KR20150141448A - Antistatic adhesive composition and polarizing plate using the same - Google Patents
Antistatic adhesive composition and polarizing plate using the same Download PDFInfo
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- KR20150141448A KR20150141448A KR1020140070191A KR20140070191A KR20150141448A KR 20150141448 A KR20150141448 A KR 20150141448A KR 1020140070191 A KR1020140070191 A KR 1020140070191A KR 20140070191 A KR20140070191 A KR 20140070191A KR 20150141448 A KR20150141448 A KR 20150141448A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
Abstract
The present invention relates to an antistatic pressure-sensitive adhesive composition and a polarizing plate produced using the same, and more particularly, to an antistatic pressure-sensitive adhesive composition comprising an acrylic copolymer polymerized with a monomer represented by the general formula (1), a crosslinking agent and an antistatic agent, An antistatic pressure-sensitive adhesive composition having excellent durability, and a polarizing plate produced using the same.
Description
The present invention relates to an antistatic pressure-sensitive adhesive composition, and more particularly, to an antistatic pressure-sensitive adhesive composition excellent in antistatic property and durability and a polarizing plate produced using the same.
An image display device is composed of a liquid crystal cell containing a liquid crystal and a polarizing plate, which are mainly bonded together by forming an adhesive layer on one surface of the polarizing plate. In addition, a surface protective film such as a retardation plate, a wide view angle compensating plate, and a brightness enhancement is additionally attached to the polarizing plate by using an adhesive or the like in order to improve the function of the image display apparatus.
Since such optical members such as the surface protective film and the polarizing plate are made of a plastic material, static electricity is generated at the time of friction and peeling, and when a voltage is applied to the liquid crystal in a state where static electricity remains, the orientation of the liquid crystal molecules is lost, Can occur. Therefore, various antistatic treatments have been carried out to prevent such defects.
Korean Unexamined Patent Publication No. 2006-0051328 discloses an ink composition comprising 5 to 100% by weight of a (meth) acrylic acid alkylene oxide adduct, 0 to 95% by weight of a (meth) acrylic monomer and 0 to 95% by weight of another polymerizable monomer Discloses a pressure-sensitive adhesive composition comprising a (meth) acryl-based polymer having an acid value of 10 to 95% by weight and an alkali metal salt, and Korean Patent Publication No. 2012-0073093 discloses a pressure- Discloses a pressure-sensitive adhesive composition comprising an acrylic polymer containing 5 to 40% by weight of a monomer having an alkylene oxide group, an ionic compound and a crosslinking agent.
These are similar to the present invention in that an acrylic copolymer obtained by copolymerizing an acrylic monomer containing a chelating functional group in a molecule is used in order to improve the compatibility of the ionic antistatic agent but the effect of improving the compatibility of the antistatic agent is insufficient And the durability is deteriorated due to the bleed out of the antistatic agent.
An object of the present invention is to provide an antistatic pressure-sensitive adhesive composition which is remarkably excellent in antistatic property and durability.
It is another object of the present invention to provide a pressure-sensitive adhesive sheet and a polarizing plate comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
It is still another object of the present invention to provide an image display apparatus including the polarizing plate.
1. A compound represented by the following formula (1):
[Chemical Formula 1]
(Wherein R < 1 > R 3 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 4 to R 9 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 10 Is hydrogen or a methyl group, and n is an integer of 1 to 10).
2. A process for preparing a compound of formula (I) according to claim 1 by reacting a compound represented by the following formula (2) with (meth) acryloyl halide:
(2)
(Wherein R < 1 > R 3 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 4 to R 9 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, 1 to 10).
3. An adhesive composition comprising an acrylic copolymer, a crosslinking agent and an antistatic agent, which is polymerized in the presence of a compound represented by the following formula (1):
[Chemical Formula 1]
(Wherein R < 1 > R 3 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 4 to R 9 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 10 Is hydrogen or a methyl group, and n is an integer of 1 to 10).
4. The pressure-sensitive adhesive composition according to 3 above, wherein the compound of formula (1) is a compound represented by the following formula (1-a)
[Chemical Formula 1-a]
(Wherein R is hydrogen or a methyl group, and n is an integer of 1 to 10).
5. The pressure-sensitive adhesive composition according to 3 above, wherein the compound of Formula 1 is contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total monomers based on the solid content.
6. The pressure-sensitive adhesive composition according to 3 above, wherein the antistatic agent is represented by the following general formula (3):
(3)
M + [(SO 2 R) 2 N] -
(Wherein M is an alkali metal and R is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms)
7. A pressure-sensitive adhesive sheet comprising an adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 3 to 6.
8. A polarizer comprising at least one side of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of items 3 to 6 above.
9. An image display device comprising the above-mentioned polarizing plate.
The acrylic copolymer prepared by polymerizing the compound represented by the formula (1) of the present invention as a monomer has a hydrophilicity stronger than that in the case where a conventionally used copolymer contains a polyethylene glycol structure and the ionization degree of the antistatic agent The pressure-sensitive adhesive composition of the present invention exhibits excellent antistatic properties as compared with the conventional pressure-sensitive adhesive composition.
Further, the present invention can prevent bleeding out by increasing the cohesive force of an antistatic agent, and exhibit improved adhesion and durability as compared with conventional pressure sensitive adhesive compositions.
FIG. 1 shows the results of NMR spectroscopy of the compound represented by the formula 1-b by the reaction scheme 1-b.
The present invention relates to a novel compound capable of remarkably improving antistatic property and durability, an antistatic property including an acrylic copolymer polymerized by incorporating a compound represented by the above formula (1) as a monomer, a crosslinking agent and an antistatic agent Sensitive adhesive composition and a polarizing plate produced using the same.
<Compound>
The compounds of the present invention are represented by the following Formula 1:
[Chemical Formula 1]
(Wherein R < 1 > R 3 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 4 to R 9 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 10 Is hydrogen or a methyl group, and n is an integer of 1 to 10).
Since the compound of the formula (1) is hydrophilic compared to the polyethylene glycol conventionally used, when the compound of the formula (1) is used as a monomer in the polymerization of the acrylic copolymer contained in the pressure-sensitive adhesive composition, the stabilizing effect of the antistatic agent is excellent, To show sex. Further, the durability is remarkably improved by the high adhesive force. Accordingly, the pressure-sensitive adhesive composition according to the present invention can exhibit remarkably improved antistatic property and durability.
The compound of formula (1) is not particularly limited and may be a compound of the following formula (1-a).
[Chemical Formula 1-a]
(Wherein R is hydrogen or a methyl group, and n is an integer of 1 to 10)
The compound of formula (1) can be prepared, for example, by reacting the compound of formula (2) with (meth) acryloyl halide. (Meth) acryloyl halide means acryloyl halide or methacryloyl halide. The (meth) acryloyl halide may preferably be (meth) acryloyl chloride.
[Reaction Scheme 1]
The reaction may be carried out in a solvent free of active hydrogen, such as toluene, chloroform, acetonitrile, at a temperature of 0 to 25 ° C for 10 to 100 minutes, and the reaction may be carried out in the presence of a tertiary amine .
≪ Pressure sensitive adhesive composition &
The pressure-sensitive adhesive composition of the present invention comprises an acrylic copolymer, a cross-linking agent, and an antistatic agent polymerized by including the compound represented by the formula (1) as a monomer.
Hereinafter, the present invention will be described in detail.
The acrylic copolymer according to the present invention is polymerized by including the compound represented by the formula (1), and as described above, it can have antistatic properties and durability superior to the conventional ones.
Specifically, the acrylic copolymer according to the present invention is polymerized by including a monomer having a specific structure of the formula (1), so that adjacent nitrogen atoms and oxygen atoms in the acrylic copolymer effectively prevent the antistatic agent from being antistatic.
In addition, compared with the case where the copolymer used in the conventional pressure-sensitive adhesive composition contains a monomer having a polyethylene glycol structure, the hydrophilicity is strong and the antistatic agent can be effectively coordinated and the antistatic agent can be effectively stabilized as the ionization degree of the antistatic agent is increased. Sensitive adhesive composition of the present invention exhibits remarkably improved antistatic property.
In addition, the acrylic copolymer according to the present invention can remarkably improve the durability by high adhesive force.
The monomer constituting the acrylic copolymer according to the present invention may be any monomer as long as it is a compound represented by the formula (1), more preferably a compound represented by the formula (1-a) The durability is remarkably improved.
In the acrylic copolymer according to the present invention, the monomer represented by the general formula (1) can be appropriately mixed according to the specific kind of the other monomers to be copolymerized. Therefore, the content and the mixing ratio are not particularly limited, but the monomer represented by the general formula It is preferable that the polymer is polymerized in an amount of 1 to 30 parts by weight based on 100 parts by weight of the monomer in terms of improvement in durability. If the amount of the compound represented by the formula (1) is less than 1 part by weight, the effect of improving the antistatic property and the durability of the antistatic agent due to the bleed-out may be insufficient. If the amount exceeds 30 parts by weight, There is a possibility that the durability is deteriorated due to the deterioration.
When the acrylic copolymer is produced using the monomer represented by the above formula (1-a), the antistatic effect is also enhanced when the amount of the acrylic copolymer is 10 parts by weight or more based on 100 parts by weight of the total monomer based on the solid content.
In addition to the monomers of formula (1), they can be further polymerized by including monomers known in the art. (Meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a polymerizable monomer having a crosslinkable functional group, wherein the (meth) acrylate is a polymer obtained by polymerizing an acrylate and a methacrylate It means all.
Examples of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, (Meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (Meth) acrylate, nonyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate and lauryl (meth) acrylate. Of these, n-butyl acrylate, Mixtures of these are preferred. These may be used alone or in combination of two or more.
The content and the mixing ratio of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms are not particularly limited and may be, for example, from 65 to 98 parts by weight based on 100 parts by weight of the total monomers based on the solid content, Preferably 85 to 95 parts by weight. When the content is less than 65 parts by weight, sufficient adhesion can not be exhibited, and when it exceeds 98 parts by weight, durability may be lowered due to deterioration of cohesive force and cohesive force.
The polymerizable monomer having a crosslinkable functional group is a component for imparting durability and cutability by reinforcing the cohesive strength or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding, and examples thereof include monomers having a carboxyl group, monomers having a hydroxy group, monomers having an amide group, etc. These may be used singly or in combination of two or more kinds. In view of improvement of corrosion resistance, it is preferable that acrylic acid is not contained.
Examples of the monomer having a carboxyl group include monovalent acids such as (meth) acrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, itaconic acid, and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; A succinic anhydride ring-opening addition adduct of 2-hydroxyalkyl (meth) acrylate in which the alkyl group has 2 to 4 carbon atoms, anhydrous succinic ring opening adduct of a hydroxyalkylene glycol (meth) acrylate having 2 to 4 carbon atoms in the alkylene group , And compounds obtained by ring-opening addition of succinic anhydride to a caprolactone adduct of 2-hydroxyalkyl (meth) acrylate having 2 or 3 carbon atoms in the alkyl group. Of these, (meth) acrylic acid is preferable.
Examples of the monomer having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl Hydroxypropyleneglycol (meth) acrylate, hydroxyalkylene glycol having 2 to 4 carbon atoms in the alkylene group (e.g., methoxyethyl (meth) acrylate, Hydroxybutyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxynonyl (meth) acrylate, 4-hydroxybutyl vinyl ether, Vinyl ether, and 10-hydroxydecyl vinyl ether, among which 4-hydroxybutyl vinyl ether is preferable.
Examples of the monomer having an amide group include (meth) acrylamide, N-isopropyl acrylamide, N-tertiary butyl acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (Meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide, and 2-hydroxyethylhexyl (meth) acrylamide. Of these, (meth) acrylamide is preferable.
The content and the mixing ratio of the polymerizable monomer having a crosslinkable functional group are not particularly limited and may be, for example, 0.1 to 15 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total monomers on the basis of solid content good. If the content is less than 0.1 part by weight, the cohesive strength of the pressure-sensitive adhesive may be lowered and durability may be deteriorated. If the content is more than 15 parts by weight, the adhesive strength may be lowered and durability may be deteriorated due to a high gel fraction.
As a polymerizable monomer known in the art in addition to the above-mentioned monomers, those used in the acrylic polymer include compounds for improving cohesion or heat resistance such as a cyano group-containing monomer, a vinyl ester monomer and an aromatic vinyl monomer, an imide group-containing monomer, an amino group- A compound having a functional group acting as a crosslinking point or improving the adhesion of a monomer containing a morpholine such as a monomer, a vinyl ether monomer or N-acryloylmorpholine can be suitably used.
Specific examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile. Specific examples of the vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl laurate, and the like.
Specific examples of the aromatic vinyl monomers include styrene, chlorostyrene, chloromethylstyrene,? -Methylstyrene, and other substituted styrenes.
Specific examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide and itaconimide.
Specific examples of the amino group-containing monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and aminoethyl (meth) acrylate.
Specific examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
Specific examples of the vinyl ether-containing monomer include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.
These monomer compounds may be used alone or in admixture of two or more.
The acrylic copolymer may further contain, in addition to the above monomers, a polymerizable monomer known in the art in a range not lowering the adhesive force, for example, 10 parts by weight or less based on 100 parts by weight of the total monomers on the basis of the solid content. For example, there may be mentioned an aromatic functional group-containing monomer for improving the light-shielding property, an alicyclic ring-containing monomer for improving the adhesion to the non-polar substrate, a polyalkylene glycol group for further suppressing the bleed- A monomer containing a functional group, and a monomer containing a metal corrosion-preventing functional group for preventing corrosion of a metal adherend.
The method for producing the copolymer is not particularly limited and can be produced by methods such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable. In addition, a solvent, a polymerization initiator, a chain transfer agent for molecular weight control and the like which are usually used in polymerization can be used.
The acrylic copolymer preferably has a weight average molecular weight (polystyrene conversion, Mw) of 200,000 to 2,000,000, more preferably 500,000 to 2,000,000 as measured by Gel Permeation Chromatography (GPC). If the weight-average molecular weight is less than 200,000, cohesion between co-polymers may be insufficient, which may cause problems in adhesion durability. If the weight average molecular weight is more than 2,000,000, a large amount of diluting solvent may be required in order to ensure fairness in coating.
The cross-linking agent according to the present invention is a component for improving the cohesive strength by appropriately crosslinking the copolymer, and the kind thereof is not particularly limited. For example, an isocyanate-based or epoxy-based cross-linking agent may be used, Can be used.
Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylene xylene diisocyanate, Diisocyanate compounds such as naphthalene diisocyanate, adducts of diisocyanate and polyhydric alcohol compounds such as trimethanol propane, isocyanurate compounds in which diisocyanate is self-condensed, burettes in which diisocyanate urea is condensed with diisocyanate, tri And polyfunctional isocyanate compounds containing three functional groups such as phenylmethane triisocyanate and methylene bistriisocyanate.
Examples of the epoxy crosslinking agent include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether , Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol Sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-isocyanurate, m-xylylenediamine, and the like.
In addition to the isocyanate crosslinking agent and the epoxy crosslinking agent, at least one crosslinking agent selected from the group consisting of melamine derivatives such as hexamethylol melamine, hexamethoxymethyl melamine, and hexabutoxymethyl melamine is further added Can be used together.
The content of the cross-linking agent is not particularly limited within a range where the function of the cross-linking agent can be accomplished. For example, 0.1 to 15 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer, . When the content is less than 0.1 part by weight, the cohesive force becomes small due to insufficient crosslinking, which may deteriorate the durability of the adhesive durability and the cutability. If the content exceeds 15 parts by weight, the residual stress due to the excessive crosslinking reaction may occur.
The antistatic agent according to the present invention is not particularly limited as long as it is used in the art.
For example, as the cation, organic cationic or alkali metal cations such as ammonium, pyridinium, imidazolium, phosphonium, and sulfonium can be used, and these can be used alone or in combination of two or more. Specific examples of ammonium include quaternary ammonium salts substituted with four alkyl groups such as tetrabutylammonium. Specific examples of pyridinium include 1-ethylpyridinium, 1-butylpyridinium, 1-hexylpyridinium, 1 Butyl-3-methylpyridinium, 1-butyl-4-methylpyridinium, 1-hexyl-3-methylpyridinium, Pyridinium in which N of pyridine is substituted with an alkyl group, and specific examples of imidazolium include imidazolium such as 1-methyl-3-butylimidazolium and 1-methyl-3-hexylimidazolium. Imidazolium substituted with an alkyl group at the 1,3-position of the sulfonium salt, and specific examples of the phosphonium include quaternary phosphonium salts having four alkyl substituents such as tetrabutylphosphonium, And specific examples of the tertiary sulfonium salt having three alkyl substituents such as tributylsulfonium. Specific examples of the alkali metal cations include a lithium salt, a sodium salt, and a potassium salt.
As the anion (sulfonate trifluoromethyl) OTf, OTs (toluene-4-sulfonate), OMs (methanesulfonate), Cl -, Br -, I -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (FSO 2) 2 N -, (CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) n -, (CN) 2 N -, C 4
Of these, sulfonylimide compounds are preferable in view of durability and antistatic property, and examples thereof include compounds represented by the following formula (3). The sulfonylimide-based anion of the following formula (3) has high electronegativity of the fluorine atoms of the anion, so that the effect of stabilizing the anion present in the nitrogen atom is high, so that the hydrophobicity of the antistatic agent is improved and the compatibility with the acrylic copolymer is excellent. There is no migration property, and it is preferable from the standpoint of imparting endurance reliability and physical properties of antistatic property.
(3)
M + [(SO 2 R) 2 N] -
(Wherein M is an alkali metal and R is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms)
The alkali metal may be lithium, sodium, potassium or cesium, preferably lithium, sodium or potassium.
More specific examples of the antistatic agent compound of Formula 3 include bis (fluorosulfonyl) imide potassium (KN (FSO 2 ) 2 ), bis (fluorosulfonyl) imide sodium (NaN (FSO 2 ) 2 ) Bis (trifluorosulfonyl) imide lithium (LiN (FSO 2 ) 2 ), bis (trifluorosulfonyl) imide potassium (KN (CF 3 SO 2 ) 2 ) de sodium (NaN (CF 3 SO 2) 2) or bis (trifluoromethyl sulfonyl) already and the like de lithium (LiN (CF 3 SO 2) 2), preferably a bis (sulfonyl fluorophenyl) imide potassium (KN (FSO 2) 2) , bis (sulfonyl fluorophenyl) may already be mentioned de sodium (NaN (FSO 2) 2) , these may be used each alone or in mixture of two or more.
The antistatic agent is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer based on the solid content. If the content is less than 0.1 part by weight, the effect of imparting antistatic properties may be insignificant. If the content is more than 10 parts by weight, bleeding out easily occurs and peeling failure may occur under heat-resistant conditions.
The pressure-sensitive adhesive composition of the present invention may further comprise a silane coupling agent. The silane coupling agent is added to improve adhesion with the pressure-sensitive adhesive, and is not particularly limited as long as it contains functional groups such as an amino group, an epoxy group, an acetoacetyl group, a polyalkylene glycol group, an acrylic group and an alkyl group. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethoxydimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane , 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethylsilane, and the like. These may be used alone or in combination of two or more.
The content of the silane coupling agent is not particularly limited and may be, for example, 0.1 to 2 parts by weight, preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of the acrylic copolymer based on the solid content. When the content is less than 0.1 part by weight, the adhesion to the substrate may be insufficient, and peeling may occur under the moisture-resistant condition. If the content is more than 2 parts by weight, peeling may occur under the heat-resistant condition.
In addition, the pressure-sensitive adhesive composition of the present invention may contain various components such as antioxidants, leveling agents, surface lubricants, dyes, pigments, light stabilizers, corrosion inhibitors, defoamers, fillers, And an additive such as an inhibitor.
<Adhesive sheet>
The present invention also provides a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
The thickness of the adhesive layer is not particularly limited and may be, for example, 3 to 100 m, preferably 10 to 100 m.
The pressure sensitive adhesive sheet of the present invention comprises an adhesive layer formed on at least one surface of a release film.
The pressure-sensitive adhesive layer can be formed by coating the pressure-sensitive adhesive composition on at least one surface of the release film. The coating method is not particularly limited and a method known in the art may be used. For example, a method such as bar coater, air knife, gravure, reverse roll, kiss roll, spray, blade, die coater, casting, Can be used.
The releasing film is not particularly limited, and a releasing film commonly used for the pressure-sensitive adhesive sheet can be used, and examples thereof include polyester resins such as polyethylene terephthalate, polybutylene terephthalide, polyethylene naphthalate and polybutylene naphthalate; Polyimide resin; Acrylic resin; Styrenic resins such as polystyrene and acrylonitrile-styrene; Polycarbonate resin; Polylactic acid resin; Polyurethane resin; Polyolefin resins such as polyethylene, polypropylene and ethylene-propylene copolymer; Vinyl resins such as polyvinyl chloride and polyvinylidene chloride; Polyamide resins; Sulfonic resin; Polyether-ether ketone resin; Allylate series resin; Or a mixture of these resins.
The thickness of the release film is not particularly limited, and may be, for example, from 5 to 500 mu m, and preferably from 10 to 100 mu m.
<Polarizer>
The present invention also provides a polarizing plate comprising an adhesive layer formed on at least one side of the pressure-sensitive adhesive composition.
The polarizing plate of the present invention comprises a polarizer, a protective film bonded to at least one surface of the polarizer, and an adhesive layer formed on the protective film with the adhesive composition.
The polarizer may be a polarizer well-known in the art, for example, a polyvinyl alcohol film produced through a process such as swelling, dyeing, crosslinking, stretching, washing, drying and the like.
The protective film is not particularly limited as long as it is a film excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like. Specifically, polyester films such as polyethylene terephthalate, polyethylene isophthalate and polybutylene terephthalate; Cellulose-based films such as diacetylcellulose and triacetylcellulose; Polycarbonate-based films; Acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene-based films such as polystyrene and acrylonitrile-styrene copolymer; Polyolefin films; Vinyl chloride film; Polyamide-based films such as nylon and aromatic polyamide; Imidazole film; Sulfone based films; Polyether ketone-based films; A sulfided polyphenylene-based film; Vinyl alcohol film; Vinylidene chloride films; Vinyl butyral film; Allylate-based films; Polyoxymethylene-based films; Urethane-based films; Epoxy-based films; Silicone-based films, and the like. Among them, a cellulose-based film having a surface saponified (saponified) by alkali or the like is preferable in consideration of polarization characteristics or durability. In addition, the protective film may have the function of an optical layer.
The adhesive layer may be coated directly on the protective film, or may be formed by adhering an adhesive sheet to the protective film.
<Image Display Device>
In addition, the present invention provides an image display device including the polarizing plate.
The image display apparatus of the present invention may further include a configuration known in the art in addition to the polarizing plate.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.
Manufacturing example 1-1: Preparation of compound of formula (1-b)
Formula 1-b is prepared by mixing 2 - ((2- (2- (dimethylamino) ethoxy) ethyl) (methyl) amino) ethanol and acryloyl chloride in toluene according to scheme 1-b, At 0 DEG C for 30 minutes. After purification, the structure was confirmed by NMR and the results are shown in Fig.
[Chemical Formula 1-b]
[Reaction Scheme 1-b]
Manufacturing example 1-2: 1- of c Compound manufacturing
A solution of 2,8,14-trimethyl-5,11-dioxa-2,8,14-triazahexadecane instead of 2 - ((2- (2- (dimethylamino) ethoxy) ethyl) -16-ol was used in place of the compound represented by the formula (1-c), the following reaction scheme 1-c was carried out under the same conditions as in Preparation Example 1-1.
[Chemical Formula 1-c]
[Reaction Scheme 1-c]
Manufacturing example 2-a: Preparation of acrylic copolymer 1
84 parts by weight of n-butyl acrylate, 10 parts by weight of methyl acrylate, 1 part by weight of 2-hydroxybutyl acrylate, and 1 part by weight of 2- ( And 5 parts by weight of (2- (2- (dimethylamino) ethoxy) ethyl) (methyl) amino) ethyl acrylate (Formula 1-b) were added thereto and 100 parts by weight of ethyl acetate was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then maintained at 62 ° C. After the mixture was homogeneously mixed, 0.07 part by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator and reacted for 6 hours to prepare an acrylic copolymer 1 (weight average molecular weight: about 1,000,000).
[Chemical Formula 1-b]
Manufacturing example 2-b: Preparation of acrylic copolymer 2
(methyl) amino) ethyl acrylate, 2-hydroxyethyl acrylate, and 1 part by weight of 2-hydroxyethyl acrylate, And 10 parts by weight of ethyl acrylate (formula (I-b)) was used instead of the monomer mixture.
Manufacturing example 2-c: Preparation of acrylic copolymer 3
84 parts by weight of n-butyl acrylate, 10 parts by weight of methyl acrylate, 1 part by weight of 2-hydroxybutyl acrylate, 2,8,14-trimethyl-5,11-dioxa-2,8,14- Hexadecane-16-day acrylate (formula (1-c)) was used instead of the monomer mixture consisting of 5 parts by weight of hexadecane-16-day acrylate.
[Chemical Formula 1-c]
Manufacturing example 2-d: Preparation of acrylic copolymer 4
except that a monomer mixture composed of 89 parts by weight of n-butyl acrylate, 10 parts by weight of methyl acrylate and 1 part by weight of 2-hydroxybutyl acrylate was used.
Manufacturing example 2-e: Preparation of acrylic copolymer 5
84 parts by weight of n-butyl acrylate, 10 parts by weight of methyl acrylate, 1 part by weight of 2-hydroxybutyl acrylate, 2- (2- (2-methoxyethoxy) ethoxy) ethyl acrylate and d) 5 parts by weight was used instead of the monomer mixture prepared in Preparation Example 2-a.
[Chemical formula 1-d]
Manufacturing example
2-f: Preparation of
84 parts by weight of n-butyl acrylate, 10 parts by weight of methyl acrylate, 1 part by weight of 2-hydroxybutyl acrylate and 5 parts by weight of 2- (dimethylamino) ethyl acrylate (formula 1-e) The procedure of Production Example 2-a was followed, except that
[Formula 1-e]
Example And Comparative Example
(1) Production of pressure-sensitive adhesive composition
The mixture according to the composition and content shown in Table 1 below was diluted in an organic solvent to prepare a pressure-sensitive adhesive composition, and the solids content was based on this.
(2) Production of pressure-sensitive adhesive sheet
The pressure-sensitive adhesive composition was prepared, coated on a film coated with silicone release agent, and dried at 100 ° C for 1 minute to form a pressure-sensitive adhesive layer of 25 μm.
Thereafter, a releasing film was laminated on the pressure-sensitive adhesive layer to produce a pressure-sensitive adhesive sheet.
(3) Production of Polarizer with Adhesive
After the release film of the pressure sensitive adhesive sheet thus prepared was peeled off, a pressure sensitive adhesive layer was laminated on an iodine polarizing plate containing a TAC protective film having a thickness of 185 탆 on both sides and a yttopolymer polarizing plate containing a cross section to prepare a polarizing plate with a pressure sensitive adhesive. In the case of a yezo-based polarizer including a TAC protective film in its cross-section, the pressure-sensitive adhesive layer was bonded so as to adhere to the polarizer on the opposite side of the TAC protective film.
(Parts by weight)
(A)
(B)
(C)
(D)
A-2: Acrylic copolymer according to Production Example 2-b
A-3: Acrylic copolymer according to Production Example 2-c
A-4: Acrylic copolymer according to Production Example 2-d
A-5: Acrylic copolymer according to Production Example 2-e
A-6: Acrylic copolymer according to Production Example 2-f
B: Cor-L (Nippon Polyurethane Industry Co., Ltd.: tolylene diisocyanate trimethylol propane adduct)
C: KBM-403 (Shin-Etsu Silicone: glycidoxypropyltrimethoxysilane)
D-1: KN (FSO 2 ) 2 (Mitsubishi: bis (fluorosulfonyl) imide potassium)
D-2: NaPF 6 (Aldrich)
Experimental Example
(1) Daejeon Preventiveness evaluation
The surface resistivity of the pressure-sensitive adhesive bonded to the polarizing plate including the double-side TAC film was measured. (Unit: Ω · cm)
(2) Evaluation of heat resistance
The release film of the pressure-sensitive adhesive layer bonded to the polarizing plate including the double-side TAC film was removed, bonded to a Corning glass, autoclaved, and then allowed to stand at a temperature of 60 DEG C for 300 hours. Observed and evaluated.
[Criteria for evaluation of heat resistance]
○: No bubbles or peeling were visually confirmed.
△: No more than 5 bubbles or peeling were observed.
Χ: 5 or more bubbles or exfoliation are identified, or there is a lot of splashing on the front.
(3) Optical durability evaluation
The release film of the pressure-sensitive adhesive layer bonded to the polarizing plate including the cross-section TAC film was removed, bonded to a Corning glass, autoclaved and left for 100 hours at a temperature of 60 DEG C and a humidity of 90% .
[Evaluation criteria of optical durability]
○: 98% or more of polarized light after heat treatment
?: 90% or more and less than 98% of polarized light after heat and humidity treatment
Χ: Less than 90% of polarized light after heat treatment
As shown in Table 2, it can be confirmed that the antistatic properties, heat resistance and optical durability of Examples 1 to 4 are superior to those of Comparative Examples.
Claims (9)
[Chemical Formula 1]
(Wherein R < 1 > R 3 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 4 to R 9 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 10 Is hydrogen or a methyl group, and n is an integer of 1 to 10).
(2)
(Wherein R < 1 > R 3 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 4 to R 9 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, 1 to 10).
[Chemical Formula 1]
(Wherein R < 1 > R 3 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 4 to R 9 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 10 Is hydrogen or a methyl group, and n is an integer of 1 to 10).
[Chemical Formula 1-a]
(Wherein R is hydrogen or a methyl group, and n is an integer of 1 to 10).
(3)
M + [(SO 2 R) 2 N] -
(Wherein M is an alkali metal and R is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140070191A KR20150141448A (en) | 2014-06-10 | 2014-06-10 | Antistatic adhesive composition and polarizing plate using the same |
| TW104116165A TW201602288A (en) | 2014-06-10 | 2015-05-21 | Antistatic adhesive composition and polarizing plate using the same |
| PCT/KR2015/005829 WO2015190826A1 (en) | 2014-06-10 | 2015-06-10 | Adhesive composition having anti-static properties, and polarizing plate manufactured using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140070191A KR20150141448A (en) | 2014-06-10 | 2014-06-10 | Antistatic adhesive composition and polarizing plate using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20150141448A true KR20150141448A (en) | 2015-12-18 |
Family
ID=54833839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140070191A KR20150141448A (en) | 2014-06-10 | 2014-06-10 | Antistatic adhesive composition and polarizing plate using the same |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20150141448A (en) |
| TW (1) | TW201602288A (en) |
| WO (1) | WO2015190826A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180111227A (en) * | 2017-03-31 | 2018-10-11 | 동우 화인켐 주식회사 | Polarizing plate and image display device comprising the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003322718A (en) * | 2002-04-30 | 2003-11-14 | Mitsubishi Polyester Film Copp | Base material for protecting film for polarizing plate |
| KR100995510B1 (en) * | 2007-01-16 | 2010-11-19 | 주식회사 엘지화학 | Acrylic pressure sensitive adhesive compositions having plasticizer |
| KR20090010292A (en) * | 2007-07-23 | 2009-01-30 | 동우 화인켐 주식회사 | Antistatic pressure sensitive adhesive composition and polarizer including the same |
| KR20110133657A (en) * | 2010-06-07 | 2011-12-14 | 동우 화인켐 주식회사 | Novel isocyanate compound, adhesive composition and polarizing plate comprising the same |
| KR101391297B1 (en) * | 2013-07-22 | 2014-05-02 | 동우 화인켐 주식회사 | Adhesive composition |
-
2014
- 2014-06-10 KR KR1020140070191A patent/KR20150141448A/en not_active Application Discontinuation
-
2015
- 2015-05-21 TW TW104116165A patent/TW201602288A/en unknown
- 2015-06-10 WO PCT/KR2015/005829 patent/WO2015190826A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180111227A (en) * | 2017-03-31 | 2018-10-11 | 동우 화인켐 주식회사 | Polarizing plate and image display device comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015190826A1 (en) | 2015-12-17 |
| TW201602288A (en) | 2016-01-16 |
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