WO2016032187A1 - Adhesive composition, adhesive layer, optical member using same, and image display device - Google Patents

Abstract

The present invention relates to: an adhesive composition comprising 100 parts by weight of an adhesive resin (A), and 0.1-20 parts by weight of a silicone alkoxy oligomer (B) having an epoxy equivalence of 100-2,000 g/mol and an alkoxy group content of 5-60 wt%, wherein the adhesive resin (A) is at least one selected from the group consisting of an acrylic adhesive resin (A1) obtained by polymerizing a monomer containing no carboxyl groups, a urethane-based adhesive resin (A2) and a polyester-based adhesive resin (A3); an optical member using the same; and an image display device. Therefore, the present invention can provide, in an adhesive composition capable of being used in a thin image display device and a thin optical member, a means capable of making the rework property facilitating exfoliation be compatible with the durability in an endurance test by heating, humidification and the like in the adhered state.

Description

Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, optical member and image display device using the same

The present invention relates to an adhesive composition, an adhesive layer, an optical member, and an image display device.

Liquid crystal panels, such as a liquid crystal display device, contain optical members, such as a polarizing plate provided with a polarizer, and various optical films for improving the display quality of a display. These optical members are attached to the liquid crystal panel using an adhesive.

In this case, the optical member may use a pressure-sensitive adhesive film formed in advance in the form of an adhesive layer on one surface. Such an adhesive film is convenient to handle and has an advantage of omitting a process of drying the adhesive. In addition, when the optical member using the adhesive film is bonded to a liquid crystal display device or the like, for example, when a bonding position is wrong or a defect occurs in which a foreign material enters the bonding surface, the optical member is peeled off from the liquid crystal panel and then rebonded. It is possible. Through this, it is possible to reduce the occurrence of defects and to reuse expensive liquid crystal cells.

On the other hand, in recent years, the demand for thin liquid crystal display devices has been sought to further reduce the thickness by using thin liquid crystal panels or thin optical members. However, since the thin liquid crystal panel, the thin optical member, or the like uses chemically etched glass or is thin, the thin liquid crystal display may be cracked or broken when using a pressure-sensitive adhesive aimed only at conventional durability.

For this reason, the adhesive used for a thin liquid crystal panel or a thin optical member does not have an adhesive residue, and is required to be easily peeled off (also referred to as "rework property"). In addition, the pressure-sensitive adhesive is also required to have adhesion durability such that no defects such as peeling or lifting occur in durability tests conducted by heating and humidification, which are usually performed as an environmental promotion test.

As described above, the pressure-sensitive adhesive used in the thin liquid crystal display device is required to achieve rework resistance and adhesion durability, but it is not easy to achieve this by the conventional technology alone.

For example, conventionally, a pressure-sensitive adhesive composition (see Patent Document 1) comprising an acrylic polymer and a polymer silane coupling agent having a siloxane skeleton in the side chain and having an alkoxyl group, an epoxy group, a polyether group, etc. (see Patent Document 1), an acrylic polymer and a silicone Various pressure-sensitive adhesive compositions for optical films such as pressure-sensitive adhesive compositions containing oligomers (see Patent Documents 2 to 4), or pressure-sensitive adhesive compositions (see Patent Documents 5 to 6) containing an acrylic copolymer containing a carboxyl group and a silane coupling agent are reported. It is. However, such pressure-sensitive adhesive compositions of Patent Documents 1 to 6 were not sufficient to attain both the reworkability and the durability required for the thin image display device and the thin optical member.

(Prior art document)

(Patent Document 1) JP H07-331206 A

(Patent Document 2) JP 2006-316256 A

(Patent Document 3) JP 2010-007044 A

(Patent Document 4) JP 2012-012537 A

(Patent Document 5) WO 2012/26456 A

(Patent Document 6) JP 2008-176173 A

One object of the present invention is a pressure-sensitive adhesive composition that can be used in a thin image display device and a thin optical member, for durability test by reworkability that can be easily peeled off and heating and humidification in an adhesive state. It is an object to provide a means capable of achieving durability.

Another object of the present invention is to provide an adhesive layer formed of the above-described pressure-sensitive adhesive composition, an optical member such as 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 is 100 parts by weight of the adhesive resin (A); 0.1 parts by weight to 20 parts by weight of a silicon alkoxy oligomer (B) having an epoxy equivalent weight of 100 g / mol to 2000 g / mol and an alkoxyl group content of 5% by weight to 60% by weight; It is a pressure-sensitive adhesive composition containing,

The said adhesive resin (A) is an adhesive composition which is 1 or more types chosen from the group which consists of an acrylic adhesive resin (A1) obtained by superposing | polymerizing the monomer which does not contain a carboxyl group, a urethane adhesive resin (A2), and a polyester adhesive resin (A3). It is about.

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

Another embodiment of the invention is an optical film; And the 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 of the above-described optical members.

Embodiments of the present invention, particularly in the pressure-sensitive adhesive composition that can be used in a thin image display device and a thin optical member, durability due to reworkability and easy heating and humidification in the adhesive state that can easily peel off the adhesive film Durability to the test is compatible.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated in detail.

Pressure-sensitive adhesive composition

One embodiment of the present invention is 100 parts by weight of the adhesive resin (A); And 0.1 parts by weight to 20 parts by weight of a silicon alkoxy oligomer (B) having an epoxy equivalent weight of 100 g / mol to 2000 g / mol and an alkoxyl group content of 5% by weight to 60% by weight; 1 type selected from the group consisting of acrylic adhesive resin (A1) obtained by polymerizing the monomer which does not contain a carboxyl group, and the said adhesive resin (A) does not contain a carboxyl group, urethane type adhesive resin (A2), and polyester type adhesive resin (A3) It relates to the pressure-sensitive adhesive composition described above. Through such a configuration, the pressure-sensitive adhesive composition of the present invention can realize both properties of reworkability and durability at an excellent level, and advantageous for use in a thin liquid crystal display device.

In the present specification, "(meth) acrylate" is a generic term for acrylate and methacrylate. Similarly, the compound containing (meth), such as (meth) acrylic acid, is also a general term for the compound which has "meta" in a name, and the compound which does not have "meta". For this reason, "(meth) acryl" includes both acryl and methacryl. "(Meth) acrylate" includes both an acrylate and a methacrylate. "(Meth) acrylic acid" includes both acrylic acid and methacrylic acid.

In the present specification, "resin" refers to oligomers, polymers, copolymers and the like obtained by polymerizing monomers used as basic units.

<Adhesive resin (A)>

Although the mechanism which can solve the subject of this invention is estimated as follows, it is not limited to this.

The adhesive resin (A) of one embodiment may not include a carboxyl group or may contain a minimum amount. In this specification, "the adhesive resin (A) contains a carboxyl group in a minimum content" means that the adhesive resin does not contain any of the carboxyl groups or contains only the terminal.

The adhesive resin (A) containing such a carboxyl group in a minimum content prevents the alkoxyl group of the silicone alkoxy oligomer (B) described below from reacting with the carboxyl group to prevent the formation of silanol groups in the side chain of the silicone alkoxy oligomer (B). Through this, the alkoxyl group which helps to improve the reworking property is modified to a silanol group, thereby preventing the amount of the alkoxyl group from being reduced. In this case, there exists an effect which prevents the rework property of an adhesion layer from falling. In addition, an increase in highly reactive silanol groups is prevented, and a coupling reaction occurs on the surface of the silanol group and the glass contained in the liquid crystal display device or the like to prevent the rework property from being lowered. In addition, the adhesive resin (A) has an advantageous effect to be applied to a liquid crystal display device having an IPS panel or the like that is weak to acidity of the carboxyl group.

In other words, the pressure-sensitive adhesive resin (A) of the present invention is produced in a direction (minimization) to lower the content of the carboxyl group as much as possible. In the above description, the "direction of lowering the content of the carboxyl group as much as possible '' means that the carboxyl group is present at the end of the adhesive resin (A) even if it is present, and is preferably produced in a direction in which the carboxyl group does not exist at all.

The adhesive resin (A) of one embodiment is an acrylic adhesive resin (A1) obtained by polymerizing a monomer containing no carboxyl group, a urethane adhesive resin (A2), a polyester adhesive resin (A3), or (A1) to (A3) It is composed of two or more selected from the group consisting of. In this case, content of the carboxyl group contained in adhesive resin (A) can be minimized. Through this, in particular, the reworkability of the adhesive layer can be remarkably improved as compared with the case of using a resin containing a large amount of carboxyl groups.

The adhesive resin (A) of one embodiment may have a weight average molecular weight of 20,000 to 2.5 million.

For example, when using an acrylic adhesive resin (A1), the weight average molecular weight of the adhesive resin (A) may be 300,000 to 2.5 million or 500,000 to 2.2 million. In the above range, the durability of the adhesive layer can be improved.

For example, when using urethane type adhesive resin (A2) and polyester type adhesive resin (A3), the weight average molecular weight of adhesive resin (A) may be 20,000-100,000 or 30,000-60,000. In the above range, the durability of the adhesive layer can be improved.

In addition, the weight average molecular weight in this specification can be measured by the measuring method described in the Example mentioned later.

The adhesive resin (A) of one embodiment may have a viscosity of, for example, 100 mPa · s to 100000 mPa · s, 300 mPa · s to 50000 mPa · s, or 500 mPa · s to 30000 mPa · s. In the above range, the coating layer to which the pressure-sensitive adhesive composition is applied can be smoothed, and uniformity of the coating layer film thickness is easily obtained.

The adhesive resin (A) of one embodiment may contain a hydroxyl group. In this case, the durability of the adhesion layer can be improved. When using the adhesive resin (A) containing a hydroxyl group, especially when using together with the crosslinking agent which is an isocyanate type compound mentioned later, a network is formed by bridge | crosslinking a hydroxyl group and an isocyanate type compound, and the durability of an adhesion layer is improved more. You can.

[Acrylic adhesive resin (A1)]

Acrylic adhesive resin (A1) is a monomer which does not contain a carboxyl group, It is not specifically limited, It can manufacture using a well-known thing. Specifically, it can manufacture by polymerizing the (meth) acrylic-type monomer which comprises a main skeleton, and the monomer which provides a side chain.

(Monomer constituting the main chain)

The (meth) acrylic monomers used in the production of the acrylic adhesive resin (A1) include alkyl (meth) acrylates, alkoxy (meth) acrylates, aryloxy (meth) acrylates, aryl (meth) acrylates and acyl (meth) s. Acrylates and the like. These may include single or 2 types or more.

Specifically, the alkyl (meth) acrylate may be a (meth) acrylate including an alkyl group having 1 to 20 carbon atoms. Such alkyl (meth) acrylates are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate and iso-butyl (meth) acrylate. , 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, iso-nonyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, and the like.

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

Specifically, aryloxy (meth) acrylate may be a (meth) acrylate including an aryloxy group having 1 to 20 carbon atoms. As such aryloxy (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned, for example. In addition to these, aryl (meth) acrylates having an aromatic group and a heterocycle described in paragraphs “0036” to “0037” of JP2010-275524A can also be used. These may be used independently or may be used in combination of 2 or more type.

Specifically, the acyl (meth) acrylate may be a (meth) acrylate including an acyl group having 1 to 20 carbon atoms. As such acyl (meth) acrylate, the (meth) acrylate containing a C2-C10 unsaturated acyl group, for example, the acryl-type (meth) acrylate of 3-9 carbon atoms on average can be used. In this case, the adhesive resin has an effect of further improving the heating durability and the wet heat durability of the adhesive layer.

(Monomer providing side chains)

As a monomer which provides the side chain used for manufacture of acrylic adhesive resin (A1), 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 6- hexanediol mono (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane Di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclo Hexyl (meth) acrylate, N-2-hydroxyethyl (meth) acrylamide, cyclohexane dimethanol monoacrylate, etc. are mentioned, Also, an alkyl glycidyl ether, an aryl glycidyl ether, and a writing are mentioned. 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 independently or may be used in combination of 2 or more type.

Among the above examples, when using a monomer having at least one hydroxyl group, a hydroxyl group can be imparted to the adhesive resin (A). In this case, the durability of the adhesive layer can be further improved. As monomers having at least one hydroxyl group, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-2-hydroxyethyl (meth) acrylamide, cyclohexanedimethanol monoacrylic Rate can be used. In one embodiment, one or more 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 included in the pressure-sensitive adhesive composition is more excellent, and the durability improvement effect is more excellent.

(Manufacture of Acrylic Adhesive Resin (A1))

The method for producing the acrylic adhesive resin (A1) is not particularly limited, and conventionally known methods such as solution polymerization method, emulsion polymerization method, suspension polymerization method, reverse phase suspension polymerization method, thin film polymerization method, spray polymerization method using a polymerization initiator, etc. Can be used. As a polymerization control method, adiabatic polymerization method, temperature controlled polymerization method, isothermal polymerization method, etc. are mentioned. Moreover, in addition to the method of starting superposition | polymerization with a polymerization initiator, the method of irradiating radiation, an electron beam, an ultraviolet-ray, etc., and initiating superposition | polymerization can also be employ | adopted. Among them, in the case of a solution polymerization method using a polymerization initiator, the molecular weight can be easily controlled and impurities can be reduced. In the solution polymerization method, for example, ethyl acetate, toluene, methyl ethyl ketone or the like is used as a solvent, and a polymerization initiator is specifically described with respect to 100 parts by weight of the total amount of the raw material monomer (the monomer constituting the main chain and the monomer providing the side chain). As 0.01 weight part-0.50 weight part, it can be made to react for 3 hours-10 hours in 60 degreeC-90 degreeC in nitrogen atmosphere, for example.

Examples of the polymerization initiator include azo, such as 2,2-azobisisobutyronitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile), and azobiscyanovaleric acid. compound; tert-butylperoxy pivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butylperoxide, cumene hydroperoxide, benzoyl peroxide, tert-butylhydride Organic peroxides such as loperoxide; Inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate; Can be used. These may be used independently or may be used together 2 or more types.

When preparing the acrylic adhesive resin (A1), the weight ratio of the monomer constituting the main chain to the monomer that provides 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 characteristic of acrylic adhesive resin (A1) can be improved further.

[Urethane adhesive resin (A2)]

Urethane type adhesive resin (A2) is polyester polyol and / or polyether polyol; Isocyanate type compound; can be manufactured by making it react.

(Polyester polyol)

The polyester polyol used for manufacture of a urethane type adhesive resin (A2) is not specifically limited, A well-known polyester polyol can be used. For example, polyester polyol used for manufacture of a urethane type adhesive resin (A2) is 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 is, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, Polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentylglycol, butylethylpentanediol and the like can be used.

Examples of the polyol component include glycerine, trimethylolpropane, pentaerythritol, and the like.

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

In the polyester polyol synthesize | combined as mentioned above, when using 2-3 polyfunctional polyester polyol, the adhesive force of a urethane type adhesive resin (A2) can be improved further.

Moreover, the number average molecular weight of polyester polyol is not specifically limited, It can use from a low molecular weight thing to a high molecular weight thing. Among them, there is also a balance with the number of functional groups of the polyester polyol, but specifically, a polyester polyol having a number average molecular weight of 1,000 to 5,000 can be used. In this case, the cohesive force of the urethane-based adhesive resin (A2) itself can be increased while maintaining the reactivity as appropriate and lowering the degree of gelation. More specifically, a polyester polyol having a number average molecular weight of 1,000 to 3,500 may be used. In this case, in this case, the cohesion force of the urethane-based adhesive resin (A2) itself can be further increased while maintaining the reactivity as appropriate and lowering the degree of gelation.

In addition, if necessary, the polyester polyol used in the production of the urethane-based adhesive resin (A2) is partially ethylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol, glycerine, trimethylol Polyhydric amines, such as glycols, such as propane and pentaerythritol, ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine, can also be manufactured using further.

(Polyether polyol)

The polyether polyol used in the production of the urethane-based adhesive resin (A2) is not particularly limited, and for example, polyalkylene glycol (molecular weight of about 100 to 5500) adduct of a polyhydric alcohol may be used. As a polyhydric alcohol, For example, Aliphatic dihydric alcohols, such as ethylene glycol, propylene glycol, 1, 4- butylene glycol (tetramethylene glycol), neopentane glycol; Glycerine, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3 , 4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5 -Heptane triol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethyl glycerine, pentaglycerine, 1,2,4-butanetriol, 1,2,4-pentane Trihydric alcohols such as triol and trimethylolpropane; Erythritol, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,3,5-pentanetetrol, 1,3, Tetrahydric alcohols such as 4,5-hexanetetrol; Pentahydric alcohols such as adonitol, arabitol, and xylitol; And hexavalent alcohols such as sorbitol, mannitol, and iditol.

Among them, dihydric to tetrahydric alcohols such as propylene glycol, 1,4-butylene glycol and glycerine can be used. In such a case, the reactivity of the polyether polyol used in the production of the urethane-based adhesive resin (A2) can be appropriately controlled.

As the polyether polyol used in the production of the urethane-based adhesive resin (A2), a difunctional to trifunctional polyether polyol prepared from the above-mentioned polyhydric alcohol may be used. In this case, there is an advantage in controlling the reactivity in the production of the urethane-based adhesive resin (A2).

In addition, the number average molecular weight of a polyether polyol is not specifically limited, It can use from a low molecular weight thing to a high molecular weight thing. Among them, there is also a balance with the number of functional groups of the polyether polyol, but specifically, a polyether polyol having a number average molecular weight of 1,000 to 5,000 can be used. In this case, the cohesive force of the urethane-based adhesive resin (A2) itself can be increased while maintaining the reactivity as appropriate and lowering the degree of gelation. More specifically, polyether polyols having a number average molecular weight of 1,000 to 3,500 may be used. In this case, in this case, the cohesion force of the urethane-based adhesive resin (A2) itself can be further increased while maintaining the reactivity as appropriate and lowering the degree of gelation.

 (Isocyanate compound)

As an isocyanate type compound used for manufacture of a urethane type adhesive resin (A2), it does not specifically limit, For example, well-known aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate, etc. are mentioned. As an aromatic polyisocyanate, 1, 3- phenylene diisocyanate, 4, 4'- diphenyl diisocyanate, 1, 4- phenylene diisocyanate, 4, 4'- diphenylmethane diisocyanate, 2, 4- tolylene di isocyanate Isocyanate, 2,6-tolylenediisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanatebenzene, dianisidine diisocyanate, 4,4 ' -Diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, etc. As aliphatic polyisocyanate, 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. Examples of the aromatic aliphatic polyisocyanate are ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-die Isocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylenediisocyanate, 1,3-tetramethylxylylenediisocyanate, etc. are mentioned. Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane diisocyanate. Isocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocy Anate methyl) cyclohexane, 1, 4-bis (isocyanate methyl) cyclohexane, etc. are mentioned.

When 4,4'- diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethyl cyclohexyl isocyanate (isophorone diisocyanate) etc. are used among the above-mentioned isocyanate type compounds. And the crosslinkability of the adhesive resin (A) can be further improved.

(Production of Urethane-based Adhesive Resin (A2))

As described above, the urethane-based adhesive resin (A2) according to the present invention comprises polyester polyol and / or polyether polyol; Isocyanate compound; It can manufacture by making it react. For example, it can be prepared by reacting a polyester polyol, a polyether polyol and an isocyanate compound.

When using polyester polyol and polyether polyol together as a polyol, the molar ratio (polyester polyol: polyether polyol) of a polyester polyol and a polyether polyol is 10: 90-90: 10, or 30: 70-, for example. 70:30. In such a case, the compatibility of the urethane-based adhesive resin (A2) can be further improved.

The amount of isocyanate compound 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 polyols used (total amount thereof when using polyester polyols and polyether polyols together). To 20 parts by weight. If it is this range, an isocyanate type compound can fully react and a hydroxyl group can remain | survive in the molecule | numerator of a urethane type adhesive resin. In such a case, a hydroxyl group may form a network with an isocyanate-based crosslinking agent described later to further improve the durability of the adhesive layer.

A well-known catalyst can be used when manufacturing urethane type adhesive resin (A2). For example, organometallic compounds, such as a tertiary amine compound, a tin compound, and a non-tin compound, etc. are mentioned.

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

As the tin compound, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tri Butyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, 2-ethylhexanoic acid tin, etc. Can be mentioned.

Examples of the non-tin compound include titanium-based compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, lead systems such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, and the like. Iron-based iron and ethyl acetylacetonate; cobalt-based benzoate and cobalt 2-ethylhexanoate; zinc-based naphthenate and zinc 2-ethylhexanoate; and zirconium naphthenate. have.

These catalysts may be used independently and may use two or more types together.

In one embodiment, when polyesterpolyol and polyetherpolyol are used together as a polyol, two or more kinds of catalysts may 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 types of catalysts is not particularly limited, and combinations of tertiary amines / organic metals, tin / non-tin, non-tin / non-tin and the like can be used. In one embodiment, a combination of non-tin / non-tin, for example, lead 2-ethylhexanoate and lead naphthenate can be used. The blending ratio may be, by weight, lead 2-ethylhexanoate / lead naphthenate <1 (the weight part of 2-ethylhexanoate is less than the weight part of lead naphthenate), for example, 0.2 to 0.8. In such cases, it may be more advantageous to control the difference in reactivity of the polyols.

The amount of the catalyst 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 isocyanate compound used.

As a solvent used when manufacturing urethane type adhesive resin (A2), it does not specifically limit, A well-known thing can be used. For example, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned. In addition, depending on the kind of polyol, isocyanate type compound, etc. which are used, a solvent may not be added.

The reaction temperature for preparing the urethane-based adhesive resin (A2) may be 100 ° C or lower, for example, 85 ° C to 95 ° C. If it is such a temperature range, it will become easy to control reaction rate and a crosslinked structure, and it will become easy to obtain urethane type adhesive resin (A2) which has a predetermined molecular weight and a chemical structure.

In addition, reaction time is not specifically limited, For example, it can react until an residual isocyanate group disappears by an infrared spectrophotometer (IR).

[Polyester type adhesive resin (A3)]

Polyester-based adhesive resin (A3) can be manufactured by making esterification reaction using a polyol component and a carboxylic acid component.

It does not specifically limit as a polyol component used for manufacture of polyester adhesive resin (A3), A well-known thing is used. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, Linear aliphatic diols such as 1,9-nonanediol and 1,10-decanediol; Neopentylglycol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl -2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanedi Aliphatic diols having hydrocarbon group side chains such as ol, 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,6-hexanediol, and the like. 2 or more types can be used. Among these, C2-C6 linear aliphatic diol, especially 1, 4- butanediol, 1, 6- hexanediol, ethylene glycol, aliphatic diol which has a C1-C4 hydrocarbon group side chain, especially neo When pentyl glycol is used, initial stage adhesiveness, mechanical strength, and heat resistance can be made to balance well.

Moreover, the polyol component used for manufacture of polyester adhesive resin (A3) may contain a small amount of polyetherdiol and a trivalent or more polyhydric alcohol as needed. As an example of such polyetherdiol and a trivalent or more polyhydric alcohol, the thing of Paragraph "0039"-"0040" of Unexamined-Japanese-Patent No. 2007-45913, for example can be employ | adopted suitably.

The carboxylic acid component used for manufacture of polyester adhesive resin (A3) is not specifically limited, A well-known thing can be used. For example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, p-oxybenzoic acid, succinic acid, glutaric acid, adipic acid, azelaic acid Saturated dicarboxylic acids such as aliphatic dicarboxylic acids such as sebacic acid, decanedicarboxylic acid and octadecanedicarboxylic acid; And unsaturated dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, hexahydrophthalic acid and dimer acids, and the like, and one or two or more thereof can be used.

As for the carboxylic acid component used for manufacture of polyester adhesive resin (A3), trimellitic acid, trimesic acid, a pyromellitic acid, a 1,2, 4- butane tricarboxylic acid, a 1,2,5- hexanetrie as needed You may contain a small amount of trivalent or more carboxylic acids, such as carboxylic acid. Among these, when using aromatic dicarboxylic acid, especially terephthalic acid, isophthalic acid, or aliphatic dicarboxylic acid having 6 to 12 carbon atoms (including carbon of carboxyl group), especially sebacic acid, the initial adhesiveness, mechanical strength and heat resistance are well balanced. Can be compatible.

(Manufacture of polyester adhesive resin (A3))

Although the usage-amount of the polyol component and the carboxylic acid component used when manufacturing polyester-type adhesive resin (A3) has balance with each kind, the polyol component per 1 equivalent of carboxylic acid component can mainly be used 1 equivalent or more. For example, 1.2 equivalents or more of polyols per equivalent of carboxylic acid component to 2 equivalents or less of polyols per equivalent of carboxylic acid component can be used. Within such a range, the carboxylic acid component in the polyester-based adhesive resin (A3) can react almost completely to ensure reworkability, and hydroxyl groups can be left in the polyester-based adhesive resin (A3) to provide adhesion. The durability of the layer may also be improved.

A well-known catalyst can be used when manufacturing polyester adhesive resin (A3). For example, titanium-based catalysts such as tetraisopropyl titanate and tetra-n-butyl titanate, antimony-based compounds such as antimony trioxide, and germanium-based compounds such as germanium oxide, zinc acetate, manganese acetate and dibutyltin oxide Etc. can be used and these 1 type, or 2 or more types can be used.

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

The solvent at the time of manufacturing polyester adhesive resin (A3) is not specifically limited, A well-known thing can be used. For example, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned. In addition, depending on the kind of polyol, carboxylic acid, etc. used, a solvent may not be added and you may add only to the density | concentration after reaction.

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

When preparing the polyester-based adhesive resin (A3) it may be carried out by gradually reducing the pressure of the reaction system from the normal pressure. Production of polyester adhesive resin (A3) can be performed in the reaction system of 10 Pa-1000 Pa, for example. In addition, you may perform several steps of depressurization over time.

In addition, reaction time is not specifically limited, It can set suitably according to the kind of polyol, carboxylic acid, etc. used by a conventional method, pressure reduction conditions, etc. For example, it may be 0.5 hour to 20 hours or 1 hour to 10 hours.

<Silicon alkoxy oligomer (B)>

The silicon alkoxy oligomer is a relatively low molecular silicone resin whose main chain is polyorganosiloxane and whose molecular terminal or side chain is sealed with an alkoxysilyl group.

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

In addition, the alkoxyl group of a silicon alkoxy oligomer (B) can use methoxy and / or ethoxy.

In addition, the alkoxyl group content of the silicone alkoxy oligomer (B) according to the present invention may be, for example, 5% to 60% by weight, 10% to 55% by weight or 15% to 50% by weight. In the above range, when the acrylic adhesive resin (A1) is used in combination with the silicone alkoxy oligomer (B) as the adhesive resin (A), it is advantageous to achieve both the reworkability and the reworkability of the pressure-sensitive adhesive composition. In addition, the silicone alkoxy oligomer (B) when using together with a silicone alkoxy oligomer (B) using urethane type adhesive resin (A2) or polyester type adhesive resin (A3) as adhesive resin (A), About an alkoxyl group content It does not specifically limit, The thing of the said range can be used.

The silicone alkoxy oligomer (B) can be used even if the epoxy equivalent and the alkoxyl group content satisfy | fill the above-mentioned range, even if it was manufactured synthetically or a commercial item.

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

As a silane coupling agent which has both an epoxy group and an alkoxyl group used for manufacture of a silicon alkoxy oligomer (B), it does not specifically limit, For example, 2- (3, 4- epoxycyclohexyl) ethyl trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. may be mentioned. .

It does not specifically limit as an alkoxysilane used for manufacture of a silicon alkoxy oligomer (B), For example, methyl trimethoxysilane, dimethyldimethoxysilane, phenyl trimethoxysilane, methyl triethoxysilane, di Methyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimeth And methoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane and the like.

In the preparation of the silicon alkoxy oligomer (B), in order for the epoxy equivalent and alkoxyl group content to meet the above-mentioned range, a compounding ratio (for example, molar ratio) of the silane coupling agent and alkoxysilane having both an epoxy group and an alkoxyl group, etc. By appropriately adjusting this can be achieved.

Moreover, when manufacturing a silicon alkoxy oligomer (B), well-known solvent, such as methanol or ethanol, can be employ | adopted suitably, for example.

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

The silicone alkoxy oligomer (B) used in the present invention is not particularly limited as a commercial product as long as the epoxy equivalent and the alkoxyl group content of the compound satisfy the above-mentioned range, and are, for example, manufactured by Shin-Etsu Chemical Co., Ltd. X-41-1053 (epoxy equivalent 830 g / mol; alkoxyl group content 50 wt%), X-41-1059A (epoxy equivalent 350 g / mol; alkoxyl group content 42 wt%), X-41-1056 (epoxy equivalent 280 g / Mol; alkoxyl group content 27 weight%) etc. can be used.

The epoxy equivalent in a silicon alkoxy oligomer (B) is 100 g / mol-2000 g / mol, for example. For example, it may be 200 g / mol to 1500 g / mol, or 250 g / mol to 1200 g / mol. In this case, the reworkability and durability of the pressure-sensitive adhesive layer can be compatible to even more excellent levels.

In one embodiment, when the acrylic adhesive resin (A1) is used as the adhesive resin (A), if the epoxy equivalent of the silicone alkoxy oligomer (B) is less than 100 g / mol, durability may be improved, but reworkability may be improved. Can not. On the other hand, when the epoxy equivalent of a silicon alkoxy oligomer (B) is more than 2000 g / mol, the rework property of an adhesive composition can be improved, but it has a bad influence on durability.

Moreover, the silicone alkoxy oligomer (B) when using together with a silicone alkoxy oligomer (B) using urethane type adhesive resin (A2) or polyester type adhesive resin (A3) as adhesive resin (A), with respect to an epoxy equivalent, It does not specifically limit, The thing of the said range can also be used.

The number average molecular weight of the silicon alkoxy oligomer (B) can be used, 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 reworkability of the pressure-sensitive adhesive composition compatible. In addition, in this specification, the number average molecular weight can be measured by the method shown in the Example mentioned later.

The addition amount of the silicone alkoxy oligomer (B) in an adhesive composition is 0.1 weight part-20 weight part with respect to 100 weight part of above-mentioned adhesive resins (A). If the added amount is less than 0.1 part by weight, the reworkability cannot be secured. On the other hand, when the addition amount is more than 20 parts by weight, since the humidification durability deteriorates when the pressure-sensitive adhesive composition is used for the polarizing plate or the like, the degree of polarization falls. For example, the addition amount of the silicon alkoxy oligomer (B) may be 0.3 parts by weight to 10 parts by weight or 0.5 parts by weight to 5 parts by weight. Within this range, the reworkability and durability of the pressure-sensitive adhesive composition can be further improved, and at the same time, two characteristics can be compatible.

<Cross-linking system (C)>

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

The addition amount in the case of containing a crosslinking agent (C) may be 0.001 weight part-30 weight part, for example, 0.01-20 weight part, or 0.05 weight part-10 weight part with respect to 100 weight part of adhesive resin (A). have. In such a case, 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. Moreover, in these, when using at least 1 sort (s) chosen from an isocyanate type compound and a peroxide, durability of an adhesion layer can be improved further.

[Isocyanate compound]

Isocyanate type compound suitably used as a crosslinking agent (C) is not specifically limited, For example, triaryl isocyanate, dimer acid diisocyanate, 2, 4- tolylene diisocyanate (2, 4-TDI), 2, 6 -Tolylene diisocyanate (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), tetramethyl xylidene diisocyanate (TMXDI), triazine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI) Ryu; Aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanatomethyl (NBDI); Alicyclic diisocyanates such as transcyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), H6-XDI (hydrogenated XDI), H12-MDI (hydrogenated MDI); Carbodiimide-modified diisocyanates of the diisocyanates; Or these isocyanurate modified diisocyanate etc. can be mentioned, These can be used 1 type (s) or 2 or more types. Moreover, you may use together with the peroxide mentioned later.

Adducts of polyol compounds such as the isocyanate compound and trimethylolpropane, and the biuret and isocyanurate bodies of these isocyanate compounds can also be suitably used.

In addition, an isocyanate type compound may be synthesize | combined or you may use a commercial item. As a commercial item of the component (D), for example, Coronate (trademark) L, Coronate (trademark) HL, Coronate (registered trademark) HX, Coronate (registered trademark) 2030, Coronate ( Trademark) 2031 (above, Nippon Polyurethane Co., Ltd.), Takenate (registered trademark) D-102, Takenate (registered trademark) D-110N, Takenate (registered trademark) D-200, Takenate (Registered trademark) D-202 (above, Mitsui Chemical Co., Ltd.), Duranate (registered trademark) 24A-100, Duranate (registered trademark) TPA-100, Duranate (registered trademark) TKA-100, Duranate (registered trademark) P301-75E, Duranate (registered trademark) E402-90T, Duranate (registered trademark) E405-80T, Duranate (registered trademark) TSE-100, Duranate (registered trademark) D-101, Duranate (registered trademark) D-201 (above, manufactured by Asahi Kasei Chemical Co., Ltd.), Sumidur (registered trademark) N-75, N-3200, N-3300 (above, Sumika Bayer Ure Tan Co., Ltd.) etc. are mentioned. Among these, Coronate (registered trademark) L, Coronate (registered trademark) HL, Coronate (registered trademark) HX, Takenate (registered trademark) D110N, Duranate (registered trademark) 24A-100, Duranate (registered trademark) ) TPA-100 is preferred, and Coronate® L, Coronate® HX, and Duranate® 24A-100 are more preferred.

Moreover, when using an isocyanate type compound as a crosslinking agent (C), it is preferable that the adhesive resin (A) used for this invention mentioned above contains a hydroxyl group. In this case, it is because a hydroxyl group and an isocyanate type compound form a network, and the durability of the adhesive composition of this invention can be improved.

[peroxide]

As a peroxide used suitably as a crosslinking agent (C), what can generate | occur | produce a radical by heating and can achieve bridge | crosslinking of an adhesive composition can be used without a restriction | limiting. Specifically, when the half-life temperature of 1 minute, for example, using a peroxide of 80 ° C to 160 ° C, or 90 ° C to 140 ° C, workability and stability can be further improved. In addition, the half-life of a peroxide is an index which means the decomposition rate of a peroxide, and is the time which the decomposition amount of a peroxide is half, about the decomposition temperature for obtaining a half-life at arbitrary time, and the half-life time at arbitrary temperature It is described in the manufacturer's catalog and the like, and is described in, for example, the organic peroxide catalog ninth edition (May 2003) issued by Nihon Yushi Corporation.

As such a peroxide, bis (2-ethylhexyl) peroxydicarbonate (1 minute half life temperature 90.6 degreeC), bis (4-t-butyl cyclohexyl) peroxy dicarbonate (1 minute half life temperature 92.1 degreeC), bis-sec Butyl peroxydicarbonate (1 minute half life temperature 92.4 ° C.), t-butyl peroxy neodecanoate (1 minute half life temperature 103.5 ° C.), t-hexyl peroxy pivalate (1 minute half life temperature 109.1 ° C.), t Butyl peroxy pivalate (half life temperature 110.3 ° C.), dilauroyl peroxide (half life temperature 116.4 ° C.), bis-n-octanoyl peroxide (half life temperature 117.4 ° C.), 1,1, 3,3-tetramethyl butylperoxy-2-ethylhexanoate (1 minute half-life temperature 124.3 ° C), bis (4-methylbenzoyl) peroxide (1 minute half-life temperature 128.2 ° C), dibenzoylperoxide (1 minute Half-life temperature 130.0 degreeC), t-butyl peroxy butyrate (1 minute half-life temperature 136.1 degreeC), etc. are mentioned. , The crosslinking reaction efficiency can be used to excellent bis (4-t- butyl-cyclohexyl) peroxy dicarbonate and di lauroyl peroxide, di-benzoyl peroxide. In particular, bis (4-t-butylcyclohexyl) peroxydicarbonate is preferable in view of decomposition temperature. These can use 1 type, or 2 or more types. Moreover, you may use together with the above-mentioned isocyanate type compound.

[Carbodiimide Compound]

As a carbodiimide compound suitably used as a crosslinking agent (C), it does not specifically limit, For example, those described in Paragraph "0039"-"0046" of Unexamined-Japanese-Patent No. 2012-246444, or those suitably Modified ones can be used.

Titanium Coupling Agent

The titanium coupling agent suitably used as the crosslinking agent (C) is not particularly limited, for example, those described in paragraph "0072" of JP-A-2014-085616, or those modified appropriately. Can be used.

Zirconium Compounds

As a zirconium compound suitably used as a crosslinking agent (C), it does not specifically limit, For example, those described in Paragraph "0073" of Unexamined-Japanese-Patent No. 2014-085616, or those modified suitably can be used. .

[Metal Aluminate]

The metal aluminate which is suitably used as the crosslinking agent (C) is not particularly limited and, for example, those described in paragraph "0058" of JP2012-229373A or those modified appropriately can be used. have.

<Silane coupling agent (D)>

The pressure-sensitive adhesive composition of one embodiment may further contain a silane coupling agent (D) from the viewpoint of improving durability.

The silane coupling agent (D) does not have a siloxane bond, and indicates that two or more of the molecules have different reactors and should be distinguished from the silicon alkoxy oligomer (B) according to the present invention.

The silane coupling agent (D) is not particularly limited. For example, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, ethyltrimethoxysilane, Diethyl diethoxysilane, n-butyl trimethoxysilane, n-hexyl triethoxysilane, n-octyl trimethoxysilane, phenyl trimethoxysilane, diphenyl dimethoxysilane, cyclohexyl methyl dimeth Methoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Glycidoxy propyl methyl diethoxy silane, γ- glycidoxy propyl trimethoxy silane, γ- glycidoxy propyl triethoxy silane, γ- methacryloxy propyl methyl dimethoxy silane, γ- methacryloxy Propyltrimethoxysilane, γ-methac Ryloxypropylmethyl diethoxysilane, γ-methacryloxypropyl triethoxysilane, γ-acryloxypropyl trimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N -β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrie Methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis- (3 -[Triethoxysilyl] propyl) tetrasulfide, (gamma) -isocyanate propyl triethoxysilane, etc. are mentioned. Moreover, the silane coupling agent which contains functional groups, such as an epoxy group (glycidoxy group), an amino group, a mercapto group, and a (meth) acryloyl group, the functional group which reacts with these functional groups, another coupling agent, The compound which has hydrolyzable silyl group obtained by making polyisocyanate etc. react with arbitrary functional groups at arbitrary ratios can also be used.

The said silane coupling agent may synthesize | combine or may use a commercial item. As a commercial item of a silane coupling agent, it is KBM-303, KBM-403, KBE-402, KBE-403, KBE-502, KBE-503, KBM-5103, KBM-573, KBM-802, KBM-803, for example. , KBE-846, KBE-9007 (above, Shin-Etsukagaku Kogyo Co., Ltd.), etc. are mentioned.

The said silane coupling agents may be used independently and may be used in combination of 2 or more type.

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

{Usage}

The pressure-sensitive adhesive composition of the present invention described above is suitable for various applications. For example, it can be used more suitably for optical members, such as an optical film. In particular, it can be used more suitably when applied to an optical film that has become thin and soft recently. Examples of such optical films include optical compensation films such as polarizing plates, retardation plates as anti-coloring agents, viewing angle magnification films for improving the viewing angle of liquid crystal monitors, brightness enhancement films for increasing the contrast of displays, and those in which they are laminated. .

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 formed by the pressure-sensitive adhesive layer formed on an optical film, the form of the optical member is a pressure-sensitive adhesive optical film or a pressure-sensitive adhesive polarizing plate, or The optical member may be provided in a liquid crystal display device, an organic EL display device, or an image display device such as a plasma display (PDP).

<Adhesive layer>

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

The pressure-sensitive adhesive layer of one embodiment may be formed by applying the pressure-sensitive adhesive composition of the present invention to one surface of a substrate or a release film, and drying and removing the solvent and the like. In addition, at the time of application | coating of an adhesive composition, 1 or more types of solvent can be added suitably.

Moreover, the separator mentioned later can be used as a base material with which an adhesion layer is apply | coated.

The coating method is not particularly limited, and various known methods can be used. For example, the roll coating method, the kiss roll coating method, the gravure coating method, the reverse coating method, the roll brush method, the spray coating method, the deep roll coating method, the bar coating method, the knife coating method, the air knife coating method, the curtain coating method, Methods, such as the extrusion coating method by a lip coat method and a die coater, are mentioned.

As a method of drying the solvent which exists in an adhesive composition, the appropriate method can be employ | adopted according to the objective. For example, the method of heat-drying a coating film can be used. The heat drying temperature may be, for example, 40 ° C to 200 ° C, 50 ° C to 180 ° C, or 70 ° C to 170 ° C. By making heating temperature into the said range, the adhesion layer which has the outstanding adhesive characteristic can be obtained.

In addition, a drying time can be set suitably. For example, it may be 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 may be appropriately set according to the use purpose. For example, when used for an optical film, it may be 1 μm to 100 μm, 5 μm to 50 μm, and 10 μm to 30 μm. In such a case, the optical film can be thinned and durability can be improved.

The adhesive layer of one embodiment may have an initial adhesive strength of 0.2 N / 25 mm to 1.6 N / 25 mm measured by JIS Z0237 under conditions of 23 ° C., 50% relative humidity, 180 ° peel angle, and 300 mm / min peel rate. In the above range, the actual reworkability and the adhesion can be compatible at an excellent level. The adhesive force of a specific adhesive layer is measured according to the reworkability measuring method of the Example mentioned later.

The pressure-sensitive adhesive layer of one embodiment was measured by JIS Z0237 under conditions of 23 ° C., 50% relative humidity, 180 ° peeling angle, and 300 mm / min peeling rate for a sample heat-treated for 48 hours under 50 ° C. drying conditions. The adhesion may be 0.3 N / 25 mm to 2.5 N / 25 mm. In the above range, the actual reworkability and adhesion can be compatible to a more excellent level. The adhesive force of a specific adhesive layer is measured according to the rework property measuring method of the Example mentioned later.

In one embodiment, the adhesive layer may have a decrease in transmittance of 0.1% to 1.0% according to the following Equation 1.

[Equation 1]

Permeability Reduction (%) = {(T0-Ts) / T0} * 100

In Equation 1, T0 is the initial transmittance measured before the durability evaluation of the sample, Ts is the transmittance after 60 hours 95% 95% RH treatment.

In the above range, the adhesive layer can be further improved optical properties.

When the pressure-sensitive adhesive layer of one embodiment is exposed to air, the pressure-sensitive adhesive layer may be protected by a peeled sheet (separator) or the like 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 films, porous materials such as paper, cloth, and nonwoven fabrics, nets, foam sheets, metal foils, and laminates thereof. Although the suitable thin body of etc. are mentioned, A plastic film is used suitably from the point which is excellent in surface smoothness.

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

In addition, the separator can be subjected to antistatic treatment such as a release agent, antifouling treatment, coating type, kneading type, vapor deposition type, etc., with a release agent, a silica powder, or the like of a silicone, fluorine, long chain alkyl or fatty acid amide, if necessary. . In particular, the peelability from the pressure-sensitive adhesive layer can be further improved by appropriately performing a peeling treatment such as silicon treatment, long chain alkyl treatment, or fluorine treatment on the surface of the separator.

<Adhesive type optical film>

Another embodiment of the present invention also provides an optical member formed by forming the pressure-sensitive adhesive layer of the present invention on at least one side of the optical film. Here, the adhesive optical film is mentioned as an example of an optical member. Moreover, an "adhesive optical film" is an optical film provided with the adhesion layer of this invention. In addition, since the optical film also includes the form of a polarizing plate, the adhesive optical film which concerns on this invention also includes the form of an adhesive polarizing plate.

In one embodiment, the above-described pressure-sensitive adhesive composition may be used by directly applying on one side or both sides of the optical film to form an adhesive layer, and in advance to form the pressure-sensitive adhesive layer on the substrate or separator described above, this one side of the optical film Or you may use by transferring to both surfaces. In addition, before the transfer, the surface of the optical film can be subjected to base treatment such as corona treatment, plasma treatment, formation of an adhesive easy layer, formation of an antistatic layer, or the like depending on the material thereof. Moreover, you may perform an adhesive process also on the surface of an adhesion layer. In one embodiment, when the adhesive easy 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 firmly bonded.

(Adhesive layer)

The material which forms the said easily bonding layer may show favorable adhesiveness in any of an adhesion layer and an optical film (for example, a transparent protective film in a polarizing plate), and can form the film excellent in cohesion force. For example, various polymers, sol of a metal oxide, silica sol, etc. can be used, Especially, polymers are used preferably.

Examples of the polymers suitably used in the present invention include oxazoline group-containing polymers, polyurethane resins, polyester resins, and polymers containing amino groups in molecules. Among these, an oxazoline group containing polymer is used more preferably.

As such an oxazoline group containing polymer, a general commercial item can be used, For example, the EPOCROS series (for example, Epocross WS700) etc. by Nihon Shokubai Co., Ltd. are mentioned, for example. Although it is possible, it is not limited to these. Moreover, what is disclosed in Paragraph "0107"-"0113" of Unexamined-Japanese-Patent No. 2011-105918 is employ | adopted suitably about polyurethane resin, polyester resin, polymers containing an amino group in a molecule | numerator, etc. Can be.

For example, the base agent for forming an adhesive easy layer can be apply | coated and dried by coating methods, such as a coating method, an immersion method, and a spraying method, on an optical film, and an adhesive easy layer can be formed.

The thickness of the easily bonding layer (dry film thickness) is about 10 nm to 5000 nm, specifically, may be 50 nm to 500 nm. Within this range, the optical properties may be maintained while having a bulky property and exhibiting sufficient strength and sufficient adhesiveness.

Although the optical film used for the adhesive optical film of this invention is not specifically limited, What is used for formation of image display apparatuses, such as a liquid crystal display device, Although it does not specifically limit to the kind. For example, a polarizing plate, a retardation plate, an optical compensation film, a brightness improving film, and those in which these are laminated can be used.

Hereinafter, the case of the embodiment whose optical film is a polarizing plate is demonstrated.

(Polarizing plate)

In one embodiment, a polarizing plate that can be used as an optical film can be manufactured by bonding a protective film and a polarizer using an adhesive by a conventionally known method and curing by heat drying or ultraviolet rays, electron beams, or the like. The apply | coated adhesive agent expresses adhesiveness by hardening with drying or an ultraviolet-ray, an electron beam, etc., and comprises an adhesive layer.

There is no restriction | limiting in particular as a polarizer, A conventionally well-known thing can be used. For example, uniaxial materials such as iodine or dichroic dye are adsorbed onto hydrophilic polymer films such as polyvinyl alcohol-based films, partially foamed polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymerized partial saponified films. And polyene oriented films such as stretched, dehydrated polyvinyl alcohol and dehydrochloric acid polyvinyl chloride.

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

As an aqueous solution of iodine, it is preferable to be immersed in the aqueous solution containing 0.1 weight%-1.0 weight% of iodine and / or potassium iodide, for example. Moreover, you may be immersed in aqueous solution, such as boric acid and potassium iodide of 50 degreeC-70 degreeC as needed, and you may be immersed in 25 degreeC-35 degreeC water, in order to wash | clean and to prevent staining. Stretching may be performed after dyeing with iodine, or stretching with dyeing, or dyeing with iodine after stretching. After dyeing and extending | stretching, you may wash with water and you may dry at 35 degreeC-55 degreeC for 1 to 10 minutes. Many kinds of such polarizers are commercially available.

In addition, the thickness of a polarizer is although it does not specifically limit, Usually, they are 5 micrometers-80 micrometers.

As a protective film, the material excellent in transparency, mechanical strength, heat stability, moisture barrier property, isotropy, etc. can be used. For example, cellulose resins such as triacetyl cellulose, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, and polyamides (Meth) acrylic resins such as resins, polyolefin resins, polymethyl methacrylates, cyclic polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, epoxy resins, and Mixtures of these may be used as the material of the protective film.

In addition, a transparent protective film is bonded to one side of the polarizer by an adhesive, but on the other side, a thermosetting resin such as (meth) acrylic, urethane, acrylic urethane, epoxy, silicone, or ultraviolet curable type as a transparent protective film or a protective layer. Resin can be used.

Although the thickness of a polarizing plate is not specifically limited, It may be 20 micrometers-200 micrometers. For example, when 100 micrometers or less, 75 micrometers or less, and 50 micrometers or less, thickness reduction is further advantageous. Such a thin polarizing plate can express the effect of the adhesive composition of this invention more remarkably.

The manufacturing method of a polarizing plate is not specifically limited, For example, after apply | coating an adhesive agent, it can carry out by bonding a polarizer and a protective film by a roll laminator etc .. After joining, you may perform a hardening process with drying, an ultraviolet-ray, an electron beam, etc. suitably. In addition, when apply | coating an adhesive agent, you may apply | coat to either of a protective film and a polarizer, and may apply to both. The adhesive may be applied so that the thickness of the adhesive layer after drying is 10 nm to 300 nm. In addition, it is not specifically limited as an adhesive agent, According to the material of a polarizer, it can employ | adopt suitably from a well-known thing. For example, when using a polyvinyl alcohol-type film as a polarizer, an acryl-type, epoxy-type, and acryl-epoxy clock can be used as a polyvinyl alcohol-type adhesive agent or an ultraviolet curing adhesive agent. The thickness of the adhesive layer may be, for example, 10 nm to 200 nm in a polyvinyl alcohol adhesive, and 0.2 μm to 10 μm in an ultraviolet curable adhesive. In this case, the adhesive layer can obtain sufficient adhesive force while obtaining a uniform in-plane thickness.

In the present invention, an adhesive polarizing plate formed by forming an adhesive layer may also be provided. In addition, since it is the same as that of the adhesive optical film mentioned above about the structure, manufacture, etc. of an adhesive polarizing plate, description is abbreviate | omitted here.

<Image display device>

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

It does not specifically limit as an image display apparatus, For example, a liquid crystal display device, an organic electroluminescence display, a plasma display (PDP), etc. are mentioned. Moreover, in the case of a thin image display apparatus, the effect of the adhesive composition mentioned above can be expressed more remarkably.

Example

Although this invention is demonstrated further in detail using the following example and a comparative example, the technical scope of this invention is not limited only to a following example.

In addition, in the following operation, unless otherwise indicated, measurement of operation, a physical property, etc. are performed on the conditions of 23 degreeC 55% RH (relative humidity).

Preparation Example 1 Preparation of Adhesive Resin (A1-1)

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, 99 parts by weight of n-butyl acrylate (manufactured by Nihon Shokubai Co., Ltd.) and 4-hydroxybutyl acrylate (Osaka Yuki Kagaku Kogyo Co., Ltd.) 1 part by weight and 0.15 part by weight of 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 100 parts by weight of ethyl acetate. Injected together, nitrogen gas was introduced with gentle stirring. After nitrogen gas substitution, the liquid temperature in the flask was controlled to around 55 ° C, and polymerization reaction was carried out for 5 hours to prepare an acrylic adhesive resin (A1-1) solution having a solid content of 15% (w / w).

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

Preparation Examples 2 to 3: Preparation of Adhesive Resin (A1-2) and (A1-3)

Except having changed the kind or ratio of the monomer which forms acrylic adhesive resin as shown in Table 1, operation similar to Production Example 1 was performed, and all solid content is 15% (w / w) adhesive resin (A1-) 2) to (A1-3) solutions were prepared.

The weight average molecular weights of the obtained adhesive resin (A1-2)-(A1-3) were all 2.1 million, and the viscosity was 8000 mPa * s.

Preparation Example 4 Preparation of Adhesive Resin (A2)

In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, polyester polyol P-1010 (bifunctional polyester polyol, OH value 112, molecular weight 1,000, manufactured by Kuraray Co., Ltd.) 51.9 weight 32.2 parts by weight of adeca polyether G-1500 (trifunctional polyether polyol, trifunctional, OH value 109, number average molecular weight 1,500, product of ADEKA Corporation), 15.9 weight of isophorone diisocyanate (manufactured by Sumitomo Bayer Co., Ltd.) 66.7 parts by weight of toluene, 0.03 parts by weight of iron 2-ethylhexanoate as a catalyst and 0.04 parts by weight of lead naphthenate were injected, and the temperature was gradually raised to 90 ° C, and the reaction was carried out for 4 hours. Using an infrared spectrophotometer (IR), 2260cm ^-1 determine residual isocyanate groups at, it cooled to terminate the reaction, if the peak of the vicinity of 2260cm ^-1 disappeared and a solid content of 60% (w / w), a viscosity of 3,000 A colorless and transparent urethane-based adhesive resin (A2) solution of mPa · s was prepared.

The number average molecular weight of the obtained urethane type adhesive resin (A2) was 15,000, the weight average molecular weight was 50,000, and the acid value was 0.5KOHmg / g.

Preparation Example 5 Preparation of Adhesive Resin (A3)

In a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 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 tetra-n-butyl as a catalyst 0.15 parts by weight of titanate was injected and heated at 150 to 270 ° C for 150 minutes to carry out esterification reaction, and then the pressure in the reaction system was gradually reduced to 133 Pa after 30 minutes, and the reaction was carried out for 180 minutes while continuing the reduced pressure. . It diluted with ethyl acetate and obtained the polyester-type adhesive resin (A3) solution of adhesive resin (A3) which is 60% of solid content (w / w) and the viscosity is 3,000 mPa * s.

The number average molecular weight of the obtained polyester adhesive resin (A3) was 13,000, the weight average molecular weight was 38,000, and the acid value was 0.3KOHmg / g.

Preparation Example 6 Preparation of Silicon Alkoxy Oligomer (B1)

440 parts by weight (2 mol) of 3-glycidoxypropylmethyldimethoxysilane, 272 parts by weight of methyltrimethoxysilane (2 moles), 70 parts by weight of methanol and 26.8 parts by weight of acetic acid, 1 liter with thermometer and water-cooled condenser It injected into a separable flask and stirred at room temperature. 49.5 weight part (2.8 mol) of ion-exchange water was thrown in this, and it stirred at room temperature for 2 hours. Thereafter, the solvent was distilled off at atmospheric pressure until the temperature of the reaction solution reached 110 ° C, thereby obtaining a liquid having a solid content of 98.0% (w / w) and a colorless transparent silicone alkoxy oligomer (B1) having a viscosity of 250 mPa · s. .

The polystyrene reduced number average molecular weight of the obtained silicon alkoxy oligomer (B1) was 15000, the epoxy equivalent was 350 g / mol, and the alkoxyl group content was 17 weight%.

Preparation Example 7 Preparation of Silicone Alkoxy Oligomer (B2)

62.8 weight part (0.285 mol) of 3-glycidoxy propylmethyldimethoxysilane, 505.2 weight part (3.715 mol) of methyl trimethoxysilane, 270 weight part of methanol, and 26.8 weight part of acetic acid, 1 L with a thermometer and a water cooling condenser It injected into a separable flask and stirred at room temperature. 49.5 weight part (2.8 mol) of ion-exchange water was thrown in this. Stir at room temperature for 2 hours. Then, the solvent was distilled off under normal pressure until the reaction liquid temperature became 110 degreeC, and the liquid of the colorless transparent silicone alkoxy oligomer (B2) of 98.5% (w / w) of solid content and the viscosity of 300 mPa * s was obtained.

The polystyrene reduced number average molecular weight of the obtained silicon alkoxy oligomer (B2) was 1000, the epoxy equivalent was 3200 g / mol, and the alkoxyl group content was 42 weight%.

Preparation Example 8 Preparation of Silicone Alkoxy Oligomer (B3)

817.3 parts by weight (3.715 mole) of 3-glycidoxypropylmethyldimethoxysilane, 36 parts by weight (0.285 mole) of methyltrimethoxysilane, 270 parts by weight of methanol and 26.8 parts by weight of acetic acid, 1 liter with thermometer and water-cooled condenser It injected into a separable flask and stirred at room temperature. 49.5 weight part (2.8 mol) of ion-exchange water was thrown in this, and it stirred at room temperature for 2 hours. Then, the solvent was distilled off under normal pressure until reaction liquid temperature became 110 degreeC, and the colorless and transparent silicone alkoxy oligomer (B3) liquid of solid content 98.2% (w / w) and the viscosity of 270 mPa * s was obtained.

The polystyrene reduced number average molecular weight of the obtained silicon alkoxy oligomer (B3) was 1000, the epoxy equivalent was 230 g / mol, and the alkoxyl group content was 2 weight%.

In addition, the measurement of the weight average molecular weight, number average molecular weight, epoxy equivalent, alkoxyl group content, a viscosity, etc. in the said manufacturing example was performed with the following method.

1) Measurement of weight average molecular weight (Mw)

It was measured by GPC (gel permeation chromatography).

Analysis equipment: manufactured by Tosoh Corporation, HLC-8120GPC

Column: Tosoh Corporation, G7000H _XL + GMH _XL + GMH _XL

Column size: Each 7.8 mm diameter x 30 cm total 90 cm

Column temperature: 40 ℃

Flow rate: 0.8 ml / min

Injection volume: 100 μl

Eluent: tetrahydrofuran

Detector: Differential Refractometer (RI)

Standard sample: Polystyrene

2) Measurement of number average molecular weight (Mn)

It was measured by GPC (gel permeation chromatography).

Analysis equipment: manufactured by Tosoh Corporation, HLC-8120GPC

Column: TSKgel, SuperHZM-H / HZ4000 / HZ2000

Column size: 6.0 mm inner diameter x 150 mm

Column temperature: 40 ℃

Flow rate: 0.6 ml / min

Injection volume: 20 μl

Eluent: tetrahydrofuran

Detector: Differential Refractometer (RI)

Standard sample: Polystyrene

3) Determination of epoxy equivalent

Epoxy equivalent was measured based on JISK7236 (2004) test method.

(Measurement of Alkyl Group Content)

The alkoxyl group content was calculated | required by the separation quantification (analytical chemical 17 (9), 1102-1107, 1968) of an alkoxyl group by a gas chromatograph.

4) Measurement of viscosity

The viscosity was temperature-controlled the polymer solution put into the glass bottle at 25 degreeC, and it measured by the Brookfield company viscometer DVII + Pro (spindle number 63, rotation speed 12rpm).

		Preparation Example 1	Preparation Example 2	Preparation Example 3	Preparation Example 4	Preparation Example 5
Sample name		A1-1	A1-2	A1-3	A2	A3
Kinds		Acrylic system	Acrylic system	Acrylic system	Urethane	Polyester
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
	Sebas	-	-	-	-	57.9
Weight average molecular weight of each sample		2.1 million	2.1 million	2.1 million	5.0 million	3.8 million
BA: n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) 2HEA: 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) 4HBA: 4-hydroxyethyl acrylate (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) AA: Acrylic acid (manufactured by Nippon Shokubai Co., Ltd.) IPDI: isophorone diisocyanate (manufactured by Sumitomo Bayer Co., Ltd.) P-1010: bifunctional polyester polyol (manufactured by Kuraray Co., Ltd.) G-1500: adeca polyether G-1500 (trifunctional) Polyether polyols)

<Example 1>

Preparation of pressure-sensitive adhesive composition

Regarding the solid content 100% (w / w) of the pressure-sensitive adhesive resin (A1-1) obtained in Production Example 1 above, X-41-1053 (epoxy equivalent 830 g) manufactured by Shin-Etsu Chemical Co., Ltd. as the silicone alkoxy oligomer (B) / Mol) 1 part by weight and 0.1 parts by weight of isocyanate crosslinking agent Takenate D110N (75% by weight ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate, number of isocyanate groups in 1 molecule: Mitsui Chemical Co., Ltd.) And the solution (solid content 15% (w / w)) of the acrylic adhesive composition were prepared.

Formation of adhesive layer

On the one side of the polyethylene terephthalate (PET) film (Mitsubishi Chemical Co., Ltd. product, MRF38) of thickness 38micrometer which performed the siliconization of the solution of the acrylic adhesive composition obtained above, of the adhesion layer after drying It applied so that thickness might be 20 micrometers, and it dried for 2 minutes at 100 degreeC, and formed the adhesion layer.

Preparation of Polarizing Plate with Adhesive Layer

(Production of a thin polarizing plate)

The polyvinyl alcohol film of 20 micrometers in thickness was extended | stretched to 3 times, dyeing for 1 minute in 30 degreeC and 0.3 weight% iodine solution between rolls from which a speed ratio differs. Thereafter, the total draw ratio was stretched up to 6 times while immersing for 0.5 minutes in an aqueous solution containing 60 ° C., 4% by weight boric acid and 10% by weight potassium iodide. Next, after wash | cleaning by immersing in 30 degreeC and the aqueous solution containing 1.5 weight% potassium iodide for 10 second, it dried at 50 degreeC for 4 minutes, and obtained the polarizer. On one side of the polarizer, an acrylic film (lactone-modified acrylic resin film) having a thickness of 20 µm was bonded with a polyvinyl alcohol-based adhesive to produce a thin-walled polarizing plate having a single thickness of 27 µm in total thickness.

(Production of Polarizing Plate with Adhesive Layer)

On the polarizer side of the thin polarizing plate obtained above, the corona treatment was performed at a corona discharge amount of 80 [W · min / m 2]. Next, the PET film which processed the silicone process in which the adhesion layer obtained above was formed in the said polarizer side was transferred, and the polarizing plate with an adhesion layer was produced.

<Examples 2 to 8 and 10 to 11>

As shown in Table 2, the kind and the addition amount of the adhesive resin (A), the kind and the addition amount of the silicon alkoxy oligomer (B), the kind and the addition amount (or addition) of the crosslinking agent (C-1) and (C-2) And the silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane) (D), and their addition amount (or not added) was changed. Other than the operation of Example 1, the polarizing plate with an adhesion layer corresponding to each Example was produced.

X-41-1056 and X-41-1059A are manufactured by Shin-Etsu Chemical Co., Ltd., and Peroyl TCP is manufactured by Nihon Yushi Corporation.

Example 9

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

Next, the primer agent was apply | coated to the polarizer side of the thin polarizing plate obtained above by the wire bar, and the adhesive bond layer (thickness 50nm) was formed. The priming agent is a solution containing an oxazoline polymer (Nihon Shokubai Co., Ltd., product name "Epocross WS-700") is diluted with a mixed solution of water and isopropyl alcohol, the solid content of 0.6 What was prepared to be% (w / w) was used.

Thereafter, the pressure-sensitive adhesive layer of the PET film on which the pressure-sensitive adhesive layer obtained above was formed on the adhesive easy layer side was bonded to each other to prepare an adhesive polarizing film of Example 9.

<Comparative Examples 1 to 20>

As shown in Table 2 and Table 3, the type and amount of the adhesive resin (A), the type and amount (or no addition) of the silicone alkoxy oligomer (B), the crosslinking agent (C-1) and (C-2) ) And the addition amount (or not added) and the type of silane coupling (D) and the addition amount (or not added) were changed in the same manner as in the operation of Example 1 to the respective comparative examples. The corresponding polarizing plate with an adhesion layer was produced.

	Adhesive resin (A)		Silicone alkoxy oligomer (B)
	Kinds	Content (parts by weight)	Kinds	Content (parts by weight)	Epoxy equivalent weight (g / mol)	Alkoxy group content (wt%)	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

	Crosslinking agent (C-1)		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	Peroyl 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	-	-	-	-

<Property evaluation>

The following evaluation was performed about each polarizing plate (sample) with an adhesion layer produced by the said Example and the comparative example. Each evaluation result is shown in Table 4.

1. Durable

Each sample was attached to an alkali free glass (Eagle XG, Corning Corporation make) of 0.7 mm in thickness by using a laminator at 37 inch size. Subsequently, autoclave treatment was carried out at 50 ° C. and 0.5 MPa for 15 minutes, and the sample was completely in contact with the acrylic glass.

In the sample where this treatment was performed,

(1) After each 500 hours of treatment at 85 ° C. (heating test),

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

(3) After carrying out the environment of 85 degreeC and -40 degreeC each for 1 hour, and carrying out a total of 300 cycles by making this one cycle (heat shock (HS) test),

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

◎: no change in appearance such as foaming, peeling, no lifting;

(Circle): Although it has a little peeling or foaming at the edge part, there is no problem practically;

(Triangle | delta): Although there exists peeling or foaming at the edge part, if there is no special use, there is no problem practically;

X: There exists remarkable peeling at the edge part, and there exists a problem practically.

2. Reworkability

Each sample was cut out to width 25mm x length 100mm, and was attached to the alkali free glass plate (Corning Company, Eagle XG) of thickness 0.7mm using a laminator.

Subsequently, autoclave treatment was carried out at 50 ° C. and 5 atmospheres for 15 minutes for complete adhesion (initial stage). Then, heat processing was performed for 48 hours under 50 degreeC dry conditions (after heating). The adhesion of each of these samples was measured as follows.

Adhesion is JIS by using a tensile tester (Orientec Co., Tenshiron Universal Testing Machine STA-1150) at 23 ° C., 50% relative humidity, peel angle 180 °, peel rate 300 mm / min. It calculated | required by measuring the adhesive force (N / 25mm) at the time of peeling based on the method of the adhesive tape and adhesive sheet test of Z0237.

In addition, about the sample similar to the object which measured the said adhesive force (but cutting to 420 mm x 320 mm), a sample is peeled from an alkali free glass plate by a human hand, and actual rework property is based on the following reference | standard. Evaluated. Evaluation of the actual reworkability was carried out three times in the above procedure, and repeated three times.

(Double-circle): All three sheets have no adhesive residue or a film fracture, and can peel easily;

○: Some of the three sheets were broken by the film, but were peeled off by peeling again;

(Triangle | delta): Although all three sheets were film broken, it peels again by peeling again;

X: Even if all three sheets generate | occur | produce adhesive residue or peeled several times, a film broke and it could not peel.

As mentioned above, the result of adhesive force and agrochemical reworkability was put together, and the reworkability of each sample was judged.

3. Optical characteristics

The central part of each sample bonded to the alkali-free glass after the durability evaluation and the 60% 95% RH 500 hours treatment was subjected to a single transmittance (% ) Ts was measured, and the decrease (%) of the transmittance | permeability calculated by the formula of following Table 1 from the before (initial stage) durability evaluation after the 60 degreeC 95% RH 500-hour process was evaluated as an optical characteristic.

[Equation 1]

Permeability Reduction (%) = {(T0-Ts) / T0} * 100

In Equation 1, T0 is the initial transmittance measured before the durability evaluation of the sample, Ts is the transmittance after 60 hours 95% 95% RH treatment.

	durability			Reworkability				Optical characteristic (%)
	85 ℃, 500h	85 ℃, 95% RH, 500h	HS test 300 cycles	Early		After heating
				Adhesive force (N / 25mm)	Actual reworkability	Adhesive force (N / 25mm)	Actual reworkability
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 clear from Table 4, the thin polarizing plates (Examples 1 to 11) with a pressure-sensitive adhesive layer using the pressure-sensitive adhesive composition of the present invention are all easily peeled off due to reworkability and heating and humidification in an adhesive state. It was found that the durability against the endurance test is excellent. In addition, also in any of the polarizing plates (Examples 1-11) with an adhesive layer using the adhesive composition of this invention, the decrease of the transmittance | permeability from before (durability) durability evaluation after 60 degreeC 95% RH 500 hours treatment is small, ie, It was also found that the optical characteristics were excellent.

Claims (16)

1. 100 parts by weight of the 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 to 60% by weight; It is a pressure-sensitive adhesive composition containing,

   The pressure-sensitive adhesive composition (A) is at least one member 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.
2. The pressure-sensitive adhesive composition of claim 1, wherein the silicon alkoxy oligomer (B) has a number average molecular weight of 300 to 10000.
3. The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition further contains a crosslinking agent (C).
4. The pressure-sensitive adhesive composition of claim 3, wherein the content of the crosslinking agent (C) is 0.01 to 20 parts by weight based on 100 parts by weight of the adhesive resin (A).
5. The pressure-sensitive adhesive composition of claim 3, wherein the crosslinking agent (C) is at least one selected from an isocyanate compound and a peroxide.
6. The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive resin (A) further contains a hydroxyl group.
7. The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition further contains 0.001 part by weight to 5 parts by weight of the silane coupling agent (D) based on 100 parts by weight of the pressure-sensitive adhesive resin (A).
8. The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive (A) has a weight average molecular weight of 20,000 to 2.5 million.
9. The pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition according to claim 1.
10. The adhesive layer of claim 9, wherein the adhesive layer has an initial adhesive strength of 0.2 N / 25 mm to 1.6 N / 25 mm measured at 23 ° C., a relative humidity of 50%, a peel angle of 180 °, and a peel rate of 300 mm / min according to JIS Z0237. Phosphorus adhesion layer.
11. The method according to claim 9, wherein the adhesive layer is subjected to JIS Z0237 under conditions of 23 ° C, 50% relative humidity, 180 ° peeling angle, and 300 mm / min peeling rate for a sample heat-treated for 48 hours under 50 ° C drying conditions. Adhesive layer having an adhesive force of 0.3 N / 25 mm to 2.5 N / 25 mm after the measured heating.
12. The pressure-sensitive adhesive layer of claim 9, wherein the pressure-sensitive adhesive layer has a transmittance reduction amount of 0.1% to 1.0% by the following Formula 1.

    [Equation 1]

    Permeability Reduction (%) = {(T0-Ts) / T0} * 100

    In Equation 1, T0 is the initial transmittance measured before the durability evaluation of the sample, Ts is the transmittance after 60 hours 95% 95% RH treatment.
13. Optical film; And an adhesive layer according to claim 9 formed on at least one surface of the optical film.
14. The optical member of claim 13, further comprising an adhesive easy layer between the optical film and the adhesive layer.
15. The optical member according to claim 13, wherein the optical film is a polarizing plate, and the thickness of the polarizing plate is 100 µm or less.
16. An image display apparatus using at least one optical member according to claim 13.