KR102201543B1 - Adhesive composition and polarizing plate comprising adhesive layer formed by using the same - Google Patents

Abstract

The present specification relates to a polarizing plate including an adhesive composition and an adhesive layer formed using the adhesive composition.

Description

A polarizing plate including an adhesive composition and an adhesive layer formed by using the same TECHNICAL FIELD [ADHESIVE COMPOSITION AND POLARIZING PLATE COMPRISING ADHESIVE LAYER FORMED BY USING THE SAME}

The present specification relates to a polarizing plate including an adhesive composition and an adhesive layer formed using the adhesive composition.

The polarizing plate has been used in a structure in which a protective film is laminated using an adhesive on one or both sides of a polarizer made of a polyvinyl alcohol (hereinafter referred to as'PVA')-based resin dyed with dichroic dye or iodine. Conventionally, a triacetyl cellulose (TAC)-based film has been mainly used as a protective film for a polarizing plate, but this TAC film has a problem that it is easily deformed in a high temperature and high humidity environment.

In order to solve the above problems, recently, a method of using polyethylene terephthalate (PET), cycloolefin polymer (COP), acrylic film, etc. alone or in combination has been proposed. At this time, as the adhesive used to attach the polarizer and the protective film, an aqueous adhesive composed of an aqueous solution of a polyvinyl alcohol-based resin or a non-aqueous adhesive classified into a radical curable adhesive and a cation curable adhesive according to a curing method is mainly used.

The cationic curable adhesive has an advantage of having excellent adhesion to films of various materials, but has many disadvantages in the manufacturing process due to a slow curing speed and a low curing degree.

In addition, in the case of a cationic UV adhesive, a cationic photoinitiator containing PF ₆ ^- is mainly used, which generates PF ₅ by UV and reacts with water and heat to generate HF. The HF generated in this way meets with aluminum and causes an oxidation reaction to discolor the aluminum frame of the panel.

Therefore, there is a need for an adhesive that does not cause discoloration of aluminum prime and does not deteriorate adhesion even when the panel is exposed in a high temperature and high humidity environment without any separate treatment.

Japanese Public Publication 2003-121644

The present specification is to provide a polarizing plate including an adhesive composition and an adhesive layer formed using the adhesive composition.

The present specification is a first epoxy-based compound; A second epoxy compound; Oxetane compounds; Photoinitiators; And in the adhesive composition comprising an additive, the additive provides an adhesive composition comprising an α-aminoketone-based additive.

In addition, the present specification is a polarizer; An adhesive layer provided on at least one surface of the polarizer and formed using the adhesive composition; And it provides a polarizing plate including a protective film provided on at least one surface on the adhesive layer.

In addition, the present specification includes a display panel; And the polarizing plate provided on one or both surfaces of the display panel.

The adhesive composition according to the exemplary embodiment of the present specification can prevent discoloration of the aluminum frame by minimizing the generation of fluorine ions.

Hereinafter, the present specification will be described in more detail.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, when a member is said to be located "on" another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

The cationic curable adhesive has the advantage of having excellent adhesion to films of various materials, but has many disadvantages in the manufacturing process due to the slow curing speed and low curing degree.

In addition, in the case of a cationic UV adhesive, a cationic photoinitiator containing PF ₆ ^- is mainly used, which generates PF ₅ by UV and reacts with water and heat to generate HF. The HF generated in this way meets with aluminum and causes an oxidation reaction to discolor the aluminum frame of the panel.

However, the adhesive composition according to the exemplary embodiment of the present specification includes an α-aminoketone-based additive, thereby minimizing the generation of fluorine ions and reducing the content of HF, thereby preventing discoloration of the aluminum frame.

The present specification is a first epoxy-based compound; A second epoxy compound; Oxetane compounds; Photoinitiators; And in the adhesive composition comprising an additive, the additive provides an adhesive composition comprising an α-aminoketone-based additive.

According to an exemplary embodiment of the present specification, the α-aminoketone-based additive is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; And at least one of 2-(dimethylamino)-1-(4-morpholinophenyl)-2- p -tolybutan-1-one.

According to an exemplary embodiment of the present specification, with respect to the total 100 parts by weight of the adhesive composition, the α-aminoketone-based additive is preferably 0.6 to 1.2 parts by weight, more preferably 0.6 to 1.0 parts by weight.

When the α-aminoketone-based additive is within the above content range, the generation of fluorine ions is minimized and the content of HF is reduced, thereby effectively preventing discoloration of the aluminum frame. When the content range is not satisfied, particularly, when the content range is exceeded, durability and adhesion of the adhesive layer formed using the adhesive composition are deteriorated.

According to an exemplary embodiment of the present specification, the first epoxy-based compound is an alicyclic epoxy-based compound.

Specifically, the alicyclic epoxy-based compound refers to an epoxy-based compound in which an epoxy group is formed between two adjacent carbon atoms constituting an aliphatic hydrocarbon ring. For example, 2-(3,4-epoxy)cyclohexyl-5,5-spiro-(3,4-epoxy)cyclohexane-m-dioxane, 3,4-epoxycyclohexylmethyl-3,4-epoxy Cyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, vinylcyclohexanedioxide, bis(3,4-epoxycyclohexylmethyl ) Adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, exo-exobis (2,3-epoxycyclopentyl) ether, endo-exobis (2,3-epoxycyclopentyl) Ether, 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane, 2,6-bis(2,3-epoxypropoxycyclohexyl-p-dioxane), 2,6-bis (2,3-epoxypropoxy)norbornene, limonenedioxide, 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadienedioxide, 1,2-epoxy-6-(2 ,3-epoxypropoxy)hexahydro-4,7-methanoindan, p-(2,3-epoxy)cyclopentylphenyl-2,3-epoxypropyl ether, 1-(2,3-epoxypropoxy) Phenyl-5,6-epoxyhexahydro-4,7-methanoindan, o-(2,3-epoxy)cyclopentylphenyl-2,3-epoxypropyl ether), 1,2-bis[5-(1 ,2-epoxy)-4,7-hexahydromethanoindanoxyl]ethanecyclopentenylphenylglycidyl ether, methylenebis(3,4-epoxycyclohexane)ethylene glycoldi(3,4-epoxycyclohexylmethyl ) Ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), c-caprolactone adduct of methanol and polyvalent (3 to 20) alcohol esterified compounds, etc. In particular, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferred, but is not limited thereto.

According to an exemplary embodiment of the present specification, with respect to the total 100 parts by weight of the adhesive composition, the first epoxy-based compound is preferably 5 to 40 parts by weight. When the content of the first epoxy-based compound satisfies the above range, curing speed and adhesion may be improved.

According to an exemplary embodiment of the present specification, the second epoxy-based compound is an aliphatic epoxy-based compound.

Specifically, the aliphatic epoxy-based compound refers to an epoxy-based compound containing an aliphatic chain or aliphatic ring in a molecule. For example, 1,4-cyclohexanedimethanol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyldiglycidyl ether, resorcinoldi Glycidyl ether, diethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, etc. In particular, it is preferable to use 1,4-cyclohexanedimethanol diglycidyl ether and neopentyl diglycidyl ether, but is not limited thereto. In addition, the second epoxy-based compound may be one or two or more compounds selected from the aliphatic epoxy-based compounds.

According to an exemplary embodiment of the present specification, with respect to the total 100 parts by weight of the adhesive composition, the second epoxy-based compound is preferably 25 to 50 parts by weight. When the content of the second epoxy compound satisfies the above range, adhesion may be improved.

According to an exemplary embodiment of the present specification, the oxetane compound is 3,3'-oxybis(methylene)bis(3-ethyloxetane; 3-ethyl-3-hydroxymethyloxetane; And 3-ethyl-3 -(2-ethylhexyloxy)methyloxetane.

According to an exemplary embodiment of the present specification, with respect to the total 100 parts by weight of the adhesive composition, the oxetane compound is preferably 10 to 40 parts by weight. When the content of the oxetane compound satisfies the above range, it has excellent water resistance.

According to an exemplary embodiment of the present specification, the photoinitiator includes at least one of an iodine-based compound and a thioxanthone-based compound.

The iodine-based compounds include diphenyliodonium hexafluorophosphate (Iod-PF6), diphenyliodonium triflate (Iod-OSO ₂ CF ₃ ), diphenyliodonium p-toluenesulfonate (Iod-OSO ₂ PhCH ₃ ), diphenyliodonium chloride (Iod-Cl), [4-methylphenyl-(4-(2-methylpropyl)phenyl)]iodonium hexafluorophosphate (Irgacure 250), and the like, [4- Methylphenyl-(4-(2-methylpropyl)phenyl)]iodonium hexafluorophosphate (Irgacure 250) is preferred, but is not limited thereto.

The thioxanthone-based compounds include thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone, diisopropyl thioxane There are tones and the like, but are not limited thereto.

According to an exemplary embodiment of the present specification, with respect to the total 100 parts by weight of the adhesive composition, the photoinitiator is preferably 0.1 to 5 parts by weight.

According to an exemplary embodiment of the present specification, the glass transition temperature of the adhesive composition is 60°C or higher, preferably 70°C or higher, and the higher the glass transition temperature is, the more thermally stable it is, so the upper limit is not separately limited. It is preferably 200°C or less.

In the present specification, the glass transition temperature is a differential scanning calorimeter (DSC, Mettler, Inc.), and when a sample of about 10 mg is sealed in a dedicated pen and heated to a constant temperature environment, the endothermic heat of the material occurs. And a value obtained by measuring the glass transition temperature by plotting the calorific value according to the temperature.

According to an exemplary embodiment of the present specification, the adhesive composition may further include a photosensitizer.

The photosensitizer may include, for example, a carbonyl compound, an organic sulfur compound, a persulfide, a redox compound, azo and diazo compounds, an anthracene compound, a halogen compound, a photoreducing dye, etc., but are limited thereto. no.

In addition, the adhesive composition of the present specification may further include a silane coupling agent, if necessary. When a silane coupling agent is included, an effect of improving adhesive wetting may be obtained by lowering the surface energy of the adhesive.

In this case, it is more preferable that the silane coupling agent includes a cationic polymerizable functional group such as an epoxy group, a vinyl group, and a radical group. In addition, in the case of using a silane coupling agent that does not contain a cationic polymerizable functional group, the effect of improving the wettability without lowering the glass transition temperature compared to a surfactant or a silane coupling agent that does not contain a cationic polymerizable functional group. There is. This is because the cationic polymerization functional group of the silane coupling agent reacts with the silane group of the adhesive composition to form a crosslinking form, thereby reducing the phenomenon that the glass transition temperature of the adhesive layer is lowered after curing.

According to an exemplary embodiment of the present specification, a polarizer; An adhesive layer provided on at least one surface of the polarizer and formed using the adhesive composition; And it provides a polarizing plate including a protective film provided on at least one surface on the adhesive layer.

In the present specification, the polarizer is not particularly limited, and a polarizer well known in the art, for example, a film made of polyvinyl alcohol (PVA) containing iodine or a dichroic dye may be used. The polarizer may be prepared by dyeing iodine or a dichroic dye on a PVA film, but the method of manufacturing the polarizer is not particularly limited. In the present specification, the polarizer refers to a state that does not include a protective film, and the polarizing plate refers to a state including a polarizer and a protective film.

In the present specification, the adhesive layer is formed by using the adhesive composition according to the exemplary embodiments of the present specification described above, and may be formed by a method well known in the art. For example, it may be carried out by applying an adhesive composition to one side of a polarizer or a protective film to form an adhesive layer, and then laminating the polarizer and the protective film, and then curing. In this case, the coating may be performed by coating methods well known in the art, for example, spin coating, bar coating, roll coating, gravure coating, and blade coating.

According to an exemplary embodiment of the present specification, the thickness of the adhesive layer is more than 0㎛ to 20㎛ or less.

Specifically, the thickness of the adhesive layer is preferably more than 0㎛ 10㎛ or less, and more preferably 0.1㎛ to 10㎛ or 0.1㎛ to 5㎛. This is because when the thickness of the adhesive layer is too thin, the uniformity and adhesion of the adhesive layer may be deteriorated, and when the thickness of the adhesive layer is too thick, the appearance of the polarizing plate may be wrinkled.

According to an exemplary embodiment of the present specification, the protective film is for supporting and protecting a polarizer, and protective films of various materials generally known in the art, for example, a cellulose-based film, a polyethylene terephthalate (PET , polyethylene terephthalate) film, cycloolefin polymer (COP, cycloolefin polymer) film, acrylic film, etc. may be used without limitation, and a cycloolefin polymer film or an acrylic film is preferred, but is not limited thereto.

Meanwhile, the acrylic film usable in the present specification may be obtained by molding a molding material including a (meth)acrylate-based resin as a main component by extrusion molding. At this time, the (meth)acrylate-based resin has a resin containing a (meth)acrylate-based unit as a main component, and not only a homopolymer resin composed of a (meth)acrylate-based unit, but also a (meth)acrylate-based unit In addition, the concept includes a copolymer resin in which other monomer units are copolymerized and a blend resin in which another resin is blended with the (meth)acrylate-based resin as described above.

Meanwhile, the (meth)acrylate-based unit may be, for example, an alkyl (meth)acrylate-based unit. Here, the alkyl (meth) acrylate unit means both an alkyl acrylate unit and an alkyl methacrylate unit, and the alkyl group of the alkyl (meth) acrylate unit is preferably 1 to 10 carbon atoms, and And more preferably 1 to 4 carbon atoms.

Further, examples of the monomer unit capable of copolymerizing with the (meth)acrylate unit include a styrene unit, a maleic anhydride unit, and a maleimide unit. In this case, examples of the styrene-based unit include, but are not limited to, styrene, α-methylstyrene, and the like; Examples of the maleic anhydride-based monomer include, but are not limited to, maleic anhydride, methyl maleic anhydride, cyclohexyl maleic anhydride, phenyl maleic anhydride, and the like; Examples of the maleimide-based monomer include, but are not limited to, maleimide, N-methyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, and the like. These may be used alone or in combination.

Meanwhile, the acrylic film may be a film including a (meth)acrylate-based resin having a lactone ring structure. Specific examples of the (meth)acrylate-based resin having a lactone ring structure include, for example, lactones described in Japanese Laid-Open Patent Publication No. 2000-230016, Japanese Laid-Open Patent Publication No. 2001-151814, Japanese Laid-Open Patent Publication No. 2002-120326, etc. And (meth)acrylate-based resins having a cyclic structure.

The method of manufacturing the acrylic film is not particularly limited, for example, (meth)acrylate resin and other polymers, additives, etc. are sufficiently mixed by any appropriate mixing method to prepare a thermoplastic resin composition, and then film-molded. Alternatively, (meth) acrylate-based resin and other polymers, additives, and the like may be prepared as a separate solution and then mixed to form a uniform mixture, and then film-molded. In addition, the acrylic film may be either an unstretched film or a stretched film. In the case of a stretched film, it may be a uniaxially stretched film or a biaxially stretched film, and in the case of a biaxially stretched film, it may be either a simultaneous biaxially stretched film or a sequential biaxially stretched film.

In addition, the acrylic film is preferably a film with a primer coating on the acrylic film or an acrylic bare film without primer coating, but is not limited thereto.

According to an exemplary embodiment of the present specification, the display panel; And the polarizing plate provided on one or both surfaces of the display panel.

In the present specification, the display panel may be a liquid crystal panel, a plasma panel, and an organic light emitting panel.

Accordingly, the image display device may be a liquid crystal display device (LCD), a plasma display device (PDP), and an organic electroluminescent display device (OLED).

More specifically, the image display device may be a liquid crystal display device including a liquid crystal panel and polarizing plates respectively provided on both sides of the liquid crystal panel, and at this time, at least one of the polarizing plates according to an exemplary embodiment of the present specification described above It may be a polarizing plate including a polarizer. That is, the polarizing plate is a polarizing plate including a polyvinyl alcohol-based polarizer dyed with iodine and/or a dichroic dye and a protective film provided on at least one surface of the polyvinyl alcohol-based polarizer, locally in a wavelength range of 400 nm to 800 nm. Has a polarization canceling region having a single transmittance of 80% or more, an arithmetic average roughness (Ra) of 200 nm or less, a polarization degree of 10% or less, and a sagging of 10 μm or less.

In this case, the type of the liquid crystal panel included in the liquid crystal display device is not particularly limited. For example, the panel is not limited to the type and has a passive matrix type such as a twisted nematic (TN) type, a super twisted nematic (STN) type, a ferroelectic (F) type, or a polymer dispersed (PD) type; An active matrix type panel such as a two terminal type or a three terminal type; Known panels, such as an IPS (In Plane Switching) panel and a vertical alignment (VA) panel, may all be applied. Further, other components constituting the liquid crystal display device, for example, types of upper and lower substrates (eg, color filter substrates or array substrates) are not particularly limited.

Hereinafter, examples will be described in detail in order to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art.

< Example >

< Comparative example 1>

(1) Preparation of adhesive composition

As the first epoxy-based compound, 35 parts by weight of Celloxide 2021p was used, and as the second epoxy-based compound, 45 parts by weight of 1,4-cyclohexanedimethanol diglycidyl ether (LD 204, Hajin Comtech) Parts were used, and as an oxetane compound, 20 parts by weight of 3,3'-oxybis(methylene)bis(3-ethyloxetane) (OXT 221) was used, and as a photoinitiator, 3 parts by weight of Irgacure 250 (BASF) and 1 part by weight of ITX (TCI) was used to prepare an adhesive composition.

(2) manufacture of polarizing plate

After each corona treatment (5v, 3 times) to the 60㎛ acrylic film to which the retardation COP film and UV absorber (LA F70) was added, 2ml of the adhesive composition prepared above was applied with a dropper to form an adhesive layer. , After attaching the corona-treated film to both sides of the PVA device, a laminator (Excellami-355Q) was passed through with a speed of 5 m/min and a pressure range of 7. Thereafter, the laminated polarizing plate was irradiated with ultraviolet rays of 2000 mJ/cm 2 on a UV irradiation device belt to prepare a polarizing plate.

< Experimental example 1>

Except for adding 1 part by weight of α-Amino ketone-based additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369, BASF)) to the adhesive composition of Comparative Example 1 In the same manner as in Comparative Example 1, an adhesive composition and a polarizing plate were prepared.

< Experimental example 2>

Α-Amino ketone additive B (2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure) to the adhesive composition of Comparative Example 1 379, BASF)) An adhesive composition and a polarizing plate were prepared in the same manner as in Comparative Example 1, except that 1 part by weight was added.

< Comparative example 2>

An adhesive in the same manner as in Comparative Example 1, except that 1 part by weight of Acrylphosphine Oxide-based additive C (2, 4, 6-Trimethylbenzoyl-diphenylphospine Oxide (Irgacure TPO, BASF)) was added to the adhesive composition of Comparative Example 1 The composition and the polarizing plate were prepared.

< Comparative example 3>

Comparative Example 1, except that 1 part by weight of Acrylphosphine Oxide-based additive D (Bis(2-, 4-, 6-Trimethylbenzoyl)-phenylphosphine Oxide (Irgacure 189, BASF)) was added to the adhesive composition of Comparative Example 1 An adhesive composition and a polarizing plate were prepared in the same manner as described above.

< Comparative example 4>

In the same manner as in Comparative Example 1, except that 1 part by weight of α-Hydroxy Ketone-based additive E (1-Hydroxy-cyclohexyl-phenyl-Keton (Irgacure 184, BASF)) was added to the adhesive composition of Comparative Example 1 An adhesive composition and a polarizing plate were prepared.

< Comparative example 5>

Α-Hydroxy Ketone additive F(2-hydroxy-1-{4[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan in the adhesive composition of Comparative Example 1 An adhesive composition and a polarizing plate were prepared in the same manner as in Comparative Example 1, except that 1 part by weight of -1-one (Irgacure 127, BASF)) was added.

< Evaluation example 1-1>-F content evaluation

The polarizing plates prepared in Experimental Examples 1, 2 and Comparative Examples 1 to 5 were cut into 120mm in width and 100mm in length, and then immersed in a vial containing 40ml of distilled water, and 72 in a chamber at a temperature of 60°C and a humidity of 90%. After leaving for a period of time, IC (Ion Chromatography) analysis was performed, and the results are shown in Table 1 below. ICS-3000 was used as the analysis device, and the procedure was performed by setting KOH (30.5mM), flow rate 1ml/min, and injection volume 25μL. As a detector, Suppressed Conductivity Detector was used.

< Evaluation example 1-2>-Al Frame discoloration evaluation

PSA coating was performed on the polarizing plates prepared in Experimental Examples 1, 2, and Comparative Examples 1 to 5, attached to an Al Frame, and left in a chamber at a temperature of 60°C and 90% humidity for 72 hours, and then the attached polarizing plate Was removed. Visually check whether or not discoloration has occurred in the Al Frame on the side where the polarizing plate was attached, and if no discoloration has occurred, it is classified as OK, and the case where discoloration with an afterimage has occurred is classified as NG, and the results are shown in the table below. It is shown in 1.

No. α-Amino ketone system Acrylphosphine Oxide type α-Hydroxy Ketone system F content
[mg/kg] Al Frame
discoloration A B C D E F Comparative Example 1 - - - - - - 72 NG Experimental Example 1 One - - - - - 22 OK Experimental Example 2 - One - - - - 32 OK Comparative Example 2 - - One - - - 45 NG Comparative Example 3 - - - One - - 56 NG Comparative Example 4 - - - - One - 71 NG Comparative Example 5 - - - - - One 69 NG

As shown in Table 1 above, Examples 1 and 2 using two α-Amino ketone-based additives of the present specification, as well as Comparative Example 1 in which no additives were used, as well as Acrylphosphine Oxide-based additives and α-Hydroxy Ketone-based additives Compared to Comparative Examples 2 to 5 using the additive, it can be seen that it shows a lower F content. Therefore, since no discoloration of the Al frame has occurred, it can be seen that Examples 1 and 2 according to an exemplary embodiment of the present specification have an excellent effect in preventing discoloration of the Al frame.

< Experimental example 3>

Except for adding 0.6 parts by weight of α-Amino ketone additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369, BASF)) to the adhesive composition of Comparative Example 1 Is, to prepare an adhesive composition in the same manner as in Comparative Example 1.

< Experimental example 4>

Except for adding 0.9 parts by weight of α-Amino ketone-based additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369, BASF)) to the adhesive composition of Comparative Example 1 Is, to prepare an adhesive composition in the same manner as in Comparative Example 1.

< Experimental example 5>

Except for adding 1.2 parts by weight of α-Amino ketone-based additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369, BASF)) to the adhesive composition of Comparative Example 1 Is, to prepare an adhesive composition in the same manner as in Comparative Example 1.

< Experimental example 6>

Α-Amino ketone additive B (2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure) to the adhesive composition of Comparative Example 1 379, BASF)) An adhesive composition was prepared in the same manner as in Comparative Example 1, except that 0.6 parts by weight were added.

< Experimental example 7>

Α-Amino ketone additive B (2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure) to the adhesive composition of Comparative Example 1 379, BASF)) An adhesive composition was prepared in the same manner as in Comparative Example 1, except that 0.9 parts by weight were added.

< Experimental example 8>

Α-Amino ketone additive B (2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure) to the adhesive composition of Comparative Example 1 379, BASF)) An adhesive composition was prepared in the same manner as in Comparative Example 1, except that 1.2 parts by weight were added.

< Experimental example 2-1>

Except for adding 0.3 parts by weight of α-Amino ketone-based additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369, BASF)) to the adhesive composition of Comparative Example 1 Is, to prepare an adhesive composition in the same manner as in Comparative Example 1.

< Experimental example 2-2>

Except for adding 1.5 parts by weight of α-Amino ketone-based additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369, BASF)) to the adhesive composition of Comparative Example 1 Is, to prepare an adhesive composition in the same manner as in Comparative Example 1.

< Experimental example 2-3>

Α-Amino ketone additive B (2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure) to the adhesive composition of Comparative Example 1 379, BASF)) An adhesive composition was prepared in the same manner as in Comparative Example 1, except for adding 0.3 parts by weight.

< Experimental example 2-4>

Α-Amino ketone additive B (2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure) to the adhesive composition of Comparative Example 1 379, BASF)) An adhesive composition was prepared in the same manner as in Comparative Example 1, except for adding 1.5 parts by weight.

< Evaluation example 2-1>-Evaluation of unreactant

After leaving 20 ml of the adhesive composition prepared in Experimental Examples 3 to 8 and Experimental Examples 2-1 to 2-4 in a vial at room temperature for 48 hours, whether there is any unreacted material suspended on a white paper background Visually, the presence or absence of non-reactant was classified into O and X (no reactant: X, non-reactant: O), and the results are shown in Table 2 below.

< Evaluation example 2-2>-F content evaluation

Except for using the adhesive composition prepared in Experimental Examples 3 to 8 and Experimental Examples 2-1 to 2-4, the polarizing plate manufactured in the same manner as in Comparative Example 1 was cut into a width of 120 mm and a length of 100 mm, and then distilled water After being immersed in a vial containing 40 ml, and left in a chamber at a temperature of 60° C. and a humidity of 90% for 72 hours, IC (Ion Chromatography) analysis was performed, and the results are shown in Table 2 below. ICS-3000 was used as the analysis device, and the procedure was performed by setting KOH (30.5mM), flow rate 1ml/min, and injection volume 25μL. As a detector, Suppressed Conductivity Detector was used.

< Evaluation example 2-3>-Al Frame discoloration evaluation

Except for using the adhesive composition prepared in Experimental Examples 3 to 8 and Experimental Examples 2-1 to 2-4, PSA coating was performed on a polarizing plate prepared in the same manner as in 1 in the comparison and attached to the Al Frame. Then, after being left in a chamber at a temperature of 60° C. and a humidity of 90% for 72 hours, the attached polarizing plate was removed. Visually check whether or not discoloration has occurred in the Al Frame on the side where the polarizing plate was attached, and if no discoloration occurred, classified as OK, and if discoloration with an afterimage, etc. occurred, classified as NG. It is shown in 2.

No. α-Amino ketone system Unreacted
Occurs or not F content
[mg/kg] Al Frame
discoloration A B Experimental Example 3 0.6 - X 29 OK Experimental Example 4 0.9 - X 23 OK Experimental Example 5 1.2 - X 19 OK Experimental Example 6 - 0.6 X 36 OK Experimental Example 7 - 0.9 X 32 OK Experimental Example 8 - 1.2 X 27 OK Experimental Example 2-1 0.3 - X 42 NG Experimental Example 2-2 1.5 - O 14 OK Experimental Example 2-3 - 0.3 X 54 NG Experimental Example 2-4 - 1.5 O 21 OK

As shown in Table 2, Experimental Examples 3 to 8, wherein the content of the two α-Amino ketone additives of the present specification satisfies 0.6 to 1.2 parts by weight, based on the total 100 parts by weight of the adhesive composition, the content range Compared to Experimental Examples 2-1 to 2-4, which do not satisfy, it can be seen that there is an excellent effect in preventing both the occurrence of unreacted water and discoloration of the Al Frame. Specifically, it can be seen that Experimental Examples 3 to 8 do not generate any unreacted material, as well as show an F content within 40 mg/kg, and thus have an excellent effect in preventing discoloration of the Al Frame.

< Experimental example 9>

In the adhesive composition of Comparative Example 1 α-Amino ketone additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369, BASF)) 0.30 parts by weight and α-Amino ketone Except for adding 0.30 parts by weight of additive B (2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure 379, BASF)) Then, an adhesive composition was prepared in the same manner as in Comparative Example 1.

< Experimental example 10>

In the adhesive composition of Comparative Example 1 α-Amino ketone additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1) 0.45 parts by weight and α-Amino ketone additive B (2- The comparative example above except that 0.45 parts by weight of dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure 379, BASF)) was added. An adhesive composition was prepared in the same manner as in 1.

< Experimental example 11>

In the adhesive composition of Comparative Example 1 α-Amino ketone additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369, BASF)) 0.60 parts by weight and α-Amino ketone Except for adding 0.60 parts by weight of additive B (2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure 379, BASF)) Then, an adhesive composition was prepared in the same manner as in Comparative Example 1.

< Experimental example 3-1>

Α-Amino ketone additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369, BASF)) 0.15 parts by weight and α-Amino ketone to the adhesive composition of Comparative Example 1 Except for adding 0.15 parts by weight of additive B (2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure 379, BASF)) Then, an adhesive composition was prepared in the same manner as in Comparative Example 1.

< Experimental example 3-2>

In the adhesive composition of Comparative Example 1 α-Amino ketone additive A (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Irgacure 369, BASF)) 0.75 parts by weight and α-Amino ketone Except for adding 0.75 parts by weight of additive B (2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl phenyl)-butan-1-one (Irgacure 379, BASF)) Then, an adhesive composition was prepared in the same manner as in Comparative Example 1.

< Evaluation example 3-1>-Evaluation of occurrence of unreactant

After leaving 20 ml of the adhesive composition prepared in Experimental Examples 9 to 11 and Experimental Examples 3-1 and 3-2 in a vial at room temperature for 48 hours, visually inspecting whether there is any unreacted material suspended on a white paper background. As confirmed as, the presence or absence of unreacted products was divided into O and X (unreacted no: X, unreacted: O), and the results are shown in Table 3 below.

< Evaluation example 3-2>-F content evaluation

Except for using the adhesive composition prepared in Experimental Examples 9 to 11 and Experimental Examples 3-1 and 3-2, the polarizing plate prepared in the same manner as in Comparative Example 1 was cut into a width of 120 mm and a length of 100 mm, and then distilled water After being immersed in a vial containing 40 ml, and left in a chamber at a temperature of 60° C. and a humidity of 90% for 72 hours, IC (Ion Chromatography) analysis was performed, and the results are shown in Table 3 below. ICS-3000 was used as the analysis device, and the procedure was performed by setting KOH (30.5mM), flow rate 1ml/min, and injection volume 25μL. As a detector, Suppressed Conductivity Detector was used.

< Evaluation example 3-3>-Al Frame discoloration evaluation

Except for using the adhesive composition prepared in Experimental Examples 9 to 11 and Experimental Examples 3-1 and 3-2, PSA coating was performed on the polarizing plate manufactured in the same manner as in 1 in the comparison and attached to the Al Frame. Then, after being left in a chamber at a temperature of 60° C. and a humidity of 90% for 72 hours, the attached polarizing plate was removed. Visually check whether or not discoloration has occurred in the Al Frame on the side where the polarizing plate was attached, and if no discoloration has occurred, it is classified as OK, and the case where discoloration with an afterimage has occurred is classified as NG, and the results are shown in the table below. It is shown in 3.

No. α-Amino ketone system Unreacted
Occurs or not F content
[mg/kg] Al Frame
discoloration A B Experimental Example 9 0.30 0.30 X 34 OK Experimental Example 10 0.45 0.45 X 28 OK Experimental Example 11 0.60 0.60 X 23 OK Experimental Example 3-1 0.15 0.15 X 47 NG Experimental Example 3-2 0.75 0.75 O 16 OK

As shown in Table 3, Experimental Examples 9 to 11 satisfying 0.3 to 1.2 parts by weight by simultaneously using two α-Amino ketone-based additives of the present specification based on 100 parts by weight of the adhesive composition, Compared to Experimental Examples 3-1 and 3-2, which do not satisfy the content range, it can be seen that there is an excellent effect in preventing both the occurrence of unreacted water and discoloration of the Al Frame. Specifically, it can be seen that Experimental Examples 9 to 11 do not generate any unreacted material, as well as show an F content within 40 mg/kg, and thus have an excellent effect in preventing discoloration of the Al Frame.

Although the preferred embodiments of the present specification have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and the detailed description of the invention, and this also belongs to the scope of the invention. .

Claims (14)

A first epoxy compound; A second epoxy compound; Oxetane compounds; Photoinitiators; And in the adhesive composition comprising an additive,
The first epoxy-based compound is an alicyclic epoxy-based compound,
The second epoxy-based compound is an aliphatic epoxy-based compound containing an aliphatic ring,
The photoinitiator includes at least one of an iodine-based compound and a thioxanthone-based compound,
The additive is an adhesive composition comprising an α-aminoketone-based additive. The method according to claim 1, wherein the α-aminoketone-based additive is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; And 2-(dimethylamino)-1-(4-morpholinophenyl)-2- p -tolybutan-1-one. The adhesive composition of claim 1, wherein the α-aminoketone-based additive is contained in an amount of 0.6 to 1.2 parts by weight based on 100 parts by weight of the adhesive composition. delete The adhesive composition according to claim 1, wherein the first epoxy-based compound is contained in an amount of 5 to 40 parts by weight based on 100 parts by weight of the total adhesive composition. delete The adhesive composition according to claim 1, wherein the second epoxy-based compound is contained in an amount of 25 to 50 parts by weight based on 100 parts by weight of the entire adhesive composition. The method of claim 1, wherein the oxetane compound is 3,3'-oxybis(methylene)bis(3-ethyloxetane; 3-ethyl-3-hydroxymethyloxetane; and 3-ethyl-3-(2- An adhesive composition comprising at least one of ethylhexyloxy)methyloxetane. The adhesive composition according to claim 1, wherein the oxetane compound is contained in an amount of 10 to 40 parts by weight based on 100 parts by weight of the total adhesive composition. The adhesive composition of claim 1, wherein the photoinitiator is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total adhesive composition. Polarizer;
An adhesive layer provided on at least one surface of the polarizer and formed using the adhesive composition according to any one of claims 1 to 3, 5 and 7 to 10; And
A polarizing plate comprising a protective film provided on at least one surface on the adhesive layer. The polarizing plate of claim 11, wherein the adhesive layer has a thickness of more than 0 μm and less than or equal to 20 μm. The method according to claim 11, wherein the protective film is a cycloolefin polymer-based film; Or a polarizing plate that is an acrylic film. Display panel; And
An image display device comprising the polarizing plate according to claim 11 provided on one or both sides of the display panel.