degree of polarization . For example, the silicone alkoxy oligomer (B) may be present in an amount of 0.3 to 10 parts by weight, or 0.5 to 5 parts by weight. Within this range of the silicone alkoxy oligomer (B), the subsequent composition can improve reworkability and durability while ensuring reworkability and durability. <Crosslinking agent (C)>

In some embodiments, the subsequent composition may further contain a cross-linking agent (C). Therefore, the crosslinking agent is used together with the acrylic adhesive resin (A1) and the silicone alkoxy oligomer (B) to further improve the durability.

In the adhesive composition, based on 100 parts by weight of the adhesive resin (A), the crosslinking agent (C) may be 0.001 to 30 parts by weight, for example, 0.01 to 20 parts by weight, or 0.05 to 10 parts by weight The amount exists. Within this range, the composition can then exhibit further improved durability.

The crosslinking agent (C) may be an isocyanate compound, a peroxide, a carbodiimide compound, a titanium coupling agent, a zirconium compound, or a metal aluminum chelate compound. Among them, when at least one of the isocyanate compound and the peroxide is used as a crosslinking agent, the adhesive composition can ensure further improved durability of the adhesive layer. [Isocyanate compound]

Examples of the isocyanate compound suitable for use as the crosslinking agent (C) may include aromatic diisocyanates such as triaryl isocyanate, dimer acid diisocyanate, 2,4-toluene diisocyanate (2,4-TDI), 2,6-Toluene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4 '-MDI), 1,4-phenylene diisocyanate, xylene diisocyanate (XDI), tetramethyl xylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI) and its analogs; aliphatic diisocyanates, such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI ) And its analogues; alicyclic isocyanates, such as trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H6-XDI (hydrogen-added XDI), H12-MDI (hydrogen-added MDI) and its analogues; the aforementioned diisocyanate carbodiimide modified diisocyanate and its analogues; and its isocyanurate modified diisocyanate and its analogues. These can be used alone or in combination thereof. Alternatively, these can be used with peroxides.

In addition, adducts of these isocyanate compounds and polyol compounds (such as trimethylolpropane) or biuret or isocyanurate of isocyanate compounds can be suitably used.

The isocyanate-based crosslinking agent (C) can be obtained by synthesis or from commercially available products. Commercial products of isocyanate-based crosslinking agent (C) may include, for example, Coronate ^® L, Coronate ^® HL, Coronate ^® HX, Coronate ^® 2030, Coronate ^® 2031 (all available from Japan Polyurethane Industry Co., Ltd. (Nippon Polyurethane Industry Co., Ltd.)); Takenate ^® D-102, Takenate ^® D-110N, Takenate ^® D-200, Takenate ^® D-202 (all available from Mitsui Chemicals Inc. )); Duranate ^® 24A-100, Duranate ^® TPA-100, Duranate ^® TKA-100, Duranate ^® P301-75E, Duranate ^® E402-90T, Duranate ^® E405-80T, Duranate ^® TSE-100, Duranate ^® D-101 And Duranate ^® D-201 (all available from Asahi Kasei Corporation); Sumidur ^® N-75, N-3200 and N-3300 (all available from Sumiga Bayeryl Carbamate Company (Sumica Bayer Urethane Co., Ltd.)), and the like. Specifically, Coronate ^® L, Coronate ^® HL, Coronate ^® HX, Takenate ^® D-110N, Duranate™ 24A-100 and Duranate ^® TPA-100 are preferred; and Coronate ^® L, Coronate ^® HX and Duranate™ 24A-100 Better.

When the isocyanate compound is used as the crosslinking agent (C), then the resin (A) preferably contains a hydroxyl group. In this embodiment, the hydroxyl and isocyanate compounds form a network structure, thereby improving the durability of the adhesive composition. [peroxide]

Any peroxide may be used as the peroxide suitably used as the crosslinking agent (C), as long as the peroxide can generate groups to achieve crosslinking of the subsequent composition. Specifically, when a peroxide having a one-minute half-life temperature of, for example, 80°C to 160°C, or 90°C to 140°C is used as the crosslinking agent, then the composition may have further improved processability or stability. Peroxide half-life is an index indicating the decomposition rate of peroxide, and means the period of time until the remaining amount of peroxide reaches half. The decomposition temperature or half-life of peroxide is described in the manufacturer’s catalog and the like, such as "Organic Peroxide Catalog (Organic Peroxide Catalog), 9th Edition (May 2003)", NOF Corporation (NOF Corporation).

Examples of such peroxides may include bis(2-ethylhexyl) peroxydicarbonate (one-minute half-life temperature: 90.6°C), bis(4-third butylcyclohexyl) peroxydicarbonate (One-minute half-life temperature 92.1°C), bis-dibutyl peroxydicarbonate (one-minute half-life temperature: 92.4°C), third-butyl peroxyneodecanoate (one-minute half-life temperature: 103.5°C), over Third hexyl oxypivalate (one-minute half-life temperature: 109.1°C), third butyl peroxypivalate (one-minute half-life temperature: 110.3°C), dilaurate peroxide (one-minute half-life temperature: 116.4°C), di-n-octyl peroxide (one-minute half-life temperature: 117.4°C), peroxy-2-ethylhexanoic acid 1,1,3,3-tetramethylbutyl ester (one-minute half-life temperature: 124.3 ℃), bis(4-methylbenzyl) peroxide (one-minute half-life temperature: 128.2°C), dibenzoyl peroxide (one-minute half-life temperature: 130.0°C) and third butyl peroxy group Butyrate (one-minute half-life temperature: 136.1°C), and bis(4-tert-butylcyclohexyl) peroxydicarbonate, dilauryl peroxide, and Dibenzoyl peroxide. Specifically, in terms of decomposition temperature, bis(4-tert-butylcyclohexyl) peroxydicarbonate is preferably used. These can be used alone or in combination thereof. In addition, peroxide-based crosslinking agents can be used together with the isocyanate compounds described above. [Carbodiimide compound]

As the crosslinking agent (C), for example, carbodiimide compounds disclosed in paragraphs "0039" to "0046" of Japanese Patent Publication No. 2012-246444 A or compounds containing these carbodiimide compounds may be suitably Use, but not limited to these. [Titanium coupling agent]

As the crosslinking agent (C), for example, the titanium coupling agent disclosed in paragraph "0072" of Japanese Patent Publication No. 2014-085616 A or compounds containing these titanium coupling agents can be suitably used, but are not limited to these. [Zirconium compound]

As the crosslinking agent (C), for example, the zirconium compound disclosed in paragraph "0073" of Japanese Patent Publication No. 2014-085616 A or a compound containing these zirconium compounds can be suitably used, but is not limited to these. [Metal aluminum chelate]

As the cross-linking agent (C), for example, the metal aluminum chelate compounds disclosed in paragraph "0058" of Japanese Patent Publication No. 2012-229373 A or compounds containing these metal aluminum chelate compounds can be suitably used, but not Limited to these. <Silane coupling agent (D)>

In one embodiment, the composition may further contain a silane coupling agent (D) to improve durability.

Silane coupling agent (D) refers to a compound that does not have a siloxane bond and has at least two different reactive groups per molecule, and must be distinguished from a silicone alkoxy oligomer (B).

Examples of the silane coupling agent (D) may include methyl trimethoxy silane, dimethyl dimethoxy silane, trimethyl methoxy silane, n-propyl trimethoxy silane, ethyl trimethoxy silane, di Ethyl diethoxysilane, n-butyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexyl Methyldimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, β-(3,4 -Epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyl diethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl Methyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N-β-(aminoethyl)-γ- Aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl Triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyl Trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis-(3-(triethoxysilane)propyl) tetrasulfide, γ -Isocyanate propyl triethoxysilane and the like, but not limited to these. Alternatively, by using a silane coupling agent having functional groups such as epoxy groups (glycidoxy groups), amine groups, mercapto groups, and (meth)acryloyl groups with functional groups exhibiting reactivity with respect to these functional groups The hydrolyzed silane-containing compound obtained by reacting the silane coupling agent, other coupling agent, or polyisocyanate at a specific ratio with respect to each of the functional groups.

The silane coupling agent can be synthesized or selected from commercially available products. Examples of commercially available products of silane coupling agent may include KBM-303, KBM-403, KBE-402, KBE-403, KBE-502, KBE-503, KBM-5103, KBM-573, KBM-802, KBM-803 , KBE-846, KBE-9007 (all can be purchased from Confidence Chemical Co., Ltd.) and their analogs.

These silane coupling agents can be used alone or in combination.

In one embodiment, the silane coupling agent (D) may be present in an amount of 0.0001 parts by weight to 10 parts by weight based on 100 parts by weight of the adhesive resin (A). For example, when the silane coupling agent is present in an amount of 0.001 to 5 parts by weight or in an amount of 0.01 to 3 parts by weight, it is possible to further improve the durability of the adhesive layer. {application}

The subsequent composition according to the invention can be used in a wide range of applications. For example, the composition can then be suitably used for optical members, such as optical films and the like. In particular, when applied to a thin soft optical film, the composition can then be used more suitably. Examples of such optical films may include polarizing plates, retardation plates, optical compensation films (such as viewing angle increasing films for improving the viewing angle of liquid crystal monitors), brightness enhancement films for improving the contrast of displays, and these plates and films. Stacked structure.

According to the present invention, the adhesive composition may be provided in the form of an adhesive layer, an optical member manufactured by forming an adhesive layer on an optical film, an optical member or an polarizing plate realized by the optical member, or used in a liquid crystal display, Image display device with electro-optical components applied to electro-luminescence display, plasma display panel (PDP) and the like. <Next Layer>

Other embodiments of the present invention provide an adhesive layer formed of the adhesive composition as described above.

In one embodiment, the adhesive layer may be formed by coating the adhesive composition described above on one surface of the substrate or the release film, followed by drying to remove the solvent. In the coating of the subsequent composition, at least one solvent may be appropriately added to the subsequent composition.

The separator described below can be used as a substrate coated with an adhesive layer.

The composition can then be applied by various methods known in the art. For example, the coating method may include roll coating, contact roll coating, gravure coating, reverse coating, roll brush, spray coating, dip roll coating, bar coating, blade coating, air knife coating, curtain coating, convex Edge coating and extrusion coating using a die coater, but not limited to these.

Any suitable drying method may be selected depending on the purpose in order to dry the solvent in the subsequent composition. For example, the coating can be dried by heating. For example, the heating temperature for drying may be in the range of 40°C to 200°C, 50°C to 180°C, or 70°C to 170°C. Within this heating temperature range, it is possible to obtain an adhesion layer exhibiting good adhesion characteristics.

The drying time can be appropriately determined as required. For example, drying may be performed for 5 seconds to 20 minutes, 5 seconds to 10 minutes, or 10 seconds to 5 minutes.

The subsequent layer may have a thickness (dry thickness) suitably determined depending on the purpose. For example, when the adhesive layer is applied to the optical film, the adhesive layer may be formed to a thickness of 1 micrometer to 100 micrometers, 5 micrometers to 50 micrometers, or 10 micrometers to 30 micrometers. Within this range, the adhesive layer can provide a thin optical film while improving durability.

In one embodiment, as measured according to JIS Z0237, under conditions of 23° C., 50% relative humidity (RH), a peel angle of 180°, and a peel rate of 300 mm/min, the subsequent layer may have Initial adhesion strength of 0.2 N/25 mm to 1.6 N/25 mm. Within this adhesive strength range, the adhesive layer can ensure a good balance between actual reworkability and adhesive strength. The initial adhesion strength of the subsequent layer can be measured by measuring the reworkability in the examples described below.

In one embodiment, as in accordance with JIS Z0237, under the conditions of 23°C, 50% RH, 180° peel angle, and 300 mm/min peel rate, samples subjected to heat treatment for 48 hours under dry conditions at 50°C As measured, the bonding layer may have a bonding strength of 0.3 N/25 mm to 2.5 N/25 mm after heating. Within this adhesive strength range, the adhesive layer can ensure a balance between actual reworkability and adhesive strength. The subsequent strength of the subsequent layer can be measured by measuring the reworkability in the examples described below.

In one embodiment, calculated by Equation 1, the subsequent layer may have a reduction in transmittance of 0.1% to 1.0%. [Equation 1] Transmission reduction rate (%) = {(T0-Ts)/T0} * 100

In Equation 1, T0 is the initial transmittance of the sample before the durability evaluation and Ts is the transmittance of the sample after treatment for 500 hours under the conditions of 60°C and 95% RH.

Within this range, the subsequent layer can exhibit further improved optical characteristics.

When the adhesive layer according to the embodiment is exposed to air, the adhesive layer may be protected by a release sheet (separator) before actual use.

As the material of the separator, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films; porous materials such as paper, cloth, and non-woven products; suitable thin papers such as mesh , Foamed sheets, metal thin films and laminates thereof, and the like, and in particular, plastic films can be suitably used in terms of good surface smoothness.

The separator generally has a thickness of 5 microns to 200 microns, or a thickness of 5 microns to 100 microns.

If necessary, the separator can be subjected to anti-fouling treatment and release treatment with silicone, fluorine, long-chain alkyl or fatty acid amide release agents, silica powder and the like, as well as coating type, kneading type or Deposited antistatic treatment. Specifically, the surface of the separator can be subjected to release treatments, such as silicone treatment, long-chain alkyl treatment, fluorine treatment, and the like, thereby improving the peeling performance of the self-adhesive layer. <Next optical film>

Other embodiments of the present invention provide an optical member manufactured by forming an adhesive layer according to an embodiment of the present invention on at least one surface of an optical film. For example, the optical member may contain an optical film. Herein, "adhesion optical film" refers to an optical film containing an adhesion layer according to an embodiment of the present invention. In addition, since the optical film can be provided in the form of a polarizing plate, the adhesive optical film according to an embodiment of the present invention contains the adhesive polarizing plate.

In one embodiment, the adhesive optical member may be manufactured by directly coating the adhesive composition on one or both surfaces of the optical film to form an adhesive layer thereon, or may be formed on the aforementioned substrate or separator The adhesion layer is formed in advance, and then the adhesion layer is transferred to one or both surfaces of the optical film to manufacture. In addition, the optical film may be subjected to surface treatments such as corona treatment, plasma treatment, formation of easy adhesion layers and the like, formation of antistatic layers and the like. In addition, the adhesive layer can be subjected to surface treatment for easy adhesion. In one embodiment, the easy adhesion layer formed between the optical film and the adhesion layer of the optical film can bond the optical film to the adhesion layer more firmly. (Easy to follow the layer)

Any material that can form a film that exhibits good cohesion and good adhesion to the adhesive layer and the optical film (for example, a transparent protective film of a polarizing plate) can be used as the material for the easy adhesive layer. For example, various polymers, metal oxide sols, silica sols, and the like can be used as materials for easy adhesion layers, and specifically, polymers are preferably used.

Examples of the polymer may include an oxazoline group-containing polymer, a polyurethane resin, a polyester resin, and an amine group-containing polymer. Specifically, oxazoline group-containing polymers are preferably used.

Polymers containing oxazoline groups can be obtained from commercially available products, such as the Epocros series available from Nippon Shokubai Co., Ltd. (such as Epcros WS- 700), but not limited to this. In addition, examples of polyurethane resins, polyester resins, and polymers containing amine groups are disclosed in paragraphs "0107" to "0113" of Japanese Patent Publication No. 2011-105918A.

For example, the easy adhesion layer can be formed by depositing an undercoat layer for the easy adhesion layer onto the optical film by coating, dipping, spraying, and the like, and then drying.

The easy adhesion layer may have a thickness (dry thickness) of 10 nm to 5000 nm, specifically 50 nm to 500 nm. Within this range, it is easy for the adhesive layer to exhibit characteristics of large volume, sufficient strength, and sufficient adhesive force while maintaining optical characteristics.

As for the optical film suitable for the subsequent optical film according to the present invention, any optical film can be used as long as the optical film can be used to form an image display device, such as a liquid crystal display. For example, the optical film may be a polarizing plate, a retardation plate, an optical compensation film, a brightness enhancement film, or a laminate thereof.

Hereinafter, an embodiment of a polarizing plate that can be used as an optical film will be described. (Polarizer)

In one embodiment, a polarizing plate that can be used as an optical film can be bonded to a polarizer by a protective agent through a typical method known in the art through an adhesive, followed by heat drying or using UV light, electron beam or Its analogues are cured by irradiation. The deposited adhesive exhibits adhesion and is formed by curing through drying or irradiation with UV light, electron beam or the like to form an adhesive layer.

As the polarizer, any typical polarizer known in the art may be used. Examples of the polarizer may include by adsorbing a dichroic material (such as iodine) or a dichroic dye to a hydrophilic polymer film (such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or a partially saponified ethylene/acetic acid Polarizer obtained by uniaxially stretching the film, a polyene oriented film (such as the dehydration product of polyvinyl alcohol film or the dehydrochlorination product of polyvinyl chloride film and the like) on the vinyl ester copolymer film, But it is not limited to this.

Specifically, the polarizer can be obtained by dyeing a polyvinyl alcohol film having an average degree of polymerization of 2,000 to 2,800 and a saponification degree of 90 mol% to 100 mol% with iodine, and then uniaxially stretching the film to It is obtained by three to eight times the initial length. More specifically, such a polarizer can be obtained by immersing, for example, a polyvinyl alcohol film in an aqueous iodine solution to dye the polyvinyl alcohol film with iodine, and then stretching the dyed polyvinyl alcohol film.

Preferably, the aqueous iodine solution contains, for example, 0.1% to 1.0% by weight of iodine and/or potassium iodide. Alternatively, the polyvinyl alcohol film may be immersed in an aqueous solution of boric acid or potassium iodide at 50°C to 70°C, or may be immersed in water at 25°C to 35°C to wash the film or prevent staining. Stretching can be performed after, during or before dyeing with iodine. After dyeing and stretching, the polyvinyl alcohol film can be washed with water and dried at 35°C to 55°C for 1 to 10 minutes. Such polarizers can also be obtained from commercially available products.

The thickness of the polarizer may be, for example, 5 microns to 80 microns, but is not limited thereto.

The protective film may be formed of a material having good characteristics in terms of transparency, mechanical strength, thermal stability, moisture barrier, isotropy, and the like. For example, the protective film may be formed of a material in the following: cellulose resin, such as triethyl cellulose; polyester resin, such as polyethylene terephthalate and polyethylene naphthalate; poly Ether resin; Poly resin; Polycarbonate resin; Polyamide resin; Polyimide resin; Polyolefin resin; (Meth) acrylic resin, such as polymethyl methacrylate; Cyclic polyolefin resin (down Norbornene resin); polyacrylate resin; polystyrene resin; polyvinyl alcohol resin; epoxy resin, and mixtures thereof.

Although the transparent protective film is bonded to one side of the polarizer via an adhesive, the other transparent protective film or protective layer may also use thermosetting resin or UV curable resin (such as (meth)acrylic resin, urethane resin, Acrylic urethane resin, epoxy resin, silicone resin and the like) are formed on the other side of the polarizer.

The thickness of the polarizing plate may be 20 microns to 200 microns, but is not limited thereto. For example, the thickness of the polarizing plate may be 100 microns or less, 100 microns, 75 microns or less than 75 microns or 50 microns or less than 50 microns to ensure favorable thickness reduction. Such a thin polarizing plate can remarkably achieve the advantageous effects of the subsequent composition according to the present invention.

The polarizing plate can be manufactured by depositing an adhesive, and then bonding the protective film to the polarizer using a roll laminator, but it is not limited thereto. After bonding the protective film to the polarizer, the curing process can be performed by drying or irradiating with UV light or electron beam. The adhesive may be deposited on one of the protective film and the polarizer, or may be deposited on the protective film and the polarizer. The adhesive can be deposited to a dry thickness of 10 nm to 300 nm. In addition, any bonding material known in the art corresponding to the polarizer can be used as the bonding agent. For example, when the polyvinyl alcohol film is used as a polarizer, a polyvinyl alcohol adhesive or a UV-curable adhesive, such as an acrylic adhesive, an epoxy adhesive, and an acrylic-epoxy adhesive can be used . The thickness of the adhesive layer may be, for example, 10 nm to 200 nm for the polyvinyl alcohol adhesive and may be 0.2 μm to 10 μm for the UV curable adhesive. Within this range, the bonding layer can exhibit sufficient bonding strength while providing uniform coplanar thickness.

Embodiments of the present invention can provide an adhesive polarizing plate including an adhesive layer formed of the adhesive composition as described above. The structure or manufacturing method of the polarizing plate is then the same as that of the subsequent optical film described above, and thus its detailed description is omitted. < Image display device >

Another embodiment of the present invention relates to an image display device including at least one of the optical components described above.

Examples of image display devices may include liquid crystal displays, organic electroluminescence (EL) displays, and plasma display panels (PDP), but are not limited thereto. In addition, the thin image display device can remarkably achieve the advantageous effects of the subsequent composition as explained above. Examples

Subsequently, the present invention will be described with reference to examples and comparative examples. However, it should be understood that the present invention is not limited to the following examples and can be implemented in different ways.

Unless otherwise stated, in the following examples, various operations and measurements of physical properties were performed under the conditions of 23°C and 55% relative humidity (RH). Preparation Example 1 : Preparation of Adhesive Resin ( A1-1 )

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen feed tube, and a cooler, add 99 parts by weight of n-butyl acrylate (available from Japan Catalyst Co., Ltd.) and 1 part by weight of 4-hydroxy acrylate Butyl ester (available from Osaka Organic Chemical Industry Ltd.) and 0.15 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator (available from Wako Pure Chemical Industries, Ltd. (product of Wako Pure Chemical Industries, Ltd.) and 100 parts by weight of ethyl acetate were put together and slowly stirred while introducing nitrogen into the flask. After replacing with nitrogen, the solution was adjusted to 55° C. and subjected to polymerization for 5 hours, thereby preparing a solution of acrylic adhesive resin (A1-1) having a solid content of 15% (w/w).

The acrylic adhesive resin (A1-1) obtained had a weight average molecular weight of 2,100,000 and a viscosity of 8,000 mPa·s. Preparation Example 2 to Preparation Example 3 : Preparation of Adhesive Resin ( A1-2 ) and Adhesive Resin ( A1-3 )

An adhesive resin (A1-2) having a solid content of 15% (w/w) and 15% (w/w) were prepared in the same manner as in Preparation Example 1, except that the types and ratios of monomers for acrylic adhesive resins were changed as listed in Table 1. Next, a solution of resin (A1-3).

Each of the obtained acrylic adhesive resin (A1-2) and acrylic adhesive resin (A1-3) had a weight average molecular weight of 2,100,000 and a viscosity of 8,000 mPa·s. Preparation Example 4 : Preparation of Adhesive Resin ( A2 )

In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen feed tube, a thermometer, and a dropping funnel, 51.9 parts by weight of polyester polyol P-1010 (bifunctional polyester polyol, OH 112 mg/ Grams, number average molecular weight: 1,000, Kuraray Co., Ltd. (Kuraray Co., Ltd.), 32.2 parts by weight of Adeka (Adeka) polyether G-1500 (trifunctional polyether polyol, OH value: 109, Number average molecular weight 1,500, ADEKA Co., Ltd.), 15.9 parts by weight of isophorone diisocyanate (available from Sumitomo Bayer Co., Ltd.), 66.7 Parts by weight of toluene and 0.03 parts by weight of iron 2-ethylhexanoate as a catalyst and 0.04 parts by weight of lead naphthenate were slowly heated to 90°C, followed by polymerization for 4 hours. In the presence of 2260 cm ^-1 with an infrared spectrophotometer (IR) inspection of the remaining isocyanate groups, so that when a peak around 2260 cm ^-1 disappeared, the polymerization reaction was complete, the mixture was then cooled, thereby preparing with 60% (w /w) A colorless and transparent solution of urethane adhesive resin (A2) with solid content and viscosity of 3,000 mPa·s.

The obtained urethane adhesive resin (A2) had a number average molecular weight of 15,000, a weight average molecular weight of 50,000, and an acid value of 0.5 KOH mg/g. Preparation Example 5 : Preparation of Adhesive Resin ( A3 )

In a four-necked separable flask with a thermometer, stirrer, distillation column and cooler, place 11.7 parts by weight of ethylene glycol, 18.6 parts by weight of neopentyl glycol, 11.8 parts by weight of m-phthalic acid, 57.9 Parts by weight of sebacic acid and 0.15 parts by weight of tetra-n-butyl titanate corresponding to the catalyst are heated to 150°C to 270°C for 150 minutes to promote esterification, then gradually depressurized to 133 Pa over 30 minutes and react 180 At the same time continue to decompress. The mixed solution was diluted with ethyl acetate to prepare a solution of a polyester adhesive resin (A3) having a solid content of 60% (w/w) and a viscosity of 3,000 mPa·s.

The polyester adhesive resin (A3) obtained had a number average molecular weight of 13,000, a weight average molecular weight of 38,000, and an acid value of 0.3 KOH mg/g. Preparation Example 6 : Preparation of silicone alkoxy oligomer ( B1 )

In a 1 L flask with a thermometer and a water-cooled condenser, place 440 parts by weight (2 mol) of 3-glycidoxypropylmethyldimethoxysilane and 272 parts by weight (2 mol) of methyl alcohol Trimethoxysilane, 70 parts by weight of methanol and 26.8 parts by weight of acetic acid, and stirred at room temperature. To the mixed solution, 49.5 parts by weight (2.8 mol) of deionized water was added, followed by stirring at room temperature for 2 hours. Subsequently, the solvent was removed from the solution by distillation under normal pressure until the solution had a temperature of 110°C, thereby preparing a silicone alkoxy oligomer having a solid content of 98.0% (w/w) and a viscosity of 250 mPa·s (B1) colorless transparent solution.

The silicone alkoxy oligomer (B1) has a number average molecular weight of 15,000 based on polystyrene standards, an epoxy equivalent weight of 350 g/mol, and an alkoxy content of 17% by weight. Preparation Example 7 : Preparation of silicone alkoxy oligomer ( B2 )

In a 1 L flask with a thermometer and a water-cooled condenser, 62.8 parts by weight (0.285 moles) of 3-glycidoxypropylmethyldimethoxysilane and 505.2 parts by weight (3.715 moles) of methyl alcohol were placed Trimethoxysilane, 270 parts by weight of methanol and 26.8 parts by weight of acetic acid, and stirred at room temperature. To the mixed solution, 49.5 parts by weight (2.8 mol) of deionized water was added, followed by stirring at room temperature for 2 hours. Subsequently, the solvent was removed from the solution by distillation under normal pressure until the solution had a temperature of 110°C, thereby preparing a silicone alkoxy oligomer having a solid content of 98.5% (w/w) and a viscosity of 300 mPa·s (B2) The colorless transparent solution.

The silicone alkoxy oligomer (B2) has a number average molecular weight of 1,000 based on polystyrene standards, an epoxy equivalent weight of 3,200 g/mol, and an alkoxy content of 42% by weight. Preparation Example 8 : Preparation of silicone alkoxy oligomer ( B3 )

In a 1 L flask with a thermometer and a water-cooled condenser, placed 817.3 parts by weight (3.715 mol) of 3-glycidoxypropylmethyldimethoxysilane and 36 parts by weight (0.285 mol) of methyl alcohol Trimethoxysilane, 270 parts by weight of methanol and 26.8 parts by weight of acetic acid and stirred at room temperature. To the mixed solution, 49.5 parts by weight (2.8 mol) of deionized water was added, followed by stirring at room temperature for 2 hours. Subsequently, the solvent was removed from the solution by distillation under normal pressure until the solution had a temperature of 110°C, thereby preparing a silicone alkoxy oligomer having a solid content of 98.2% (w/w) and a viscosity of 270 mPa·s (B3) The colorless transparent solution.

The silicone alkoxy oligomer (B3) has a number average molecular weight of 1000 based on polystyrene standards, an epoxy equivalent weight of 230 g/mol, and an alkoxy content of 2% by weight.

In the preparation examples, the weight average molecular weight, number average molecular weight, epoxy equivalent, alkoxy content, and viscosity were measured by the following methods. 1) Measure the weight average molecular weight (Mw)

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC). · Analyzer: Tosoh Corporation product, HLC-8120GPC · Tubular column: Tosoh Corporation product, G7000HXL+GMHXL+GMHXL · Tubular column size: each 7.8 mm φ×30 cm, total: 90 cm· Column temperature: 40°C • Flow rate: 0.8 ml/min • Injection volume: 100 μl • Dissolving agent: tetrahydrofuran • Detector: refractometer (RI) • Standard sample: polystyrene 2) Measure the number average molecular weight (Mn)

The number average molecular weight (Mn) was measured by gel permeation chromatography (GPC). · Analyzer: Tosoh Co., Ltd. product, HLC-8120GPC · Column: TSKgel, SuperHZM-H/HZ4000/HZ2000 · Column size: 6.0 mm ID × 150 mm · Column temperature: 40°C · Flow rate: 0.6 Ml/min · Injection volume: 20 microliters · Dissolving agent: tetrahydrofuran · Detector: refractometer (RI) · Standard sample: polystyrene 3) Measure epoxy equivalent

The epoxy equivalent was measured according to JIS K7236 (2004). (Measure alkoxy content)

The alkoxy content was measured by gas chromatography based on the separation and quantification of alkoxy groups (Analytical Chemistry (Analytical Chemistry) 17(9), 1102-1107, 1968). 4) Measuring viscosity

＜ 實例 1＞ 製備接著組成物 After adjusting the temperature of the polymer solution in the glass bottle to 25°C, the viscosity was measured using a Brookfield viscometer DVII+Pro (axis number 63, 12 revolutions per minute). Table 1

< Example 1> Preparation of the next composition

Relative to 100% (w/w) of the solution (in terms of solid content) of the adhesive resin (A1-1) prepared in Preparation Example 1, 1 part by weight of the corresponding silicone alkoxy oligomer ( B) X-41-1053 (epoxy equivalent of 830 g/mol, Shin-Etsu Chemical Co., Ltd.) and 0.1 part by weight of the equivalent of isocyanate crosslinking agent (Takenate) D110N (xylene diisocyanate trihydroxy A 75% by weight ethyl acetate solution of methylpropane adduct, number of isocyanate groups per molecule: 3, Mitsui Chemicals Co., Ltd.) to prepare a solution of acrylic acid adhesion composition (solid content: 15% (w/w)). Forming an adhesive layer

The obtained solution of acrylic adhesive composition was applied to a 38-micron thick polyethylene terephthalate (PET) film (MRF38, Mitsubishi Chemical Polyester Film, Co., Ltd.) subjected to silicone treatment . Ltd.) on one surface so that the adhesive layer has a thickness of 20 μm after drying. Subsequently, the coating layer is dried at 100° C. for 2 minutes to form the adhesive layer. Attach the adhesive layer and manufacture a polarizer (manufacture of a thin polarizer) )

A 20-micron-thick polyvinyl alcohol film was stretched to a length three times its original length through rollers having different speed ratios, while being dyed in a 0.3% by weight iodine solution at 30°C for 1 minute. Subsequently, the stretched polyvinyl alcohol film was immersed in an aqueous solution containing 4% by weight boric acid and 10% by weight potassium iodide at 60°C for 0.5 minutes and stretched to a total elongation of 6 times its original length. Subsequently, the stretched film was immersed in an aqueous solution containing 1.5% by weight of potassium iodide at 30°C for 10 seconds to wash the stretched film, which was further dried at 50°C for 4 minutes, thereby obtaining a polarizer. Subsequently, a 20-micron-thick acrylic film (lactone-modified acrylic resin film) was bonded to one side of the polarizer using a polyvinyl alcohol-based adhesive, thereby manufacturing a side-protective polarizer with a total thickness of 27 micrometers.

(Manufacture of polarizer with adhesive layer attached)

Make the polarizer of the thin polarizer at 80[W. min/m ² ] under corona discharge. Subsequently, the obtained PET film having an adhesive layer formed thereon and subjected to silicone treatment was transferred to a polarizer of a polarizing plate, thereby manufacturing a polarizing plate with an adhesive layer attached.

<Example 2 to Example 8 and Example 10 to Example 11>

In addition to the changes listed in Table 2 and Table 3, the resin (A), silicone alkoxy oligomer (B), crosslinking agent (C-1) and crosslinking agent (C-2), and silane coupling agent (D) Except for the type and amount of (KBM-403, 3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.), polarized light attached to the adhesive layer of each example was prepared in the same manner as in Example 1. board.

In addition, X-41-1056 and X-41-1059A are products of Shin-Etsu Chemical Co., Ltd. and Peroyl TCP is a product of NOF Corporation.

<Example 9>

In addition to the changes listed in Table 2 and Table 3, the resin (A), silicone alkoxy oligomer (B), crosslinking agent (C-1) and crosslinking agent (C-2), and silane coupling agent Except for the kind and amount of (D), a thin polarizing plate was prepared in the same manner as in Example 1.

Subsequently, the polarizer of the thin polarizer was coated with a primer with a wire rod to form a 50 nm-thick easy adhesion layer. The primer is prepared by diluting a solution containing oxazoline polymer (WS-700, Japan Catalyst Co., Ltd.) in a mixed solution of water and isopropyl alcohol to have a solid content of 0.6% (w/w).

Subsequently, the obtained PET film having the adhesive layer formed thereon and subjected to silicone treatment was bonded to the easy adhesive layer of the polarizing plate, thereby manufacturing the adhesive polarizing film of Example 9. < Comparative Example 1 to Comparative Example 20>

表3

＜ 特性評估 ＞ In addition to the changes listed in Tables 2 and 3, the resin (A), silicone alkoxy oligomer (B), crosslinking agent (C-1) and crosslinking agent (C-2), and silane coupling agent Except for the type and amount of (D), the polarizing plate with the adhesion layer attached to each comparative example was prepared in the same manner as in Example 1. Table 2

table 3

< Characteristic evaluation >

Each of the attached polarizing plates (samples) prepared in Examples and Comparative Examples was evaluated as follows. The evaluation results are shown in Table 4. 1. Durability

Each of the samples was cut to a size of 37 inches and attached to a 0.7 mm thick alkali-free glass substrate (Eagle XG, Corning Corporation) using a laminator. Subsequently, the glass substrate was heat-pressed at 50° C. and 5 MPa for 15 minutes to completely attach the polarizing plate to the alkali-free glass substrate.

Subsequently, the samples were subjected to the following tests: (1) standing at 85°C for 500 hours (heating test), (2) standing at 60°C/95% RH for 500 hours (humidity test), and (3 ) Subjected to 300 thermal shock (HS) test cycles, where each cycle includes the process of standing the sample at 85°C for 1 hour and at -40°C for 1 hour.

After each test, the appearance of the interface between the polarizing film and the glass substrate was evaluated with naked eyes based on the following criteria. ◎: No change in appearance (such as bubbles, delamination, and detachment) ○: Although there is a slight differential layer or bubbles at the end, there is no problem in use △: Although there is a slight differential layer or bubbles at the end, except for some special uses in normal use, no problem ×:. in use, due to the end of the significant problem of delamination reworkability 2

Each of the samples was cut to a size of 25 mm wide×100 mm long and attached to a 0.7 mm thick alkali-free glass substrate (Igle XG, Corning Corporation) using a laminator.

Subsequently, the glass substrate with the polarizing film attached was hot-pressed at 50° C. and 5 atmospheres for 15 minutes to completely attach the polarizing plate to the alkali-free glass substrate, thereby providing an initial glass substrate. Subsequently, the initial glass substrate was allowed to stand under dry conditions at 50° C. for 48 hours, thereby providing a heated glass substrate. Subsequently, the adhesive strength of each sample was measured by the following method.

Using a tensile tester (Orientec Universal Testing Machine (Orientec Universal Testing Machine), STA-1150), measured at 23°C, 50% RH, 180° peel angle and 300 mm/min peel rate Adhesion strength (N/25 mm) when the polarizing film is peeled from each glass substrate. Here, peeling was performed according to the JIS Z0237 test method of the adhesive tape and adhesive sheet.

In addition, the polarizing film (sample) subjected to the same treatment as in the evaluation of the adhesive strength was cut into a size of 420 mm wide by 320 mm long and the alkali-free glass substrate was peeled off manually to prepare a sample, and then the actual evaluation was performed under the following criteria Reworkability. Three samples were prepared in this way and the evaluation of the actual reworkability was repeated three times. ◎: All three glass substrates can be cleanly separated without remaining glue and damage to the polarizing film. ○: Although some of the three glass substrates suffered from cracking of the polarizing film, the polarizing film was separated by repeated peeling. △: Although all three glass substrates suffered from cracking of the polarizing film, the polarizing film was separated by repeated peeling. ×: All three glass substrates suffer from residual glue, or may not be separated even by repeated peeling due to cracking of the polarizing film.

The results of the evaluation of the strength and actual reworkability are summarized to determine the reworkability of each of the samples. 3. Optical characteristics

For each of the samples bonded to the alkali-free glass substrate before and after the evaluation of durability under conditions of 60°C and 95% RH for 500 hours, use an integrating sphere type spectral transmittance tester (DOT-3C, Murakami Color Research Laboratory Co., Ltd. (Murakami Color Research Laboratory Co., Ltd.) measures the transmittance (Ts, %) of the central portion of each of the samples. Subsequently, the reduction rate of the transmittance (%) before and after the evaluation of durability under the conditions of 60° C. and 95% RH for 500 hours under Equation 1 was calculated and used to evaluate optical characteristics. [Equation 1] Decrease rate of transmittance (%) = {(T0-Ts)/T0} * 100, where T0 is the initial transmittance of the sample measured before the durability evaluation and Ts is at 60°C and 95% The transmittance of the samples after 500 hours of durability was evaluated under RH. Table 4

In Table 4, it can be seen that all the thin polarizing plates (Examples 1 to 11) containing the adhesive layer formed by the adhesive composition according to the present invention are reworkable to enable easy peeling and by heating in the bonded state And the durability aspects related to the humidity durability test show excellent characteristics. In addition, all the thin polarizing plates (Examples 1 to 11) containing the adhesive layer formed by the adhesive composition according to the present invention had a reduction rate of low transmittance after 500 hours of evaluation of durability under conditions of 60°C and 95% RH , That is, excellent optical characteristics.

no

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Claims (11)

A heat-curing adhesive composition comprising: 100 parts by weight of an adhesive resin (A), the adhesive resin (A) having a weight average molecular weight of 20,000 to 2,500,000; 0.5 to 20 parts by weight of silicone alkoxy oligomer Substance (B), the silicone alkoxy oligomer (B) has an epoxy equivalent weight of 100 g/mol to 2000 g/mol and contains 5% to 43% by weight of alkoxy groups, and has an amount of 300 to 10,000 Number average molecular weight; and 0.01 to 20 parts by weight of a cross-linking agent (C), the cross-linking agent (C) includes at least one of an isocyanate compound and a peroxide, wherein the adhesive resin (A) includes At least one selected from the group consisting of: acrylic adhesive resin (A1), urethane adhesive resin (A2) and polyester adhesive resin (A3), which are Prepared by polymerization, and calculated by Equation 1, the adhesive layer formed from the thermally cured adhesive composition has a transmittance reduction rate of 0.1% to 1.0%: [Equation 1] transmittance reduction rate (%)={ (T0-Ts)/T0}*100, where T0 is the initial transmittance of the sample before the durability evaluation and Ts is the transmittance of the sample after treatment for 500 hours under the conditions of 60°C and 95% relative humidity. The thermal curing adhesive composition as described in item 1 of the patent application, wherein the adhesive resin (A) further contains a hydroxyl group. The heat-curing adhesive composition as described in item 1 of the patent application scope further includes: 0.001 to 5 parts by weight of the silane coupling agent (D) based on 100 parts by weight of the adhesive resin (A). An adhesive layer is formed of the thermal curing adhesive composition as described in item 1 of the patent application. The adhesive layer as described in item 4 of the patent application scope, which is measured under the conditions of 23° C., 50% relative humidity, a peel angle of 180°, and a peel rate of 300 mm/min according to JIS Z0237. The layer has an initial adhesion strength of 0.2 N/25 mm to 1.6 N/25 mm. Adhesive layer as described in item 4 of the patent application scope, in which drying at 50°C under the conditions of 23°C, 50% relative humidity, 180° peel angle and 300 mm/min peeling rate according to JIS Z0237 As measured by a sample subjected to a heat treatment for 48 hours under the conditions, the adhesive layer has a heat-adhesion adhesive strength of 0.3 N/25 mm to 2.5 N/25 mm. The adhesive layer as described in item 4 of the patent application range, wherein the adhesive layer has a transmission rate reduction rate of 0.1% to 1.0% as calculated by Equation 1: [Equation 1] transmission rate reduction rate (%) ={(T0-Ts)/T0}* 100, where T0 is the initial transmittance of the sample before durability evaluation and Ts is the transmittance of the sample after treatment for 500 hours at 60°C and 95% relative humidity . An optical member comprising: an optical film; and an adhesive layer as described in item 4 of the patent application scope, formed on at least one surface of the optical film. The optical member as described in item 8 of the scope of the patent application further includes: an easy adhesion layer between the optical film and the adhesion layer. The optical member as described in item 8 of the patent application scope, wherein the light The film is a polarizing plate having a thickness of 100 microns or less. An image display device includes at least one optical component as described in item 8 of the patent application scope.