KR20170106210A - Optical member with adhesive layer - Google Patents

Abstract

Provided is an optical member having an adhesive layer which exhibits high adhesion force to a liquid crystal cell and the like and can be easily peeled off immediately after bonding. As the optical member having an optical member and the adhesive layer including an adhesive layer laminated on the optical member, provided is the optical member having an adhesive member having the ratio of P_50 to P_23 (P_50/P_23) is 4.5 or more, if peeling force between the optical member having the adhesive layer and non-alkali glass when the optical member having an optical member is laminated on a non-alkali glass plate through the adhesive layer and stored under temperature of the 23C for 24 hours is P_23, and if peeling force between the optical member having the adhesive layer and non-alkali glass when the optical member having an optical member is laminated on the non-alkali glass plate through the adhesive layer and stored under temperature of the 50C for 48 hours is P_50.

Description

[0001] OPTICAL MEMBER WITH ADHESIVE LAYER [0002]

The present invention relates to an optical member having a pressure-sensitive adhesive layer.

A polarizing plate in which a protective film is laminated on one surface or both surfaces of a polarizer is used as an image display device such as a liquid crystal display device and an organic electroluminescence (organic EL) display device, and more particularly, And is widely used in various mobile devices. An optical member such as a polarizing plate is an optical member having a pressure-sensitive adhesive layer formed by laminating a pressure-sensitive adhesive layer thereon, and is often used by being bonded to, for example, a liquid crystal cell or the like in a liquid crystal display device (see, for example, Patent Document 1).

The optical member having such a pressure-sensitive adhesive layer is required to exhibit high adhesion after being bonded to a liquid crystal cell or the like. On the other hand, when there is a problem in joining to a liquid crystal cell or the like, it is also required to be readily peelable immediately.

Patent Document 1: JP-A-2010-066755

However, an optical member having a conventional pressure-sensitive adhesive layer showing adhesion to a liquid crystal cell or the like has high adhesion even immediately after bonding, and peeling from a liquid crystal cell or the like is not easy even immediately after bonding.

An object of the present invention is to provide an optical member having a pressure-sensitive adhesive layer which can exhibit a high adhesion force to a liquid crystal cell or the like and can easily peel off immediately after bonding.

The present invention provides an optical member having a pressure-sensitive adhesive layer described below.

[1] An optical member having a pressure-sensitive adhesive layer comprising an optical member and a pressure-sensitive adhesive layer laminated on the optical member,

Wherein the optical member having the pressure-

The peeling force between the optical member having the pressure-sensitive adhesive layer and the alkali-free glass when the laminate was laminated on the alkali-free glass plate through the pressure-sensitive adhesive layer and stored for 24 hours under an environment of 23 ° C was regarded as P ₂₃ ,

When the peel force between the optical member having the pressure-sensitive adhesive layer and the alkali-free glass is P ₅₀ when the pressure-sensitive adhesive layer is laminated on the non-alkali glass plate and stored for 48 hours under an environment of 50 ° C,

Ratio (P ₅₀ / P ₂₃₎ an optical member having a pressure-sensitive adhesive layer of 4.5 or higher and the P ₅₀ P ₂₃ above.

The P ₂₃ is usually 0.5 N / 25 mm or more.

The pressure-sensitive adhesive layer may be a layer comprising a pressure-sensitive adhesive composition containing a (meth) acrylic monomer (A) having a constituent unit derived from a (meth) acrylic monomer having a hydroxyl group and having a content of the constituent unit of 3.5 wt% , And a pressure-sensitive adhesive composition containing a (meth) acrylic resin (A) having a content of the constituent unit of more than 3.5% by weight.

This pressure-sensitive adhesive composition may contain a crosslinking catalyst (C-1) and a compound (C-2) containing an alkyleneoxy group and further include an isocyanate crosslinking agent (B-1). The pressure-sensitive adhesive composition may further contain an ionic compound (D). The pressure-sensitive adhesive composition may further contain a silane compound (E).

The present invention also provides the following pressure-sensitive adhesive composition.

[2] A method for producing a laminated film, comprising the steps of: forming a film on a first film made of a cyclic polyolefin resin to form a layer, and storing the first alkali-free glass plate on the formed first layer for 24 hours under an environment of 23 ° C Alkali glass plate is laminated on the second layer formed on the second film made of a cyclic polyolefin resin by _setting the peeling force between the first non-alkali glass plate and the first non-alkali glass plate to be P _CO23 , when the second layer and a peel force between the second non-alkali glass plate when 48 hours storage under the 50 ℃ environment from one state to P _CO50, ratio (P _CO50 / P of the P _CO50 and the P _{CO23 CO23} ) of 4.5 or more.

According to the present invention, it is possible to provide an optical member having a pressure-sensitive adhesive layer which is easily peeled off immediately after bonding while exhibiting a high adhesion to a liquid crystal cell or the like at a relatively high temperature.

1 is a schematic sectional view showing an example of an optical member having a pressure-sensitive adhesive layer according to the present invention.
2 is a schematic cross-sectional view showing another example of the optical member having the pressure-sensitive adhesive layer according to the present invention.
3 is a schematic cross-sectional view showing still another example of the optical member having the pressure-sensitive adhesive layer according to the present invention.
4 is a schematic cross-sectional view showing still another example of the optical member having the pressure-sensitive adhesive layer according to the present invention.

The pressure-sensitive adhesive layer constituting the optical member having the pressure-sensitive adhesive layer of the present invention is composed of, for example, a pressure-sensitive adhesive composition containing a (meth) acrylic resin (A) containing a structural unit derived from a (meth) acrylic monomer having a hydroxyl group.

≪ Pressure sensitive adhesive composition &

[1] (meth) acrylic resin (A)

(Meth) acrylic resin (A) is represented by the following formula (I):

(Meth) acrylate ester represented by the following general formula (1), preferably a polymer containing a structural unit derived from a (meth) acrylic monomer having a hydroxyl group. In the present specification, "(meth) acryl" means acryl and / or methacryl, and "(meth)" when referring to (meth) acrylate is also intended.

In the formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 14 carbon atoms or an alkoxy group having 1 to 10 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms And an aralkyl group having 7 to 21 carbon atoms. R ² is preferably an alkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms.

Examples of the (meth) acrylic acid ester represented by the formula (I) include (meth) acrylic acid alkyl esters. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (Meth) acrylic acid alkyl esters such as n-butyl acrylate, n-octyl (meth) acrylate and lauryl (meth) acrylate; (Meth) acrylic acid alkyl esters such as isopropyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and isooctyl (meth) acrylate are branched. The alkyl moiety of the (meth) acrylic acid alkyl ester has preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.

Specific examples of the (meth) acrylic acid ester represented by the formula (I) in the case where R ² is an alkyl group substituted with an alkoxy group, that is, when R ² is an alkoxyalkyl group, include 2-methoxyethyl (meth) Methacrylic acid ethoxymethyl and the like. The number of carbon atoms of the alkyl group in the alkoxyalkyl group is preferably 1 to 8, more preferably 1 to 6. The number of carbon atoms of the alkoxy group in the alkoxyalkyl group is preferably 1 to 8, more preferably 1 to 4. Specific examples of the (meth) acrylic acid ester represented by the formula (I) in the case where R ² is an aralkyl group having 7 to 21 carbon atoms include benzyl (meth) acrylate and the like. The carbon number of the aralkyl group is preferably 7 to 11.

The (meth) acrylic acid ester represented by the formula (I) may be used alone, or two or more kinds thereof may be used in combination. Among them, the (meth) acrylic acid ester preferably contains a (meth) acrylic acid alkyl ester, more preferably an alkyl acrylate, and more preferably n-butyl acrylate. The (meth) acrylic resin (A) preferably contains at least 50% by weight of constituent units derived from n-butyl acrylate among the entire constituent units constituting the (meth) acrylic resin (A). Of course, other (meth) acrylic esters represented by the formula (I) may be used in addition to n-butyl acrylate.

The content of the structural unit derived from the (meth) acrylic acid ester represented by the formula (I) is usually 60% by weight or more and less than 100% by weight in the total structural units constituting the (meth) acrylic resin (A) 70 to 99.9% by weight, and more preferably 80 to 99.6% by weight.

The (meth) acrylic resin (A) contains a structural unit derived from a (meth) acrylic monomer having a hydroxyl group. The incorporation of this constituent unit is advantageous in enhancing the adhesion between the pressure-sensitive adhesive layer and the optical member and the durability of the pressure-sensitive adhesive layer. The (meth) acrylic monomer having a hydroxyl group is preferably a (meth) acrylic acid ester having a hydroxyl group. Specific examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) (Meth) acrylic acid, or diethylene glycol mono (meth) acrylate, such as 2- (3-chloro-2-hydroxypropyl) Partial ester of a functional alcohol and (meth) acrylic acid, and the like. From the viewpoints of adhesion between the pressure-sensitive adhesive layer and the optical member and durability (particularly heat resistance) of the pressure-sensitive adhesive layer, the monomer having a hydroxyl group is preferably a (meth) acrylic acid ester having a hydroxyl group, More preferable. The alkyl group in the alkyl group-containing alkyl ester of (meth) acrylic acid preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms.

The content of the structural unit derived from a (meth) acrylic monomer having a hydroxyl group may be, for example, 3.5% by weight or less, more preferably 3.5% by weight or more, and generally 10% by weight or less, of the total structural units constituting the (meth) acrylic resin By weight or less.

The (meth) acrylic resin (A) may contain a structural unit derived from a monomer having a polar functional group other than the (meth) acrylic monomer having a hydroxyl group. The monomer having such a polar functional group is preferably a (meth) acrylic monomer having a polar functional group.

Examples of the polar functional group of the monomer include a carboxyl group (free carboxyl group), an amino group, and a heterocyclic group (e.g., an epoxy group).

Specific examples of the monomer having another polar functional group include monomers having a carboxyl group such as (meth) acrylic acid,? -Carboxyethyl (meth) acrylate; Acrylonitrile, acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexyl Monomers having a heterocyclic group such as methyl (meth) acrylate, glycidyl (meth) acrylate, and 2,5-dihydrofuran; Monomers having an amino group different from a heterocyclic ring such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and the like. The monomers having other polar functional groups may be used alone, or two or more monomers may be used in combination.

The use of a monomer having another polar functional group, particularly a (meth) acrylic monomer having a carboxyl group, in addition to the (meth) acrylic monomer having a hydroxyl group is preferable because the adhesion between the pressure-sensitive adhesive layer and the optical member and the durability (especially heat resistance) Which is advantageous in increasing the height.

The content of the constituent unit derived from a (meth) acrylic monomer having a monomer having another polar functional group, preferably a carboxyl group is preferably 5% by weight or less based on the total constituent units constituting the (meth) acrylic resin (A) By weight, and more preferably 4% by weight or less. If the content of the constituent unit derived from a monomer having another polar functional group exceeds 5% by weight, the durability of the pressure-sensitive adhesive layer, particularly the heat resistance tends to be insufficient. On the other hand, the content of the constituent unit derived from a monomer having another polar functional group is usually 0.1% by weight or more, preferably 0.2% by weight or more, and more preferably 0.3% by weight or more, If the content of the constituent unit derived from a monomer having another polar functional group is less than 0.1% by weight, the use effect is hardly recognized. The constitutional unit derived from the monomer having all of the polar functional groups including the (meth) acrylic monomer having a hydroxyl group is usually 0.1 to 15% by weight, preferably 0.1 to 15% by weight, of the total constitutional units constituting the (meth) acrylic resin 0.2 to 10% by weight.

(Meth) acrylic resin (A) is a monomer having one olefinic double bond and at least one aromatic ring in the molecule (provided that the monomer represented by the formula (I) or the monomer having the polar functional group May be further included. Suitable examples include (meth) acrylic monomers having an aromatic ring. The (meth) acrylic monomers having such an aromatic ring include neopentyl glycol benzoate (meth) acrylate and the like. In particular, the following formula (II):

(Meth) acrylic acid ester having an aryloxyalkyl group such as a phenoxyethyl group-containing (meth) acrylic acid ester represented by the following formula The monomer having one olefinic double bond and at least one aromatic ring in the molecule such as a phenoxyethyl group-containing (meth) acrylate ester may be used alone, or two or more kinds thereof may be used in combination.

In the formula (II), R ³ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 8, and R ⁴ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. When R ⁴ is an alkyl group, the number of carbon atoms thereof may be about 1 to 9. When the aralkyl group is an aralkyl group, the number of carbon atoms thereof is about 7 to 11, and when it is an aryl group, the number of carbon atoms thereof may be about 6 to 10.

Examples of the alkyl group having 1 to 9 carbon atoms for R ⁴ in formula (II) include methyl, butyl, nonyl and the like. Examples of the aralkyl group having 7 to 11 carbon atoms include benzyl, phenethyl and naphthylmethyl, Examples of the group include phenyl, tolyl, and naphthyl.

Specific examples of the phenoxyethyl group-containing (meth) acrylic acid ester represented by the formula (II) include 2-phenoxyethyl (meth) acrylate, 2- (2-phenoxyethoxy) ethyl (Meth) acrylic acid ester of nonylphenol, 2- (o-phenylphenoxy) ethyl (meth) acrylate and the like. Among them, the phenoxyethyl group-containing (meth) acrylic acid ester is preferably selected from the group consisting of 2-phenoxyethyl (meth) acrylate, 2- (o-phenylphenoxy) ethyl (meth) Phenoxyethoxy) ethyl.

The content of the constituent unit derived from a monomer having an aromatic ring is usually 0 to 20% by weight (for example, 6 to 12% by weight) among all the constituent units constituting the (meth) acrylic resin (A). However, in order to bring the glass transition temperature of the (meth) acrylic resin (A) into a predetermined range to be described later, it is preferable not to include a monomer-derived constituent unit having an aromatic ring.

The (meth) acrylic resin (A) is a monomer other than the (meth) acrylic monomer, the monomer having a polar functional group and the monomer having an aromatic ring represented by the above-mentioned formula (I) (hereinafter also referred to as "other monomers"). ) May be contained. Examples of other monomers include structural units derived from a (meth) acrylic monomer having an alicyclic structure in the molecule (preferably a (meth) acrylic acid ester having an alicyclic structure in the molecule), a structural unit derived from a styrene monomer , A constituent unit derived from a vinyl monomer, a constituent unit derived from a monomer having a plurality of (meth) acryloyl groups in the molecule, and a constituent unit derived from a (meth) acrylamide compound. As the other monomers, only one type may be used alone, or two or more types may be used in combination.

The alicyclic structure in the (meth) acrylic acid ester having an alicyclic structure in the molecule means a cycloparaffin structure having a carbon number of usually 5 or more, preferably 5 to 7 or so. Specific examples of the (meth) acrylic acid ester having an alicyclic structure include (meth) acrylic acid esters such as isobornyl acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclododecyl Methylcyclohexyl, trimethylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclohexylphenyl (meth) acrylate, cyclohexyl α-ethoxyacrylate and the like.

Specific examples of the styrene-based monomer include styrene; Alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; Halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene and iodostyrene; Nitrostyrene, acetylstyrene, methoxystyrene, divinylbenzene, and the like.

Specific examples of the vinyl monomer include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate; Vinyl halides such as vinyl chloride and vinyl bromide; Vinylidene halides such as vinylidene chloride; Nitrogen-containing aromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; Conjugated diene monomers such as butadiene, isoprene, and chloroprene; Acrylonitrile, methacrylonitrile and the like.

Specific examples of the monomer having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate such as ethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate and tripropylene glycol di A monomer having a (meth) acryloyl group; Monomers having three (meth) acryloyl groups in the molecule such as trimethylolpropane tri (meth) acrylate, and the like.

Specific examples of the (meth) acrylamide compound include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (Meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (4-hydroxybutyl) (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (3-dimethylaminopropyl) (Meth) acrylamide, N- [2- (2-oxo-1-imidazolidinyl) ethyl] (meth) acrylamide, 2-acryloylamino- (Methoxymethyl) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- (1-methylethoxymethyl ) (Meth) acrylamide, N- (1-methylpropoxymethyl) (meth) acrylamide, N- (Methoxymethyl) (meth) acrylamide [alias: N- (isobutoxymethyl) (meth) acrylamide], N- (butoxymethyl) (meth) acrylamide, N- (1,1-dimethylethoxymethyl (Meth) acrylamide, N- (2-ethoxyethyl) (meth) acrylamide, N- (2-methoxyethyl) Amide, N- [2- (1-methylethoxy) ethyl] (meth) acrylamide, N- [2- (1-methylpropoxy) ethyl] (Meth) acrylamide, N- (2-butoxyethyl) (meth) acrylamide, N- (2-butoxyethyl) (1,1-dimethylethoxy) ethyl] (meth) acrylamide, and the like. Among them, preferred are N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) Hydroxy-methyl) < / RTI > acrylamide is preferably used.

The (meth) acrylic resin (A) generally contains 0 to 20% by weight, preferably 0 to 10% by weight, of constituent units derived from other monomers among all the constituent units constituting the (meth) acrylic resin (A).

The pressure-sensitive adhesive composition may contain two or more (meth) acrylic resins belonging to the (meth) acrylic resin (A). Further, the pressure-sensitive adhesive composition may contain another (meth) acrylic resin different from the (meth) acrylic resin (A). Examples of other (meth) acrylic resins are (meth) acrylic resins having a constituent unit derived from a (meth) acrylic monomer represented by the formula (I) and having no polar functional group. The content of the (meth) acrylic resin (A) in the total of all (meth) acrylic resins is preferably 60 wt% or more, more preferably 60 wt% % Or more, more preferably 80 wt% or more, and further preferably 90 wt% or more.

(Meth) acrylic resin (A) has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of -10 占 폚 or lower, preferably -15 占 폚 or lower, more preferably -20 占 폚 or lower to be. According to the pressure-sensitive adhesive composition according to the present invention containing the (meth) acrylic resin (A) having a Tg of -20 占 폚 or lower, adhesion between the pressure-sensitive adhesive layer and the optical member and durability of the pressure-sensitive adhesive layer can be improved. From the viewpoint of durability, the Tg of the (meth) acrylic resin (A) is usually -55 ° C or higher, preferably -50 ° C or higher.

The (meth) acrylic resin (A) preferably has a weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) in the range of 500,000 to 2,000,000, Is more preferable. When the Mw is 500,000 or more, the adhesion between the pressure-sensitive adhesive layer and the optical member under a high-temperature and high-humidity environment is improved, and the possibility of peeling or peeling between the pressure-sensitive adhesive layer and the optical member tends to decrease. The workability tends to be improved. If the Mw is less than 2,000,000, the pressure-sensitive adhesive layer is liable to follow and fluctuate even when the size of the optical member changes when the pressure-sensitive adhesive layer is bonded to the optical member. Therefore, When the optical member having a pressure-sensitive adhesive layer is applied to a liquid crystal display device due to the following property, there is no difference between the brightness of the periphery of the liquid crystal cell and the brightness of the center portion, Color unevenness tends to be suppressed. The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually about 2 to 10, preferably 3 to 7.

The (meth) acrylic resin (A) and other (meth) acrylic resins optionally usable in combination can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method and an emulsion polymerization method . In the production of the (meth) acrylic resin, usually a polymerization initiator is used. The polymerization initiator is used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the total amount of all the monomers used in the production of the (meth) acrylic resin. The (meth) acrylic resin may be produced by a method in which the polymerization is proceeded by an active energy ray such as ultraviolet rays.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, and the like are used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and the like. As the thermal polymerization initiator, for example, 2,2'-azobisisobutylonitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile Azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxy valeronitrile) Azo compounds such as azobis (2-methylpropionate) and 2,2'-azobis (2-hydroxymethylpropionitrile); Butyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, Organic peroxides such as neodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide; And inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide. A redox-type initiator using a peroxide and a reducing agent in combination may also be used as a polymerization initiator.

As the method for producing the (meth) acrylic resin, the solution polymerization method is preferable among the methods described above. An example of the solution polymerization method is to mix a monomer and an organic solvent to be used, add a thermal polymerization initiator under a nitrogen atmosphere, and stir at about 40 to 90 ° C, preferably about 50 to 80 ° C for about 3 to 15 hours. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization, or may be added while being dissolved in an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; Esters such as ethyl acetate and butyl acetate; Aliphatic alcohols such as propyl alcohol and isopropyl alcohol; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and the like.

[2] Crosslinking agent (B)

The pressure-sensitive adhesive composition is prepared by blending a crosslinking agent in addition to the above-mentioned (meth) acrylic resin. The crosslinking agent is a compound having at least two functional groups in the molecule capable of crosslinking with a constituent unit derived from a (meth) acrylic monomer, particularly a polar functional group-containing monomer in the (meth) acrylic resin. Specific examples thereof include an isocyanate compound, , Metal chelate compounds, and aziridine compounds.

The isocyanate compound (hereinafter also referred to as isocyanate crosslinking agent (B-1)) is a compound having at least two isocyanato groups (-NCO) in the molecule, and examples thereof include tolylene diisocyanate, hexamethylene diisocyanate, iso Xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like. Furthermore, it is also possible to use an adduct in which an isocyanate compound is reacted with a polyol such as glycerol or trimethylolpropane, or an isocyanate compound in the form of a dimer, a trimer, or the like, or a crosslinking agent used in a pressure-sensitive adhesive composition. Two or more isocyanate compounds may be mixed and used.

The epoxy compound is a compound having at least two epoxy groups in the molecule, and examples thereof include bisphenol A type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglyceride N, N, N ', N'-tetraglycidyl-m, N, N'-tetramethyl aniline, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, -Xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and the like. Two or more kinds of epoxy compounds may be mixed and used.

Examples of the metal chelate compound include compounds in which acetylacetone or ethyl acetoacetate is coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium or zirconium have.

The aziridine compound is a compound having at least two skeletons of a three-membered ring composed of one nitrogen atom and two carbon atoms, also called ethyleneimine, in the molecule, and examples thereof include diphenylmethane-4,4'-bis (1-aziridine Carboxamide), toluene-2,4-bis (1-aziridine carboxamide), triethylene melamine, isophthaloyl bis-1- (2-methyl aziridine), tris- Oxides, hexamethylene-1,6-bis (1-aziridine carboxamide), trimethylolpropane-tri-? -Aziridinylpropionate, tetramethylolmethane-tri-? -Aziridinylpropionate And the like.

Among these crosslinking agents, an isocyanate crosslinking agent (B-1), particularly xylylene diisocyanate, tolylenediisocyanate, hexamethylene diisocyanate, or an isocyanate compound is reacted with a polyol such as glycerol or trimethylolpropane, A mixture of isocyanate compounds, and the like are preferably used. When the (meth) acrylic resin (A) has a polar functional group selected from a free carboxyl group, a hydroxyl group, an amino group and an epoxy ring, it is particularly preferable to use an isocyanate crosslinking agent (B-1) as at least one of the crosslinking agent . Examples of suitable isocyanate crosslinking agent (B-1) include xylylene diisocyanate, an adduct obtained by reacting xylylene diisocyanate with a polyol, a dimer of xylylene diisocyanate, a trimer of xylylene diisocyanate, tolylene diisocyanate, An adduct obtained by reacting isocyanate with a polyol, a trimer of tolylene diisocyanate and a trimer of tolylene diisocyanate, an adduct obtained by reacting hexamethylene diisocyanate and hexamethylene diisocyanate with a polyol, an excess amount of hexamethylene diisocyanate And trimer of hexamethylene diisocyanate.

The crosslinking agent (B) is usually compounded in a proportion of 0.01 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic resin (A). The blending amount of the crosslinking agent (B) is preferably about 0.1 to 5 parts by weight, and more preferably about 0.2 to 3 parts by weight, based on 100 parts by weight of the (meth) acrylic resin (A). (B) relative to 100 parts by weight of the (meth) acrylic resin (A) is preferably 0.01 part by weight or more, particularly preferably 0.1 part by weight or more, since the durability of the pressure-sensitive adhesive layer tends to be improved, , It is preferable that the white part is not noticeable when the optical member having the adhesive is applied to the liquid crystal display device.

[3] Compound (C)

The pressure-sensitive adhesive composition usually contains a crosslinking catalyst (C-1) and a compound (C-2) containing an alkyleneoxy group. According to the pressure-sensitive adhesive composition according to the present invention containing the crosslinking catalyst (C-1) and the compound (C-2) containing an alkyleneoxy group, it was found that, when stored at a relatively high temperature of 50 캜 for 48 hours, The ratio (P ₅₀ / P ₂₃ ) of the peeling force (P ₅₀ ) to the peeling force (P ₂₃ ) against the alkali-free glass plate when stored at 23 ° C for 24 hours can be easily made to be not less than 4.5.

As the crosslinking catalyst (C-1), an organic acid salt is usually used, and it is preferably a salt comprising an organic acid having a carboxylic acid terminal and a base, that is, an organic carboxylic acid salt. When an organic carboxylic acid salt is used as the crosslinking catalyst (C-1), the counter cation of the carboxylate anion is preferably a counter cation of not more than 3 equivalents. The organic acid salt may be used alone, or two or more kinds thereof may be used in combination.

Examples of the counter cation include a metal ion, an ammonium ion, and a cation having a heterocyclic structure. Preferable examples of the metal ion include an alkali metal ion and an alkaline earth metal ion. Preferable examples of the cation having a heterocyclic structure include a pyrrolinium ion, an imidazolium ion, a triazonium ion, a pyrrolidinium ion, a pyridinium ion, and a piperidinium ion.

Examples of the carboxylate anion of the organic acid salt include a straight chain saturated alkylcarboxylate ion such as formic acid ion, acetic acid ion, propionic acid ion, heptanoic acid ion, octanoic acid ion and lauric acid ion; Linear unsaturated alkyl carboxylate ions such as (meth) acrylic acid and oleic acid; Aromatic carboxylate ions such as benzoic acid and cinnamic acid; Carboxylate ions having a heterocyclic structure such as nicotinic acid; Dicarboxylate ions such as succinic acid, fumaric acid and phthalic acid; And carboxylate anions having an oxyethylene skeleton such as 2- (2-ethoxy) ethoxycarboxylate ion.

The content of the crosslinking catalyst (C-1) is usually 0.0001 to 5 parts by weight, preferably 0.0005 to 3 parts by weight, more preferably 0.0007 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic resin (A) More preferably 0.001 to 1 part by weight, particularly preferably 0.0015 to 0.5 part by weight. When the content is within this range, it is possible to obtain a pressure-sensitive adhesive composition which is excellent in adhesion between the pressure-sensitive adhesive layer and the optical member, durability when the pressure-sensitive adhesive layer is bonded to the optical member, and can shorten the curing time of the pressure-sensitive adhesive layer.

The compound (C-2) containing an alkyleneoxy group is a compound containing at least one alkyleneoxy group in the molecule. The alkyleneoxy group is preferably included in the compound (C-2) as the alkylenedioxy group (-O-alkylene-O-). Examples of the alkyleneoxy group include, but are not limited to, an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group. Examples of the compound containing an alkyleneoxy group include polyalkylene glycols, specifically, polyethylene glycol, polypropylene glycol, polybutylene glycol, and copolymers of two or more of these polyalkylene glycols.

The average number of repeating alkyleneoxy groups constituting the polyalkylene glycol is not particularly limited but is usually 1 to 50, preferably 2 to 40, more preferably 3 to 30. Here, the "average number of repeating alkyleneoxy groups" is the average number of repeating alkyleneoxy units in the "polyalkyleneoxy chain" moiety contained in the molecular structure of the polyalkylene glycol. At least one of the hydroxyl groups of the polyalkylene glycol may be substituted with an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group. Examples thereof include polyalkylene glycol monomethyl ether, polyalkylene glycol monoethyl ether, polyalkylene glycol dimethyl ether, and polyalkylene glycol diethyl ether.

Further, the compound (C-2) having an alkyleneoxy group may contain at least one double bond in the molecule in addition to the alkyleneoxy group. A preferable example of the double bond is a double bond included in the (meth) acryloyl group. The alkyleneoxy group-containing compound (C-2) may be used alone or in combination of two or more. According to the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition containing the compound (C-2) having an alkyleneoxy group, it is possible to suppress the peeling force of the pressure-sensitive adhesive layer of the release film laminated on the pressure- It is possible.

Preferable examples of the alkylenedioxy group are alkylenedioxy groups having 1 to 4 carbon atoms from the viewpoints of adhesion between the pressure sensitive adhesive layer and the optical member and durability when the pressure sensitive adhesive layer is bonded to the optical member, A linear or branched alkylene dioxy group having 1 to 3 carbon atoms, and more preferably an ethylene dioxy group (-OC ₂ H ₄ -O-). The alkyleneoxy group is preferably an alkyleneoxy group having 1 to 4 carbon atoms, more preferably a linear or branched alkyleneoxy group having 1 to 3 carbon atoms And more preferably an ethyleneoxy group (-OC ₂ H ₄ -).

(C-2) is preferably a compound represented by the following formula (C-2a): wherein R <

(C-2a) containing a (meth) acryloyl group and more preferably a compound (C-2a). In the formulas, h represents an integer of 1 to 6, Q ¹ represents a hydrogen atom or a methyl group, and Q ⁰ represents an hivalent group having at least one alkylenedioxy group. The compound (C-2) may contain two or more kinds of the compound (C-2a). h is preferably an integer of 1 to 3.

The hivalent group having at least one alkylenedioxy group represented by Q ⁰ may be a hivalent hydrocarbon group having at least one alkylenedioxy group and is preferably a monovalent to trivalent hydrocarbon group having at least one ethylenedioxy group . Examples of the hydrocarbon group include the groups represented by Q ⁰¹ , Q ⁰² , Q ⁰³ and Q ⁰⁴ below.

In Q ^01, Q ² is optionally substituted alkoxy group having a carbon number of 1 to 3 good and represents an alkyl group, an aryl group or an aralkyl group having from 1 to 4 carbon atoms, L represents an alkylene group of a single bond or a group having from 1 to 4 carbon atoms, i represents an integer of 1 to 50 (e.g., 1 to 30). The number of carbon atoms of the aryl group which may be Q ² is preferably 6 to 20, and the number of carbon atoms of the aralkyl group is preferably 7 to 20. In Q ⁰² , j represents an integer of 1 to 40 (e.g., 1 to 30). In Q ⁰³ , y and z each independently represent an integer of 1 to 40 (e.g., 1 to 30), and y + z may be an integer of 1 to 40 (e.g., 1 to 30). In Q ^04, e, f and g are independently an integer of 1-20 (e.g. 1-10), respectively, e + f + g can be an integer from 1 to 30 (e.g. 1 to 25).

(C-2a-1) shown below as a compound (C-2a)

(C-2a-1) shown below. The compound (C-2) may contain two or more kinds of the compound (C-2a-1). The compound (C-2a-1) is a compound wherein Q ⁰ in the formula (C-2a) is Q ⁰¹ . Q ¹ , L, i and Q ² have the same meanings as defined above. In the compound (C-2a-1), L is preferably a single bond, and i is preferably an integer of 7 to 35, more preferably an integer of 9 to 25. Q ² is preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 20 carbon atoms, and specific examples of Q ² include a methyl group, ethyl group, n-propyl group, i-propyl group, phenyl group and biphenyl group.

As specific examples of the compound (C-2a-1), Q ¹ , L, i and Q ² are those shown in the following Table 1.

Another example of the compound (C-2a) preferably used is a compound wherein Q ⁰ in the formula (C-2a) is Q ⁰⁴ . In this case, h in the formula (C-2a) is 3. The compound (C-2) may contain two or more compounds having Q ⁰ of Q ⁰⁴ . In Q ⁰⁴ , e + f + g is preferably an integer of 5 to 25.

Another example of the compound (C-2a) which is preferably used is a compound wherein Q ⁰ in the formula (C-2a) is Q ⁰³ . In this case, h in the formula (C-2a) becomes 2. The compound (C-2) may contain two or more compounds having Q ⁰ of Q ⁰³ . In Q ⁰³ , y + z is preferably an integer of 5 to 25.

The content of the compound (C-2) is usually 0.1 to 5 parts by weight, preferably 0.15 to 5 parts by weight, more preferably 0.2 to 4.5 parts by weight based on 100 parts by weight of the (meth) acrylic resin (A) More preferably 0.5 to 4 parts by weight. When the content is within this range, it is possible to obtain a pressure-sensitive adhesive composition which is excellent in adhesion between the pressure-sensitive adhesive layer and the optical member, durability when the pressure-sensitive adhesive layer is bonded to the optical member, and can shorten the curing time of the pressure- The anti-swelling effect of the peeling force can be obtained.

[4] ionic compound (D)

The pressure-sensitive adhesive composition may further contain an ionic compound (D) as an antistatic agent for imparting antistatic properties to the pressure-sensitive adhesive layer. The ionic compound (D) is a compound having an inorganic or organic cation and an inorganic or organic anion. Two or more kinds of ionic compounds (D) may be used.

Examples of the inorganic cation include an alkali metal ion such as a lithium cation [Li ⁺ ], a sodium cation [Na ⁺ ] and a potassium cation [K ⁺ ] or an alkali metal ion such as a beryllium cation [Be ²⁺ ], a magnesium cation [Mg ²⁺ ] And alkaline earth metal ions such as cation [Ca ²⁺ ].

Examples of the organic cations include imidazolium cations, pyridinium cations, pyrrolidinium cations, ammonium cations, sulfonium cations and phosphonium cations.

Among the above cationic components, the organic cationic component is preferably used since it has excellent compatibility with the pressure-sensitive adhesive composition. Among the organic cation components, particularly the pyridinium cation and the imidazolium cation are preferably used from the viewpoint that they are difficult to be charged when the peeling film provided on the pressure-sensitive adhesive layer is peeled off.

As the inorganic anion, e.g., chloride anion [Cl ^-], bromide anion [Br ^-], iodide anion [I ^-], tetrachloro-aluminate anion [AlCl ₄ ^-], heptamethylene Chlorodifluoromethane aluminate anion [Al ₂ Cl ₇ ^- ], tetrafluoroborate anion [BF ₄ ^- ], hexafluorophosphate anion [PF ₆ ^- ], perchlorate anion [ClO ₄ ^- ], nitrate anion [NO ₃ ^- ], hexafluoroacetate anion AsF ₆ ^- ], hexafluoroantimonate anion [SbF ₆ ^- ], hexafluoroniobate anion [NbF ₆ ^- ], hexafluorotantalate anion [TaF ₆ ^- ], dicyanamide anion [ ₂ N ^- ] and the like.

As the organic anions, for example, acetate anion [CH ₃ COO ^-], acetate anion trifluoroacetate [CF ₃ COO ^-], methane sulfonate anion [CH ₃ SO ₃ ^-], trifluoromethanesulfonate anion [CF ₃ SO ^_3], p- toluenesulfonate anion _{[p-CH 3 C 6 H 4} SO 3 - ], a bis (alkylsulfonyl fluorophenyl) imide anion [(FSO _{2) 2} N ^-], methane-bis (trifluoro sulfonyl) imide anion _{[(CF 3 SO 2) 2 N} - ], methanesulfonyl) bumetanide anion and tris (trifluoro _{[(CF 3 SO 2) 3 C} - ], dimethyl phosphinate anion [(CH _{3) 2} POO ^-], (poly) fluoro-dihydro fluoride anion [F (HF) _n ^-] (n is 1-3 or so), thiocyanate anion [SCN ^-], perfluoro butane sulfonate anion [C ₄ F ₉ SO ₃ ^- ], bis (pentafluoroethanesulfonyl) imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ^- ], perfluorobutanoate anion [C ₃ F ₇ COO ^- ], (Methanesulfonyl trifluoromethyl) (trifluoromethanesulfonyl carbonyl) imide anion [(CF ₃ SO ₂₎ (CF ₃ CO) N ^-], perfluoro-1,3-propane sulfonate anion ^[- O ₃ S (CF ₂ ) ₃ SO ₃ ^- ], carbonate anion [CO ₃ ^2- ], and the like.

Among the above-mentioned anion components, an anion component particularly containing a fluorine atom is preferably used because it gives an ionic compound (D) having an excellent antistatic property. Specific examples of the anion component containing a fluorine atom include a bis (fluorosulfonyl) imide anion, a hexafluorophosphate anion or a bis (trifluoromethanesulfonyl) imide anion.

Specific examples of the ionic compound (D) can be appropriately selected from combinations of the cationic component and the anionic component. Examples of the ionic compound (D) having an organic cation can be categorized according to the structure of the organic cation, and the following can be given.

Pyridinium salts:

N-hexylpyridinium hexafluorophosphate,

N-octylpyridinium hexafluorophosphate,

N-octyl-4-methylpyridinium hexafluorophosphate,

N-butyl-4-methylpyridinium hexafluorophosphate,

N-decalpyridinium bis (fluorosulfonyl) imide,

N-dodecylpyridinium bis (fluorosulfonyl) imide,

N-tetradecylpyridinium bis (fluorosulfonyl) imide,

N-hexadecylpyridinium bis (fluorosulfonyl) imide,

N-dodecyl-4-methylpyridinium bis (fluorosulfonyl) imide,

N-tetradecyl-4-methylpyridinium bis (fluorosulfonyl) imide,

N-hexadecyl-4-methylpyridinium bis (fluorosulfonyl) imide,

N-benzyl-2-methylpyridinium bis (fluorosulfonyl) imide,

N-benzyl-4-methylpyridinium bis (fluorosulfonyl) imide,

N-hexylpyridinium bis (trifluoromethanesulfonyl) imide,

N-octylpyridinium bis (trifluoromethanesulfonyl) imide,

N-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,

N-butyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide.

Imidazolium salt:

1-ethyl-3-methylimidazolium hexafluorophosphate,

1-ethyl-3-methylimidazolium p-toluenesulfonate,

Ethyl-3-methylimidazolium bis (fluorosulfonyl) imide,

1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide,

1-butyl-3-methylimidazolium methanesulfonate,

1-butyl-3-methylimidazolium bis (fluorosulfonyl) imide.

Pyrrolidinium salt:

N-butyl-N-methylpyrrolidinium hexafluorophosphate,

N-butyl-N-methylpyrrolidinium bis (fluorosulfonyl) imide,

N-butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide.

Quaternary ammonium salts:

Tetrabutylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate,

Tetrabutylammonium p-toluenesulfonate,

(2-hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) imide,

(2-hydroxyethyl) trimethylammonium dimethylphosphinate.

Examples of the ionic compound (D) having an inorganic cation include the following.

Lithium bromide,

Lithium iodide,

Lithium tetrafluoroborate,

Lithium hexafluorophosphate,

Lithium thiocyanate,

Lithium perchlorate,

Lithium trifluoromethanesulfonate,

Lithium bis (fluorosulfonyl) imide,

Lithium bis (trifluoromethanesulfonyl) imide,

Lithium bis (pentafluoroethanesulfonyl) imide,

Lithium tris (trifluoromethanesulfonyl) methanide,

Lithium p-toluenesulfonate,

Sodium hexafluorophosphate,

Sodium bis (fluorosulfonyl) imide,

Sodium bis (trifluoromethanesulfonyl) imide,

Sodium p-toluenesulfonate,

Potassium hexafluorophosphate,

Potassium bis (fluorosulfonyl) imide,

Potassium bis (trifluoromethanesulfonyl) imide,

Potassium p-toluenesulfonate.

The ionic compound (D) is preferably a solid at room temperature. The antistatic property can be maintained for a long period of time as compared with the case of using the ionic compound (D) which is a liquid at room temperature. From the viewpoint of long-term stability of such antistatic property, it is preferable that the ionic compound (D) has a melting point of 30 占 폚 or higher, more preferably 35 占 폚 or higher. On the other hand, if the melting point is too high, the compatibility with the (meth) acrylic resin (A) becomes poor, so the melting point is preferably 90 ° C or lower, more preferably 70 ° C or lower, further preferably 50 ° C or lower.

The content of the ionic compound (D) in the pressure-sensitive adhesive composition is preferably 0.2 to 8 parts by weight, more preferably 0.2 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic resin (A) Preferably 0.3 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight. When the content of the ionic compound (D) is 0.2 parts by weight or more, it is advantageous in improving the antistatic performance, and when it is 8 parts by weight or less, it is advantageous in maintaining the durability of the pressure-sensitive adhesive layer.

[5] Silane Compound (E)

The pressure-sensitive adhesive composition may further contain a silane compound (E). As a result, the adhesion between the pressure-sensitive adhesive layer and the optical member such as a glass substrate can be enhanced.

Examples of the silane compound (E) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethyl Silane, and the like. Two or more kinds of silane compounds may be used.

The silane compound (E) may be a silicone oligomer type. Examples of the silicone oligomer in the form of a (monomer) oligomer include the following.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer,

3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer,

3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer,

3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer

A mercaptopropyl group-containing copolymer;

Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer,

Mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer,

Mercaptomethyltriethoxysilane-tetramethoxysilane copolymer,

The mercaptomethyltriethoxysilane-tetraethoxysilane copolymer

A mercapto methyl group-containing copolymer;

3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer,

3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer,

3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer,

3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer,

3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,

3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer

A copolymer containing a 3-glycidoxypropyl group;

3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,

3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,

3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,

3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer,

3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,

3-methacryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer

A methacryloyloxypropyl group-containing copolymer;

3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,

3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,

3-acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,

3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer,

3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,

3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer

A copolymer containing an acryloyloxypropyl group;

Vinyltrimethoxysilane-tetramethoxysilane copolymer,

Vinyltrimethoxysilane-tetraethoxysilane copolymer,

Vinyltriethoxysilane-tetramethoxysilane copolymer,

Vinyltriethoxysilane-tetraethoxysilane copolymer,

Vinyl methyl dimethoxysilane-tetramethoxysilane copolymer,

Vinyl methyl dimethoxysilane-tetraethoxysilane copolymer,

Vinyl methyldiethoxysilane-tetramethoxysilane copolymer,

Vinyl methyldiethoxysilane-tetraethoxysilane copolymer

A vinyl group-containing copolymer such as a vinyl group-containing copolymer;

3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer,

3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer,

3-aminopropyltriethoxysilane-tetramethoxysilane copolymer,

3-aminopropyltriethoxysilane-tetraethoxysilane copolymer,

3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer,

3-Aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer

And the like.

Most of the silane compounds (E) exemplified above are liquids. The content of the silane compound (E) in the pressure-sensitive adhesive composition is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.2 (parts by weight) based on 100 parts by weight of the (meth) acrylic resin To 0.4 parts by weight. If the content of the silane compound (E) is 0.01 parts by weight or more, the effect of improving the adhesion between the pressure-sensitive adhesive layer and optical members such as a glass substrate can be easily obtained. When the content is 10 parts by weight or less, bleeding-out of the silane compound (E) from the pressure-sensitive adhesive layer can be suppressed.

[6] Other components

The pressure sensitive adhesive composition may contain additives such as a crosslinking catalyst, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, a light scattering fine particle and a resin other than the (meth) acrylic resin (A). In addition, it is also useful to blend an ultraviolet curable compound into the pressure-sensitive adhesive composition to form a pressure-sensitive adhesive layer, and then cure by irradiating ultraviolet rays to form a harder pressure-sensitive adhesive layer. Examples of the crosslinking catalyst include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin and melamine resin For example.

<Pressure-sensitive adhesive layer>

The pressure-sensitive adhesive layer according to the present invention includes the pressure-sensitive adhesive composition according to the present invention described above, and typically comprises the pressure-sensitive adhesive composition according to the present invention. The pressure-sensitive adhesive layer can be obtained by dissolving or dispersing each component constituting the pressure-sensitive adhesive composition in a solvent to obtain a pressure-sensitive adhesive composition containing a solvent, and then applying the pressure-sensitive adhesive composition on a substrate film and drying. The pressure-sensitive adhesive layer according to the present invention is excellent in adhesion and durability, and can shorten the required curing time.

The base film is generally a plastic film, and a typical example thereof is a release film (separator) subjected to release treatment. The release film may be a release treatment such as a silicone treatment applied to a surface of a film formed of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate, on which a pressure-sensitive adhesive layer is formed. For example, an optical member having a pressure-sensitive adhesive layer can be obtained by directly applying a pressure-sensitive adhesive composition on a release-treated surface of a release film to form a pressure-sensitive adhesive layer, and laminating a pressure-sensitive adhesive layer having the release film on the optical member. Further, the pressure sensitive adhesive composition may be directly applied to the surface of the optical member to form a pressure sensitive adhesive layer, and if necessary, a release film may be laminated on the outer surface of the pressure sensitive adhesive layer to provide an optical member having a pressure sensitive adhesive layer. When the pressure-sensitive adhesive layer is provided on the surface of the optical member, it is preferable to perform surface activation treatment such as plasma treatment, corona treatment or the like on the bonding surface of the optical member and / or the bonding surface of the pressure-sensitive adhesive layer, desirable.

The thickness of the pressure-sensitive adhesive layer is preferably from 5 to 45 탆, more preferably from 10 to 30 탆, and further preferably from 15 to 25 탆. When the thickness of the pressure-sensitive adhesive layer is within this range, it is advantageous in terms of adhesion between the pressure-sensitive adhesive layer and the optical member and durability when the pressure-sensitive adhesive layer is bonded to the optical member. For the same reason, the pressure-sensitive adhesive layer preferably has a gel fraction of 30 to 85%.

In the pressure-sensitive adhesive composition of the present invention, it is preferable that the pressure-sensitive adhesive composition is formed into a layered pressure-sensitive adhesive composition (first layer) on a first film made of a cyclic polyolefin resin, The peeling force between the first layer and the first alkali-free glass plate when the alkali glass plate was laminated and stored for 24 hours under an environment of 23 캜 was _defined as P _CO23 , and a layered form was formed on the second film made of the cyclic polyolefin- (Second layer) formed as a layered pressure-sensitive adhesive composition, and a third non-alkali glass plate was laminated on the second layer, and then stored for 48 hours in an environment of 50 ° C. 2 when the release force between the non-alkali glass plate by P _CO50, the ratio (P _CO50 / _CO23 P) is 4.5 or more of P _CO50 and _CO23 P.

When a resin film of an optical member such as a polarizing plate is bonded to a liquid crystal cell substrate made of an alkali-free glass through a pressure-sensitive adhesive layer composed of such a pressure-sensitive adhesive composition, there is a phenomenon in which the optical member is peeled off immediately after bonding, Work is facilitated. Further, since the peeling force is increased by heating after bonding, the optical member such as the polarizing plate can be bonded more strongly to the liquid crystal cell or the like, which is preferable.

P _CO23 is usually 0.5 N / 25 mm or more, usually 5 N / 25 mm or less, preferably 3 N / 25 mm or less in that it can be easily bonded to a liquid crystal cell substrate made of alkali-free glass. P _{CO 50} is usually 2 N / 25 mm or more, usually 20 N / 25 mm or less, preferably 18 N / 25 mm or less in that it can be adhered to a liquid crystal cell or the like with sufficient peeling force even at a relatively high temperature .

&Lt; Optical member having pressure-sensitive adhesive layer >

The pressure-sensitive adhesive layer according to the present invention can be suitably used as a pressure-sensitive adhesive layer for bonding an optical member such as a polarizing plate to a liquid crystal cell substrate, particularly a liquid crystal cell substrate made of alkali-free glass. The optical member having the pressure-sensitive adhesive layer according to the present invention may be one in which a pressure-sensitive adhesive layer is laminated on an optical member such as a polarizing plate, for example, and another optical member is further laminated on the outer surface of the pressure-sensitive adhesive layer.

[1] First Embodiment

One preferred embodiment of the optical member having the pressure-sensitive adhesive layer according to the present invention comprises a resin film as an optical member and a pressure-sensitive adhesive layer laminated on at least one surface thereof. The resin film is exemplified by a surface protective film (protective film) which is bonded to an optical film such as a polarizer, a protective film and a retardation film, an optical film to be protected, and the like and used for protecting the surface from scratches and dirt .

A polarizer is a film having a function of extracting linearly polarized light from incident natural light, and a suitable example is that a dichroic dye such as iodine or a dichroic dye is adsorbed and aligned on a uniaxially stretched polyvinyl alcohol resin film. The thickness of the polarizer is not particularly limited, but is usually 0.5 to 35 탆.

The protective film may be a polyolefin resin such as a translucent (preferably optically transparent) resin such as a chain polyolefin resin (polypropylene resin), a cyclic polyolefin resin (norbornene resin, etc.); Cellulose-based resins such as triacetylcellulose and diacetylcellulose; Polyester-based resin; Polycarbonate resin; (Meth) acrylic resins; Polystyrene type resin; Polyether ether ketone resins; And a film made of a thermoplastic resin such as a polysulfone resin.

Examples of the chain polyolefin-based resin include a homopolymer of a chain olefin such as a polyethylene resin and a polypropylene resin, and a copolymer composed of two or more chain olefins.

The cyclic polyolefin-based resin is a generic name of a resin that is polymerized using a cyclic olefin as a polymerization unit. Specific examples of the cyclic polyolefin-based resin include ring-opened (co) polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers (typically, random copolymers) of cyclic olefins and chain olefins such as ethylene and propylene, Graft polymers modified with carboxylic acids or their derivatives, and hydrides thereof. Among them, a norbornene resin using a norbornene monomer such as norbornene or a polycyclic norbornene monomer as the cyclic olefin is preferably used.

The cellulose-based resin is a partial or complete esterified product of cellulose, and examples thereof include acetic acid ester, propionic acid ester, butyric acid ester and mixed ester thereof of cellulose. Among them, triacetylcellulose, diacetylcellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferably used.

The polyester-based resin is a resin other than the cellulose-based resin having an ester bond, and is generally composed of a polycondensation product of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol. As the polycarboxylic acid or its derivative, a dicarboxylic acid or a derivative thereof can be used, and examples thereof include terephthalic acid, isophthalic acid, dimethylterephthalate, and dimethyl naphthalenedicarboxylate. Examples of polyhydric alcohols include diols such as ethylene glycol, propanediol, butanediol, neopentyl glycol, and cyclohexanedimethanol.

Specific examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, polycyclohexane Dimethyl naphthalate.

The polycarbonate resin is composed of a polymer having a monomer unit bonded through a carbonate group. The polycarbonate resin may be a resin such as a modified polycarbonate having modified polymer skeleton, a copolymerized polycarbonate, or the like.

The (meth) acrylic resin may be a polymer having methacrylic acid ester as a main monomer, and is preferably a copolymer in which a small amount of another comonomer component is copolymerized. The (meth) acrylic resin is more preferably a copolymer of methyl methacrylate and methyl acrylate, and the third monofunctional monomer may be further copolymerized.

Examples of the third monofunctional monomer include ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2- Methacrylic acid esters other than methyl methacrylate such as ethyl; Acrylic esters other than methyl acrylate such as ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate; Hydroxyalkyl acrylate esters such as methyl 2- (hydroxymethyl) acrylate, methyl 2- (1-hydroxyethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate and butyl 2- (hydroxymethyl) acrylate; Unsaturated acids such as methacrylic acid and acrylic acid; Halogenated styrenes such as chlorostyrene and bromostyrene; Substituted styrenes such as vinyltoluene and? -Methylstyrene; Unsaturated nitriles such as acrylonitrile and methacrylonitrile; Unsaturated acid anhydrides such as maleic anhydride and citraconic anhydride; And unsaturated imides such as phenylmaleimide and cyclohexylmaleimide. The third monofunctional monomer may be used alone, or two or more monofunctional monomers may be used in combination.

A polyfunctional monomer may be further copolymerized with the (meth) acrylic resin. Examples of the multifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) (Meth) acrylate, and tetradecaethylene glycol di (meth) acrylate, esterified with acrylic acid or methacrylic acid at both terminal hydroxyl groups of the oligomer; Propylene glycol or its oligomer with both terminal hydroxyl groups being esterified with acrylic acid or methacrylic acid; Acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate and butanediol di (meth) acrylate esterified with acrylic acid or methacrylic acid; Bisphenol A, an alkylene oxide adduct of bisphenol A, or both terminal hydroxyl groups of the halogen substituents thereof esterified with acrylic acid or methacrylic acid; Trimethylol propane and pentaerythritol esterified with acrylic acid or methacrylic acid, and those in which epoxy groups of glycidyl acrylate or glycidyl methacrylate are added to these terminal hydroxyl groups by ring opening; A dibasic acid such as succinic acid, adipic acid, terephthalic acid, phthalic acid, and halogen substituents thereof, and an alkylene oxide adduct thereof, and the like, in which an epoxy group of glycidyl acrylate or glycidyl methacrylate is ring- Aryl (meth) acrylate; And aromatic divinyl compounds such as divinylbenzene. Among them, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and neopentyl glycol dimethacrylate are preferably used.

The (meth) acrylic resin may be modified by further performing a reaction between the functional groups of the copolymer. Examples of the reaction include a condensation reaction in a polymer chain between a methyl ester group of methyl acrylate and a hydroxyl group of 2- (hydroxymethyl) acrylate, a condensation reaction between a carboxyl group of acrylic acid and a hydroxyl group of 2- (hydroxymethyl) A dehydration condensation reaction in a polymer chain, and the like. The (meth) acrylic resin may have any structure of a glutarimide derivative, a glutaric acid anhydride derivative or a lactone ring structure.

The (meth) acrylic resin may contain additives as required. Examples of additives include lubricants, antiblocking agents, heat stabilizers, antioxidants, antistatic agents, light stabilizers, impact resistance improvers, surfactants and the like.

The (meth) acrylic resin may contain acrylic rubber particles from the viewpoints of the film formability to the film and the impact resistance of the film. The acrylic rubber particles are particles composed of an elastomer mainly composed of an acrylate ester as an essential component and substantially of a single layer structure composed of only this elastomer but those having a multilayer structure composed of this elastomer as a single layer have. As an example of the elastic polymer, a crosslinked elastic copolymer comprising an alkyl acrylate as a main component and another copolymerizable vinyl monomer and a crosslinkable monomer are copolymerized. Examples of the alkyl acrylate which is the main component of the elastomer include those having 1 to 8 carbon atoms in the alkyl group such as methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, Acrylic acid is preferably used. Examples of other vinyl monomers copolymerizable with the alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid esters such as methyl methacrylate, Aromatic vinyl compounds, and vinyl cyan compounds such as acrylonitrile. Examples of the crosslinkable monomer include crosslinkable compounds having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate and (Meth) acrylates of the same polyhydric alcohol, alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate, and divinylbenzene.

A laminate of a film made of a (meth) acrylic resin containing no rubber particles and a film made of a (meth) acrylic resin containing rubber particles may be used as a protective film.

The retardation film is an optical film exhibiting optical anisotropy. In addition to the resin that can be used for the protective film, the retardation film may be formed of a resin such as polyvinyl alcohol resin, polyarylate resin, polyimide resin, polyether sulfone resin, A stretched film obtained by stretching a resin film comprising a rid / polymethyl methacrylate resin, a liquid crystal polyester resin, a saponified ethylene-vinyl acetate copolymer, a polyvinyl chloride resin, etc. to a degree of 1.01 to 6 times. Among them, a polycarbonate resin film, a cyclic polyolefin resin film, a (meth) acrylic resin film or a cellulose resin film is preferably a uniaxially or biaxially stretched film. In the present specification, a zero retardation film is also included in the retardation film (however, it may also be used as a protective film). In addition, a film called a uniaxial retardation film, a wide viewing angle retardation film, and a low light elasticity retardation film is also applicable as a retardation film.

The zero retardation film refers to a film having an in-plane retardation value R _e and a thickness direction retardation value R _th of -15 to 15 nm. This retardation film is suitably used for an IPS mode liquid crystal display device. The in-plane phase difference value R _e and the thickness direction phase difference value R _th are preferably -10 to 10 nm, and more preferably -5 to 5 nm. The in-plane phase difference value R _e and the thickness direction phase difference value R _th are values at a wavelength of 590 nm.

The in-plane phase difference value R _e and the thickness direction phase difference value R _th satisfy the following equations:

_{Re = (n x -n y)} × d

R _th = _{[(n x + n y) /} 2-n z × d]

. Wherein, n _x is a refractive index in a slow axis direction (x axis direction) in the film plane, n _y is a refractive index in the fast axis direction (y-axis direction perpendicular in a plane on the x-axis) in the film plane, n _z is the film Is the refractive index in the thickness direction (z-axis direction perpendicular to the film surface), and d is the thickness of the film.

As the zero retardation film, for example, a resin film made of a polyolefin resin such as a cellulose resin, a chain polyolefin resin and a cyclic polyolefin resin, a polyethylene terephthalate resin or a (meth) acrylic resin can be used. Particularly, a cellulose resin, a polyolefin resin or a (meth) acrylic resin is preferably used since it is easy to control the phase difference and is easily available. For example, a retardation film may be obtained by laminating a (meth) acrylic resin layer on one side or both sides of a retardation developing layer made of a resin different from the (meth) acrylic resin.

A film exhibiting optical anisotropy by application and orientation of a liquid crystalline compound or a film exhibiting optical anisotropy by application of an inorganic layer compound can also be used as a retardation film. Such a phase difference film is referred to as a temperature compensation type retardation film, a film in which a rod-shaped liquid crystal sold under the trade name of &quot; NH film &quot; from JX Nikkoseki Energie Co., Quot; WV Film &quot;, a completely biaxially oriented film sold by Sumitomo Chemical Co., Ltd. under the trade name of &quot; VAC Film &quot;quot; new VAC film &quot; and the like.

On the other hand, the surface protective film is a film used for the purpose of protecting the surface of an optical film or the like to be protected from scratches or dirt. For example, a polarizer, a protective film, a retardation film, Various optical films such as reflective sheets generally flow in a state where a surface protective film is adhered to the surface thereof (the surface opposite to the pressure-sensitive adhesive layer in the case of having a pressure-sensitive adhesive layer on one surface). The surface protective film is usually peeled off after bonding the optical film to a liquid crystal cell or the like.

Examples of the base material of the surface protective film include polyolefin-based resins such as polyethylene, polypropylene and polymethylpentene; Fluorinated polyolefin-based resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene; Polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate / isophthalate copolymer; Polyamides such as nylon 6, nylon 6,6; Vinyl polymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol and vinylon; Cellulose-based resins such as triacetylcellulose, diacetylcellulose, and cellophane; (Meth) acrylic resins such as methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate and butyl polyacrylate; In addition, a film made of a thermoplastic resin such as polystyrene, polycarbonate, polyarylate, or polyimide may be mentioned. The optical member having the pressure-sensitive adhesive layer according to the present invention, in which the resin film is a surface protective film, is provided with a pressure-sensitive adhesive layer on the substrate.

In the optical member having the pressure-sensitive adhesive layer according to the present embodiment, it is preferable that the above-mentioned release film is adhered to the surface of the pressure-sensitive adhesive layer and temporarily adhered and protected until use. The optical member having the pressure-sensitive adhesive layer according to the present embodiment in which the release film is adhered can be produced by a method in which a pressure-sensitive adhesive composition is applied onto a release film to form a pressure-sensitive adhesive layer and a resin film is further laminated on the pressure- A pressure-sensitive adhesive composition is applied to form a pressure-sensitive adhesive layer, and a release film is bonded to the pressure-sensitive adhesive surface.

The optical member having the pressure-sensitive adhesive layer according to the present embodiment is obtained by laminating an optical member having a pressure-sensitive adhesive layer when it is stored for 24 hours under an environment at a temperature of 23 占 폚 in a state of being laminated on a non- separation between the peel force between the P ₂₃ to the polarizer, and the optical member having a pressure-sensitive adhesive layer when the free 48 hours storage in a stacked state in the alkali glass plate under a temperature of 50 ℃ environment by a pressure-sensitive adhesive layer constituting it with a non-alkali glass when the force as P _50, and P ₅₀ and P ₂₃ of the ratio (P ₅₀ / P ₂₃₎ is 4.5 or more, preferably 5.0 or more, and is normally 20 or less. P as is ₅₀ and the ratio (P ₅₀ / P ₂₃₎ is the range of P _23, so-called rework is easy, and since the peel force increased by heating after bonding, more strongly the optical members such as polarizing plate-free A liquid crystal cell substrate made of alkali glass or the like.

P ₂₃ is usually 0.5 N / 25 mm or more, usually 5 N / 25 mm or less, and preferably 3 N / 25 mm or less in that it can be easily bonded to a liquid crystal cell substrate made of alkali-free glass. P ₅₀ is usually 2 N / 25 mm or more, usually 20 N / 25 mm or less, and preferably 15 N / 25 mm or less in that it can adhere to a liquid crystal cell or the like with sufficient peeling force even at a relatively high temperature .

[2] Second Embodiment

Another preferred embodiment of the optical member having the pressure-sensitive adhesive layer according to the present invention comprises a laminate of a resin film and a pressure-sensitive adhesive layer laminated on at least one side thereof. The laminate of the resin film is preferably a laminate of optical films selected from optical films such as polarizers, protective films, retardation films and the like. A typical example of the laminate of the optical film is a polarizing plate. Also in the optical member having the pressure-sensitive adhesive layer according to the present embodiment, it is preferable that a release film is adhered to the surface of the pressure-sensitive adhesive layer and temporarily adhered and protected until use.

Examples of the polarizing plate include a linear polarizing plate that absorbs linearly polarized light having a vibration plane in any direction incident on the film surface and transmits linearly polarized light having a vibration plane orthogonal thereto and a linearly polarizing plate having a straight line having a vibration surface in any direction A polarized light separating plate having a property of reflecting polarized light and transmitting linearly polarized light having a vibration plane perpendicular to the polarized light, and an elliptically polarizing plate obtained by laminating a retardation film on a linearly polarizing plate.

The linearly polarizing plate generally has a structure in which the above-mentioned protective film is bonded to one or both sides of the above-mentioned polarizer. When a protective film is bonded to both surfaces of a polarizer, a pressure-sensitive adhesive layer can be formed on at least one surface of the protective film. When a protective film is bonded only to one surface of the polarizer, a pressure-sensitive adhesive layer can be formed on the surface of the polarizer (surface on which the protective film is not bonded). The elliptically polarizing plate is obtained by laminating a retardation film on a linearly polarizing plate, but the linearly polarizing plate generally has the same constitution as above. When the pressure-sensitive adhesive layer is laminated on the elliptically polarizing plate, an adhesive layer is usually laminated on the retardation film side.

A specific example of an optical member having a pressure-sensitive adhesive layer in the case where the optical member is a polarizing plate will be described with reference to the drawings. 1, a protective film 3 having a surface treatment layer 2 is adhered to one surface of a polarizer 1 on a surface opposite to the surface treatment layer 2 to form a polarizing plate 10, . A pressure sensitive adhesive layer 20 is provided on the surface of the polarizer 1 opposite to the protective film 3 to constitute a polarizing plate 25 (optical member having a pressure sensitive adhesive layer) having a pressure sensitive adhesive layer. The pressure-sensitive adhesive layer 20 can be bonded to the glass substrate 30 on the side opposite to the polarizing plate 10, and the glass substrate 30 will be described later.

The polarizing plate 25 having the pressure-sensitive adhesive layer shown in Fig. 2 is the same as that shown in Fig. 1 except that the polarizing plate 10 includes the second protective film 4 adhered to the other surface of the polarizer 1. The pressure-sensitive adhesive layer (20) is laminated on the outer surface of the second protective film (4). The polarizing plate 25 having the pressure-sensitive adhesive layer shown in Fig. 3 is the same as the polarizing plate 10 except that the polarizing plate 10 includes the retardation film 7 adhered to the other surface of the polarizer 1 via the interlayer adhesive 8, Respectively. 4 except that the polarizing plate 10 includes a retardation film 7 adhered to the outer surface of the second protective film 4 through the interlayer adhesive 8, 2. In the example shown in Figs. 3 and 4, the pressure-sensitive adhesive layer 20 is adhered to the retardation film 7.

The surface treatment layer 2 formed on the surface of the protective film 3 may be a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, or the like. It is also possible to provide a plurality of layers. As a suitable example of the retardation film 7, if the polarizing plate 10 includes the retardation film 7 as in the example shown in Figs. 3 and 4, if the liquid crystal display device is a small- . In this case, it is general to arrange the absorption axis of the polarizer 1 and the slow axis of the retardation film 7 so as to intersect at almost 45 degrees. However, when the angle is shifted to some extent at 45 degrees according to the characteristics of the liquid crystal cell have. On the other hand, in a large-sized liquid crystal display device such as a television, a retardation film 7 having various retardation values is used in accordance with the characteristics of the liquid crystal cell for the purpose of compensating the retardation of the liquid crystal cell or compensating the viewing angle. In this case, it is general that the absorption axis of the polarizer 1 and the slow axis of the retardation film 7 are arranged so as to be substantially orthogonal or substantially parallel. When the retardation film 7 is constituted by a 1/4 wavelength plate, a uniaxially or biaxially stretched film is suitably used. When the retardation film 7 is provided for compensation of phase difference of the liquid crystal cell or compensation for viewing angle, in addition to the uniaxial or biaxially stretched film, a film oriented in the thickness direction in addition to uniaxial or biaxial stretching, Or the like, and an optical compensation film, such as a film in which the retardation-releasing material is applied and aligned, may be used as the retardation film 7.

As the interlayer pressure-sensitive adhesive 8 in Figs. 3 and 4, a common (meth) acrylic pressure-sensitive adhesive is usually used, but it is also possible to use the pressure-sensitive adhesive layer according to the present invention. In the case where the absorption axis of the polarizer 1 and the slow axis of the retardation film 7 are arranged so as to be almost orthogonal or almost parallel to each other as in the above-mentioned large liquid crystal display device, It is also possible to use. Examples of the adhesive include an aqueous adhesive agent composed of an aqueous solution or an aqueous dispersion and exhibiting an adhesive force by evaporating water as a solvent, and an ultraviolet curable adhesive agent which is cured by irradiation with ultraviolet rays to develop an adhesive force. The polarizer 1 and the protective films 3 and 4 are also usually bonded using an adhesive.

[3] Third Embodiment

Another preferred embodiment of the optical member having the pressure-sensitive adhesive layer according to the present invention is characterized in that in addition to the outer surface of the pressure-sensitive adhesive layer in the optical member having the pressure-sensitive adhesive layer according to the first or second embodiment, . The other optical member is preferably a glass substrate, and FIGS. 1 to 4 also show a state in which a polarizing plate having a pressure-sensitive adhesive layer according to the second embodiment is bonded to the glass substrate 30.

Examples of the glass substrate 30 include glass substrates for liquid crystal cells, glass for antiglare, glass for sunglasses, and the like. Examples of the material of the glass substrate 30 include soda lime glass, low alkali glass, and alkali-free glass. Among them, the glass substrate is preferably a glass substrate of a liquid crystal cell.

In the liquid crystal cell, a polarizing plate is usually laminated on both sides thereof with a pressure-sensitive adhesive layer. Of these polarizing plates, only the polarizing plate disposed on the front side (viewing side) of the liquid crystal cell may be a polarizing plate having the pressure- Only a polarizing plate disposed on the back side (backlight side) may be a polarizing plate having a pressure-sensitive adhesive layer according to the present invention, or both of them may be a polarizing plate having a pressure-sensitive adhesive layer according to the present invention. The driving method of the liquid crystal cell may be any conventionally known method. The polarizing plate disposed on the back side (backlight side) usually has no surface treatment layer 2. Various optical films known to be disposed on the back side of the liquid crystal cell, such as a brightness enhancement film, a light converging film, a diffusion film, etc., may be provided on the outer surface of the polarizing plate disposed on the back side.

An optical member having a pressure-sensitive adhesive layer such as a polarizing plate having a pressure-sensitive adhesive layer can be suitably used for a liquid crystal display device. The liquid crystal display device includes, for example, a personal computer including a notebook type, a desktop type, a PDA (Personal Digital Assistant) and the like; Various mobile devices such as smart phones and tablet type terminals; television; A vehicle-mounted display; Electronic Dictionary; digital camera; Digital video camera; Electronic desk calculator; It can be suitably used as a liquid crystal display device for a clock or the like.

[Example]

EXAMPLES The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, parts and percentages indicating amounts used or contents are based on weight unless specifically noted.

Production Examples 1 to 3: Production of (meth) acrylic resin (A) for pressure-sensitive adhesive layer>

A reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirrer was charged with 120 parts of ethyl acetate, replacing air in the apparatus with nitrogen gas to remove oxygen, and then raising the internal temperature to 75 ° C. A monomer mixture having the composition shown in Table 2 was added dropwise to the reaction system (polymerization initiator) over a period of 2 hours while maintaining the internal temperature at 74 to 76 占 폚. After the addition of the whole amount of a solution obtained by dissolving 0.05 part of azobisisobutyronitrile . The reaction was completed by keeping the internal temperature at 74 to 76 ° C for 5 hours. Finally, ethyl acetate was added to adjust the concentration of the (meth) acrylic resin to 40% to prepare an ethyl acetate solution of the (meth) acrylic resin (A).

Weight average molecular weight (Mw), number average molecular weight (Mn) and glass transition temperature (Tg) of the (meth) acrylic resin (A) obtained in Production Examples 1 to 3 were measured. Mw and Mn were measured by using four columns of "TSKgel XL" manufactured by Tosoh Corporation and "Shodex GPC KF-802" manufactured by Showa Denko KK and sold by Shoko Tsusho Co., Five samples were placed in series, and tetrahydrofuran was used as an eluent to measure a standard polystyrene conversion at a sample concentration of 5 mg / mL, a sample introduction amount of 100 μL, a temperature of 40 ° C., and a flow rate of 1 mL / did. Tg was measured under the conditions of a measurement temperature range of -80 to 50 占 폚 and a temperature increase rate of 10 占 폚 / min in a nitrogen atmosphere using a differential scanning calorimeter (DSC) "DSC6000" manufactured by Sanyo Chemical Industries, Ltd. Respectively. Table 2 summarizes the monomer composition (weight%) of the monomer mixture used and the Mw, molecular weight distribution Mw / Mn and Tg of the (meth) acrylic resin (A) obtained in Production Examples 1 to 3.

The abbreviations in the column "monomer composition" in Table 2 mean the following monomers.

BA: n-butyl acrylate,

MA: methyl acrylate,

PEA: 2-phenoxyethyl acrylate,

PEA2: 2- (2-phenoxyethoxy) ethyl acrylate,

HEA: 2-hydroxyethyl acrylate

BMAA: butoxymethyl acrylamide,

AA: Acrylic acid.

&Lt; Examples 1 to 10, Comparative Example 1 >

(1) Preparation of pressure-sensitive adhesive composition

(B), the compound (C) and the silane compound (E) shown in Table 3 were added to 100 parts by weight of the solid content of the (meth) acrylic resin (A) ), And ethyl acetate was further added so that the solid concentration became 28 wt% to prepare a solution of the pressure-sensitive adhesive composition. The compounding amount of each compounding ingredient shown in Table 3 is the number of parts by weight as the active ingredient contained in the case where the product used contains a solvent or the like.

Details of the respective blending ingredients represented by abbreviations in Table 3 are as follows.

(Meth) acrylic resin (A) Production Example 1 Production of (meth) acrylic resin (A),

(Meth) acrylic resin (A) Production Example 2: The (meth) acrylic resin (A) obtained in Production Example 2,

(Meth) acrylic resin (A) Production Example 3: (Meth) acrylic resin (A) obtained in Production Example 3,

B1: Trimethylol propane of tolylene diisocyanate An ethyl acetate solution (solid content concentration 75%) of the duct body, &quot; Colonate L &quot; obtained from Nippon Polyurethane Co.,

C1: Sodium acetate: Wako Pure Chemical Industries, Ltd. (a 0.5 wt% solution was dissolved in ethyl alcohol to prepare a pressure-sensitive adhesive composition and added)

C2: "AM-230G" obtained from Shin Nakamura Kagaku Kogyo Co., Ltd. (the following formula:

Methoxypolyethylene glycol acrylate represented by the following formula

C3: "AM-130G" obtained from Shin Nakamura Kagaku Kogyo Co., Ltd. (the following formula:

Methoxypolyethylene glycol acrylate represented by the following formula

C4: "M-130G" obtained from Shin Nakamura Kagaku Kogyo Co., Ltd. (the following formula:

Methoxypolyethylene glycol methacrylate represented by the following formula

C5: "M-230G" obtained from Shin Nakamura Kagaku Kogyo Co., Ltd. (the following formula:

Methoxypolyethylene glycol methacrylate represented by the following formula

S1: 3-glycidoxypropyltrimethoxysilane, &quot; KBM403 &quot; obtained from Shinetsu Kagaku Kogyo Co., Ltd.

(2) Production of pressure-sensitive adhesive layer

Each of the pressure-sensitive adhesive compositions prepared in the above (1) was applied to the surface of the release treatment of a release film (PLR-382051 obtained from a release tape made of a polyethylene terephthalate film subjected to release treatment) with an applicator And dried at 100 캜 for 1 minute to prepare a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet).

(3) Production of a polarizing plate having a pressure-sensitive adhesive layer

A first protective film having a thickness of 50 占 퐉 and made of a cyclic polyolefin resin was bonded to one side of a polarizer having a thickness of 23 占 퐉 in which iodine was adsorbed and aligned on a uniaxially stretched polyvinyl alcohol film with an adhesive agent, A second polarizing plate having a thickness of 80 占 퐉 and made of an acrylic resin was bonded to the polarizing plate by using an adhesive different from the above. Next, the outer surface of the first protective film was subjected to corona treatment, and the surface (pressure-sensitive adhesive layer side) opposite to the separator in the pressure-sensitive adhesive layer prepared in the above (2) was bonded to the corona-treated surface with a laminator , A temperature of 23 캜 and a relative humidity of 65% to obtain a polarizing plate having a pressure-sensitive adhesive layer.

(4) Evaluation of durability

The separator was peeled off from the polarizing plate having the pressure-sensitive adhesive layer prepared in the above (3), and the pressure-sensitive adhesive layer side thereof was adhered to both surfaces of a glass substrate for liquid crystal cell ("Eagle XG" . Using these samples, the following three durability tests were carried out.

[Durability test]

· Heat resistance test held at a temperature of 80 ° C for 1000 hours under dry conditions,

· Moisture resistance test in which the sample is held for 1000 hours under an environment of a temperature of 60 ° C and a relative humidity of 90%

Heat shock (HS) test in which one cycle is carried out by keeping the temperature at 80 ° C for 30 minutes and then at 30 ° C for 30 minutes under the drying condition of -40 ° C and repeating this for 500 cycles.

The samples after each test were visually observed and durability was evaluated according to the following evaluation criteria. The results are shown in Table 4.

A: There is no change in appearance such as peeling, peeling, and foaming,

B: Almost no change in appearance such as peeling, peeling, foaming,

C: Appearance changes such as lifting, peeling, foaming,

D: Appearance changes such as peeling, peeling, foaming and the like are remarkably recognized.

(5) Evaluation of reworkability

The polarizing plate having the pressure-sensitive adhesive layer prepared in the above (3) was cut into test pieces having a size of 25 mm x 150 mm. Subsequently, the separator was peeled off from the test piece, and the pressure-sensitive adhesive layer side thereof was adhered to a glass substrate for liquid crystal cell ("Eagle XG" manufactured by Corning Incorporated), and autoclave for 20 minutes at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) I did it. Subsequently, the sample was held in an oven at 50 DEG C for 50 hours, and then the test piece adhered to the glass substrate was heated in a 180 DEG direction (polarizer plate) at a tensile rate of 300 mm / min for each adhesive layer under the atmosphere of a temperature of 23 DEG C and a relative humidity of 50% And peeling off in a direction parallel to the surface of the glass substrate in the peeled and inverted state). The state of the surface of the glass substrate after the peeling test was visually observed, and the lithography workability was evaluated according to the following evaluation criteria. The results are shown in Table 4.

A: There is no dark part and glue on the surface of the glass plate,

B: Almost no dark part and grass residue were recognized on the surface of the glass plate,

C: Almost no scum is recognized on the surface of the glass plate, but a dark portion is recognized.

D: Glue on the surface of the glass plate is recognized.

(6) Evaluation of peel strength of optical member having pressure-sensitive adhesive layer

A test piece having a width of 25 mm and a length of 150 mm was cut from the polarizing plate having the pressure-sensitive adhesive layer prepared in (3) above. Then, the separator was peeled off from the test piece, and the pressure-sensitive adhesive layer side thereof was laminated on a glass substrate for liquid crystal cell (trade name: EAGLE XG, available from Corning Incorporated, Japan) with the attachment device (Lamiparka, Alkali glass plate]. A test piece to which the obtained glass substrate was adhered (optical member having a pressure-sensitive adhesive layer with a glass substrate adhered thereto) was pressed in an autoclave at a temperature of 50 占 폚 and a pressure of 5 kgf / cm2 (490.3 kPa) for 20 minutes. Further, the film was left under the conditions of an atmosphere of 23 DEG C for 24 hours and an atmosphere of 50 DEG C for 48 hours. The sample after standing was chucked by a tensile tester (&quot; AUTOGRAPH AGS-X &quot;, manufactured by Shimadzu Seisakusho Co., Ltd.), and the test piece adhered to the glass substrate under the environment of a temperature of 23 캜 and a relative humidity of 55% At a tensile rate of 300 mm / min. The peel strength measured at this time was evaluated as the peeling force (peeling force between the test piece (pressure-sensitive adhesive layer) and the non-alkali glass plate). Here, the peel force in the condition of being stored in an atmosphere of 23 캜 for 24 hours is defined as P ₂₃ , and the peel force in the condition of being stored in an atmosphere of 50 캜 for 48 hours is defined as P ₅₀ . The results are shown in Table 4. Here, P ₂₃ and P ₅₀ correspond to the above-mentioned P _CO23 and P _CO50 .

1: Polarizer 2: Surface treatment layer 3: 4: Protective film 7: Phase difference film 8: Interlayer adhesive 10: Polarizing plate 20: Pressure sensitive adhesive layer 25: Polarizer having a pressure sensitive adhesive layer 30: Glass substrate

Claims (9)

1. An optical member having a pressure-sensitive adhesive layer comprising an optical member and a pressure-sensitive adhesive layer laminated on the optical member,
Wherein the optical member having the pressure-
The peeling force between the optical member having the pressure-sensitive adhesive layer and the alkali-free glass when the laminate was laminated on the alkali-free glass plate through the pressure-sensitive adhesive layer and stored for 24 hours under an environment of 23 ° C was regarded as P ₂₃ ,
When the peel force between the optical member having the pressure-sensitive adhesive layer and the alkali-free glass is P ₅₀ when the pressure-sensitive adhesive layer is laminated on the non-alkali glass plate and stored for 48 hours under an environment of 50 ° C,
Ratio (P ₅₀ / P ₂₃₎ an optical member having a pressure-sensitive adhesive layer of 4.5 or higher and the P ₅₀ P ₂₃ above. The optical member according to claim 1, wherein the P ₂₃ has a pressure-sensitive adhesive layer of 0.5 N / 25 mm or more. The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the pressure-sensitive adhesive layer comprises a (meth) acrylic resin (A) containing a structural unit derived from a (meth) acrylic monomer having a hydroxyl group and having a content of the structural unit of more than 3.5% And a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition. The optical member according to claim 3, wherein the pressure-sensitive adhesive composition comprises a pressure-sensitive adhesive layer containing a crosslinking catalyst (C-1) and a compound (C-2) containing an alkyleneoxy group. The optical member according to claim 4, wherein the pressure-sensitive adhesive composition further comprises a pressure-sensitive adhesive layer containing an isocyanate-based crosslinking agent (B-1). The optical member according to claim 3, wherein the pressure-sensitive adhesive composition further comprises a pressure-sensitive adhesive layer containing an ionic compound (D). The optical member according to claim 3, wherein the pressure-sensitive adhesive composition further comprises a pressure-sensitive adhesive layer containing a silane compound (E). A laminated optical member in which an alkali-free glass plate is laminated on the pressure-sensitive adhesive layer side of an optical member having the pressure-sensitive adhesive layer according to any one of claims 1 to 3. Wherein the first film is formed into a layer shape on a first film made of a cyclic polyolefin resin and the first non-alkali glass plate is laminated on the formed first layer, The peeling force between the first non-alkali glass plate is P _CO23 ,
Wherein the second film is formed into a layer shape on a second film made of a cyclic polyolefin resin and the second non-alkali glass plate is laminated on the formed second layer, and the film is stored for 48 hours under an environment of 50 캜. the second free when the release force between the alkali glass plate by P _{CO50, CO50} and the P ratio (P _CO50 / _CO23 P) is 4.5 or more pressure-sensitive adhesive composition of the P _CO23.

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