KR20160024748A - Adhesive composition, adhesive layer, optical member and display device including thereof - Google Patents

Abstract

The present invention relates to a pressure-sensitive adhesive composition comprising 100 parts by weight of a pressure-sensitive adhesive resin (A) 0.1 to 20 parts by weight of a silicon alkoxy oligomer (B) having an epoxy equivalent of 100 g / mol to 2000 g / mol and an alkoxyl group content of 5% by weight to 60% by weight; , Wherein the pressure-sensitive adhesive resin (A) is one kind selected from the group consisting of an acrylic pressure-sensitive adhesive resin (A1) obtained by polymerizing a monomer containing no carboxyl group, a urethane- Or more, an optical member using the same, and an image display device. Thus, the present invention provides a pressure-sensitive adhesive composition which can be used for a thin image display device and a thin optical member, which is excellent in reworkability which can be easily peeled off, durability against durability test by heating and humidification Can be provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a pressure-sensitive adhesive composition, an adhesive layer, an optical member using the adhesive layer, and an image display device.

The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer, an optical member, and an image display apparatus.

A liquid crystal panel such as a liquid crystal display device includes an optical member such as a polarizing plate having a polarizer and various optical films for improving display quality of the display. These optical members are attached to the liquid crystal panel using a pressure sensitive adhesive.

At this time, the optical member may be an adhesive film having a pressure sensitive adhesive formed on the first surface thereof in the form of an adhesive layer. Such a pressure-sensitive adhesive film is convenient to handle, and has the advantage of omitting the step of drying the pressure-sensitive adhesive. Further, when an optical member using an adhesive film is bonded to a liquid crystal display device or the like, for example, when a defective position of a bonding position or a foreign matter entering the bonding surface occurs, the optical member is peeled off from the liquid crystal panel, It is possible. This can reduce the occurrence of defects and reuse expensive liquid crystal cells and the like.

On the other hand, a thin liquid crystal display device whose demand is increasing in recent years is seeking to further reduce the thickness by using a thin liquid crystal panel or a thin optical member. However, thin liquid crystal panels, thin optical members, and the like use chemically etched glass or have a thin thickness, so that if a pressure sensitive adhesive intended only for conventional durability is used, the thin liquid crystal display device may be split or broken.

Therefore, a pressure-sensitive adhesive to be used for a thin liquid crystal panel or a thin optical member is required to have a releasability (also referred to as " reworkability ") that does not have an adhesive remaining and can easily be peeled off. In addition, the pressure-sensitive adhesive is also required to have adhesion durability to such an extent that defects such as peeling or peeling are not generated in the durability test such as heating and humidification, which are usually conducted as environmental promotion tests.

As described above, a pressure-sensitive adhesive to be used in a thin liquid crystal display device is required to have both reworkability and adhesion durability, but it has not been easy to achieve this by conventional techniques alone.

For example, conventionally, a pressure-sensitive adhesive composition comprising an acryl-based polymer and a polymer-type silane coupling agent containing a main chain in a siloxane skeleton and having an alkoxyl group, an epoxy group and a polyether group in the side chain (see Patent Document 1), an acrylic polymer A pressure-sensitive adhesive composition for an optical film, such as a pressure-sensitive adhesive composition comprising a silicone oligomer (see Patent Documents 2 to 4), or a pressure-sensitive adhesive composition comprising an acrylic copolymer containing a carboxyl group and a silane coupling agent (see Patent Documents 5 to 6) Reported. However, the pressure-sensitive adhesive compositions of the above-mentioned Patent Documents 1 to 6 are not sufficient for achieving both the reworkability and durability required for thin image display devices and thin optical members in particular.

JP, H07-331206, A JP 2006-316256 A JP 2010-007044E JP 2012-012537 A WO 2012/26456 A JP 2008-176173 A

It is an object of the present invention to provide a pressure-sensitive adhesive composition which can be used for a thin image display device and a thin optical member, which is excellent in releasability which can be easily peeled off, durability test for heating, And to provide a means for achieving durability at the same time.

Another object of the present invention is to provide an optical member such as a pressure-sensitive adhesive layer formed by the above-mentioned pressure-sensitive adhesive composition, a pressure-sensitive adhesive polarizing plate having the pressure-sensitive adhesive layer, and an image display apparatus using the optical member.

One embodiment of the present invention relates to a pressure-sensitive adhesive composition comprising 100 parts by weight of a pressure-sensitive adhesive resin (A) 0.1 to 20 parts by weight of a silicon alkoxy oligomer (B) having an epoxy equivalent of 100 g / mol to 2000 g / mol and an alkoxyl group content of 5% by weight to 60% by weight; Wherein the pressure-sensitive adhesive composition is a pressure-

The pressure-sensitive adhesive resin (A) is at least one kind selected from the group consisting of an acrylic pressure-sensitive adhesive resin (A1), a urethane pressure-sensitive adhesive resin (A2) and a polyester pressure-sensitive adhesive resin (A3) obtained by polymerizing a monomer containing no carboxyl group .

Another embodiment of the present invention relates to an adhesive layer formed by the above-described pressure-sensitive adhesive composition.

Yet another embodiment of the present invention is an optical film comprising: an optical film; And an adhesive layer formed on at least one surface of the optical film.

Another embodiment of the present invention relates to an image display apparatus using at least one optical member described above.

The embodiments of the present invention are applicable to a pressure-sensitive adhesive composition which can be used for a thin image display device and a thin optical member, in particular for a durability test which can be easily peeled off, Durability can be compatible with each other.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

Pressure-sensitive adhesive composition

One embodiment of the present invention relates to a pressure-sensitive adhesive composition comprising 100 parts by weight of a pressure-sensitive adhesive resin (A) And 0.1 to 20 parts by weight of a silicone alkoxy oligomer (B) having an epoxy equivalent of 100 g / mol to 2000 g / mol and an alkoxyl group content of 5% by weight to 60% by weight; Wherein the adhesive resin (A) comprises one kind selected from the group consisting of an acrylic adhesive resin (A1), a urethane adhesive resin (A2) and a polyester adhesive resin (A3) obtained by polymerizing a monomer containing no carboxyl group Sensitive adhesive composition. Through such a constitution, the pressure-sensitive adhesive composition of the present invention can achieve both advantageous properties for use in a thin liquid-crystal display device by achieving both excellent workability and durability.

In the present specification, "(meth) acrylate" is a generic term of acrylate and methacrylate. (Meth) acrylic acid (meth) acrylic acid and the like are also collectively referred to as a compound having "meta" and a compound having no "meta" in the name. For this reason, the term " (meth) acrylic " includes both acrylic and methacrylic. The term "(meth) acrylate" includes both acrylate and methacrylate. The term "(meth) acrylic acid" includes both acrylic acid and methacrylic acid.

In the present specification, the term " resin " is collectively referred to as oligomers, polymers, copolymers, etc. obtained by polymerizing monomers used as basic units.

≪ Adhesive Resin (A) >

The mechanisms that can solve the problems of the present invention are presumed as follows, but the present invention is not limited thereto.

The adhesive resin (A) in one embodiment may not contain a carboxyl group or may contain a minimum amount. In the present specification, "adhesive resin (A) contains a carboxyl group in a minimum amount" means that the adhesive resin does not contain a carboxyl group at all, or contains only a terminal.

The adhesive resin (A) containing such a carboxyl group in a minimum amount prevents the alkoxyl group of the silicon alkoxy oligomer (B) described below from reacting with the carboxyl group to generate a silanol group in the side chain of the silicon alkoxy oligomer (B). As a result, there is an effect of preventing the alkoxyl group, which helps improve the reworkability, from being reduced by the silanol group to reduce the amount of the alkoxyl group. In this case, there is an effect of preventing degradation of reworkability of the adhesive layer. In addition, the increase in the silane-reactive group having high reactivity is prevented, and the coupling reaction is caused to occur on the surface of the glass contained in the silanol group and the liquid crystal display device or the like to prevent the workability from deteriorating. The adhesive resin (A) has an advantageous effect in application to a liquid crystal display device having an IPS panel or the like which is weak in the acidity of a carboxyl group.

In other words, the pressure-sensitive adhesive resin (A) of the present invention is produced in a direction (minimization) in which the content of the carboxyl group is reduced as much as possible. Means a direction in which the carboxyl group is present but is present in the end of the pressure-sensitive adhesive resin (A), preferably in a direction in which no carboxyl group is present.

The pressure-sensitive adhesive resin (A) of one embodiment is obtained by polymerizing an acrylic pressure-sensitive adhesive resin (A1), a urethane pressure-sensitive adhesive resin (A2), a polyester pressure-sensitive adhesive resin (A3) or (A1) to (A3) obtained by polymerizing a monomer containing no carboxyl group And at least two kinds selected from the group consisting of In this case, the content of the carboxyl group contained in the adhesive resin (A) can be minimized. This makes it possible to remarkably improve the reworkability of the adhesive layer, particularly when a resin containing a large amount of carboxyl groups is used.

The pressure-sensitive adhesive resin (A) of one embodiment may have a weight average molecular weight of 20,000 to 250.

For example, when the acrylic pressure-sensitive adhesive resin (A1) is used, the weight-average molecular weight of the pressure-sensitive adhesive resin (A) may be from 300,000 to 250,000 or from 500,000 to 220,000. Within the above range, the durability of the adhesive layer can be improved.

For example, when the urethane-based pressure-sensitive adhesive resin (A2) and the polyester-based pressure-sensitive adhesive resin (A3) are used, the weight-average molecular weight of the pressure-sensitive adhesive resin (A) may be 20,000 to 100,000 or 30,000 to 6,000. Within the above range, the durability of the adhesive layer can be improved.

In the present specification, the weight average molecular weight can be measured by a measuring method described in Examples to be described later.

The pressure-sensitive adhesive resin (A) of one embodiment may have a viscosity of, for example, 100 mPa · s to 100,000 mPa · s, 300 mPa · s to 50000 mPa · s, or 500 mPa · s to 30000 mPa · s. Within the above range, the coating layer coated with the pressure-sensitive adhesive composition can be smoothened and uniformity of the thickness of the coating layer can be easily obtained.

The adhesive resin (A) in one embodiment may contain a hydroxyl group. In this case, the durability of the adhesive layer can be improved. When a pressure-sensitive adhesive resin (A) containing a hydroxyl group is used, a hydroxyl group and an isocyanate-based compound are crosslinked when used in combination with a crosslinking agent which is an isocyanate-based compound to be described later, whereby a network is formed to further improve the durability of the pressure- .

[Acrylic pressure-sensitive adhesive resin (A1)]

The acrylic pressure-sensitive adhesive resin (A1) is a monomer which does not contain a carboxyl group, and is not particularly limited, and can be produced by using known ones. Specifically, it can be produced by polymerizing a (meth) acrylic monomer constituting the main skeleton and a monomer providing the side chain.

(Monomer constituting the main chain)

The (meth) acrylic monomers used in the production of the acrylic pressure-sensitive adhesive resin (A1) include alkyl (meth) acrylates, alkoxy (meth) acrylates, aryloxy (meth) acrylates, aryl (meth) Acrylate and the like. These may be used alone or in combination of two or more.

Specifically, the alkyl (meth) acrylate may be a (meth) acrylate containing an alkyl group having 1 to 20 carbon atoms. Such alkyl (meth) acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- butyl (meth) acrylate, isobutyl (Meth) acrylate, stearyl (meth) acrylate, iso-nonyl (meth) acrylate, iso-octyl ) Acrylate, cyclohexyl (meth) acrylate, and the like.

Specifically, the alkoxy (meth) acrylate may be a (meth) acrylate containing an alkylalkoxy group having 1 to 20 carbon atoms. Such alkoxy (meth) acrylates may include, for example, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and the like.

Specifically, the aryloxy (meth) acrylate may be a (meth) acrylate containing an aryloxy group having 1 to 20 carbon atoms. Examples of such aryloxy (meth) acrylates include phenoxyethyl (meth) acrylate and the like. In addition to these, aryl (meth) acrylates having an aromatic group and a heterocyclic ring described in paragraphs [0036] to [0037] of Japanese Patent Application Laid-Open No. 2010-275524 can also be used. These may be used alone or in combination of two or more.

Specifically, the acyl (meth) acrylate may be a (meth) acrylate having an acyl group having 1 to 20 carbon atoms. Specific examples of such acyl (meth) acrylates include (meth) acrylates having an unsaturated acyl group having 2 to 10 carbon atoms, for example, acrylic (meth) acrylates having an average carbon number of 3 to 9. In this case, the adhesive resin has the effect of further improving the heating durability and wet heat durability of the adhesive layer.

(Monomers providing side chains)

Examples of the monomer providing the side chain used in the production of the acrylic adhesive resin (A1) include monomers such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, hexyl (meth) acrylate, N-2-hydroxyethyl (meth) acrylamide and cyclohexanedimethanol monoacrylate. In addition, alkyl glycidyl ether, Sidil (meth) containing a glycidyl group, such as acrylate compounds and (meth) compound obtained by addition reaction of acrylic acid, and vinyl compounds such as vinylpyridine or styrene. These may be used alone or in combination of two or more.

Among the above examples, when a monomer having at least one hydroxyl group is used, a hydroxyl group may be added to the pressure-sensitive adhesive resin (A). In this case, the durability of the adhesive layer can be further improved. Examples of the monomer having at least one hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-2-hydroxyethyl (meth) acrylamide, cyclohexanedimethanol monoacryl Rate can be used. In one embodiment, at least one of 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and N-2-hydroxyethyl (meth) acrylamide can be used. In this case, the crosslinking force and compatibility with other resins contained in the pressure-sensitive adhesive composition are more excellent and the durability-improving effect is more excellent.

(Production of acrylic pressure-sensitive adhesive resin (A1)) [

The method for producing the acrylic pressure-sensitive adhesive resin (A1) is not particularly limited, and any known method such as a solution polymerization method using a polymerization initiator, an emulsion polymerization method, a suspension polymerization method, a reverse phase suspension polymerization method, a thin film polymerization method, Can be used. Examples of polymerization control methods include an adiabatic polymerization method, a temperature control polymerization method, and an isothermal polymerization method. In addition to the method of initiating polymerization by a polymerization initiator, a method of initiating polymerization by irradiation with radiation, electron beam, ultraviolet ray, or the like may be employed. Among them, in the case of the solution polymerization method using a polymerization initiator, the molecular weight can be easily controlled and impurities can also be reduced. The solution polymerization can be carried out by, for example, using ethyl acetate, toluene, methyl ethyl ketone or the like as a solvent, and using a polymerization initiator as a polymerization initiator in an amount of 100 parts by weight based on the total amount of the starting monomer (monomers constituting the main chain and monomers constituting the side chain) May be added in an amount of 0.01 to 0.50 parts by weight, and the mixture may be reacted under a nitrogen atmosphere at a reaction temperature of 60 ° C to 90 ° C for 3 hours to 10 hours, for example.

Examples of the polymerization initiator include azo compounds such as 2,2-azobisisobutyronitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile) and azobiscyanovaleric acid. compound; tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethyl hexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, tert- Organic peroxides such as roper oxide; And inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate; Can be used. These may be used alone or in combination of two or more.

In producing the acrylic pressure-sensitive adhesive resin (A1), the weight ratio of the monomer constituting the main chain to the monomer providing the side chain may be, for example, 99.99: 0.01 to 80:20 or 99.9: 0.1 to 90:10. In this case, the adhesive property of the acrylic pressure-sensitive adhesive resin (A1) can be further improved.

[Urethane-based pressure-sensitive adhesive resin (A2)]

The urethane-based pressure-sensitive adhesive resin (A2) comprises a polyester polyol and / or a polyether polyol; An isocyanate-based compound.

(Polyester polyol)

The polyester polyol used in the production of the urethane-based pressure-sensitive adhesive resin (A2) is not particularly limited, and a known polyester polyol may be used. For example, the polyester polyol used in the production of the urethane-based pressure-sensitive adhesive resin (A2) may be an acid component such as polycarboxylic acid; And a glycol component or a polyol component.

As the acid component, for example, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid and the like can be used.

The glycol component can be, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, Polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and the like.

Examples of the polyol component include glycerin, trimethylol propane, pentaerythritol, and the like.

In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (beta -methyl- gamma -valerolactone) and polyvalerolactone can also be used.

Among the polyester polyols synthesized as described above, when a polyester polyol having 2 to 3 functional groups is used, the adhesion of the urethane-based pressure-sensitive adhesive resin (A2) can be further improved.

The number average molecular weight of the polyester polyol is not particularly limited, and it can be from a low molecular weight to a high molecular weight. Among these, there is a balance with the number of functional groups of the polyester polyol, but specifically polyester polyols having a number average molecular weight of 1,000 to 5,000 can be used. In this case, the cohesiveness of the urethane-based pressure-sensitive adhesive resin (A2) itself can be increased while maintaining the reactivity appropriately and lowering the degree of gelation. More specifically, a polyester polyol having a number average molecular weight of 1,000 to 3,500 can be used. In this case, in this case, the cohesiveness of the urethane-based pressure-sensitive adhesive resin (A2) itself can be further increased while maintaining the reactivity properly and lowering the degree of gelation.

If necessary, the polyester polyol used in the production of the urethane-based pressure-sensitive adhesive resin (A2) may contain at least one selected from the group consisting of ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, Glycols such as propane and pentaerythritol, and polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine and xylylenediamine may also be prepared.

(Polyether polyol)

The polyether polyol used in the production of the urethane-based pressure-sensitive adhesive resin (A2) is not particularly limited and, for example, a polyalkylene glycol (molecular weight of about 100 to 5500) adduct of a polyhydric alcohol can be used. Examples of polyhydric alcohols include aliphatic dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butylene glycol (tetramethylene glycol) and neopentane glycol; Glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl- , 4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, -Heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerine, pentaglycerine, 1,2,4-butanetriol, 1,2,4-pentane Trivalent alcohols such as triol and trimethylol propane; Erythritol, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,3,5-pentanetetrol, 1,3, Quaternary alcohols such as 4,5-hexanetrol; Pentahydric alcohols such as adonitol, arabitol and xylitol; And hexahydric alcohols such as sorbitol, mannitol, and iditol.

Among them, divalent to tetravalent alcohols such as propylene glycol, 1,4-butylene glycol and glycerin can be used. In this case, the reactivity of the polyether polyol used in the production of the urethane-based pressure-sensitive adhesive resin (A2) can be appropriately controlled.

The polyether polyol used in the production of the urethane-based pressure-sensitive adhesive resin (A2) may be a bifunctional or trifunctional polyether polyol prepared from the above-described polyhydric alcohol. In this case, there is an advantage in favor of controlling the reactivity in the production of the urethane-based pressure-sensitive adhesive resin (A2).

The number average molecular weight of the polyether polyol is not particularly limited, and a polyol having a low molecular weight and a high molecular weight can be used. Among them, although there is a balance with the number of functional groups of the polyether polyol, specifically, a polyether polyol having a number average molecular weight of 1,000 to 5,000 can be used. In this case, the cohesiveness of the urethane-based pressure-sensitive adhesive resin (A2) itself can be increased while maintaining the reactivity appropriately and lowering the degree of gelation. More specifically, a polyether polyol having a number average molecular weight of 1,000 to 3,500 can be used. In this case, in this case, the cohesiveness of the urethane-based pressure-sensitive adhesive resin (A2) itself can be further increased while maintaining the reactivity properly and lowering the degree of gelation.

 (Isocyanate compound)

The isocyanate compound used in the production of the urethane-based pressure-sensitive adhesive resin (A2) is not particularly limited, and examples thereof include known aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates and alicyclic polyisocyanates. Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- Isocyanate, isocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, Diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, etc. The aliphatic polyisocyanate includes trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, Decamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. The aromatic aliphatic polyisocyanate includes ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-di Isocyanate-1,4-dimethylbenzene,?,? '- diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylene diisocyanate, Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- Cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), 1,4-bis Ananedimethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, and the like.

Among the above-mentioned isocyanate compounds, when 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophoronediisocyanate) , The crosslinking property of the adhesive resin (A) can be further improved.

(Production of urethane-based pressure-sensitive adhesive resin (A2)

As described above, the urethane-based pressure-sensitive adhesive resin (A2) according to the present invention comprises a polyester polyol and / or a polyether polyol; An isocyanate-based compound. For example, by reacting a polyester polyol, a polyether polyol and an isocyanate-based compound.

When the polyester polyol and the polyether polyol are used together as the polyol, the molar ratio of the polyester polyol and the polyether polyol (polyester polyol: polyether polyol) is, for example, 10:90 to 90:10, 70:30. In this case, the compatibility of the urethane-based pressure-sensitive adhesive resin (A2) can be further improved.

The amount of the isocyanate compound to be used is, for example, 1 part by weight to 30 parts by weight, or 3 parts by weight (based on 100 parts by weight of the total amount of the polyol to be used (when the polyester polyol and the polyether polyol are used together) To 20 parts by weight. In such a range, the isocyanate compound can be almost completely reacted, and the hydroxyl group can remain in the molecule of the urethane-based pressure-sensitive adhesive resin. In such a case, the hydroxyl group forms a network with an isocyanate-based crosslinking agent described later, so that the durability of the adhesive layer can be further improved.

When the urethane-based pressure-sensitive adhesive resin (A2) is produced, a known catalyst can be used. For example, organic metal compounds such as tertiary amine compounds, tin compounds, non-saponified compounds, and the like can be given.

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

Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tri Butyl tin sulphide, tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyltin trichloroacetate, 2-ethylhexanoic acid tin, etc. .

Examples of the non-saponiferous compound include titanium-based, oleic lead, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, such as dibutyltitanium dichloride, tetrabutyl titanate and butoxy titanium trichloride; Iron such as iron ethylhexanoate and iron acetylacetonate, cobalt such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate have.

These catalysts may be used alone or in combination of two or more.

In one embodiment, when the polyester polyol and the polyether polyol are used together as a polyol, two or more kinds of catalysts can be used rather than a single catalyst. In this case, it is advantageous to control the difference in reactivity of the polyols.

The combination of two or more kinds of catalysts is not particularly limited and a combination of a tertiary amine / organic metal system, a tin system / non-sapphire system, a non-sapphire system / non-sapphire system and the like can be used. In one specific example, a combination of non-saponified / non-sapphire based, for example, 2-ethylhexanoate and naphthene, can be used. The compounding ratio thereof is, in terms of parts by weight, 2-ethylhexanoate / naphthenene-lead acetate <1 (the weight portion of 2-ethylhexanoate is less than the weight of naphthene). In this case, it may be more advantageous to control the difference in reactivity of the polyols.

The amount of the catalyst to be used may be 0.01 part by weight to 1.0 part by weight based on 100 parts by weight of the total amount of the polyol and the isocyanate compound to be used.

The solvent used for producing the urethane-based pressure-sensitive adhesive resin (A2) is not particularly limited, and any known solvent may be used. Examples thereof include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Depending on the type of polyol or isocyanate compound used, a solvent may not be added.

The reaction temperature for producing the urethane-based pressure-sensitive adhesive resin (A2) may be 100 占 폚 or lower, for example, 85 占 폚 to 95 占 폚. With such a temperature range, it becomes easy to control the reaction rate and the crosslinking structure, and it becomes easy to obtain the urethane-based pressure-sensitive adhesive resin (A2) having a predetermined molecular weight and chemical structure.

The reaction time is not particularly limited, and the reaction can be carried out until the residual isocyanate group disappears by, for example, an infrared spectrophotometer (IR).

[Polyester-based pressure-sensitive adhesive resin (A3)]

The polyester-based pressure-sensitive adhesive resin (A3) can be produced by carrying out an esterification reaction using a polyol component and a carboxylic acid component.

The polyol component used in the production of the polyester-based pressure-sensitive adhesive resin (A3) is not particularly limited and known ones are used. For example, there may be mentioned ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Straight-chain aliphatic diols such as 1,9-nonanediol and 1,10-decanediol; Methyl-1, 3-propanediol, 2-methyl-2, 3-propanediol, 2-methyl- Propane diol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl- Aliphatic diol having a hydrocarbon group side chain such as 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,6-hexanediol, etc., Two or more species can be used. Among them, a straight chain aliphatic diol having 2 to 6 carbon atoms, especially an aliphatic diol having 1,4-butanediol, 1,6-hexanediol, ethylene glycol or a side chain of a hydrocarbon group having 1 to 4 carbon atoms, When pentyl glycol is used, the initial tackiness, mechanical strength and heat resistance can be well balanced.

The polyol component used in the production of the polyester-based pressure-sensitive adhesive resin (A3) may contain a small amount of polyether diol or trihydric or higher polyhydric alcohol, if necessary. As examples of such polyether diols and trivalent or more polyhydric alcohols, those described in paragraphs &quot; 0039 &quot; to &quot; 0040 &quot; of Japanese Patent Application Laid-Open No. 2007-45913 can be appropriately employed.

The carboxylic acid component used in the production of the polyester-based pressure-sensitive adhesive resin (A3) is not particularly limited, and known ones can be used. Examples thereof include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and p-oxybenzoic acid, succinic acid, glutaric acid, adipic acid, , Saturated dicarboxylic acids such as aliphatic dicarboxylic acids such as sebacic acid, decanedicarboxylic acid and octadecanedicarboxylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, hexahydrophthalic acid and dimeric acids, and the like, and these may be used singly or in combination.

The carboxylic acid component used in the production of the polyester-based pressure-sensitive adhesive resin (A3) may contain, if necessary, trimellitic acid, trimesic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5- A small amount of a trivalent or more carboxylic acid such as a carboxylic acid may be contained. Among them, when an aromatic dicarboxylic acid, especially terephthalic acid, isophthalic acid, or an aliphatic dicarboxylic acid having 6 to 12 carbon atoms (including carbon of a carboxyl group), especially sebacic acid, is used, the initial tackiness, mechanical strength, .

(Production of polyester-based pressure-sensitive adhesive resin (A3)) [

The amount of the polyol component and the carboxylic acid component used in the production of the polyester-based pressure-sensitive adhesive resin (A3) may be in a balance with each kind, but mainly one equivalent or more of the polyol component per 1 equivalent of the carboxylic acid component may be used. For example, a polyol of 1.2 equivalents or more per equivalent of a carboxylic acid component and 2 equivalents or less per equivalent of a carboxylic acid component can be used. In such a range, the carboxylic acid component in the polyester-based pressure-sensitive adhesive resin (A3) can be substantially completely reacted, and the reworkability can be ensured, and the hydroxyl group can remain in the polyester-based pressure-sensitive adhesive resin (A3) The durability of the layer may be improved.

In the production of the polyester-based pressure-sensitive adhesive resin (A3), a known catalyst can be used. Examples thereof include titanium-based catalysts such as tetraisopropyl titanate and tetra-n-butyl titanate, antimony catalysts such as antimony trioxide, germanium-based catalysts such as germanium oxide, and catalysts such as zinc acetate, manganese acetate, dibutyltin oxide And the like, and one or more of these may be used.

The amount of the catalyst to be used may be 0.01 part by weight to 1.0 part by weight with respect to 100 parts by weight of the total copolymerization component (total amount of polyol and carboxylic acid). Within this range, the ester reaction can sufficiently proceed, and the reaction time can be shortened, and the side reaction can be reduced.

The solvent for producing the polyester-based pressure-sensitive adhesive resin (A3) is not particularly limited, and known ones can be used. Examples thereof include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Depending on the kind of the polyol or carboxylic acid to be used, a solvent may not be added or may be added only to the concentration adjustment after the reaction.

The reaction temperature for producing the polyester-based pressure-sensitive adhesive resin (A3) may be, for example, 100 ° C to 400 ° C, 120 ° C to 300 ° C, or 150 ° C to 280 ° C.

In the production of the polyester-based pressure-sensitive adhesive resin (A3), the pressure of the reaction system may be gradually reduced from the atmospheric pressure. The production of the polyester-based pressure-sensitive adhesive resin (A3) can be carried out, for example, in a reaction system of 10 Pa to 1000 Pa. In addition, the decompression may be performed in several steps over time.

The reaction time is not particularly limited and may be suitably set according to the kind of the polyol or carboxylic acid used in accordance with the conventional method, the decompression conditions, and the like. For example, from 0.5 hour to 20 hours or from 1 hour to 10 hours.

&Lt; Silicon alkoxy oligomer (B) >

Silicone alkoxy oligomers are relatively low molecular weight silicone resins whose main chain is a polyorganosiloxane and the molecular end or side chain is blocked with an alkoxysilyl group.

The silicone alkoxy oligomer (B) may be one having at least one organic substituent selected from methyl, phenyl, epoxy, mercapto, amino, methacrylic and acrylic. In one embodiment, one having at least one selected from methyl and epoxy can be used.

The alkoxyl group of the silicon alkoxy oligomer (B) may be methoxy and / or ethoxy.

The content of the alkoxyl group of the silicon alkoxy oligomer (B) according to the present invention may be, for example, 5 wt% to 60 wt%, 10 wt% to 55 wt%, or 15 wt% to 50 wt%. When the acrylic pressure-sensitive adhesive resin (A1) is used in combination with the silicone alkoxy oligomer (B) as the pressure-sensitive adhesive resin (A) in the above-mentioned range, it is advantageous to simultaneously balance the reworkability and reworkability of the pressure-sensitive adhesive composition. The silicone alkoxy oligomer (B) when used in combination with the silicone alkoxy oligomer (B) is obtained by using the urethane-based pressure-sensitive adhesive resin (A2) or the polyester- And is not particularly limited, and those having the above-mentioned range can be used.

The silicone alkoxy oligomer (B) may be either a product produced by synthesis or a commercially available product, provided that the relative epoxy equivalent and the content of the alkoxyl group satisfy the above-mentioned range.

The silicon alkoxy oligomer (B) can be produced, for example, by hydrolyzing a silane coupling agent having both an epoxy group and an alkoxyl group and an alkoxysilane in the presence of an acid or the like, and conducting a condensation reaction.

The silane coupling agent having both an epoxy group and an alkoxyl group used in the production of the silicon alkoxy oligomer (B) is not particularly limited and includes, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. .

The alkoxysilane used in the production of the silicon alkoxy oligomer (B) is not particularly limited and includes, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, N-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, Bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane can be given.

To prepare the silicone alkoxy oligomer (B), in order for the related epoxy equivalent and alkoxyl group content to satisfy the above-mentioned range, the compounding ratio (for example, molar ratio) of the silane coupling agent having both an epoxy group and the alkoxyl group Can be achieved.

Further, in the production of the silicon alkoxy oligomer (B), for example, a known solvent such as methanol or ethanol may be suitably employed.

The reaction temperature for producing the silicon alkoxy oligomer (B) is not particularly limited and can be adjusted according to the raw material to be used. For example, at room temperature. The reaction time can be adjusted according to the raw material to be used, and can be, for example, 0.5 to 5 hours.

The silicone alkoxy oligomer (B) to be used in the present invention is not particularly limited as long as the relative epoxy equivalent and alkoxyl group content satisfy the above-mentioned range, and the commercially available silicone alkoxy oligomer (B) is commercially available from Shin-Etsu Chemical Co., X-41-1056 (epoxy equivalent: 830 g / mol; alkoxyl group content: 50 wt%), X-41-1059A (epoxy equivalent: 350 g / mol; alkoxyl group content: / Mol; an alkoxyl group content of 27% by weight) and the like can be used.

The epoxy equivalent of the silicone alkoxy oligomer (B) is, for example, 100 g / mol to 2000 g / mol. For example, from 200 g / mol to 1500 g / mol or from 250 g / mol to 1200 g / mol. In this case, the reworkability and durability of the pressure-sensitive adhesive layer can be made more excellent.

In one embodiment, when the acrylic adhesive resin (A1) is used as the adhesive resin (A), when the epoxy equivalent of the silicone alkoxy oligomer (B) is less than 100 g / mol, durability can be improved, I can not. On the other hand, if the epoxy equivalent of the silicone alkoxy oligomer (B) is more than 2000 g / mol, the reworkability of the pressure-sensitive adhesive composition can be improved but the durability is adversely affected.

The silicone alkoxy oligomer (B) when used in combination with the silicone alkoxy oligomer (B) by using the urethane-based pressure-sensitive adhesive resin (A2) or the polyester-based pressure-sensitive adhesive resin (A3) And is not particularly limited, and those having the above-mentioned range may also be used.

The number average molecular weight of the silicone alkoxy oligomer (B) may be, for example, 200 to 50000, 300 to 10000 or 500 to 5000. Within this range, it is more advantageous to make both the durability and the releasability of the pressure-sensitive adhesive composition compatible. In the present specification, the number average molecular weight can be measured by the method shown in Examples described later.

The amount of the silicone alkoxy oligomer (B) added to the pressure-sensitive adhesive composition is 0.1 part by weight to 20 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive resin (A). If the addition amount is less than 0.1 part by weight, the reworkability can not be secured. On the other hand, when the amount is more than 20 parts by weight, the humidity resistance durability deteriorates when the pressure-sensitive adhesive composition is used in a polarizing plate or the like, and the degree of polarization is reduced. For example, the amount of the silicon alkoxy oligomer (B) to be added may be 0.3 part by weight to 10 parts by weight or 0.5 parts by weight to 5 parts by weight. Within the above range, the reworkability and durability of the pressure-sensitive adhesive composition can be further improved, and both properties can be achieved.

&Lt; Crosslinking agent (C) >

The pressure-sensitive adhesive composition of one embodiment may further contain a crosslinking agent (C). In this case, the acrylic pressure-sensitive adhesive resin (A1) and the silicone alkoxy oligomer (B) can be used together to further improve the durability.

The amount of the crosslinking agent (C) to be added is 0.001 to 30 parts by weight, for example, 0.01 to 20 parts by weight, or 0.05 to 10 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive resin (A) have. In this case, the durability can be further improved.

The crosslinking agent (C) is not particularly limited and may be an isocyanate compound, a peroxide, a carbodiimide compound, a titanium coupling agent, a zirconium compound, or a metal aluminate chelate. Among them, when at least one selected from an isocyanate compound and a peroxide is used, the durability of the adhesive layer can be further improved.

[Isocyanate compound]

The isocyanate compound suitably used as the crosslinking agent (C) is not particularly limited, and examples thereof include triaryl isocyanate, dimeric acid diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI) (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) , Aromatic diisocyanates such as 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), triazine isocyanate (TODI) and 1,5-naphthalene diisocyanate (NDI) Ryu; Aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate and norbornadi isocyanatomethyl (NBDI); Alicyclic diisocyanates such as trans cyclohexane 1,4-diisocyanate, isophoronediisocyanate (IPDI), H6-XDI (hydrogenated XDI) and H12-MDI (hydrogenated MDI); Carbodiimide-modified diisocyanates of the above diisocyanates; Or an isocyanurate-modified diisocyanate thereof, and these may be used alone or in combination of two or more. It may also be used in combination with a peroxide to be described later.

Adducts of the isocyanate compound and the polyol compound such as trimethylol propane, and the buretecene and isocyanurate compounds of these isocyanate compounds can also be suitably used.

The isocyanate compound may be synthesized or a commercially available product may be used. Commercially available products of component (D) include, for example, Coronate (R) L, Coronate (R) HL, Coronate (R) HX, Coronate (R) 2030, Coronate Takenate (registered trademark) D-102, Takenate (registered trademark) D-110N, Takenate (registered trademark) D-200, Takenate (registered trademark) (Registered trademark) D-202 (manufactured by Mitsui Chemicals, Inc.), Duranate (registered trademark) 24A-100, Duranate (registered trademark) TPA-100, Duranate (registered trademark) Duraate (registered trademark) P301-75E, Duraanate (registered trademark) E402-90T, Duraanate (registered trademark) E405-80T, Duraanate (registered trademark) TSE- Duraate (registered trademark) D-201 (manufactured by Asahi Kasei Kagaku Co., Ltd.), Sumidur (registered trademark) N-75, N-3200, N-3300 Tan Co., Ltd.). Of these, Coronate® L, Coronate® HL, Coronate® HX, Takenate® D110N, Duraanate® 24A-100, Dyuranate® (registered trademark) TPA-100 is more preferable, and Coronate (registered trademark) L, Coronate (registered trademark) HX, and Dyuranate (registered trademark) 24A-100 are more preferable.

When the isocyanate compound is used as the crosslinking agent (C), the above-mentioned pressure-sensitive adhesive resin (A) used in the present invention preferably contains a hydroxyl group. In this case, the hydroxyl group and the isocyanate compound form a network, so that the durability of the pressure-sensitive adhesive composition of the present invention can be improved.

[peroxide]

As the peroxide suitably used as the crosslinking agent (C), those capable of generating radicals by heating to achieve crosslinking of the pressure-sensitive adhesive composition can be used without limitation. Concretely, when a one-minute half-life temperature is used, for example, a peroxide having a temperature of 80 ° C to 160 ° C, or 90 ° C to 140 ° C, workability and stability can be further improved. The half-life period of peroxide is an index indicating the rate of decomposition of peroxide. The period of time during which the decomposition amount of peroxide is halved. The half-life period at a certain temperature or the decomposition temperature for obtaining half- , Manufacturer catalog, etc., and is described in, for example, Ninth Edition (May 2003) of Organic Peroxide Catalog published by Nippon Oil &amp;

Examples of the peroxide include bis (4-t-butylcyclohexyl) peroxydicarbonate (half-life temperature for one minute is 92.1 ° C), bis (sec-butylcyclohexyl) peroxydicarbonate Butylperoxydicarbonate (1 minute half-life temperature 92.4 占 폚), t-butyl peroxyneodecanoate (1 minute half life temperature 103.5 占 폚), t-hexyl peroxypivalate N-octanoyl peroxide (half-life temperature for 1 minute: 117.4 占 폚), 1,1-dihydroxybutyrate (1 minute half-life temperature: 110.3 占 폚) (1 minute half life temperature 124.3 占 폚), bis (4-methylbenzoyl) peroxide (1 minute half life temperature 128.2 占 폚), dibenzoyl peroxide Half-life temperature of 130.0 占 폚) and t-butyl peroxybutyrate (1 minute half-life temperature of 136.1 占 폚). , The crosslinking reaction efficiency can be used to excellent bis (4-t- butyl-cyclohexyl) peroxy dicarbonate and di lauroyl peroxide, di-benzoyl peroxide. Particularly, bis (4-t-butylcyclohexyl) peroxydicarbonate is preferable from the viewpoint of decomposition temperature. These may be used alone or in combination of two or more. The isocyanate compound may be used in combination with the above-mentioned isocyanate compound.

[Carbodiimide compound]

The carbodiimide compound suitably used as the crosslinking agent (C) is not particularly limited, and examples thereof include those described in paragraphs &quot; 0039 &quot; to &quot; 0046 &quot; of Japanese Patent Laid- The formula can be used.

[Titanium coupling agent]

Examples of the titanium coupling agent suitably used as the crosslinking agent (C) include, for example, those described in paragraph &quot; 0072 &quot; of Japanese Patent Laid-Open Publication No. 2014-085616, Can be used.

[Zirconium compound]

The zirconium compound suitably used as the cross-linking agent (C) is not particularly limited, and for example, those described in paragraph [0073] of Japanese Patent Laid-Open Publication No. 2014-085616, or those suitably modified can be used .

[Metal aluminum chelate]

The metal aluminum chelate suitably used as the crosslinking agent (C) is not particularly limited, and for example, those described in paragraph &quot; 0058 &quot; of Japanese Patent Laid-Open Publication No. 2012-229373, have.

&Lt; Silane coupling agent (D) >

The pressure-sensitive adhesive composition of one embodiment may further contain a silane coupling agent (D) in view of improvement in durability.

The silane coupling agent (D) means that two or more of the molecules have different reactors without having a siloxane bond, and should be distinguished from the silicon alkoxy oligomer (B) according to the present invention.

The silane coupling agent (D) is not particularly limited and includes, for example, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, ethyltrimethoxysilane, N-butyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, Vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Methacryloxypropylmethyldimethoxysilane,? -Methacryloxy Propyl trimethoxysilane, gamma -metac ? -Acryloxypropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropylmethyldimethoxysilane, N -? - methacryloxypropyltrimethoxysilane, (aminoethyl) -? - aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropyltriethoxysilane,? -aminopropyltrimethoxysilane,? -aminopropyltri Mercaptopropyltrimethoxysilane,? -Mercaptopropylmethyldimethoxysilane, bis- (3-mercaptopropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane, - [triethoxysilyl] propyl) tetrasulfide, and? - isocyanate propyl triethoxysilane. In addition, a silane coupling agent having a functional group such as an epoxy group (glycidoxy group), an amino group, a mercapto group, or a (meth) acryloyl group, a silane coupling agent containing a functional group having reactivity with these functional groups, A compound having a hydrolyzable silyl group obtained by reacting a polyisocyanate or the like at an arbitrary ratio with respect to each functional group may be used.

The silane coupling agent may be synthesized or a commercially available product may be used. Examples of commercially available silane coupling agents include KBM-303, KBM-403, KBE-402, KBE-403, KBE-502, KBE-503, KBM-5103, KBM-573, KBM- , KBE-846, and KBE-9007 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

These silane coupling agents may be used alone or in combination of two or more.

In one embodiment, the silane coupling agent (D) may be added in an amount of 0.0001 part by weight to 10 parts by weight based on 100 parts by weight of the adhesive resin (A). For example, 0.001 to 5 parts by weight or 0.01 to 3 parts by weight, the durability of the adhesive layer can be further improved.

{Usage}

The above-mentioned pressure-sensitive adhesive composition of the present invention is suitable for various uses. For example, an optical member such as an optical film. In particular, it can be more suitably used when it is applied to an optical film which has recently become thin and light. Such an optical film may be an optical compensation film such as a polarizing plate, a retardation plate for preventing coloring, a viewing angle enlarging film for improving the viewing angle of a liquid crystal monitor, a luminance improving film for enhancing the contrast of a display, .

In the present invention, the form of the pressure-sensitive adhesive layer formed by the above-described pressure-sensitive adhesive composition, the form of the optical member in which the pressure-sensitive adhesive layer is formed on the optical film and the like, the form in which the optical member is the pressure- , A mode in which the optical member is applied to an image display device such as a liquid crystal display device, an organic EL display device, a plasma display (PDP), or the like.

<Adhesive Layer>

Another embodiment of the present invention provides an adhesive layer formed by the above-described pressure-sensitive adhesive composition.

The pressure-sensitive adhesive layer of one embodiment can be formed by applying the above-described pressure-sensitive adhesive composition of the present invention onto one side of a substrate or a release film, and drying and removing the solvent or the like. Further, at the time of applying the pressure-sensitive adhesive composition, one or more kinds of solvents may be appropriately added.

As a substrate to which the adhesive layer is applied, a separator described later can be used.

The coating method is not particularly limited, and various known methods can be used. For example, a roll coating method, a kiss roll coating method, a gravure coating method, a reverse coating method, a roll brush method, a spray coating method, a dip roll coating method, a bar coating method, a knife coating method, an air knife coating method, An extrusion coating method using a lip coater method, a die coater, or the like.

As a method for drying the solvent present in the pressure-sensitive adhesive composition, an appropriate method may be adopted depending on the purpose. For example, a method of heating and drying the coating film can be used. The heat drying temperature may be, for example, from 40 캜 to 200 캜, from 50 캜 to 180 캜, or from 70 캜 to 170 캜. By setting the heating temperature within the above range, an adhesive layer having excellent adhesive properties can be obtained.

In addition, the drying time can be appropriately set. For example, 5 seconds to 20 minutes, 5 seconds to 10 minutes, or 10 seconds to 5 minutes.

The thickness (dry film thickness) of the pressure-sensitive adhesive layer is not particularly limited and can be appropriately set in accordance with the intended use. For example, when used in an optical film, it may be 1 탆 to 100 탆, 5 탆 to 50 탆, and 10 탆 to 30 탆. In this case, the durability can be improved while thinning the optical film.

The adhesive layer in one embodiment may have an initial adhesive strength of 0.2 N / 25 mm to 1.6 N / 25 mm as measured by JIS Z0237 under conditions of 23 deg. C, a relative humidity of 50%, a peeling angle of 180 and a peeling speed of 300 mm / min. Within the above range, the actual reworkability and adhesion can be made compatible at a superior level. The specific adhesive strength of the adhesive layer is measured according to the method of measuring the workability of the following examples.

The pressure-sensitive adhesive layer of one embodiment was subjected to heat treatment at 50 ° C for 48 hours under the conditions of 23 ° C, 50% relative humidity, 180 ° peel angle, and 300 mm / min peel rate, measured by JIS Z0237 The adhesive force may be 0.3 N / 25 mm to 2.5 N / 25 mm. Within the above range, the actual reworkability and adhesion can be made to a more excellent level. The specific adhesive strength of the adhesive layer is measured according to the method of measuring the workability of the later-described embodiment

The adhesive layer of one embodiment may have a transmittance reduction amount of 0.1% to 1.0% according to the following formula 1.

[Formula 1]

Transmittance reduction amount (%) = {(T0-Ts) / T0} * 100

In the above formula (1), T0 is the initial transmittance measured before the durability evaluation of the sample, and Ts is the transmittance after treatment at 60 DEG C and 95% RH for 500 hours.

In this range, the adhesive layer can further improve the optical properties.

When the adhesive layer of one embodiment is exposed to the air, the adhesive layer can be protected with a sheet (separator) or the like which has been peeled off until it is provided for practical use.

Examples of the constituent material of the separator include plastic films such as polyethylene, polypropylene, polyethylene terephthalate and polyester film, porous materials such as paper, cloth and nonwoven fabric, nets, foamed sheets, metal foils, , But plastic films are suitably used because of their excellent surface smoothness.

The thickness of the separator is usually about 5 to 200 占 퐉 or about 5 to 100 占 퐉.

If necessary, the separator can be subjected to antistatic treatment such as mold releasing treatment, antifouling treatment, coating type, kneading type, and vapor deposition type with silicone, fluorine, long chain alkyl or fatty acid amide releasing agent or silica powder . Particularly, when the surface of the separator is appropriately subjected to the peeling treatment such as the silicon treatment, the long-chain alkyl treatment, the fluorine treatment, etc., the peelability from the adhesive layer can be further improved.

&Lt; Adhesive type optical film &

Another embodiment of the present invention provides an optical member in which the adhesive layer of the present invention is formed on at least one side of an optical film. Here, an example of the optical member is an adhesive optical film. The term "adhesive optical film" refers to an optical film having the adhesive layer of the present invention. Further, since the optical film also includes the form of a polarizing plate, the adhesive optical film according to the present invention also includes the form of a pressure-sensitive polarizing plate.

In one embodiment, the above-mentioned pressure-sensitive adhesive composition may be used by directly applying the pressure-sensitive adhesive composition on one side or both sides of the optical film to form an adhesive layer, and the adhesive layer may be previously formed on the base material or the separator, Or may be transferred to both surfaces. Before transfer, the surface of the optical film may be subjected to a treatment such as corona treatment, plasma treatment, formation of an easy-to-adhere layer, formation of an antistatic layer and the like depending on the material thereof. Also, the adhesion facilitating treatment may be performed on the surface of the adhesive layer. In one embodiment, when the easy-to-adhere layer is formed between the optical film and the pressure-sensitive adhesive layer for an optical film of the present invention, the optical film and the pressure-sensitive adhesive layer can be more strongly adhered.

(Easy adhesion layer)

The material for forming the adhesion facilitating layer may be one which exhibits good adhesion to both the adhesive layer and the optical film (for example, a transparent protective film in a polarizing plate) and forms a film having excellent cohesive strength. For example, various polymers, sols of metal oxides, silica sol, and the like can be used. Among them, polymers are particularly preferably used.

Examples of polymers suitable for use in the present invention include oxazoline group-containing polymers, polyurethane resins, polyester resins, and polymers containing amino groups in the molecule. Of these, oxazoline group-containing polymers are more preferably used.

Examples of such oxazoline group-containing polymers include commercially available products such as EPOCROS series (for example, Epocross WS700) manufactured by Nippon Shokubai Co., But are not limited to these. In addition, polyurethane-based resins, polyester-based resins, polymers containing amino groups in molecules, and the like are disclosed in Japanese Patent Laid-Open Publication No. 2011-105918, paragraphs 0107 to 0113 .

For example, an undercoating agent for forming an easy-to-adhere layer can be coated on an optical film by a coating method such as a coating method, a dipping method, or a spraying method, and then dried to form an easy-to-adhere layer.

The thickness (dry film thickness) of the adhesion-facilitating layer is about 10 nm to 5000 nm, specifically, 50 nm to 500 nm. With such a range, it is possible to maintain the optical characteristics while exhibiting a bulky property and exhibiting sufficient strength and sufficient adhesion.

The optical film used in the adhesive optical film of the present invention is not particularly limited and includes those used for forming an image display device such as a liquid crystal display device, but the type is not particularly limited. For example, a polarizing plate, a retardation plate, an optical compensation film, a brightness enhancement film, or a laminate thereof may be used.

Hereinafter, a case of an embodiment in which the optical film is a polarizing plate will be described.

(Polarizer)

In one embodiment, a polarizing plate that can be used as an optical film can be produced by bonding a protective film and a polarizer using an adhesive by a conventionally known method, followed by heat drying or curing by ultraviolet rays or electron beams. The applied adhesive develops adhesiveness by curing with drying, ultraviolet ray, electron beam or the like to constitute an adhesive layer.

The polarizer is not particularly limited and conventionally known polarizers can be used. For example, a dichroic material such as iodine or a dichroic dye is adsorbed on a hydrophilic polymer film such as a polyvinyl alcohol film, a partially foamed polyvinyl alcohol film, or an ethylene / vinyl acetate copolymer system partially saponified film, A stretched polyvinyl alcohol film, a stretched polyvinyl alcohol film, a polyvinyl alcohol dehydrated film, a polyvinyl chloride dehydrochlorinated film, and the like.

Among them, a polarizer prepared by dyeing a polyvinyl alcohol film having an average degree of polymerization of 2000 to 2800 and a degree of saponification of 90 to 100 mol% by iodine and uniaxially stretching by 3 to 8 times can be used. More specifically, such a polarizer can be obtained, for example, by dipping a polyvinyl alcohol film in an aqueous solution of iodine and stretching it.

The iodine aqueous solution is preferably immersed in an aqueous solution containing, for example, 0.1% by weight to 1.0% by weight of iodine and / or potassium iodide. If necessary, it may be immersed in an aqueous solution of boric acid or potassium iodide at 50 to 70 DEG C, or may be immersed in water at 25 DEG C to 35 DEG C in order to prevent washing or staining. The stretching may be performed after dyeing with iodine, or may be stretched while being dyed, followed by stretching, followed by dyeing with iodine. After dyeing and stretching, it may be washed with water and dried at 35 ° C to 55 ° C for 1 minute to 10 minutes. A variety of such polarizers are commercially available.

The thickness of the polarizer is not particularly limited, but is generally from 5 탆 to 80 탆.

As the protective film, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like can be used. Examples thereof include cellulose resins such as triacetyl cellulose, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyamides (Meth) acrylic resin, cyclic polyolefin resin (norbornene resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, epoxy resin, and the like, such as polyolefin resin, polystyrene resin, These mixtures can be used as the material of the protective film.

On the other hand, a transparent protective film or a thermosetting resin such as a (meth) acryl-based, urethane-based, acrylic urethane-based, epoxy-based or silicone- Resin can be used.

The thickness of the polarizing plate is not particularly limited, but may be 20 탆 to 200 탆. For example, when the thickness is 100 mu m or less, 75 mu m or less, or 50 mu m or less, thinning is more advantageous. Such a thin polarizing plate can more remarkably exhibit the effect of the pressure-sensitive adhesive composition of the present invention.

The method for producing the polarizing plate is not particularly limited and, for example, after the application of the adhesive, the polarizing plate and the protective film can be bonded together by a roll laminator or the like. After the bonding, the curing process may be carried out suitably by drying, ultraviolet rays, electron beams, or the like. When the adhesive is applied, it may be applied to either the protective film or the polarizer, or may be applied to both. The adhesive may be applied such that the thickness of the adhesive layer after drying is 10 nm to 300 nm. The adhesive is not particularly limited and may be appropriately adopted from those known in accordance with the material of the polarizer. For example, when a polyvinyl alcohol-based film is used as the polarizer, an acrylic, epoxy, or acrylic-epoxy system may be used as the polyvinyl alcohol-based adhesive or the ultraviolet-curable adhesive. The thickness of the adhesive layer may be, for example, 10 nm to 200 nm for the polyvinyl alcohol adhesive and 0.2 to 10 m for the ultraviolet curable adhesive. In this case, the adhesive layer can obtain a sufficient adhesive force while obtaining a uniform in-plane thickness.

In the present invention, an adhesive type polarizing plate in which an adhesive layer is formed can also be provided. The configuration and manufacturing of the adhesive type polarizing plate are the same as those in the case of the above-mentioned adhesive type optical film, and the description is omitted here.

<Image Display Device>

Another embodiment of the present invention relates to an image display apparatus using at least one of the optical members described above.

The image display device is not particularly limited, and examples thereof include a liquid crystal display device, an organic EL display device, and a plasma display (PDP). In the case of a thin image display apparatus, the effect of the above-described pressure-sensitive adhesive composition can be more remarkably exhibited.

Example

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the technical scope of the present invention is not limited to the following Examples.

In the following operation, unless otherwise stated, the measurement of the operation, physical properties and the like is carried out under conditions of 23 占 폚 and 55% RH (relative humidity).

Production Example 1: Preparation of adhesive resin (A1-1)

In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser, 99 parts by weight of n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 4 parts by weight of 4-hydroxybutyl acrylate (Osaka Yuki Kagakukyo Ltd.) and 0.15 part by weight of 2,2'-azobisisobutyronitrile (manufactured by Wako Junyaku Kogyo Co., Ltd.) as a polymerization initiator were added to 100 parts by weight of ethyl acetate, And nitrogen gas was introduced with gentle stirring. After replacing the nitrogen gas, the liquid temperature in the flask was controlled to about 55 캜 and polymerization reaction was carried out for 5 hours to prepare a solution of an acrylic pressure-sensitive adhesive resin (A1-1) having a solid content of 15% (w / w).

The weight average molecular weight of the obtained acrylic pressure-sensitive adhesive resin (A1-1) was 2.1 million, and the viscosity was 8000 mPa · s.

Production Examples 2 to 3: Preparation of adhesive resins (A1-2) and (A1-3)

The adhesive resin (A1-A) having a solid content of 15% (w / w) was obtained in the same manner as in Production Example 1, except that the kind or the ratio of the monomers forming the acrylic adhesive resin was changed as shown in Table 1. [ 2) to (A1-3) were prepared.

The weight average molecular weights of the pressure-sensitive adhesive resins (A1-2) to (A1-3) obtained were all 2.1 million, and the viscosity was 8000 mPa · s.

Production Example 4: Preparation of adhesive resin (A2)

To the four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was added 51.9 weight parts of polyester polyol P-1010 (bifunctional polyester polyol, OH of 112, molecular weight of 1,000, Kuraray Co., 32.2 parts by weight of Adeka polyether G-1500 (trifunctional polyether polyol, trifunctional, OH of 109, number average molecular weight of 1,500, manufactured by ADEKA), 15.9 parts by weight of isophoronediisocyanate (Sumitomo Bayer Co., Ltd.) , 66.7 parts by weight of toluene, 0.03 part by weight of 2-ethylhexanoate as a catalyst and 0.04 part by weight of naphthenic acid were charged, gradually heated to 90 캜 and reacted for 4 hours. Residual isocyanate groups were observed at around 2260 cm ^-1 using an infrared spectrophotometer (IR). When the peak around 2260 cm ^-1 disappeared, the reaction was terminated and the solid content was 60% (w / w) m &lt; 2 &gt; / s.

The resulting urethane-based pressure-sensitive 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.

Production Example 5: Preparation of adhesive resin (A3)

A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 11.7 parts by weight of ethylene glycol, 18.6 parts by weight of neopentyl glycol, 11.8 parts by weight of isophthalic acid, 57.9 parts by weight of sebacic acid, And 0.15 part by weight of titanate were charged and the mixture was heated at 150 to 270 DEG C for 150 minutes to carry out the esterification reaction. Subsequently, the pressure of the reaction system was gradually reduced to 30 minutes later, the pressure was reduced to 133 Pa, . And diluted with ethyl acetate to obtain a polyester-based pressure-sensitive adhesive resin (A3) solution of a pressure-sensitive adhesive resin (A3) having a solid content of 60% (w / w) and a viscosity of 3,000 mPa · s.

The resulting polyester-based pressure-sensitive adhesive resin (A3) had a number average molecular weight of 13,000, a weight average molecular weight of 38,000, and an acid value of 0.3 KOHmg / g.

Preparation Example 6: Preparation of silicone alkoxy oligomer (B1)

440 parts by weight (2 mol) of 3-glycidoxypropylmethyldimethoxysilane, 272 parts by weight (2 mol) of methyltrimethoxysilane, 70 parts by weight of methanol and 26.8 parts by weight of acetic acid were added to a 1 liter Injected into a separable flask, and stirred at room temperature. 49.5 parts by weight (2.8 mol) of ion-exchanged water was charged into the flask, and the mixture was stirred at room temperature for 2 hours. Thereafter, the solvent was distilled off at normal pressure until the temperature of the reaction solution became 110 ° C to obtain a liquid of a colorless transparent silicone alkoxy oligomer (B1) having a solid content of 98.0% (w / w) and a viscosity of 250 mPa · s .

The resulting silicone alkoxy oligomer (B1) had a polystyrene reduced number average molecular weight of 15000, an epoxy equivalent of 350 g / mol and an alkoxyl group content of 17% by weight.

Preparation Example 7: Preparation of silicon alkoxy oligomer (B2)

6285 parts by weight (0.285 mole) of 3-glycidoxypropylmethyldimethoxysilane, 505.2 parts by weight (3.715 mole) of methyltrimethoxysilane, 270 parts by weight of methanol and 26.8 parts by weight of acetic acid were added to a 1 liter Injected into a separable flask, and stirred at room temperature. 49.5 parts by weight (2.8 moles) of ion-exchanged water was added into the flask. And the mixture was stirred at room temperature for 2 hours. Thereafter, the solvent was distilled off at normal pressure until the temperature of the reaction liquid became 110 캜 to obtain a liquid of a colorless transparent silicone alkoxy oligomer (B2) having a solid content of 98.5% (w / w) and a viscosity of 300 mPa..

The resulting silicone alkoxy oligomer (B2) had a polystyrene reduced number average molecular weight of 1000, an epoxy equivalent of 3200 g / mol and an alkoxyl group content of 42% by weight.

Preparation Example 8: Preparation of silicone alkoxy oligomer (B3)

(3.715 mols) of 3-glycidoxypropylmethyldimethoxysilane, 36 weight parts (0.285 mole) of methyltrimethoxysilane, 270 weight parts of methanol and 26.8 weight parts of acetic acid were added to a 1 liter Injected into a separable flask, and stirred at room temperature. 49.5 parts by weight (2.8 mol) of ion-exchanged water was charged into the flask, and the mixture was stirred at room temperature for 2 hours. Thereafter, the solvent was distilled off at normal pressure until the reaction liquid temperature became 110 캜 to obtain a colorless transparent silicone alkoxy oligomer (B3) liquid having a solid content of 98.2% (w / w) and a viscosity of 270 mPa..

The resulting silicone alkoxy oligomer (B3) had a polystyrene reduced number average molecular weight of 1000, an epoxy equivalent of 230 g / mol and an alkoxyl group content of 2% by weight.

The weight average molecular weight, number average molecular weight, epoxy equivalent, alkoxyl group content, viscosity and the like in the above Production Examples were measured by the following methods.

1) Measurement of weight average molecular weight (Mw)

It was measured by GPC (gel permeation chromatography).

· Analyzer: Toso Co., Ltd., HLC-8120GPC

· Column: Toso products, G7000H _XL + GMH _XL + GMH _XL

· Column size: Each 7.8 mmφ × 30 cm 90 cm in total

Column temperature: 40 ° C

· Flow rate: 0.8 ml / min

Injection amount: 100 μl

Eluent: Tetrahydrofuran

Detector: Differential refractometer (RI)

Standard sample: Polystyrene

2) Measurement of the number average molecular weight (Mn)

It was measured by GPC (gel permeation chromatography).

· Analyzer: Toso Co., Ltd., HLC-8120GPC

· Column: TSKgel, SuperHZM-H / HZ4000 / HZ2000

Column size: 6.0 mm Inner diameter x 150 mm

Column temperature: 40 ° C

· Flow rate: 0.6 ml / min

· Injection amount: 20 μl

Eluent: Tetrahydrofuran

Detector: Differential refractometer (RI)

Standard sample: Polystyrene

3) Measurement of epoxy equivalence

The epoxy equivalent was measured in accordance with the JIS K7236 (2004) test method.

(Measurement of alkoxyl group content)

The content of the alkoxyl groups was determined by the separation and quantification of alkoxyl groups by gas chromatography (Analytical Chemistry 17 (9), 1102-1107, 1968).

4) Measurement of viscosity

The viscosity was measured by a Brookfield viscometer DVII + Pro (spindle number 63, number of revolutions of 12 rpm) while controlling the temperature of the polymer solution in a glass bottle at 25 캜.

Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Sample name A1-1 A1-2 A1-3 A2 A3 Kinds Acrylic Acrylic Acrylic Urethane-based Polyester-based Monomer component (parts by weight) BA 99 99 95 - - 2HEA - 0.1 - - - 4HBA One - - - AA - 0.9 5 - - P-1010 - - - 51.9 - G-1500 - - - 32.2 - IPDI - - - 15.9 - Ethylene glycol - - - - 11.7 Neopentyl glycol - - - - 18.6 Isophthalic acid - - - - 11.8 Sebasan - - - - 57.9 The weight average molecular weight 2.1 million 2.1 million 2.1 million 5.0 million 3.8 million BA: n-butyl acrylate (manufactured by Nihon Shokubai Co., Ltd.)
2HEA: 2-hydroxyethyl acrylate (manufactured by Nihon Shokubai Co., Ltd.)
4HBA: 4-hydroxyethyl acrylate (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.)
AA: Acrylic acid (manufactured by Nihon Shokubai Co., Ltd.)
IPDI: Isophorone diisocyanate (manufactured by Sumitomo Bayer Co., Ltd.)
P-1010: difunctional polyester polyol (Kuraray Co., Ltd.)
G-1500: Adeka polyether G-1500 (trifunctional polyether polyol)

&Lt; Example 1 >

Preparation of pressure-sensitive adhesive composition

As the silicone alkoxy oligomer (B), X-41-1053 (epoxy equivalent weight: 830 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the solid content of the adhesive resin (A1-1) / Mol) and 0.1 part by weight of an isocyanate crosslinking agent, Takenate D110N (75% by weight ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate, 3 isocyanate groups in one molecule, manufactured by Mitsui Chemicals, Inc.) , A solution (solid content 15% (w / w)) of the acrylic pressure-sensitive adhesive composition was prepared.

Formation of adhesive layer

The solution of the acrylic pressure-sensitive adhesive composition thus obtained was applied on one side of a silicone-treated polyethylene terephthalate (PET) film (MRF38, manufactured by Mitsubishi Kagaku Polyester Film Co., Ltd.) having a thickness of 38 탆, And dried at 100 캜 for 2 minutes to form a pressure-sensitive adhesive layer.

Production of Polarizer with Adhesive Layer

(Fabrication of Thin Polarizer)

A polyvinyl alcohol film having a thickness of 20 占 퐉 was stretched to 3 times while dyeing in an iodine solution at a concentration of 0.3 wt% at 30 占 폚 for 1 minute between rolls having different velocity ratios. Thereafter, the total draw ratio was increased up to 6 times by immersing in an aqueous solution containing boric acid at a concentration of 4 wt% at a concentration of 4 wt% and potassium iodide at a concentration of 10 wt% for 0.5 min. Subsequently, the substrate was washed by immersing in an aqueous solution containing potassium iodide at a concentration of 1.5% by weight at 30 DEG C for 10 seconds, and then dried at 50 DEG C for 4 minutes to obtain a polarizer. An acrylic film (lactone-modified acrylic resin film) having a thickness of 20 占 퐉 was bonded to one surface of the polarizer with a polyvinyl alcohol-based adhesive to prepare a thin polarizing plate having a total thickness of 27 占 퐉.

(Production of Polarizer with Adhesive Layer)

The polarizer side of the thin polarizer thus obtained was subjected to a corona treatment with a corona discharge amount of 80 [W · min / m 2]. Next, on the side of the polarizer, a silicon film-treated PET film on which the adhesive layer obtained as described above was formed was transferred to produce a polarizer with a pressure-sensitive adhesive layer.

&Lt; Examples 2 to 8 and 10 to 11 >

As shown in Table 2, the kind of the pressure-sensitive adhesive resin (A) and its addition amount, the kind of the silicon alkoxy oligomer (B) and its addition amount, the kind of the crosslinking agents (C-1) and (C- ) And a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane) (D) and the addition amount thereof (or not added) In the same manner as in the operation of Example 1, a polarizing plate with a pressure-sensitive adhesive layer corresponding to each of Examples was produced.

X-41-1056 and X-41-1059A are manufactured by Shin-Etsu Chemical Co., Ltd., and Peryl TCP is manufactured by Nippon Oil Co., Ltd.

&Lt; Example 9 >

As shown in Table 2, the kind of the pressure-sensitive adhesive resin (A) and its addition amount, the kind of the silicon alkoxy oligomer (B) and its addition amount, the kind of the crosslinking agents (C-1) and (C- ) And the kind of the silane coupling (D) and the addition amount (or not added) of the silane coupling agent (A) were changed to the thin polarizing plate in the same manner as in the operation of Example 1.

Next, a wire primer was applied to the polarizer side of the thin polarizing plate obtained above to form an easy-to-adhere layer (thickness: 50 nm). The priming agent was diluted with a mixed solution of water and isopropyl alcohol (manufactured by Nihon Shokubai Co., Ltd., product name "Epochros WS-700") containing an oxazoline polymer to prepare a solution having a solid concentration of 0.6 % (w / w).

Thereafter, a pressure-sensitive adhesive layer of a PET film subjected to silicone treatment on which the above-obtained pressure-sensitive adhesive layer was formed was bonded to the easy-to-adhere layer side to prepare the pressure-sensitive polarizing film of Example 9.

&Lt; Comparative Examples 1 to 20 &

(C-1) and (C-2) as the crosslinking agents (C-1) and (C-2) ), The kind of the silane coupling agent (the addition amount thereof) (or the addition amount thereof) and the kind of the silane coupling agent (D) and the addition amount thereof (or not added) were changed. To prepare a corresponding polarizer with a pressure-sensitive adhesive layer.

The adhesive resin (A) The silicone alkoxy oligomer (B) Kinds content
(Parts by weight) Kinds content
(Parts by weight) Epoxy equivalent
(g / mol) Alkoxy group content
(weight%) Number average molecular weight Example 1 A1-1 100 X-41-1053 One 830 50 1200 Example 2 A1-1 100 X-41-1056 One 280 17 700 Example 3 A1-1 100 X-41-1056 0.5 280 17 700 Example 4 A1-1 100 X-41-1056 10 280 17 700 Example 5 A1-1 100 X-41-1059A One 350 43 1000 Example 6 A1-1 100 B1 One 350 17 15000 Example 7 A1-1 100 X-41-1056 One 280 17 700 Example 8 A1-1 100 X-41-1056 One 280 17 700 Example 9 A1-1 100 X-41-1056 One 280 17 700 Example 10 A2 100 X-41-1056 One 280 17 700 Example 11 A3 100 X-41-1056 One 280 17 700 Comparative Example 1 A1-1 100 - 0 - - - Comparative Example 2 A1-1 100 X-41-1056 0.05 280 17 700 Comparative Example 3 A1-1 100 X-41-1056 22 280 17 700 Comparative Example 4 A1-1 100 B2 One 3200 42 1000 Comparative Example 5 A1-1 100 B3 One 230 2 1000 Comparative Example 6 A1-3 100 X-41-1056 One 280 17 700 Comparative Example 7 A1-3 100 X-41-1056 5 280 17 700 Comparative Example 8 A1-3 100 - 0 - - - Comparative Example 9 A1-2 100 X-41-1056 One 280 17 700 Comparative Example 10 A1-3 100 X-41-1056 One 280 17 700 Comparative Example 11 A2 100 - 0 - - - Comparative Example 12 A2 100 X-41-1056 0.05 280 17 700 Comparative Example 13 A2 100 X-41-1056 22 280 17 700 Comparative Example 14 A2 100 B2 One 3200 42 1000 Comparative Example 15 A2 100 B3 One 230 2 1000 Comparative Example 16 A3 100 - 0 - - - Comparative Example 17 A3 100 X-41-1056 0.05 280 17 700 Comparative Example 18 A3 100 X-41-1056 22 280 17 700 Comparative Example 19 A3 100 B2 One 3200 42 1000 Comparative Example 20 A3 100 B3 One 230 2 1000

The crosslinking agent (C-1) The crosslinking agent (C-2) Silane coupling agent (D) Kinds content
(Parts by weight) Kinds content
(Parts by weight) Kinds content
(Parts by weight) Example 1 D110N 0.1 - - - - Example 2 D110N 0.1 - - - - Example 3 D110N 0.1 - - - - Example 4 D110N 0.1 - - - - Example 5 D110N 0.1 - - - - Example 6 D110N 0.1 - - - - Example 7 D110N 0.1 Perroil TCP 0.1 - - Example 8 D110N 0.1 - - KBM-403 0.1 Example 9 D110N 0.1 - - - - Example 10 D110N 3 - - - - Example 11 D110N 3 - - - - Comparative Example 1 D110N 0.1 - - - - Comparative Example 2 D110N 0.1 - - - - Comparative Example 3 D110N 0.1 - - - - Comparative Example 4 D110N 0.1 - - - - Comparative Example 5 D110N 0.1 - - - - Comparative Example 6 D110N 0.1 - - - - Comparative Example 7 D110N 0.1 - - - - Comparative Example 8 D110N 0.1 - - - - Comparative Example 9 D110N 0.1 - - - - Comparative Example 10 D110N 3 - - - - Comparative Example 11 D110N 3 - - - - Comparative Example 12 D110N 3 - - - - Comparative Example 13 D110N 3 - - - - Comparative Example 14 D110N 3 - - - - Comparative Example 15 D110N 3 - - - - Comparative Example 16 D110N 3 - - - - Comparative Example 17 D110N 3 - - - - Comparative Example 18 D110N 3 - - - - Comparative Example 19 D110N 3 - - - - Comparative Example 20 D110N 3 - - - -

&Lt; Evaluation of physical properties &

The following evaluations were carried out on each polarizing plate (sample) with an adhesive layer prepared in the above Examples and Comparative Examples. The results of each evaluation are shown in Table 4.

1. Durability

Each sample was attached to a non-alkali glass (Eagle XG, a product of Corning Incorporated) having a thickness of 37 inches and a thickness of 0.7 mm using a laminator. Then, the sample was autoclaved at 50 DEG C and 0.5 MPa for 15 minutes to completely adhere the sample to the non-acrylic glass.

To the sample subjected to such treatment,

(1) treatment at 85 캜 for 500 hours (heating test),

(2) After treatment (humidification test) for 500 hours in an atmosphere of 60 DEG C / 95% RH,

(3) A heat shock (HS) test was conducted after a total of 300 cycles of 85 ° C and -40 ° C for 1 hour,

The appearance between the polarizing plate and the glass was visually evaluated based on the following criteria.

A: No appearance change such as foaming, peeling, no peeling was observed;

?: A little, but peeling or foaming at the end, but no problem in practical use;

DELTA: peeling or foaming at the end, but no special problem unless it is a special use;

X: There is a significant peeling at the end portion, and there is a problem in practical use.

2. Re-workability

Each sample was cut into a width of 25 mm and a length of 100 mm, and the plate was attached to a non-alkali glass plate (Eagle XG, product of Corning Incorporated) having a thickness of 0.7 mm using a laminator.

Then, the autoclave treatment was carried out at 50 DEG C and 5 atm for 15 minutes to completely adhere (initial). Thereafter, heat treatment was carried out for 48 hours under a drying condition of 50 캜 (after heating). The adhesion of each sample was measured as follows.

The adhesive strength was measured at a peel angle of 180 deg. And a peeling rate of 300 mm / min under the conditions of 23 deg. C and a relative humidity of 50% in a tensile tester (Orienc Co., Ltd., Tensilon universal material testing machine STA- (N / 25 mm) at the time of peeling in accordance with the method of testing the adhesive tape and the adhesive sheet of Z0237.

Further, samples were peeled from a non-alkali glass plate by a human hand with respect to a sample (cut in a length of 420 mm × a width of 320 mm) similar to the object to which the adhesive force was measured, and the actual reworkability Respectively. The evaluation of the actual reworkability was carried out by repeating the evaluation three times in this order and three times.

&Amp; cir &amp; &amp; cir &amp; &amp; cir &amp;

?: Some of the three films were broken but peeled off again by peeling;

?: All three films were broken but peeled off again by peeling;

X: The adhesive was left on all three sheets, or the film could not be peeled off even after peeling a few times.

The results of the adhesion and the workability of the sample were collected and the reworkability of each sample was evaluated.

3. Optical properties

The central portion of each sample bonded to the alkali-free glass before the durability evaluation and after the treatment for 60 hours and 95% RH for 500 hours was measured for the unit transmittance (%) using an integral formula transmittance meter (product of Murakami Color Research Laboratories: DOT- ) Ts, and the reduction amount (%) of the transmittance calculated according to the formula in the following Table 1 from the initial evaluation before the durability evaluation after the treatment at 60 占 폚 and 95% RH for 500 hours was evaluated as optical characteristics.

[Formula 1]

Transmittance reduction amount (%) = {(T0-Ts) / T0} * 100

In the above formula (1), T0 is the initial transmittance measured before the durability evaluation of the sample, and Ts is the transmittance after treatment at 60 DEG C and 95% RH for 500 hours.

durability Re-workability Optical characteristic
(%) 85 ° C,
500h 85 ° C,
95% RH,
500h HS test
300 cycles Early After heating Adhesion
(N / 25 mm) real
Re-workability Adhesion
(N / 25 mm) real
Re-workability Example 1 ◎ ◎ ◎ 1.1 ◎ 2.4 ○ 0.4 Example 2 ◎ ◎ ◎ 0.5 ◎ 1.2 ◎ 0.5 Example 3 ◎ ◎ ◎ One ◎ 2 ◎ 0.2 Example 4 ◎ ◎ ◎ 0.2 ◎ 0.3 ◎ 0.8 Example 5 ◎ ◎ ◎ 0.6 ◎ 1.3 ◎ 0.5 Example 6 ○ ○ ○ 0.2 ◎ 0.5 ◎ 0.2 Example 7 ◎ ◎ ◎ 0.9 ◎ 1.5 ◎ 0.5 Example 8 ◎ ◎ ◎ One ◎ 1.6 ◎ 0.5 Example 9 ◎ ◎ ◎ 0.5 ◎ 1.2 ◎ 0.5 Example 10 ◎ ◎ ◎ 1.2 ◎ 1.7 ◎ 0.5 Example 11 ◎ ◎ ◎ 1.5 ◎ 1.5 ◎ 0.5 Comparative Example 1 ○ ○ ○ 3.1 △ 6.5 × 0.4 Comparative Example 2 ○ ○ ○ 3.2 △ 6.3 × 0.4 Comparative Example 3 ○ × ○ 0.2 ◎ 0.2 ◎ 30.6 Comparative Example 4 ○ × ○ 0.6 ◎ One ◎ 0.5 Comparative Example 5 ○ × ○ 0.7 ◎ 1.2 ◎ 0.3 Comparative Example 6 ◎ ◎ ◎ 4.5 × 12.5 × 0.8 Comparative Example 7 ◎ ◎ ◎ 4.2 × 11.4 × One Comparative Example 8 ◎ ◎ ◎ 6.2 × 11.5 × 0.6 Comparative Example 9 ◎ ◎ ◎ 2.7 ○ 4.8 × 0.5 Comparative Example 10 ◎ ◎ ◎ 3.5 △ 6.5 × 0.6 Comparative Example 11 ○ △ ○ 2.2 ○ 4.5 × 0.3 Comparative Example 12 ○ △ ○ 2.5 ○ 5.2 × 0.5 Comparative Example 13 × × ○ 0.1 ◎ 0.2 ◎ 25.2 Comparative Example 14 ○ × ○ 0.4 ◎ 0.8 ◎ 0.5 Comparative Example 15 ○ × ○ 0.5 ◎ One ◎ 0.4 Comparative Example 16 ○ △ ○ 1.5 △ 4.3 × 0.3 Comparative Example 17 ○ △ ○ 1.7 △ 4.8 × 0.3 Comparative Example 18 ○ × ○ 0.1 △ 0.6 × 26.5 Comparative Example 19 ○ × ○ 0.4 ◎ 0.9 ◎ 0.3 Comparative Example 20 ○ × ○ 0.6 ◎ 1.2 ◎ 0.4

As is apparent from Table 4, the thin polarizing plates (Examples 1 to 11) with an adhesive layer using the pressure-sensitive adhesive composition of the present invention were excellent in releasability which can be easily peeled off, And it was found that the durability against the durability test was excellent. Further, in any of the polarizing plates with a pressure-sensitive adhesive layer (Examples 1 to 11) using the pressure-sensitive adhesive composition of the present invention, the amount of decrease in the transmittance before the durability evaluation (initial) after treatment at 60 ° C and 95% RH for 500 hours was small, And the optical characteristics were also excellent.

Claims (16)

100 parts by weight of a pressure-sensitive adhesive resin (A); 0.1 to 20 parts by weight of a silicon alkoxy oligomer (B) having an epoxy equivalent of 100 g / mol to 2000 g / mol and an alkoxyl group content of 5% by weight to 60% by weight; Wherein the pressure-sensitive adhesive composition is a pressure-
Wherein the pressure-sensitive adhesive resin (A) is at least one kind selected from the group consisting of an acrylic pressure-sensitive adhesive resin (A1), a urethane pressure-sensitive adhesive resin (A2) and a polyester pressure-sensitive adhesive resin (A3) obtained by polymerizing a monomer containing no carboxyl group. The pressure-sensitive adhesive composition according to claim 1, wherein the silicone alkoxy oligomer (B) has a number average molecular weight of 300 to 10,000. The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition further comprises a crosslinking agent (C). The pressure-sensitive adhesive composition according to claim 3, wherein the content of the crosslinking agent (C) is 0.01 part by weight to 20 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive resin (A). The pressure-sensitive adhesive composition according to claim 3, wherein the cross-linking agent (C) is at least one selected from an isocyanate-based compound and a peroxide. The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive resin (A) further contains a hydroxyl group. The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition further comprises 0.001 to 5 parts by weight of a silane coupling agent (D) based on 100 parts by weight of the pressure-sensitive adhesive resin (A). The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive resin (A) has a weight average molecular weight of 20,000 to 2,500,000. An adhesive layer formed by the pressure-sensitive adhesive composition according to claim 1. The pressure-sensitive adhesive sheet according to claim 9, wherein the adhesive layer has an initial adhesive strength of 0.2 N / 25 mm to 1.6 N / 25 mm measured by JIS Z0237 under conditions of 23 deg. C, a relative humidity of 50%, a peeling angle of 180 and a peeling rate of 300 mm / / RTI &gt; The pressure-sensitive adhesive sheet according to claim 9, wherein the pressure-sensitive adhesive layer is formed on the sample heated at 50 캜 for 48 hours under conditions of 23 캜, relative humidity of 50%, peeling angle of 180 占 and peeling rate of 300 mm / min according to JIS Z0237 And an adhesive strength after heating of 0.3 N / 25 mm to 2.5 N / 25 mm. The pressure-sensitive adhesive sheet according to claim 9, wherein the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer having a transmittance reduction amount of 0.1% to 1.0%
[Formula 1]
Transmittance reduction amount (%) = {(T0-Ts) / T0} * 100
In the above formula (1), T0 is the initial transmittance measured before the durability evaluation of the sample, and Ts is the transmittance after treatment at 60 DEG C and 95% RH for 500 hours. Optical film; And an adhesive layer according to claim 9 formed on at least one side of the optical film. The optical member according to claim 13, further comprising an easy adhesion layer between the optical film and the adhesive layer. 14. The optical member according to claim 13, wherein the optical film is a polarizing plate, and the polarizing plate has a thickness of 100 m or less. An image display apparatus using at least one optical member according to claim 13.