KR101727948B1 - Adhesive composition, adhesive and adhesive sheet - Google Patents

Abstract

An object of the present invention is to provide a pressure-sensitive adhesive composition, a pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet which can effectively suppress the generation of static electricity and also exhibit excellent adhesive strength and durability under a predetermined environment.
The pressure-sensitive adhesive composition of the present invention for solving the above-mentioned problems is a pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer as component (A) and an antistatic agent as component (B), wherein the antistatic agent as component (B) The content of the fluorine-containing sulfonylimide salt which is potassium potassium is set to a value within a range of 0.05 to 15 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A).

Description

[0001] ADHESIVE COMPOSITION, ADHESIVE AND ADHESIVE SHEET [0002]

The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet. More particularly, the present invention relates to a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer which can effectively suppress the generation of static electricity and has excellent adhesion and durability under a predetermined environment, a pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet using such pressure-sensitive adhesive.

Conventionally, the manufacture of a liquid crystal display device is performed by laminating a polarizing plate on the surface of a liquid crystal cell in which a liquid crystal component is sandwiched between two glass plates.

The lamination of such a polarizing plate is performed by pressing the pressure-sensitive adhesive layer provided on one side of the polarizing plate against the surface of the liquid-crystal cell and then pressing it.

However, in general, the polarizing plate is bonded to the liquid crystal cell immediately after the release film laminated on the pressure-sensitive adhesive layer of the polarizing plate is peeled off. At this time, static electricity is easily generated and the polarizing plate is also charged , And such adverse effects on the liquid crystal display device due to such static electricity have been a problem.

More specifically, a problem has arisen that, due to the generation of static electricity, foreign matter tends to adhere to the surface of the polarizing plate, the liquid crystal alignment tends to be disordered, or electrostatic destruction of the peripheral circuit elements tends to occur.

Similarly, there has been a problem that static electricity is liable to be generated even when the polarizing plate attached to the liquid crystal cell once is changed for reasons such as misalignment.

In order to solve such a problem of static electricity, a conductive agent which is obtained by dissolving a specific salt in a specific solvent and a pressure-sensitive adhesive containing the same are disclosed (for example, see Patent Document 1).

That is, Patent Document 1 discloses a conductive agent comprising a bis (fluorosulfonyl) imide represented by the following general formula (1) and a salt comprising an alkali metal ion dissolved in a polyether polyol, and a pressure- And the like.

(In the general formula (1), M represents a cation component)

Japanese Patent Laid-Open No. 2008-163271 (Claims)

However, the imide salt as the conductivity-imparting agent disclosed in Patent Document 1 tends to insufficiently impart the conductivity because the cation is limited to substantially lithium ions, as is clear from the examples, It is difficult to inhibit it.

Further, the lithium-containing imide salt has a problem that when it is exposed for a long time under a high-temperature environment, the lithium-containing imide salt tends to bleed easily or tends to deteriorate the adhesive strength and durability.

In view of the above, the inventors of the present invention have made extensive efforts to provide a pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer as the component (A) and an antistatic agent as the component (B) A pressure-sensitive adhesive composition which can effectively suppress the generation of static electricity and also has excellent adhesive strength and durability under a predetermined environment can be obtained even when an adhesive sheet such as an optical film using such a pressure-sensitive adhesive composition is peeled from an adherend And has completed the present invention.

That is, an object of the present invention is to provide a pressure-sensitive adhesive composition, a pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet which can effectively suppress the generation of static electricity and also have excellent adhesive force and durability under a predetermined environment.

According to the present invention, there is provided a pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer as the component (A) and an antistatic agent as the component (B), wherein the antistatic agent as the component (B) is a fluorine-containing sulfonyl (Meth) acrylic acid ester polymer, which is a component (A), in a range of 0.05 to 15 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer, Can be solved.

That is, since the pressure-sensitive adhesive composition of the present invention contains a fluorine-containing sulfonylimide salt as a cationic potassium salt in a predetermined ratio to the (meth) acrylic acid ester polymer, excellent antistatic property can be effectively Can be exercised.

Therefore, when the pressure-sensitive adhesive composition of the present invention is used as a pressure-sensitive adhesive for sheet stacking of an optical film or the like by curing (a concept including photocuring and thermal crosslinking), for example, , The generation of static electricity can be effectively suppressed and the durability can be exerted even in a harsh environment such as repetition of high temperature, moist heat, and high temperature and low temperature, in addition to excellent adhesive force.

Further, with the pressure-sensitive adhesive composition of the present invention, it has become possible to provide a pressure-sensitive adhesive composition which is inexpensive, readily available, and contains potassium, which is inexpensive and which is inexpensive, Since excellent antistatic property can be efficiently obtained by the imide salt, it is advantageous in economy.

In the pressure-sensitive adhesive composition of the present invention, it is preferable that the (meth) acrylic acid ester polymer as the component (A) has a structural part derived from a (meth) acrylic acid ester monomer, a structural part derived from a hydroxyl group- The content of the hydroxyl group-containing vinyl monomer is in the range of 0.1 to 20% by weight based on the total amount of the monomer components in the copolymerization, and the mixing ratio of the carboxyl group-containing vinyl monomer is 0 Or 0 to 6% by weight (note that 0% by weight is not included), and also contains a crosslinking agent as the component (C).

With such a configuration, excellent antistatic properties can be effectively exhibited over a long period of time. In particular, even when exposed for a long time under a high-temperature environment, bleeding can be suppressed and deterioration of adhesive strength and durability can be effectively prevented.

In addition, since the crosslinking agent (thermal crosslinking agent) as the component (C) is contained, excellent adhesion properties and durability can be effectively exhibited.

Therefore, in the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition on the substrate, the occurrence of static electricity can be effectively suppressed even when the pressure-sensitive adhesive sheet is peeled from the release film, It is possible to exhibit excellent durability even in a harsh environment such as high temperature, moist heat and repetition of high temperature and low temperature.

In the pressure-sensitive adhesive composition of the present invention, it is preferable that the content of the crosslinking agent as the component (C) is in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A) desirable.

By such a constitution, the adhesive force and the storage elastic modulus when used as a pressure-sensitive adhesive can be adjusted to a more favorable range.

Further, in constituting the pressure-sensitive adhesive composition of the present invention, it is preferable that the crosslinking agent as the component (C) contains an isocyanate crosslinking agent.

By such a constitution, the adhesive force and the storage elastic modulus in the case of using a pressure-sensitive adhesive can be adjusted to a more favorable range.

In the pressure-sensitive adhesive composition of the present invention, it is preferable that the (meth) acrylic acid ester polymer as component (A) contains a structural part derived from a (meth) acrylic acid ester monomer and a structural part derived from a hydroxyl group- (Meth) acrylic acid ester polymer having a proportion of the hydroxyl group-containing vinyl monomer in the range of 1 to 20% by weight based on the total amount of the monomer components in the copolymerization, And a second (meth) acrylic acid ester polymer containing a structural moiety derived from a carboxyl group-containing vinyl monomer, wherein the amount of the hydroxyl group in the first (meth) acrylic acid ester polymer is H1, The equivalent ratio expressed by C1 / H1 is set to a value within the range of 0.01 to 1.0, and the amount of the carboxyl group in the polymer (D) Minutes preferably contains a photo-curing component as.

With such a configuration, excellent antistatic properties can be effectively exhibited over a long period of time. In particular, even when exposed for a long time under a high-temperature environment, bleeding can be suppressed and deterioration of adhesive strength and durability can be effectively prevented.

Therefore, even when the adhesive sheet is peeled off from the peel film, for example, when the adhesive is cured and used as a pressure-sensitive adhesive for sheet stacking of an optical film or the like, the generation of static electricity can be effectively suppressed, It is possible to exhibit excellent durability even in a harsh environment such as high temperature, moist heat and repetition of high temperature and low temperature.

In the pressure-sensitive adhesive composition of the present invention, the proportion of the (meth) acrylic acid ester polymer / the second (meth) acrylic acid ester polymer in the (meth) acrylic acid ester polymer as the component (A) ) Is preferably within a range of 99/1 to 60/40.

By such a constitution, it is possible to easily adjust the balance between the antistatic property, the adhesive force and the durability under a predetermined environment when the photocurable adhesive is used.

In the second (meth) acrylic acid ester polymer contained in the (meth) acrylic acid ester polymer which is the component (A) in constituting the pressure sensitive adhesive composition of the present invention, when the second (meth) acrylic acid ester polymer is polymerized The content of the carboxyl group-containing vinyl monomer is preferably within a range of 1 to 30% by weight.

By such a constitution, more excellent adhesive property and durability can be obtained in the case of using a pressure-sensitive adhesive by photocuring.

Further, in constituting the pressure-sensitive adhesive composition of the present invention, it is preferable that the photo-curing component (D) is a polyfunctional (meth) acrylate monomer having an isocyanurate structure.

By such a constitution, the adhesive force and the storage elastic modulus in the case of photo-curing to form a pressure-sensitive adhesive can be adjusted to a more favorable range.

In the pressure-sensitive adhesive composition of the present invention, the content of the photocurable component as the component (D) is set to a value within a range of 1 to 25 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A) .

By such a constitution, the adhesive force and the storage elastic modulus in the case of photo-curing to form a pressure-sensitive adhesive can be adjusted to a more favorable range.

In forming the pressure-sensitive adhesive composition of the present invention, the fluorine-containing sulfonylimide salt, which is a cationic potassium salt as an antistatic agent as the component (B), is preferably used as the potassium bis (fluorosulfonyl) imide or potassium bis (perfluoro Alkylsulfonyl) imide.

By such a constitution, it is possible to exhibit excellent antistatic properties even with a smaller amount of blending, and to further suppress bleeding.

In addition, in constituting the pressure-sensitive adhesive composition of the present invention, it is preferable that the dispersion aid is further an alkylene glycol dialkyl ether in addition to the dispersion aid of the antistatic agent as the component (B).

By such a constitution, it is possible to effectively improve the antistatic property of the fluorine-containing sulfonylimide salt which is the cationic potassium salt when the pressure-sensitive adhesive is cured, and in addition to the fact that such a dispersion aid itself bleeds from the pressure- , Can be effectively suppressed.

Further, another embodiment of the present invention is a pressure-sensitive adhesive which is formed as a pressure-sensitive adhesive through a process including the following steps (1) to (3).

(1) A pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer as component (A) and an antistatic agent as component (B), wherein the antistatic agent as the component (B) is a fluorine-containing sulfonylimide salt And a pressure-sensitive adhesive composition whose content is within a range of 0.05 to 15 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A)

(2) a step of applying a pressure-sensitive adhesive composition to a release film to form a pressure-sensitive adhesive composition layer

(3) a step of curing the pressure-sensitive adhesive composition layer to form a pressure-sensitive adhesive layer

That is, by such a constitution, even when the pressure-sensitive adhesive sheet using such a pressure-sensitive adhesive is peeled off, for example, from the release film, the generation of static electricity can be effectively suppressed, while the adhesive force is excellent and durability An excellent pressure-sensitive adhesive can be obtained.

Another aspect of the present invention is a pressure-sensitive adhesive sheet comprising a substrate and a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive described above.

That is, by such a constitution, even when the sheet is peeled off from the peeling film, for example, the occurrence of static electricity can be effectively suppressed, and a pressure-sensitive adhesive sheet excellent in durability even under a predetermined environment can be obtained have.

In forming the pressure-sensitive adhesive sheet of the present invention, it is preferable that the base material is an optical film base and that a pressure-sensitive adhesive layer is provided on at least one side of the optical film base.

By such a constitution, it is possible to effectively prevent occurrence of static electricity when peeling the pressure-sensitive adhesive sheet having an optical film base from the release film, and to provide an optical film base having excellent adhesive force and excellent durability under a predetermined environment A pressure-sensitive adhesive sheet can be obtained.

In the present invention, the release film is also defined as a kind of the base material, but from the viewpoint of preventing confusion with the optical film base material and the like, the optical film base material and the like are referred to as " base material " But may be simply referred to as a release film.

In forming the pressure-sensitive adhesive sheet of the present invention, it is preferable that the substrate is a release film and another release film is laminated on the opposite side of the release film in the pressure-sensitive adhesive layer.

Even in this case, the occurrence of static electricity can be effectively suppressed when the pressure-sensitive adhesive layer is peeled from the release film, and the handling property of the pressure-sensitive adhesive sheet can be improved.

Figs. 1 (a) to 1 (d) are schematic views provided for explaining a method of using a pressure-sensitive adhesive composition or the like and a method for producing a pressure-sensitive adhesive sheet.
2 is a view for explaining the relationship between the content of potassium bis (fluorosulfonyl) imide and the surface resistivity and adhesion of the pressure-sensitive adhesive layer.
Fig. 3 is a view for explaining the relationship between the compounding ratio of the carboxyl group-containing vinyl monomer and the surface resistivity and adhesion of the pressure-sensitive adhesive. Fig.
Fig. 4 is another diagram for explaining the relationship between the content of potassium bis (fluorosulfonyl) imide and the surface resistivity and adhesive force of the pressure-sensitive adhesive. Fig.
Fig. 5 is a view for explaining the relationship between C1 / H1 and the surface resistivity and adhesive force of the pressure-sensitive adhesive. Fig.
FIG. 6 is another diagram for illustrating the relationship between the content of potassium bis (fluorosulfonyl) imide and the surface resistivity and adhesion of the pressure-sensitive adhesive. FIG.
Figs. 7 (a) to 7 (d) are views for explaining the use of a pressure-sensitive adhesive composition or the like and a method for producing a pressure-sensitive adhesive sheet.
8 is another schematic diagram provided for explaining the use of the pressure-sensitive adhesive composition or the like.

[First Embodiment]

The first embodiment of the present invention is a pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer as the component (A) and an antistatic agent as the component (B), wherein the antistatic agent as the component (B) Containing sulfonylimide salt in the range of 0.05 to 15 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A).

That is, for example, it is the pressure-sensitive adhesive composition 1 used in the embodiment illustrated in Figs. 1 (a) to 1 (d).

Hereinafter, the first embodiment of the present invention will be described in detail with reference to the drawings appropriately.

The pressure-sensitive adhesive compositions according to the second and third embodiments described later are included in the category of the pressure-sensitive adhesive composition as the first embodiment, respectively. However, for convenience of explanation, the pressure-sensitive adhesive composition will be described as another embodiment separately from the first embodiment.

1. Component (A): (meth) acrylic acid ester polymer

(1) Type

First, in the present invention, (meth) acrylic acid ester means both of acrylic acid ester and methacrylic acid ester.

As the (meth) acrylic acid ester monomer as the constitutional unit of the (meth) acrylic acid ester polymer in the present invention, it is preferable to use a (meth) acrylic acid ester monomer having an alkyl group having a carbon number of 1 to 20.

This is because when the number of carbon atoms in the alkyl group in the (meth) acrylic acid ester monomer is more than 20, orientation and crystallization of the side chains may impair the tackiness of the resulting composition. On the other hand, when the number of carbon atoms in the alkyl group is small, the storage elastic modulus becomes excessively large, and on the contrary, the durability tends to become insufficient.

Examples of such (meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (Meth) acrylate, dicyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl Stearyl (meth) acrylate, and the like, or a combination of two or more of these monomers.

From the viewpoint of adjusting the storage elastic modulus to a more favorable range, the number of carbon atoms of the alkyl group in the (meth) acrylic acid ester monomer is more preferably in the range of 2 to 18, more preferably in the range of 3 to 12 Is more preferable.

It is also preferable to use a monomer having a functional group in the molecule.

(Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylate and the like. Examples of the functional group include at least one of hydroxyl group, carboxyl group, amino group and amide group as the functional group. (Meth) acrylic acid hydroxyalkyl esters such as 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; Acrylamides such as acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-methylol acrylamide and N-methylol methacrylamide; (Meth) acrylic acid monoalkylaminoalkyl such as monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate and monoethylaminopropyl (meth) acrylate; And ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and citraconic acid.

In addition, as long as the effects of the present invention are not impaired, monomers such as (meth) acrylic acid esters having an alkyl group having more than 20 carbon atoms can be used.

The (meth) acrylic acid ester polymer preferably contains, as the constitutional unit, a (meth) acrylic acid ester monomer having a number of carbon atoms in the alkyl group of 1 to 20, and at least one (meth) And the copolymerization ratio (by weight) thereof is preferably within a range of 99.9: 0.1 to 80:20.

The reason for this is that by constituting the (meth) acrylic acid ester polymer in this way, the pressure-sensitive adhesive properties such as the desired adhesive force and the storage elastic modulus can be more effectively obtained and the compatibility with the fluorine-containing sulfonylimide, This can be improved.

That is, when the copolymerization ratio of the (meth) acrylic acid ester monomer exceeds 99.9: 0.1, it is difficult to sufficiently bring out the antistatic property of the fluorine-containing sulfonylimide salt as the component (B) . Further, the compatibility with other components is lowered, and the interaction with a preparation such as a silane coupling agent is weakened, and durability tends to be lowered. On the other hand, if the copolymerization ratio of the (meth) acrylic acid ester monomer is less than 80:20, on the other hand, the miscibility with other components decreases, and the optical properties and durability are likely to be lowered.

Therefore, the copolymerization ratio (by weight) of the (meth) acrylic acid ester monomer in which the number of carbon atoms in the alkyl group is in the range of 1 to 20 and the monomer having at least one kind selected from the group consisting of hydroxyl group, carboxyl group, Is more preferably in the range of 99.5: 0.5 to 85: 15, and still more preferably in the range of 99: 1 to 90: 10.

In forming the (meth) acrylic acid ester polymer of the present invention, a (meth) acrylic acid ester monomer in which the number of carbon atoms in the alkyl group is in the range of 1 to 20, a monomer having a hydroxyl group in the molecule, Is preferably a copolymer with a monomer having a carboxyl group.

In this case, the copolymerization ratio (by weight) of the (meth) acrylic acid ester monomer having a carbon number of the alkyl group within the range of 1 to 20 and the monomer having a hydroxyl group or a carboxyl group in the molecule is preferably 95: 5 to 99: 1 . The copolymerization ratio (by weight) of the monomer having a hydroxyl group in the molecule and the monomer having a carboxyl group in the molecule is preferably in the range of 50: 100 to 10: 100. The copolymerization ratio (by weight) of the (meth) acrylic acid ester monomer having a carbon number of the alkyl group in the range of 1 to 20, the monomer having a hydroxyl group in the molecule, and the monomer having a carboxyl group in a molecule is 95: 0.5: To 99: 0.5: 0.5.

(Meth) acrylic acid ester monomers in which the number of carbon atoms in the alkyl group is in the range of 1 to 20 are, for example, (meth) acrylic acid esters having no hydroxyl group, carboxyl group, amino group and amide group in the molecule Means a monomer.

The above-mentioned copolymerization ratio represents a theoretical value calculated from the charge amount of the monomer as the constituent unit.

The copolymerization type is not particularly limited, and may be a random, block or graft copolymer.

(2) Weight average molecular weight

The weight average molecular weight of the (meth) acrylic acid ester polymer is preferably in the range of 100,000 to 220,000.

This is because when the weight average molecular weight of the (meth) acrylic acid ester polymer is less than 100,000, the durability under a predetermined environment may become insufficient. On the other hand, when the weight average molecular weight of the (meth) acrylic acid ester polymer exceeds 220,000, it is difficult to suppress the reduction of the workability due to an increase in viscosity and the like, to be.

Accordingly, the weight average molecular weight of the (meth) acrylic acid ester polymer is more preferably within a range of from 500,000 to 200,000, and more preferably within a range of from 1,000,000 to 1,800,000.

The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method in terms of polystyrene.

Although the (meth) acrylic acid ester polymer has been described above, the (meth) acrylic acid ester polymer in the present invention may be used singly or in combination of two or more different monomer components or different molecular weights.

2. Antistatic agent

(1) Component (B): alkali metal salt

(1) -1 type

The pressure-sensitive adhesive composition of the present invention is characterized by containing as the alkali metal salt a fluorine-containing sulfonylimide salt which is cationic potassium.

This is because the fluorine-containing sulfonylimide salt (hereinafter sometimes referred to as a potassium / fluorine-containing sulfonylimide salt) which is cationic potassium salt is not only inexpensive but also has excellent antistatic properties over a long period of time Because it can exert. This is because, even when exposed for a long time under a high-temperature environment, in the case of using a pressure-sensitive adhesive as a curing agent, bleeding can be suppressed and deterioration of adhesive strength and durability can be effectively prevented.

More specifically, potassium bis (fluorosulfonyl) imide and potassium bis (perfluoroalkylsulfonyl) imide or both are preferable as the kind of the potassium / fluorine-containing sulfonylimide salt.

This is because, if these potassium / fluorine-containing sulfonylimide salts are used, not only the bleeding is smaller but also the excellent antistatic property is exhibited even in a relatively small amount.

Therefore, when such a potassium / fluorine-containing sulfonylimide salt is contained in the (meth) acrylic acid ester polymer, even when the film is peeled from the adherend when it is cured to form a pressure-sensitive adhesive for film adhesion, It is possible to suppress effectively.

Examples of the potassium bis (perfluoroalkylsulfonyl) imide include potassium bis (trifluoromethylsulfonyl) imide, potassium bis (pentafluoroethylsulfonyl) imide and the like .

Among them, potassium bis (trifluoromethylsulfonyl) imide is particularly preferable from the viewpoint of being capable of exhibiting antistatic property by addition of a small amount since the molecular size is the smallest.

Further, in potassium bis (fluorosulfonyl) imide and potassium bis (perfluoroalkylsulfonyl) imide, the size of the molecule of potassium bis (fluorosulfonyl) imide is smaller than that of potassium bis So that the antistatic property can be exhibited without affecting it.

It is also preferable to use lithium bis (fluorosulfonyl) imide and the like as other alkali metal salts for these potassium / fluorine-containing sulfonylimide salts.

In this case, the content of the other alkali metal salt is preferably within a range of 1 to 100 parts by weight, more preferably within a range of 10 to 50 parts by weight, based on 100 parts by weight of the potassium / fluorine-containing sulfonylimide salt .

(1) -2 content

The content of the potassium / fluorine-containing sulfonylimide salt as the component (B) is set to a value within a range of 0.05 to 15 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A) .

This is because the content of the potassium / fluorine-containing sulfonylimide salt in such a range can effectively suppress the generation of the above-mentioned static electricity, while the adhesive force when the adhesive is cured to form a pressure- This is because the durability can be maintained stably.

That is, when the content of the predetermined potassium / fluorine-containing sulfonylimide salt is less than 0.05 part by weight, the provision of the antistatic property to the pressure-sensitive adhesive made by curing the pressure-sensitive adhesive composition becomes insufficient, and the generation of static electricity is stably suppressed It may be difficult.

On the other hand, when the content of the predetermined potassium / fluorine-containing sulfonylimide salt exceeds 15 parts by weight, there is a case where the adhesive force when the adhesive is cured and the durability under a predetermined condition is excessively lowered to be.

Accordingly, the content of the predetermined potassium / fluorine-containing sulfonylimide salt is more preferably in the range of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A) More preferably in the range of 5 to 6 parts by weight.

From the standpoint of stably suppressing the surface resistivity of the pressure-sensitive adhesive made by curing the pressure-sensitive adhesive composition to 1 10 ¹⁰ ? /? Or less while maintaining the durability under a predetermined environment more effectively, It is still more preferable that the content of the sulfonium salt is in the range of 2 to 4 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer.

Next, the relationship between the content of potassium bis (fluorosulfonyl) imide and the surface resistivity and adhesion of the pressure-sensitive adhesive will be described with reference to Fig.

That is, in FIG. 2, the content (parts by weight) of potassium bis (fluorosulfonyl) imide relative to 100 parts by weight of the (meth) acrylic acid ester polymer is taken as the axis of abscissa, A characteristic curve (A) showing a surface resistivity (Ω / □) in a pressure-sensitive adhesive obtained by curing the composition and a characteristic curve (A) obtained after 1 day of bonding to the glass surface of the pressure- (N / 25 mm) is shown (in accordance with Examples 3 to 6).

Details of the pressure-sensitive adhesive composition and conditions for measuring the surface resistivity and the adhesive strength are described in the examples.

In these characteristic curves A and B, the surface resistivity and the adhesive force in the pressure-sensitive adhesive tend to decrease as the content of potassium bis (fluorosulfonyl) imide increases.

From the viewpoint of suppressing the generation of static electricity, it is desirable to increase the content of potassium bis (fluorosulfonyl) imide to reduce the value of the surface resistivity in view of such tendency, while from the viewpoint of maintaining a predetermined adhesive force , And the content of potassium bis (fluorosulfonyl) imide needs to be limited to a predetermined value or less.

More specifically, when the content of potassium bis (fluorosulfonyl) imide is less than 0.05 part by weight, the surface resistivity of the pressure-sensitive adhesive becomes excessively large, exceeding 1 x 10 ¹² ? /? And the content of potassium bis (fluorosulfonyl) imide exceeds 15 parts by weight, the adhesive force of the pressure-sensitive adhesive becomes excessively low, which is less than 0.8 N / 25 mm.

Therefore, in the characteristic curves A and B, it is preferable that the content of potassium bis (fluorosulfonyl) imide is within a range of 0.05 to 15 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer .

(2) Dispersing agent

(2) -1 type

Further, in order to improve the dispersibility in a pressure-sensitive adhesive composition of a predetermined potassium / fluorine-containing sulfonylimide salt and a pressure-sensitive adhesive obtained by curing it, it is preferable to further add a dispersion aid to the (meth) acrylic acid ester polymer Do.

As the dispersion aid, a polyoxyethylene glycol-polyoxypropylene glycol block copolymer or the like may be used, but an alkylene glycol dialkyl ether is preferable.

The reason for this is that by using such a predetermined dispersion aid, it is possible to effectively improve the antistatic property of a predetermined potassium / fluorine-containing sulfonylimide salt in a pressure-sensitive adhesive obtained by curing a pressure-sensitive adhesive composition, The reason for this is that it is possible to effectively suppress bleeding from the pressure-sensitive adhesive itself.

That is, in the case of an alkylene glycol dialkyl ether, a pressure-sensitive adhesive made by curing a pressure-sensitive adhesive composition forms a complex with a potassium ion in a predetermined potassium / fluorine-containing sulfonylimide salt, This is because an ionization state can be effectively generated and maintained.

In addition, if the alkylene glycol dialkyl ether is used, the compatibility between the predetermined potassium / fluorine-containing sulfonylimide salt and the (meth) acrylic acid ester polymer or the like can be improved.

In addition, the alkylene glycol dialkyl ether and the potassium / fluorine-containing sulfonylimide salt may be mixed in advance to prepare a pressure-sensitive adhesive composition in which the potassium / fluorine-containing sulfonylimide salt is dissolved in the alkylene glycol dialkyl ether Or the potassium / fluorine-containing sulfonylimide salt may be added to other components in the pressure-sensitive adhesive composition by dissolving it in another diluting solvent such as ethyl acetate, and the alkylene glycol dialkyl ether may be added to the other components of the pressure- Other components in the pressure-sensitive adhesive composition may be added separately.

The number of repeating units of the polyoxyalkylene chain in the alkylene glycol dialkyl ether is preferably within a range of 2 to 10. [

This is because when the number of repeating units is out of the range of 2 to 10, it may be difficult to stably chelate potassium ions in a predetermined potassium / fluorine-containing sulfonylimide salt.

Therefore, the number of repeating units of the oxyalkylene chain in the alkylene glycol dialkyl ether is more preferably in the range of 3 to 8, and still more preferably in the range of 4 to 6.

The alkyl group bonded to the oxygen atom at both ends of the alkylene glycol dialkyl ether usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms.

Specific examples of the alkylene glycol dialkyl ether include octaethylene glycol dibutyl ether, octaethylene glycol diethyl ether, octaethylene glycol dimethyl ether, hexaethylene glycol dibutyl ether, hexaethylene glycol diethyl ether, hexaethylene glycol dimethyl Ether, tetraethylene glycol dibutyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dimethyl ether and the like, or a combination thereof.

Of these, tetraethylene glycol diethyl ether and tetraethylene glycol dimethyl ether are particularly preferable.

(2) -2 Addition ratio

Further, it is preferable that the ratio (molar ratio) of the predetermined potassium / fluorine-containing sulfonylimide salt to the alkylene glycol dialkyl ether is in the range of 30:70 to 70:30.

This is because the addition ratio of the potassium / fluorine-containing sulfonylimide salt of the potassium / fluorine-containing sulfonylimide salt to the total of the potassium / fluorine-containing sulfonylimide salt and the alkylene glycol dialkyl ether is 100 The molar number of addition is less than 30), the alkylene glycol dialkyl ether which does not interact with the predetermined potassium / fluorine-containing sulfonylimide salt is excessively present in the pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition, This is because the glycol dialkyl ether tends to bleed from the pressure-sensitive adhesive.

On the other hand, if the mixing ratio exceeds 70:30, the pressure-sensitive adhesive made by curing the pressure-sensitive adhesive composition may have insufficient ionization of the predetermined potassium / fluorine-containing sulfonylimide salt and excessively lower the dispersibility Or the like.

Therefore, it is more preferable that the ratio (molar ratio) of addition of the predetermined potassium / fluorine-containing sulfonylimide salt to the alkylene glycol dialkyl ether is in the range of 40:60 to 60:40, more preferably 45: And more preferably in the range of 55 to 55: 45.

(3) Total content

It is also preferable that the total content of the predetermined potassium / fluorine-containing sulfonylimide salt and the alkylene glycol dialkyl ether is within a range of 1 to 30 parts by weight, relative to 100 parts by weight of the (meth) acrylic acid ester polymer desirable.

This is because if the total content is less than 1 part by weight, it may become difficult to sufficiently exhibit antistatic property in a pressure-sensitive adhesive made by curing the pressure-sensitive adhesive composition.

On the other hand, when the total content exceeds 30 parts by weight, in the pressure-sensitive adhesive made by curing the pressure-sensitive adhesive composition, the predetermined potassium / fluorine-containing sulfonylimide salt tends to precipitate, the durability tends to deteriorate excessively, It is likely that the renglycol dialkyl ether tends to bleed.

Therefore, it is preferable that the total content of the predetermined potassium / fluorine-containing sulfonylimide salt and the alkylene glycol dialkyl ether is within a range of 2 to 20 parts by weight, relative to 100 parts by weight of the (meth) acrylic acid ester polymer And more preferably in the range of 3 to 14 parts by weight.

3. Component (C): Crosslinking agent

(1) Type

Further, the pressure-sensitive adhesive composition of the present invention preferably further contains a crosslinking agent.

This is because the inclusion of an isocyanate crosslinking agent enables the adhesive force and storage elastic modulus of the pressure-sensitive adhesive composition to be controlled within a more favorable range when the pressure-sensitive adhesive composition is cured (thermally crosslinked) to form a pressure-sensitive adhesive.

That is, if the isocyanate-based crosslinking agent is used, the (meth) acrylic acid ester polymer can be chemically crosslinked by reacting with the hydroxyl group or the carboxyl group of the (meth) acrylic acid ester polymer.

In addition, if it is an isocyanate crosslinking agent, adhesion between the pressure-sensitive adhesive and the adherend can be improved.

Examples of the isocyanate crosslinking agent include, but are not limited to, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2- Butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, etc. Aliphatic diisocyanates such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate , 4,4'-methylenebis (cyclohexylisocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate Alicyclic diisocyanates such as 1,4-bis (isocyanatomethyl) cyclohexane and 1,3-bis (isocyanatomethyl) cyclohexane, such as m-phenylene diisocyanate, p-phenylenediisocyanate, Diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, 4,4'-toluidine di Aromatic diisocyanates such as isocyanate, dianisidine diisocyanate and 4,4'-diphenyl ether diisocyanate, for example, 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω'-di Aromatic aliphatic diisocyanates such as isocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene or mixtures thereof such as triphenylmethane- , 4 ', 4 "-triisocyanate, 1,3,5-tri Triisocyanates such as cyanate benzene, 2,4,6-triisocyanate toluene and 1,3,5-triisocyanate hexane, for example, 4,4'-diphenyldimethylmethane-2,2'-5,5 -Tetraisocyanate, dimers derived from the above-mentioned polyisocyanate monomers, trimers, biuret, allophanates, carbon dioxide gases, and 2,4,6-oxadiazinetrione rings obtained from the polyisocyanate monomers described above, Such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, cyclo Molecular weight polyol having a weight average molecular weight of less than 200, such as hexane dimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, trimethylol propane, pentaerythritol and sorbitol, Adducts to cyanate, for example, polyester polyols having a molecular weight of 200 to 200,000, polyether polyols, polyether ester polyols, polyester amide polyols, polycaprolactone polyols, polyvalero lactone polyols, acrylic polyols , Polycarbonate polyol, polyhydroxyalkane, castor oil, polyurethane polyol, and the like.

(2) Content

The content of the isocyanate crosslinking agent is preferably in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer.

This is because when the content of the isocyanate crosslinking agent is less than 0.01 part by weight, crosslinking between the (meth) acrylic acid ester polymers becomes insufficient, and when it becomes difficult to obtain sufficient adhesion and durability when the pressure- There is. On the other hand, when the content of the isocyanate crosslinking agent exceeds 10 parts by weight, the crosslinking between the (meth) acrylic acid ester polymers becomes excessive, and the adhesive strength and durability when used as a pressure-sensitive adhesive tends to decrease inversely It is because.

Accordingly, the content of the isocyanate-based crosslinking agent is more preferably in the range of 0.1 to 5 parts by weight, more preferably in the range of 0.2 to 2 parts by weight, based on 100 parts by weight of the (meth) acrylic acid ester polymer .

4. Component (D): Photocurable component

The pressure-sensitive adhesive composition of the present invention may further contain a photo-curable component.

This is because the inclusion of the photo-curable component allows the adhesive force and storage elastic modulus when the pressure-sensitive adhesive composition is made into a pressure-sensitive adhesive to be adjusted to a more favorable range, and further, the seasoning period can be omitted or shortened .

(1) Type

Examples of such photocurable components include polyfunctional (meth) acrylate monomers having a molecular weight of less than 1000, acrylate oligomers, and acrylate polymers having a group having a (meth) acryloyl group introduced into the side chain. Lt; / RTI >

As the polyfunctional (meth) acrylate-based monomer having a weight average molecular weight of less than 1000, various polyfunctional (meth) acrylate-based monomers ranging from bifunctional to hexafunctional can be used. They may be used in combination.

(Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl (Meth) acrylate of glycol adipate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide (Meth) acrylate, di (meth) acryloxyethyl isocyanurate, allyl cyclohexyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dimethylol dicyclopentanedi (Meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, neopentyl glycol modified trimethylol propane di (meth) acrylate, adamantanedi (meth) , And 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, for example, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (Meth) acrylate, propylene oxide modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) (Meth) acrylate such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate, such as propionic acid-modified dipentaerythritol penta (meth) acrylate (Meth) acrylates such as dipentaerythritol hexa (metha) acrylate and caprolactone-modified dipentaerythritol hexa (metha) acrylate. 1 species such as bots may be used alone or in combination of two or more thereof.

As such a polyfunctional (meth) acrylate-based monomer, it is preferable that the skeleton structure has a cyclic structure, for example, a carbon cyclic structure and a heterocyclic structure or a cyclic structure.

Examples of the polyfunctional (meth) acrylate-based monomer having such a cyclic structure include isocyanurate such as di (meth) acryloxyethyl isocyanurate and tris (meth) acryloxyethyl isocyanurate (Meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol modified trimethylol propane Di (meth) acrylate, adamantanedi (meth) acrylate, and the like, and particularly preferably has an isocyanurate structure.

The acrylate oligomer preferably has a weight average molecular weight of 50,000 or less. Examples of such acrylate oligomers include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polybutadiene acrylate, and silicone acrylate.

Examples of the polyester acrylate oligomer include a polyester oligomer obtained by esterifying a hydroxyl group of a polyester oligomer having a hydroxyl group at both ends with a (meth) acrylic acid obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol, Can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The epoxy acrylate oligomer can be obtained, for example, by allowing (meth) acrylic acid to react with an oxirane ring of a relatively low molecular weight bisphenol epoxy resin or novolac epoxy resin, followed by esterification. Also, an epoxy acrylate oligomer of carboxy modified form obtained by partially modifying the epoxy acrylate oligomer with a dibasic carboxylic acid anhydride may be used. The urethane acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol or a polyester polyol with a polyisocyanate with (meth) acrylic acid, and the polyol acrylate oligomer is obtained by, And then esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

The weight average molecular weight of the above-mentioned acrylate oligomer is a value in terms of standard polymethyl methacrylate measured by GPC, and is preferably 50,000 or less, more preferably 500 to 50,000, 3,000 to 40,000. These acrylate oligomers may be used singly or in combination of two or more kinds.

Examples of the acrylate polymer in which a group having a (meth) acryloyl group is introduced into the side chain include a (meth) acrylic acid ester described in the above-mentioned (meth) acrylic acid ester polymer, a monomer having a functional group in the molecule , And reacting a part of the functional group of the copolymer with a compound having a (meth) acryloyl group and a group reacting with the functional group. The weight-average molecular weight of the acrylate-based polymer is usually 500,000 to 200,000 in terms of polystyrene.

(2) Content

The content of the photo-curable component is preferably within a range of 5 to 50 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer.

This is because when the content of the photo-curable component is less than 5 parts by weight, it becomes difficult to improve the adhesive strength and the storage elastic modulus when it is used as a pressure-sensitive adhesive. On the other hand, when the content of the photo-curable component exceeds 50 parts by weight, it is difficult to maintain the optical properties when the adhesive is used, which makes it difficult to apply the composition to an optical film It is because.

Therefore, the content of the photo-curable component is more preferably in the range of 10 to 30 parts by weight, more preferably 15 to 20 parts by weight, relative to 100 parts by weight of the (meth) acrylic acid ester polymer .

(3) Photopolymerization initiator

In order to cure the photo-curing component with ultraviolet rays or the like, it is preferable to add a photo-polymerization initiator for initiating the reaction. Examples of such photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) -Propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethyl anthraquinone, 2- -Aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, Phenon dimethyl ketal, p-dimethylamino 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. .

The content of the photopolymerization initiator is preferably within a range of 1 to 30 parts by weight based on 100 parts by weight of the photocurable component.

This is because when the content of the photopolymerization initiator is less than 1 part by weight, a proper crosslinking density may not be obtained even after the photopolymerization. On the other hand, if the content of the photopolymerization initiator exceeds 30 parts by weight, the remaining photopolymerization initiator or the decomposition product thereof tends to bleed after the photopolymerization, or the physical properties may be easily deteriorated.

Therefore, the content of the photopolymerization initiator is more preferably within a range of 5 to 20 parts by weight, and still more preferably within a range of 7.5 to 15 parts by weight, based on 100 parts by weight of the photocurable component.

5. Silane coupling agent

It is also preferable to add a so-called silane coupling agent to the pressure-sensitive adhesive composition of the present invention.

Such a silane coupling agent contributes to effectively improving the adhesion between an object made of glass such as a liquid crystal cell and an optical film such as a polarizing film.

As such a silane coupling agent, an organosilicon compound having at least one alkoxysilyl group in the molecule is preferred to have good compatibility with the pressure-sensitive adhesive composition and also to have optical transparency.

More specifically, examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl tri Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3 -Chloropropyltrimethoxysilane or the like is preferably used.

The content of the silane coupling agent is preferably within a range of 0.001 to 10 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer.

The reason for this is that when the content of the silane coupling agent is less than 0.001 part by weight, it may become difficult to sufficiently exert the effect of improving the adhesion between the polarizing plate and the liquid crystal cell or the like. On the other hand, when the content of the silane coupling agent exceeds 10 parts by weight, the tackiness and durability may be lowered.

Accordingly, the content of the silane coupling agent is more preferably in the range of 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, relative to 100 parts by weight of the (meth) acrylic acid ester polymer .

6. Dilution solvent

In the pressure-sensitive adhesive composition of the present invention, a solvent may be used for the purpose of improving the dispersibility of each component or adjusting the viscosity to a proper value when the pressure-sensitive adhesive composition is applied to a release film or the like.

As such a solvent, for example, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, ethyl isobutyl ketone, methyl alcohol, ethyl alcohol and isopropyl alcohol are preferable, and the concentration of the pressure- Is preferably within a range of 5 to 30% by weight.

7. Additives

As the additive, it is also preferable to add a tackifier, an antioxidant, an ultraviolet absorber, a light stabilizer, a softening agent, a filler, a high refractive index agent, a diffusing agent and the like to the pressure sensitive adhesive composition.

In this case, depending on the type of the additive, the content thereof is preferably within a range of 0.1 to 20 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer.

[Second Embodiment]

A second embodiment of the present invention is a pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer as the component (A) and an antistatic agent as the component (B), wherein the antistatic agent as the component (B) (Meth) acrylic acid ester polymer as the component (A), and the content of the component (A), that is, the component (meth) acrylate, is 0.1 to 15 parts by weight, ) Acrylic ester polymer comprises a structural part derived from a (meth) acrylic acid ester monomer, a structural part derived from a hydroxyl group-containing vinyl monomer, and a structural part derived from a carboxyl group-containing vinyl monomer, wherein the total amount of monomer components , The mixing ratio of the hydroxyl group-containing vinyl monomer is within a range of 0.1 to 20 wt%, the mixing ratio of the carboxyl group-containing vinyl monomer is 0 or 0 to 6 wt% (C), and a crosslinking agent as component (C).

Here, the second embodiment is a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive rich in stress relaxation property. For this reason, for example, when the polarizing plate is used for bonding the liquid crystal cell to the polarizing plate, the pressure of the pressure-sensitive adhesive is relaxed even if the polarizing plate is shrunk by exposure to a harsh environment. Therefore, it is presumed that the deviation of the polarization axis of the polarizing plate due to the stress can be minimized. Therefore, the polarizing plate to which the pressure-sensitive adhesive of the present embodiment is applied is excellent in light fastness to light.

The pressure-sensitive adhesive composition according to the second embodiment corresponds to the sub-concept of the pressure-sensitive adhesive composition according to the first embodiment.

Therefore, in the second embodiment, the pressure-sensitive adhesive composition according to the second embodiment will be specifically described focusing on the characteristic content thereof.

1. Component (A): (meth) acrylic acid ester polymer

First, the (meth) acrylic acid ester polymer of the component (A) in the pressure-sensitive adhesive composition according to the second embodiment comprises a (meth) acrylic acid ester monomer as a constituent unit, a vinyl monomer having a hydroxyl group in the molecule (hereinafter referred to as a hydroxyl group-containing vinyl monomer (Hereinafter referred to as a carboxyl group-containing vinyl monomer), and other vinyl monomers as required.

Alternatively, the (meth) acrylic acid ester polymer of component (A) may not use the above-mentioned carboxyl group-containing vinyl monomer as its monomer component.

More specifically, as the (meth) acrylic acid ester monomer in the constituent unit of the (meth) acrylic acid ester polymer, it is preferable to use a (meth) acrylic acid ester monomer in which the number of carbon atoms in the alkyl group is in the range of 1 to 20.

As the type of the (meth) acrylic acid ester monomer in which the number of carbon atoms of the alkyl group is in the range of 1 to 20, it is preferable to use the same one as described in the first embodiment.

Further, the (meth) acrylic acid ester monomer in the (meth) acrylic acid ester polymer is a main component constituting the polymer, and therefore, it is usually preferably at least 50% by weight of the total monomer constituting the (meth) acrylic acid ester polymer By weight, more preferably in the range of 74 to 99.9% by weight, and still more preferably in the range of 86.5 to 97.1% by weight.

The pressure-sensitive adhesive composition according to the second embodiment is characterized by containing a hydroxyl group-containing vinyl monomer as a copolymerization component of the (meth) acrylic acid ester polymer.

More specifically, examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl Hydroxyethyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, or allyl alcohol.

Further, from the viewpoint of compatibility with the (meth) acrylic acid ester monomer which is the main component of the (meth) acrylic acid ester polymer, it is more preferable to be a (meth) acrylic acid hydroxyalkyl ester, and 2-hydroxyethyl And 4-hydroxybutyl (meth) acrylate are particularly preferable.

In the pressure-sensitive adhesive composition according to the second embodiment, the blending ratio of the hydroxyl group-containing vinyl monomer is set to a value within a range of 0.1 to 20% by weight based on the total amount of the monomer components when the (meth) acrylic acid ester polymer is polymerized .

This is because if the compounding ratio of the vinyl monomer having such a functional group is less than 0.1% by weight, the effect of adding the antistatic agent as the component (B) may not be exhibited.

On the other hand, if the compounding ratio of the vinyl monomer exceeds 20% by weight, the durability may be lowered.

Accordingly, the compounding ratio of the hydroxyl group-containing vinyl monomer is more preferably in the range of 0.2 to 15% by weight, more preferably in the range of 0.4 to 10% by weight based on the total amount of the monomer components in the polymerization of the (meth) acrylic acid ester polymer %. ≪ / RTI >

In the pressure-sensitive adhesive composition as the second embodiment, it is preferable that the blending ratio of the carboxyl group-containing vinyl monomer as the copolymerization component of the (meth) acrylic acid ester polymer is in the range of , 0 or 0 to 6% by weight (note that 0% by weight is not included).

This is because if the blend ratio exceeds 6% by weight, the adhesive force becomes too high, and the re-peelability may deteriorate or the surface resistivity may become too high. On the other hand, if the compounding ratio is too small, the durability may deteriorate depending on other compositions in the pressure-sensitive adhesive composition.

Therefore, the blending ratio of the carboxyl group-containing vinyl monomer is more preferably in the range of 1 to 5% by weight, more preferably 2.5 to 3.5% by weight based on the total amount of the monomer components in the polymerization of the (meth) acrylic acid ester polymer %. ≪ / RTI >

Next, with reference to Fig. 3, the relationship between the compounding ratio of the above-mentioned carboxyl group-containing vinyl monomers, the surface resistivity of the pressure-sensitive adhesive layer and the adhesive force after 14 days of fusion are described.

That is, in FIG. 3, the abscissa indicates the mixing ratio (% by weight) of the carboxyl group-containing vinyl monomer to the total amount of the monomer components when the (meth) acrylic acid ester polymer as the component (A) , A characteristic curve (A) obtained by taking the surface resistivity (? /?) In the obtained pressure-sensitive adhesive layer and a characteristic curve (N / 25 mm) obtained after 14 days of bonding to the glass surface of the obtained pressure- (B) are shown (in accordance with Examples 15, 16, 18, 23, 24, 26 and Reference Example 3).

The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer was dried at 90 DEG C for 1 minute, left under the conditions of 23 DEG C and 50% RH for 14 days, and thermally crosslinked sufficiently.

Details of the pressure-sensitive adhesive layer and conditions for measuring the surface resistivity and the adhesive force are described in Examples.

First, in the characteristic curve (A), the surface resistivity of the pressure-sensitive adhesive composition tends to increase gradually as the blending ratio of the carboxyl group-containing vinyl monomer increases.

Further, in the characteristic curve (B), the adhesive force in the pressure-sensitive adhesive composition increases as the mixing ratio of the carboxyl group-containing vinyl monomer increases.

Taking this tendency into consideration, from the viewpoint of suppressing the generation of static electricity, it is preferable to limit the compounding ratio of the carboxyl group-containing vinyl monomer to a predetermined value or less, and also from the viewpoint of preventing the adhesive force from becoming too high, It is preferable to limit the ratio to a predetermined value or less.

More specifically, when the blending ratio of the carboxyl group-containing vinyl monomer exceeds 6 wt%, the surface resistivity may exceed 1 x 10 ¹² ? / ?. In this case, a pressure-sensitive adhesive sheet There is a possibility that it is difficult to stably suppress the generation of static electricity.

In addition, the adhesive strength may exceed 50 N / 25 mm, for example, there is a possibility that the re-peeling property when the polarizing plate with a pressure-sensitive adhesive layer is attached to a liquid crystal cell or the like is insufficient.

Therefore, in the characteristic curves A and B, the blending ratio of the carboxyl group-containing vinyl monomer to the total amount of the monomer components when the (meth) acrylic acid ester polymer as the component (A) is polymerized is 0 or 0 to 6 wt% (Note that 0 wt% is not included).

Examples of such carboxyl group-containing vinyl monomers include acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and citraconic acid.

Among them, acrylic acid and methacrylic acid are particularly preferable in view of the compatibility with the (meth) acrylic acid ester monomer which is the main component of the monomer constituting the (meth) acrylic acid ester polymer.

As the copolymerization component of the (meth) acrylic acid ester polymer, other vinyl monomers may be used.

Examples of such vinyl monomers include acrylamides such as acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-methylol acrylamide and N-methylol methacrylamide; (Meth) acrylic acid monoalkylaminoalkyl such as (meth) acrylic acid monomethylaminoethyl, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate and monoethylaminopropyl (meth) (Meth) acrylic acid esters containing an aliphatic ring such as cyclohexyl; (Meth) acrylic acid esters containing an aromatic ring such as phenyl (meth) acrylate, and the like.

When the above-mentioned other vinyl monomer is contained as a constituent component in the (meth) acrylic acid ester polymer, from the viewpoint of not impairing the effect of the present invention, the proportion of the monomer component in the polymerization of the (meth) acrylic acid ester polymer Is preferably less than 20% by weight based on the total amount of the components.

In forming the (meth) acrylic acid ester polymer in the pressure-sensitive adhesive composition according to the second embodiment, in particular, a (meth) acrylic acid ester monomer having an alkyl group of 1 to 20 carbon atoms, a hydroxyl group- It is preferable to use at least a ternary (meth) acrylic acid ester copolymer with a monomer.

That is, the (meth) acrylic acid ester polymer includes a structure derived from a (meth) acrylic acid ester monomer having an alkyl group of 1 to 20 carbon atoms, a structure derived from a hydroxyl group-containing vinyl monomer, and a structure derived from a carboxyl group- .

In this case, the copolymerization ratio (by weight) of the (meth) acrylic acid ester in which the alkyl group has 1 to 20 carbon atoms, the vinyl monomer having a hydroxyl group in the molecule and the vinyl monomer having a carboxyl group in the molecule is 94.5: 0.5: 5: 99: 0.5: 0.5.

The above-mentioned copolymerization ratio represents a theoretical value calculated from the charging amount of the monomer as the constituent unit.

The copolymerization type is not particularly limited, and may be a random, block or graft copolymer.

The weight average molecular weight of the (meth) acrylic acid ester polymer is preferably as in the first embodiment.

2. Component (B): Antistatic agent

The component (B) relates to the kind, content, and dispersion aid, and can be as described in the first embodiment.

4, the relationship between the content of potassium bis (fluorosulfonyl) imide, the surface resistivity of the pressure-sensitive adhesive layer, and the adhesive force after 14 days of fusion will be described.

That is, in FIG. 4, the abscissa indicates the content (parts by weight) of potassium bis (fluorosulfonyl) imide relative to 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A) (N / 25 mm) after 14 days from the adhesion of the obtained pressure-sensitive adhesive layer to the glass surface of the obtained pressure-sensitive adhesive layer was taken as the characteristic curve (A) (In accordance with Examples 17 to 20).

The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer was dried at 90 DEG C for 1 minute, left under the conditions of 23 DEG C and 50% RH for 14 days, and thermally crosslinked sufficiently.

In these characteristic curves A and B, the surface resistivity and the adhesive force in the pressure-sensitive adhesive layer tend to decrease as the content of potassium bis (fluorosulfonyl) imide increases.

From the viewpoint of suppressing the generation of static electricity, it is desirable to increase the content of potassium bis (fluorosulfonyl) imide to reduce the value of the surface resistivity in view of such tendency, while from the viewpoint of maintaining a predetermined adhesive force , And the content of potassium bis (fluorosulfonyl) imide needs to be limited to a predetermined value or less.

More specifically, when the content of potassium bis (fluorosulfonyl) imide is less than 0.05 part by weight, when the surface resistivity of the pressure-sensitive adhesive exceeds 1 x 10 ¹² ? /? And the antistatic performance is lowered . On the other hand, when the content of potassium bis (fluorosulfonyl) imide exceeds 15 parts by weight, the adhesive force of the pressure-sensitive adhesive becomes a value of less than 0.1 N / 25 mm, May occur.

Therefore, it is understood that in the characteristic curves A and B, the content of potassium bis (fluorosulfonyl) imide should be within a range of 0.05 to 15 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer do.

In addition, although FIG. 4 shows an example of potassium bis (fluorosulfonyl) imide, it has been found that a potassium bis (perfluoroalkylsulfonyl) imide has a characteristic curve showing the same tendency.

3. Component (C): Crosslinking agent

The pressure-sensitive adhesive composition according to the second embodiment is characterized by containing a crosslinking agent as the component (C).

The crosslinking agent is preferably an isocyanate crosslinking agent, an aziridine crosslinking agent, an epoxy crosslinking agent, or a metal chelating crosslinking agent. Among them, an isocyanate crosslinking agent is particularly preferably used.

This is because, by containing an isocyanate crosslinking agent, the adhesive force and storage elastic modulus of the pressure-sensitive adhesive composition can be adjusted to a more favorable range.

That is, if the isocyanate-based crosslinking agent is used, the (meth) acrylic acid ester polymer can be chemically crosslinked by reacting with the hydroxyl group or the carboxyl group of the (meth) acrylic acid ester polymer.

In addition, if it is an isocyanate crosslinking agent, adhesion between the pressure-sensitive adhesive composition and an adherend can be improved.

As the specific kind of such an isocyanate crosslinking agent, the same as described in the first embodiment is suitably used.

The content of the crosslinking agent as the component (C) is preferably from 0.01 to 10 parts by weight per 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A), as described in the first embodiment .

4. Photocurable component

In addition, the pressure-sensitive adhesive composition according to the second embodiment is preferably one that does not contain a photo-curable component because the storage elastic modulus (G ') value becomes excessively high and the stress relaxation property may decrease.

However, if the effect of the present invention is not impaired, a predetermined amount of photocurable component such as a polyfunctional (meth) acrylate monomer can be contained.

Specifically, it is more preferable that the blending amount of the photocurable component is set to a value of less than 5 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer of the component (A) so that the value of the storage elastic modulus is not excessively increased , And more preferably in the range of 0.1 to 3 parts by weight.

When a photocurable component is contained in a predetermined amount, it is preferable to incorporate a predetermined amount of a photopolymerization initiator in correspondence thereto.

[Third embodiment]

A third embodiment of the present invention is a pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer as the component (A) and an antistatic agent as the component (B), wherein the antistatic agent as the component (B) (Meth) acrylic acid ester polymer as the component (A), and the content of the component (A), that is, the component (meth) acrylate, is 0.1 to 15 parts by weight, ) Acrylic ester polymer comprises a structural part derived from a (meth) acrylic acid ester monomer and a structural part derived from a hydroxyl group-containing vinyl monomer, wherein the mixing ratio of the hydroxyl group-containing vinyl monomer to the total amount of the monomer components in copolymerization (Meth) acrylic acid ester polymer having a value in the range of 1 to 20% by weight and a structural part derived from a (meth) acrylic acid ester monomer and a carboxyl group- (Meth) acrylic acid ester polymer, wherein the amount of the hydroxyl group in the first (meth) acrylic acid ester polymer is H1 and the amount of the carboxyl group in the second (meth) acrylic acid ester polymer is C1, the equivalent ratio expressed by C1 / H1 is set to a value within a range of 0.01 to 1.0, and a photo-curable component as the component (D) is contained.

Here, the pressure-sensitive adhesive according to the third embodiment is a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive having a high storage modulus and excellent dimensional stability. Therefore, it is presumed that, for example, when applied to the bonding of the polarizing plate and the liquid crystal cell, the pressure-sensitive adhesive can suppress the shrinkage of the polarizing plate itself even when exposed to a harsh environment. Therefore, the polarizing plate with a pressure-sensitive adhesive layer using the pressure-sensitive adhesive of this embodiment is excellent in light fastness to light.

The pressure-sensitive adhesive composition as the third embodiment also corresponds to the lower concept of the pressure-sensitive adhesive composition as the first embodiment, like the pressure-sensitive adhesive composition according to the second embodiment.

Therefore, in the third embodiment, the pressure-sensitive adhesive composition according to the third embodiment will be specifically described focusing on the characteristic content thereof.

1. Component (A): (meth) acrylic acid ester polymer

(1) Type

First, the (meth) acrylic acid ester polymer as the component (A) in the pressure-sensitive adhesive composition according to the third embodiment contains a structural part derived from a (meth) acrylic acid ester monomer and a structural part derived from a hydroxyl group- (Meth) acrylic acid ester polymer having a content of a hydroxyl group-containing vinyl monomer in a range of 1 to 20% by weight, based on the total amount of the monomer components in the copolymerization, and (meth) And a second (meth) acrylic acid ester polymer containing a structural part derived from the carboxyl group-containing vinyl monomer and a structural part derived from the carboxyl group-containing vinyl monomer.

Here, the first (meth) acrylic acid ester polymer and the second (meth) acrylic acid ester polymer commonly have a structural moiety derived from a (meth) acrylic acid ester monomer.

As such a (meth) acrylic acid ester monomer, it is preferable to use a (meth) acrylic acid ester monomer whose alkyl group has a carbon number of 1 to 20.

As the type of the (meth) acrylic acid ester monomer in which the number of carbon atoms of the alkyl group is in the range of 1 to 20, it is preferable to use the same one as described in the first embodiment.

Since the (meth) acrylic acid ester monomer in the first and second (meth) acrylic acid ester polymers is a main component constituting these polymers, usually 50% by weight or more of the total monomers constituting the (meth) acrylic acid ester polymer, By weight, more preferably within a range of 60 to 99% by weight, and still more preferably within a range of 80 to 98% by weight.

In the first (meth) acrylic acid ester polymer, it is particularly preferable that the (meth) acrylic acid ester monomer be 92 to 97% by weight of the total monomer constituting the (meth) acrylic acid ester polymer, In the acrylic acid ester polymer, it is particularly preferable that the (meth) acrylic acid ester monomer accounts for 85 to 93% by weight of the total monomer constituting the (meth) acrylic acid ester monomer.

In the pressure-sensitive adhesive composition according to the third embodiment, the first (meth) acrylic acid ester polymer is preferably a copolymer of a vinyl monomer having a hydroxyl group in the molecule (a (meth) acrylic acid An ester monomer).

This is because, by introducing a predetermined amount of a vinyl monomer having a hydroxyl group in the molecule, both the good antistatic property and the durability under a predetermined environment can be effectively achieved, and the adhesive force can be easily controlled.

Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) (Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, or allyl alcohol, Can be preferably used.

In the pressure-sensitive adhesive composition as the third embodiment, it is preferable that the content of the hydroxyl group-containing vinyl monomer in the first (meth) acrylic acid ester polymer is in the range of 1 to 20 wt% relative to the total amount of the monomer components in the copolymerization thereof To be a value within a predetermined range.

The reason for this is that when the content of the hydroxyl group-containing vinyl monomer is less than 1% by weight, the effect of addition is not exhibited, and furthermore, it becomes difficult to thermally crosslink with an isocyanate-based crosslinking agent or the like to obtain a durable pressure- This is because there are cases.

On the other hand, when the content of the hydroxyl group-containing vinyl monomer is more than 20% by weight, the content of the (meth) acrylic acid ester monomer whose relative number of carbon atoms in the alkyl group is in the range of 1 to 20 is decreased, , And the optical properties and durability of the resulting pressure-sensitive adhesive composition tend to decrease.

Therefore, the content of the hydroxyl group-containing vinyl monomer is more preferably within a range of from 2 to 10% by weight, more preferably from 3 to 8% by weight based on the total amount of the monomer components in copolymerizing the first (meth) acrylic acid ester polymer %. ≪ / RTI >

On the other hand, the second (meth) acrylic acid ester polymer is characterized by containing, as a copolymerization component of the (meth) acrylic acid ester polymer, a vinyl monomer having a carboxyl group in the molecule.

This is because, by introducing a predetermined amount of a vinyl monomer having a carboxyl group into a molecule, the durability under a predetermined condition becomes good, and when a heat crosslinking agent is used, the crosslinking reaction by the vinyl monomer can be promoted.

Examples of such vinyl monomers having a carboxyl group in the molecule include acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and the like.

In view of compatibility with the (meth) acrylic acid ester monomer, acrylic acid or methacrylic acid is particularly preferable.

In the second (meth) acrylic acid ester polymer, the content of the carboxyl group-containing vinyl monomer is preferably within a range of 1 to 30% by weight based on the total amount of the monomer components in the copolymerization thereof.

This is because if the content of the carboxyl group-containing vinyl monomer is less than 1% by weight, the durability may be lowered.

On the other hand, when the content of the carboxyl group-containing vinyl monomer is more than 30% by weight, the adhesive force becomes too high, and the re-peeling property becomes worse or the content of the (meth) acrylic acid ester monomer having the alkyl group in the range of 1 to 20 Resulting in a decrease in compatibility between the copolymerization components and a tendency that the optical properties and durability of the obtained pressure sensitive adhesive are likely to be lowered.

Therefore, the content of the carboxyl group-containing vinyl monomer is more preferably in the range of 3 to 15% by weight, more preferably 7 to 12% by weight based on the total amount of the monomer components in the copolymerization of the second (meth) acrylic acid ester polymer %. ≪ / RTI >

It is also preferable that the first (meth) acrylic acid ester polymer and the second (meth) acrylic acid ester polymer contain a copolymerization component other than the above-mentioned monomer in a predetermined amount.

Examples of such a copolymerization component include acrylamides such as acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-methylol acrylamide and N-methylol methacrylamide; (Meth) acrylic acid monoalkylaminoalkyl such as (meth) acrylic acid monomethylaminoethyl, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate and monoethylaminopropyl (meth) (Meth) acrylic acid esters containing an aliphatic ring such as cyclohexyl; (Meth) acrylic acid esters containing an aromatic ring such as phenyl (meth) acrylate, and the like.

When the above-mentioned copolymerizable component is contained, the content of the copolymerizable component is not particularly limited so long as it does not impair the effect of the present invention. Is preferably less than 20% by weight based on the total amount of the components.

Incidentally, the content of the monomer component in the above-mentioned (meth) acrylic acid ester polymer means the theoretical value calculated from the amount of the monomers constituting each constituent unit.

The copolymerization type is not particularly limited, and may be a random, block or graft copolymer.

(2) Equivalent ratio

In the pressure-sensitive adhesive composition according to the third embodiment, when the amount of the hydroxyl group in the first (meth) acrylic acid ester polymer is H1 and the amount of the carboxyl group in the second (meth) acrylic acid ester polymer is C1, / H1 is set to a value within a range of 0.01 to 1.0.

The reason for this is that when the equivalent ratio is less than 0.01, there is a case where the adhesive force in the case of using a pressure-sensitive adhesive as a light curing agent is markedly lowered or the durability under a predetermined environment becomes insufficient.

On the other hand, when the equivalent ratio exceeds 1.0, the adhesive strength becomes too high in the case of using a pressure-sensitive adhesive as a photo-curing agent, resulting in insufficient releasability and too high a surface resistivity in the pressure-sensitive adhesive layer, It may be difficult to sufficiently suppress the temperature of the liquid.

Therefore, the equivalence ratio represented by C1 / H1 is more preferably within a range of 0.1 to 0.8, and still more preferably within a range of 0.3 to 0.6.

Next, the relationship between the equivalent ratio expressed by C1 / H1 and the surface resistivity and adhesive force of the pressure-sensitive adhesive made by photo-curing the pressure-sensitive adhesive composition will be described with reference to Fig.

That is, in FIG. 5, the abscissa indicates the ratio of the number of hydroxyl groups in the first (meth) acrylic acid ester polymer to the number of carboxyl groups in the second (meth) acrylic acid ester polymer, (Ω / □) in a pressure-sensitive adhesive obtained by photo-curing the obtained pressure-sensitive adhesive composition at the left ordinate and the equivalent ratio (-) represented by the following formula (N / 25 mm) after 14 days of adhesion to a glass surface of a pressure-sensitive adhesive made by photo-curing (in accordance with Examples 30, 32 and 37).

Details of the pressure-sensitive adhesive composition, the photo-curing conditions, and the measurement conditions of the surface resistivity and the adhesive force are described in Examples.

In such characteristic curves A and B, the surface resistivity and the adhesive force in the pressure-sensitive adhesive made by photo-curing the pressure-sensitive adhesive composition tend to increase as the value of C1 / H1 increases.

Taking this tendency into consideration, it is necessary to set the value of C1 / H1 within a predetermined range from the viewpoint of suppressing the generation of static electricity, and from the viewpoint of maintaining a predetermined adhesive force, the value of C1 / Value is required.

More specifically, when the value of C1 / H1 is less than 0.01, the adhesive strength may be cut off to 0.1 N / 25 mm, and when used in an adhesive sheet such as an optical film, problems such as peeling may occur have.

On the other hand, when the value of C1 / H1 exceeds 1.0, the surface resistivity may exceed 1 10 ¹² ? / ?. When the adhesive sheet such as an optical film is peeled off from the adherend, It may be difficult to stably inhibit the occurrence or the adhesive force may exceed 50 N / 25 mm, which may result in insufficient releasability.

Therefore, in the characteristic curves A and B, it is understood that the equivalence ratio expressed by C1 / H1 should be a value within the range of 0.01 to 1.0.

(3) Mixing ratio

The mixing ratio of the first (meth) acrylic acid ester polymer constituting the (meth) acrylic acid ester polymer serving as the component (A) to the first (meth) acrylic acid ester polymer / second (meth) acrylic acid ester polymer It is preferable to set the blending ratio (weight basis) to be displayed within the range of 99/1 to 60/40.

This is because if the compounding ratio is larger than 99/1, the durability under a predetermined environment may become insufficient.

On the other hand, if the compounding ratio is smaller than 60/40, the adhesive strength becomes too high in the case of using a pressure-sensitive adhesive as a photo-curing agent, and the re-peeling property may become insufficient.

Therefore, in forming the (meth) acrylic acid ester polymer which is the component (A), the compounding ratio (by weight) expressed by the first (meth) acrylic acid ester polymer / the second (meth) acrylic acid ester polymer is from 96/4 to 80 / More preferably within the range of 20/20 to 20/90, and still more preferably within the range of 93/7 to 88/12.

(4) Weight average molecular weight

The weight average molecular weights of the first and second (meth) acrylic acid ester polymers constituting the (meth) acrylic acid ester polymer as the component (A), as described in the first embodiment, It is preferable to set the value within the range of only "

2. Component (B): Antistatic agent

The component (B) relates to the kind, content, and dispersion aid, and can be as described in the first embodiment.

Using FIG. 6, the relationship between the content of potassium bis (fluorosulfonyl) imide and the surface resistivity and adhesive force of the pressure-sensitive adhesive made by photo-curing the pressure-sensitive adhesive composition will be described.

6, the abscissa indicates the content (weight) of potassium bis (fluorosulfonyl) imide relative to 100 parts by weight of the (meth) acrylic acid ester polymer (total amount of the first and second (meth) acrylic acid ester polymers) (Ω / □) in a pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition obtained by taking the pressure-sensitive adhesive composition obtained in Example 1 (N / 25 mm) at 14 days after the kneading to the surface of the substrate (in accordance with Examples 31 to 34).

Details of the pressure-sensitive adhesive composition, the photo-curing conditions, and the measurement conditions of the surface resistivity and the adhesive force are described in Examples.

First, in the characteristic curve (A), the surface resistivity of a pressure-sensitive adhesive obtained by photo-curing a pressure-sensitive adhesive composition tends to decrease as the content of potassium bis (fluorosulfonyl) imide increases.

On the other hand, in the characteristic curve (B), the adhesive force in the pressure-sensitive adhesive made by photo-curing the pressure-sensitive adhesive composition tends to decrease very slowly as the content of potassium bis (fluorosulfonyl) imide increases.

From the viewpoint of suppressing the generation of static electricity, it is preferable to increase the content of potassium bis (fluorosulfonyl) imide to reduce the value of the surface resistivity, while maintaining the predetermined adhesion force It is understood that the content of potassium bis (fluorosulfonyl) imide needs to be limited to a predetermined value or less.

More specifically, when the content of potassium bis (fluorosulfonyl) imide is less than 0.05 part by weight, there is a possibility that the surface resistivity of the pressure sensitive adhesive exceeds 1 x 10 ¹² ? / ?.

On the other hand, when the content of potassium bis (fluorosulfonyl) imide exceeds 15 parts by weight, it is difficult to stably maintain the adhesive force of the pressure-sensitive adhesive at a predetermined value or more, for example, 0.1 N / mm or more There is a possibility that problems such as peeling may occur when used in an optical film or the like.

Therefore, in the characteristic curves A and B, it is preferable that the content of potassium bis (fluorosulfonyl) imide is within a range of 0.05 to 15 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer .

6 shows an example of potassium bis (fluorosulfonyl) imide. However, it has been found that a characteristic curve showing the same tendency is obtained for other prescribed potassium / fluorine-containing sulfonylimide salts.

3. Component (D): Photocuring component

The pressure-sensitive adhesive composition according to the third embodiment is characterized by containing a photo-curable component as the component (D).

This is because the inclusion of such a photo-curable component can control the adhesive force and storage elastic modulus when the pressure-sensitive adhesive composition is photo-cured by using a pressure-sensitive adhesive, to a more favorable range, and shorten the seasoning period.

Accordingly, the change in the adhesive property due to the aging (time) is reduced, and more excellent durability can be obtained.

(1) Type

Examples of such photocurable components include polyfunctional (meth) acrylate-based monomers having a weight average molecular weight of less than 1000, acrylate oligomers, and acrylate-based polymers having a group having a (meth) acryloyl group introduced into the side chain Etc. are commonly used.

As the concrete kind of the photo-curing component, the same as described in the first embodiment is suitably used. In particular, as the polyfunctional (meth) acrylate monomer, a cyclic structure, for example, carbon It is preferable to use a polyfunctional (meth) acrylate-based monomer having a cyclic structure and a cyclic structure or a cyclic structure.

More specifically, examples thereof include those having an isocyanurate structure such as di (meth) acryloxyethylisocyanurate and tris (meth) acryloxyethylisocyanurate, and those having an isocyanurate structure such as dimethylolcyclohexane di Acrylate, neopentyl glycol-modified trimethylolpropane di (meth) acrylate, adamantanedi (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol di And the like, and particularly preferably has an isocyanurate structure.

(2) Content

The content of the photocurable component as the component (D) is preferably within a range of 1 to 25 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A).

This is because when the content of the photo-curing component is less than 1 part by weight, it becomes difficult to improve the adhesive strength and the storage elastic modulus when it is used as a pressure-sensitive adhesive. On the other hand, when the content of the photo-curable component exceeds 25 parts by weight, it is difficult to maintain the optical properties when the adhesive is used as a pressure-sensitive adhesive, thereby making it difficult to apply the composition to an optical film It is because.

Accordingly, the content of the photo-curable component is more preferably in the range of 5 to 20 parts by weight, more preferably 10 to 15 parts by weight, relative to 100 parts by weight of the (meth) acrylic acid ester polymer .

(3) Photopolymerization initiator

In order to cure the photocurable component (D) with ultraviolet rays or the like, it is preferable to add a photopolymerization initiator for initiating the reaction.

As such a photopolymerization initiator, those similar to those described in the first embodiment can be used.

The content of the photopolymerization initiator is preferably within a range of 1 to 30 parts by weight based on 100 parts by weight of the photocurable component as described in the first embodiment.

In the case of ultraviolet curing or the like, a photopolymerization initiator is used in order to more quickly and surely cure. However, in the case of electron curing or the like, since the energy level is high, the photopolymerization initiator can be omitted or reduced as much as possible.

4. Component (C): Crosslinking agent

Further, the pressure-sensitive adhesive composition according to the third embodiment preferably contains a crosslinking agent as the component (C).

The reason for this is that by containing a cross-linking agent, the adhesive force and storage elastic modulus when the pressure-sensitive adhesive composition is cured to form a pressure-sensitive adhesive can be adjusted to a more favorable range.

That is, by adding a crosslinking agent, it is possible to chemically crosslink the (meth) acrylic acid ester polymers with each other by reacting with a hydroxyl group or a carboxyl group of the (meth) acrylic acid ester polymer.

In addition, if it is a crosslinking agent, adhesion between the pressure-sensitive adhesive obtained by photo-curing the pressure-sensitive adhesive composition and an adherend can be improved.

The kind of the cross-linking agent is not particularly limited, but the same cross-linking agent as described in the first embodiment can be used.

The content of the crosslinking agent as the component (C) is preferably from 0.01 to 10 parts by weight per 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A), as described in the first embodiment .

[Fourth Embodiment]

A fourth embodiment of the present invention is a pressure-sensitive adhesive which is formed as a pressure-sensitive adhesive through a process including the following steps (1) to (3).

(1) A pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer as component (A) and an antistatic agent as component (B), wherein the antistatic agent as the component (B) is a fluorine-containing sulfonylimide salt And a pressure-sensitive adhesive composition whose content is within a range of 0.05 to 15 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A)

(2) a step of applying a pressure-sensitive adhesive composition to a release film to form a pressure-sensitive adhesive composition layer

(3) a step of curing the pressure-sensitive adhesive composition layer to form a pressure-sensitive adhesive layer

Hereinafter, a fourth embodiment of the present invention will be described in detail with reference to the drawings appropriately.

1. Process (1) (preparation process of pressure-sensitive adhesive composition)

The step (1) is a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester polymer as the component (A) and an antistatic agent as the component (B), wherein the antistatic agent as the component (B) is a fluorine- Sensitive adhesive composition in which the content is in the range of 0.05 to 15 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A).

More specifically, for example, it is preferable to prepare a dispersion of the component (B) by adding a fluorine-containing sulfonylimide salt as a predetermined cationic potassium salt to a solvent such as ethyl acetate with stirring.

Subsequently, it is preferable to dilute the component (A) with a diluting solvent as desired and drop the dispersion of the obtained component (B) under stirring to obtain a homogeneous mixed solution.

Subsequently, to the obtained mixed solution, other additives such as the component (C), the component (D) and the dispersing aid are added according to the demand, and the mixture is stirred until homogeneous, It is preferable to obtain a solution of the pressure-sensitive adhesive composition by further adding a solvent.

2. Process (2) (Application step of pressure-sensitive adhesive composition)

Step (2) is a step of forming a coating layer (1) by applying a pressure-sensitive adhesive composition to a release film (2) as shown in Fig. 1 (a).

Examples of such a release film include a polyester film such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; a polyolefin film such as polypropylene and polyethylene; and a silicone resin, a fluororesin, and an alkyd resin And a release agent is applied to provide a release layer.

It is preferable that the thickness of the release film is in the range of usually 20 to 150 mu m.

Examples of the method of applying the pressure-sensitive adhesive composition on the release film include a pressure-sensitive adhesive composition in which a solvent is added using a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, To form a coating layer (coating film), followed by drying.

At this time, the thickness of the coating layer is preferably in the range of 1 to 100 mu m at the time of drying, more preferably in the range of 5 to 50 mu m.

The drying conditions are usually 50 to 150 占 폚, preferably 10 to 10 minutes.

This is because if the thickness of the coating layer is too thin, sufficient adhesion property may not be obtained, and conversely, if it is too thick, the residual solvent may be a problem.

3. Process (3) (Curing Process of Coating Layer)

Step (3) is a step of curing the applied layer of the pressure-sensitive adhesive composition to form a pressure-sensitive adhesive layer.

That is, as shown in Fig. 1 (b), the substrate 101 such as an optical film substrate is cured in the state of being laminated on the surface of the coated layer 1 in a dried state on the peeling film 2, Layer 10 is preferable.

Hereinafter, the photocuring step and the seasoning step will be described separately.

(1) Photocuring process

The photo-curing step is a step of curing a photo-curing component, for example, a polyfunctional (meth) acrylate-based monomer or the like, contained in the pressure-sensitive adhesive composition.

More specifically, as shown in Fig. 7 (c), a step of irradiating an active energy ray to cure the coating layer 1 applied to the release film 2 to form a pressure-sensitive adhesive layer 10 .

The irradiation of the active energy ray is preferably carried out without delay after the pressure-sensitive adhesive composition is coated on the release film, dried and laminated. This is because the photocuring component may be phase-separated from other components in the coating layer of the pressure-sensitive adhesive composition formed on the peeling film over time.

Examples of such active energy rays include ultraviolet rays and electron beams.

The ultraviolet ray can be obtained by a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, a metal halide lamp or the like, and an electron beam can be obtained by an electron beam accelerator or the like.

It is also preferable to irradiate the active energy ray within the range of 50 to 1000 mJ / cm ² .

This is because, when the irradiation amount of the active energy ray is less than 50 mJ / cm ² , it becomes difficult to sufficiently perform the reaction between the photo-curable components, and it becomes difficult to obtain the desired adhesive property. On the other hand, when the irradiation amount of the active energy ray exceeds 1000 mJ / cm ² , the pressure-sensitive adhesive or the substrate may be destroyed.

Therefore, it is more preferred to be investigated are preferred, and active energy ray of 120~500mJ / cm ² than that for a pressure-sensitive adhesive composition, irradiating with an active energy beam of 100~700mJ / cm ^2.

It is also preferable that the active energy ray is irradiated from the side of the release film 2 as shown in Fig. 7 (c).

This is because the irradiation can be performed efficiently without damaging the substrate such as the polarizing plate.

(2) Seasoning process

The seasoning process is carried out when the pressure-sensitive adhesive composition contains a heat-crosslinking agent such as an isocyanate-based crosslinking agent.

That is, from the viewpoint of increasing the cohesive strength of the pressure-sensitive adhesive layer to be formed by crosslinking the components (A), it is preferable to form a pressure-sensitive adhesive composition with a heat crosslinking agent and provide a seasoning process.

More specifically, the base material is laminated on the surface of the applied layer of the pressure-sensitive adhesive composition in a dried state on the release film, and the pressure-sensitive adhesive layer is formed in a state in which the base material is laminated by taking a seasoning period.

The temperature of the seasoning process is preferably 20 to 50 占 폚, more preferably 23 to 30 占 폚, from the viewpoint of not damaging the pressure-sensitive adhesive or the base material, and uniformly curing the pressure-

The humidity is preferably 30 to 75% RH, and more preferably 45 to 65% RH.

The seasoning period is preferably 3 to 20 days, more preferably 5 to 14 days.

The thermal crosslinking in the coating layer of the pressure-sensitive adhesive composition is carried out through the above-described drying step and the seasoning step.

4. Adhesive Properties

(1) Storage modulus

Further, in the case of a pressure-sensitive adhesive made by curing the pressure-sensitive adhesive composition according to the first and second embodiments, the storage elastic modulus G 'at 23 캜 is preferably set within a range of 0.01 to 0.8 MPa.

This is because by setting the storage elastic modulus G 'within this range, the durability under a predetermined environment can be improved more effectively.

That is, when the storage elastic modulus G 'is less than 0.01 MPa, it may be difficult to sufficiently improve the durability under a predetermined environment. On the other hand, when the storage elastic modulus G 'exceeds 0.8 MPa, it may become difficult to obtain a desired adhesive force.

Therefore, the storage elastic modulus G 'at 23 캜 is more preferably in the range of 0.05 to 0.75 MPa, and still more preferably in the range of 0.10 to 0.29 MPa.

In the case of a pressure-sensitive adhesive obtained by curing a pressure-sensitive adhesive composition according to the third embodiment, the storage elastic modulus G 'at 23 캜 is preferably within a range of 0.1 to 10 MPa, and more preferably within a range of 0.3 to 5 MPa And more preferably in the range of 0.45 to 3 MPa.

As a method of measuring the storage elastic modulus G ', for example, the storage elastic modulus G' of a test piece can be measured using the twist shear method according to JIS K7244-6 under the following conditions.

Frequency: 1Hz

Temperature: 23 ° C

(2) Adhesion

In addition, it is preferable that the adhesive force of the pressure-sensitive adhesive after 1 day of application to the adherend (glass surface) and after 14 days of application is within the range of 0.1 to 50 N / 25 mm.

This is because if the adhesive force is less than 0.1 N / 25 mm, the durability under certain conditions may become insufficient. On the other hand, when the adhesive force exceeds 50 N / 25 mm, the re-peeling property may excessively decrease.

Therefore, the adhesive force of the pressure-sensitive adhesive is more preferably in the range of 0.5 to 40 N / 25 mm, and more preferably in the range of 1 to 30 N / 25 mm.

The method for measuring the adhesive force will be described in Examples.

(3) Surface resistivity

It is also preferable that the surface resistivity of the pressure-sensitive adhesive is set to a value within a range of 1 x 10 ^{7 to} 1 x 10 ¹² ? / ?.

This is because if the surface resistivity is less than 1 × 10 ⁷ Ω / □, the durability and optical properties may deteriorate due to secondary agglomeration of component (B).

On the other hand, when the surface resistivity exceeds 1 x 10 < ¹² > OMEGA / & squ &, it sometimes becomes difficult to stably suppress the generation of static electricity when the adhesive sheet is peeled from the adherend.

Therefore, the surface resistivity of the pressure-sensitive adhesive is more preferably in the range of 5 x 10 ^{7 to} 5 x 10 ¹¹ ? /?, More preferably in the range of 1 x 10 ^{8 to} 1 x 10 ¹¹ ? / More preferable.

The method of measuring the surface resistivity will be described in Examples.

[Fifth Embodiment]

A fifth embodiment of the present invention is a pressure-sensitive adhesive sheet comprising a substrate and a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive described above.

Hereinafter, the fifth embodiment of the present invention will be described in detail with reference to the drawings mainly on the points different from the first to fourth embodiments.

1. Equipment

In the present invention, it is preferable that the base material is an optical film base, and that at least one side of the optical film base is provided with a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive described in the fourth embodiment.

As shown in Figs. 1 and 7, the base material 101 in the adhesive sheet 100 of the present invention is not particularly limited, and examples thereof include polyvinyl alcohol, polyethylene terephthalate, triacetylcellulose, polycarbonate , Liquid crystal polymers, cycloolefins, polyimides, polyamides, polyamideimides, polyphenylene ethers, polyether ketones, polyether ether ketones, polysulfones, polyethersulfone, polyphenylsulfides, polyarylates, And an optical film base such as an alicyclic structure-containing polymer and an aromatic polymer.

From the point of view of use, an optical film substrate used for a liquid crystal display such as a polarizing plate, a polarizing layer protective film, a viewing angle increasing film, an antiglare film, a retardation plate and the like is preferable.

For example, according to the present invention, it is possible to obtain an advantage that the occurrence of light leakage can be effectively suppressed even when the substrate is made of a polarizing plate.

Further, according to the present invention, since the polarizer can be adhered well to a polarizer or the like, the polarizer itself produced by stretching an iodine-containing polyvinyl alcohol resin as a raw material of a polarizer can be also used as a base material 101). A polarizer in which one surface of the polarizer is covered with a protective film such as triacetylcellulose or polyethylene terephthalate is also an object.

The pressure-sensitive adhesive sheet in the case of using a substrate as a polarizer may be referred to as a polarizer with a pressure-sensitive adhesive layer.

The thickness of the base material is not particularly limited, but is preferably a value within a range of usually 1 to 1000 占 퐉.

The reason for this is that when the thickness of the substrate is less than 1 탆, the mechanical strength and handleability may be excessively decreased, or it may become difficult to form the film with a uniform thickness. On the other hand, if the thickness of the base material exceeds 1000 mu m, the handling property may be excessively lowered or economically disadvantageous.

Therefore, the thickness of the substrate is more preferably in the range of 5 to 500 mu m, and more preferably in the range of 10 to 200 mu m.

In the case where the base material is a release film, it is preferable to set the value within a range of usually 20 to 150 mu m.

It is also preferable that the surface of the substrate 101 on which the coating layer is formed is subjected to surface treatment.

Examples of such a surface treatment include primer treatment, corona treatment, and flame treatment. Among them, primer treatment is particularly preferable.

This is because the adhesion of the pressure-sensitive adhesive layer to the substrate can be further improved by using the substrate having such a primer layer formed thereon.

Examples of the material constituting such a primer layer include cellulose ester (for example, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose nitrate, and combinations thereof), polyacryl, polyurethane, polyvinyl alcohol , Polyvinyl ester, polyvinyl acetal, polyvinyl ether, polyvinyl ketone, polyvinyl carbazole, polyvinyl butyral, and combinations thereof.

The thickness of the primer layer is not particularly limited, but is preferably set to a value within a range of 0.05 탆 to 10 탆.

2. Adhesive layer

The pressure-sensitive adhesive layer 10 in the pressure-sensitive adhesive sheet 100 of the present embodiment is characterized by being a pressure-sensitive adhesive layer comprising a specific pressure-sensitive adhesive described as the fourth embodiment.

The concrete contents of such a pressure-sensitive adhesive can be as already described in the fourth embodiment, and a description thereof will be omitted.

The thickness of the pressure-sensitive adhesive layer 10 is preferably within a range of 1 to 100 mu m.

The reason for this is that by setting the thickness of the pressure-sensitive adhesive layer within this range, the pressure-sensitive adhesive properties such as desired adhesive force and storage elastic modulus can be more stably exhibited. That is, when the thickness is less than 1 占 퐉, it becomes difficult to develop a desired adhesive force, and defects such as mangling and peeling may easily occur.

On the other hand, when the thickness exceeds 100 mu m, defects such as contamination of an adherend or residual pool may easily occur.

Accordingly, the thickness of the pressure-sensitive adhesive layer is more preferably in the range of 5 to 70 mu m, and more preferably in the range of 10 to 50 mu m.

As a method for forming a pressure-sensitive adhesive layer on a base material such as an optical film base material, as shown in Figs. 1A to 1C and Figs. 7A to 7C, The surface of the layer 1 free from the release film 2 is directly laminated to the base material 101 such as an optical film base material and then cured to form a base material such as an optical film base material It is preferable to obtain the pressure-sensitive adhesive sheet 100a.

Alternatively, the pressure-sensitive adhesive composition applied on the release film may be cured first to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive composition may be laminated on a substrate such as an optical film base.

It is also preferable that the base material is a release film and another release film is laminated on the opposite side of the release film in the pressure-sensitive adhesive layer.

That is, the pressure-sensitive adhesive composition is coated on the release film 2 and dried to form the coating layer 1 shown in Fig. Here, in place of the substrate 101 shown in Fig. 7, a separate peeling film 2 is laminated on the coating layer 1. Fig.

Thereafter, as shown in Fig. 7 (c), the release film 2 is cured on both sides of the pressure-sensitive adhesive layer 10 shown in Fig. 8 by curing under the same conditions as in the fourth embodiment, Sensitive adhesive sheet 100b.

It is preferable that both of the surfaces of the both sides of the release film 2 in contact with the pressure-sensitive adhesive layer 10 are peeled off.

It is also preferable that the peeling force in one of the two peeling films is different from the peeling force in the other.

The reason for this is that, when the obtained pressure-sensitive adhesive sheet is used, the pressure-sensitive adhesive layer can be peeled off without damaging the pressure-sensitive adhesive layer.

Further, in the pressure-sensitive adhesive sheet of this embodiment, a pressure-sensitive adhesive sheet having a substrate such as an optical film base can be obtained by peeling one of the release films and bonding the resulting pressure-sensitive adhesive layer to a base material such as an optical film base material and bonding them.

At this time, surface treatment such as a corona treatment, a plasma treatment, and a saponification treatment can be performed on the pressure-sensitive adhesive layer side or the substrate side of the optical film base material.

Such an aspect is necessary in the case of manufacturing a pressure sensitive adhesive, and in the case where the pressure sensitive adhesive should be transported only due to reasons such as the use of the pressure sensitive adhesive in a separate place or the like.

As a method for bonding the obtained optical film to an adherend, as shown in Figs. 1 (c) to (d) and 7 (a) to (d) It is preferable that the film 2 is peeled off and then the surface of the pressure-sensitive adhesive layer 10 shown in the figure is adhered to the adherend.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples.

[Examples 1 to 14 and Comparative Example 1]

1. Preparation of pressure-sensitive adhesive composition

As shown in Table 1, each component was mixed at a predetermined ratio to prepare a pressure-sensitive adhesive composition.

The content of each component in Table 1 is shown below. The numerical values in the table indicate values converted to solid contents.

(1) (meth) acrylic acid ester polymer

BA / HEA / AA (98.5 / 0.5 / 1) Mw = 1.7 million

98.5 parts by weight of butyl acrylate (BA), 0.5 part by weight of 2-hydroxyethyl acrylate (HEA) and 1 part by weight of acrylic acid (AA) were polymerized in accordance with a conventional method to obtain (meth) acrylic acid ester To obtain a polymer.

The obtained (meth) acrylic acid ester polymer was a 20% by weight ethyl acetate solution.

BA / HEA / AA (97.5 / 0.5 / 2) Mw = 1.7 million

BA / HEA / AA (96.5 / 0.5 / 3) Mw = 1.7 million

BA / HEA / AA (95.5 / 0.5 / 4) Mw = 1.7 million

BA / HEA / AA (94.5 / 0.5 / 5) Mw = 1.7 million

BA / HEA (99/1) Mw = 1.7 million

BA / HEA (98.5 / 0.5) Mw = 1.7 million

BA / HEA (95/5) Mw = 1.7 million

BA / AA (99/1) Mw = 170 million

BA / AA (95/5) Mw = 170 million

BA / AA (90/10) Mw = 170 million

Was obtained in the same manner as BA / HEA / AA (98.5 / 0.5 / 1), except that the polymerization ratio of butyl acrylate, 2-hydroxyethyl acrylate and acrylic acid was changed in the ratio in parentheses.

The same is true for the dilution when adjusting the pressure-sensitive adhesive composition.

(2) Alkali metal salts

KFSI: potassium bis (fluorosulfonyl) imide

LiTFSI: Lithium bistrifluoromethanesulfoniumimide < RTI ID = 0.0 >

(3) Dispersing agent

TG: tetraethylene glycol dimethyl ether

· Ethyl acetate

Polyether polyol: polyoxyethylene glycol-polyoxypropylene glycol block copolymer

· Adipic acid ester

(4) polyfunctional acrylate monomer

· Tris (acryloxyethyl) isocyanurate

(Aronix M-315, manufactured by Toagosei Co., Ltd.)

(5) Photopolymerization initiator

Benzophenone / 1-hydroxycyclohexyl phenyl ketone = 1/1 (weight ratio)

(Irgacure 500, manufactured by Chiba Specialty Chemicals Co., Ltd.)

(6) Isocyanate-based crosslinking agent

· Trimethylol propane adduct Toluene diisocyanate

(Coronate L, Mw: 657, solid content 75%, manufactured by Nippon Polyurethane Industry Co., Ltd.)

(7) Silane coupling agent

KBE9007: 3-isocyanate propyl triethoxysilane

(KBE9007, manufactured by Shin-Etsu Chemical Co., Ltd.)

KBM403: 3-glycidoxypropyltrimethoxysilane

(KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.)

The weight average molecular weight of the (meth) acrylic acid ester polymer was measured by a gel permeation chromatography method (hereinafter abbreviated as GPC method).

That is, first, a calibration curve was prepared using polystyrene. Hereinafter, the weight average molecular weight is represented by a polystyrene reduced value.

Then, (meth) the concentration of the object to be measured, such as acrylic ester polymer to prepare a tetrahydrofuran (THF) solution of 1% by weight, Tosoh Corporation (Ltd.), GEL PERMEATION CHROMATOGRAPH HLC-8020 (TSK _GEL GMH _XL, TSK _GEL GMH _XL , and TSK _GEL G2000 _HXL ), the weight average molecular weight was measured at 40 ° C in a THF solvent at 1 ml / min.

As a guard column, TSK GUARD COLUMN made by TOSOH CORPORATION was used.

2. Coating process of pressure-sensitive adhesive composition

Subsequently, toluene was added to a release layer of a polyethylene terephthalate release film (SP-PET3811, manufactured by LINTEC CORPORATION) having a thickness of 38 mu m as a release film to dilute the pressure-sensitive adhesive composition so as to have a solid content of 15 wt% Was 25 占 퐉, using a knife-type coater.

Subsequently, the film was subjected to a drying treatment at 90 占 폚 for 1 minute, and then laminated on a polarizing plate having a thickness of 180 占 퐉.

3. Curing of the pressure-sensitive adhesive composition layer

(1) Thermal curing (curing period)

Subsequently, the coated layer of the pressure-sensitive adhesive composition obtained as described above and the laminate composed of the polarizing plate were left (seasoned) under the conditions of 23 ° C and 50% RH for 14 days to thermally crosslink the pressure-sensitive adhesive composition sufficiently To obtain a pressure-sensitive adhesive sheet with a pressure-sensitive adhesive layer of Example 1.

(2) Photocuring

In Examples 12 and 13, a polyfunctional acrylate-based monomer as a photo-curable component and a photo-polymerization initiator were contained. Therefore, photo-curing was carried out before the thermal curing described above.

That is, ultraviolet rays (UV) were irradiated from the side of the release film of the polarizing plate with a pressure-sensitive adhesive composition layer under the following conditions and photo-cured.

Lamp: High-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.)

Light quantity: 300 mJ / cm ²

Illumination: 300 mW / cm ²

UV light intensity and illuminometer: UVF-PFA1 (manufactured by EI Graphics Corporation)

4. Evaluation

(1) Evaluation of cohesion

The adhesive force of the polarizing plate with a pressure-sensitive adhesive after one day and fourteen days after bonding to the adherend (glass surface) was measured.

That is, the obtained polarizer with a pressure-sensitive adhesive layer was cut into a size of 25 mm in width × 100 mm in length using a cutting device (Super Cutter, manufactured by Oginosei Shoji Co., Ltd.) to produce a sample.

Then, the release film was peeled from the obtained sample, and the pressure-sensitive adhesive layer side of the sample was bonded to a non-alkali glass (Eagle XG, manufactured by Corning Incorporated).

Subsequently, the alkali-free glass to which the sample was adhered was charged into an autoclave (manufactured by Kurarasa Seisakusho Co., Ltd.), pressurized at 0.5 MPa, 50 캜 for 20 minutes, % RH Under the environment for 24 hours (one day).

Subsequently, the sample was peeled off from the alkali-free glass under the following conditions using a tensile tester (Tensilon made by Orientec Co., Ltd.), and the adhesive strength was measured. The obtained results are shown in Table 2.

Peeling speed: 300 mm / min

Peeling angle: 180 °

Likewise, after the sample was bonded to an alkali-free glass, a solution of 50% R.H. The adhesive strength was measured when the sample was allowed to stand under the environment for 336 hours (14 days). The obtained results are shown in Table 2.

(2) Evaluation of durability

The durability of the polarizer with a pressure-sensitive adhesive under predetermined conditions was evaluated.

That is, the obtained polarizing plate with a pressure-sensitive adhesive layer was cut into a size of 233 mm x 309 mm using a cutting device (Super Cutter, manufactured by Oginose Seiko Co., Ltd.) to produce a sample.

Subsequently, the release film was peeled off from the obtained sample, and the pressure-sensitive adhesive layer side of the sample was bonded (bonded) to alkali-free glass (Eagle XG, manufactured by Corning Incorporated).

Subsequently, the alkali-free glass to which the sample was bonded was charged into an autoclave (manufactured by Kurarasa Seisakusho Co., Ltd.), pressurized at 5 kg / cm ² at 50 ° C for 20 minutes, / dry and 60 ° C / 90% RH, respectively, and left for 200 hours.

Then, the state of the sample was observed using a 10-fold loupe and evaluated according to the following criteria. The obtained results are shown in Table 2.

◎: No defect has occurred

?: No defects were observed at the sides of the outer peripheral edge (outer peripheral edge) of 0.6 mm or more at the four sides

?: Any one of the four sides has foam, stripe, or peeling of 0.6 mm or more from the outer peripheral edge

X: Foaming, stripe, and peeling of 1.0 mm or more from the outer peripheral edge occurred in any one of the four sides

(3) Evaluation of surface resistivity

The surface resistivity of the pressure-sensitive adhesive was measured in accordance with JIS K6911.

That is, the surface resistivity (? /?) Of the pressure-sensitive adhesive was measured under the following conditions. The obtained results are shown in Table 2.

Sample form: A pressure-sensitive adhesive formed in a sheet shape of 50 mm x 50 mm

Thickness of the pressure-sensitive adhesive: 25 탆

Measuring environment: 23 ± 2 ° C, 50 ± 2% R.H.

Measuring instrument: HIRESTA-UP MCP-HT450 manufactured by Mitsubishi Kagaku Co., Ltd.

Applied voltage: 100V

The value after 30 seconds from the start of measurement was taken as the surface resistivity (? /?).

[Table 1]

[Table 2]

[Example 15]

1. Preparation of pressure-sensitive adhesive composition

100 parts by weight of the (meth) acrylic acid ester polymer as the component (A), 2.5 parts by weight of the antistatic agent as the component (B), 0.5 parts by weight of the crosslinking agent as the component (C), and 0.2 parts by weight of the silane coupling agent . Separately from the predetermined potassium / fluorine-containing sulfonylimide salt, 2.5 parts by weight of a dispersion aid for improving the dispersibility was mixed with other components in the pressure-sensitive adhesive composition.

The numerical values in Table 1 indicate values converted to solid contents.

(1) For the component (A)

(Solvent: ethyl acetate (1: 1)) as a monomer component by using 98.5 parts by weight of butyl acrylate (BA), 0.5 part by weight of 2-hydroxyethyl acrylate (HEA), and 1 part by weight of acrylic acid ) To obtain a (meth) acrylic acid ester polymer having a weight average molecular weight of 170,000 as represented by the following component (A).

(A): BA / HEA / AA (98.5 / 0.5 / 1) Mw = 1.7 million

Subsequently, the obtained (meth) acrylic acid ester polymer was adjusted to a solid concentration by using an ethyl acetate solution to prepare a 20 wt% (meth) acrylic acid ester polymer solution.

The weight average molecular weight of the (meth) acrylic acid ester polymer was measured by a gel permeation chromatography method (hereinafter abbreviated as GPC method).

That is, first, a calibration curve was prepared using polystyrene. Hereinafter, the weight average molecular weight is represented by a polystyrene reduced value. Then, (meth) the concentration of the object to be measured, such as acrylic ester polymer to prepare a tetrahydrofuran (THF) solution of 1% by weight, Tosoh Corporation (Ltd.), GEL PERMEATION CHROMATOGRAPH HLC-8020 (TSK _GEL GMH _XL, TSK _GEL GMH _XL , and TSK _GEL G2000 _HXL ), the weight average molecular weight was measured at 40 ° C in a THF solvent at 1 ml / min. As a guard column, TSK GUARD COLUMN made by Tosoh Corporation was used.

(2) Potassium / fluorine-containing sulfonylimide salt and its dispersion preparation

As the component (B), the following potassium / fluorine-containing sulfonylimide salt was uniformly mixed in the (meth) acrylic acid ester polymer.

Further, the potassium / fluorine-containing sulfonylimide salt and the following dispersion auxiliary were separately mixed in the (meth) acrylic acid ester polymer.

Component (B): Potassium bis (fluorosulfonyl) imide (hereinafter sometimes referred to as KFSI)

Dispersion aid: tetraethylene glycol dimethyl ether (hereinafter sometimes referred to as TG)

(3) For component (C)

(Meth) acrylic acid ester polymer using the following compounds as the component (C).

Component (C): trimethylolpropane adduct Toluene diisocyanate (sometimes referred to as TMPTDI)

(Trade name: Coronate L, Mw: 657, solid content: 75%, manufactured by Nippon Polyurethane Industry Co., Ltd.)

(4) For silane coupling agent

As the silane coupling agent, the following compounds were used and mixed into the (meth) acrylic acid ester polymer.

Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (sometimes referred to as KBM403)

(KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.)

2. Application of pressure-sensitive adhesive composition

Subsequently, toluene was added to a release layer of a polyethylene terephthalate release film (SP-PET3811, manufactured by LINTEC CO., LTD.) Having a thickness of 38 mu m as a release film to dilute the pressure-sensitive adhesive composition so as to have a solid concentration of 15 wt% So that the thickness was 25 占 퐉.

Subsequently, the film was dried at 90 DEG C for 1 minute, and then laminated on a polarizing plate having a thickness of 180 mu m.

3. Seasoning of the pressure-sensitive adhesive composition

Subsequently, the coated layer of the pressure-sensitive adhesive composition obtained as described above and the laminate composed of the polarizing plate were left (seasoned) under the conditions of 23 ° C and 50% RH for 14 days to thermally crosslink the pressure-sensitive adhesive composition sufficiently To obtain a pressure-sensitive adhesive sheet with a pressure-sensitive adhesive layer of Example 15.

4. Evaluation

(1) Adhesion

The adhesive strength of the polarizing plate with a pressure-sensitive adhesive layer after 1 day and 14 days after bonding to an adherend was measured.

That is, the obtained polarizing plate with a pressure-sensitive adhesive layer was cut into a size of 25 mm in width × 100 mm in length using a cutting device (Super Cutter, manufactured by Oginosei Shoji Co., Ltd.), and a measurement sample was obtained.

Then, the release film was peeled off from the obtained measurement sample, and then the glass plate was bonded to alkali-free glass (Eagle XG, manufactured by Corning Incorporated).

Subsequently, an alkali-free glass to which the measurement sample was bonded was introduced into an autoclave (manufactured by Kuraray Seisakusho Co., Ltd.), and the mixture was pressurized at 0.5 MPa, 50 ° C for 20 minutes, 50% RH for one day.

Subsequently, the adhesive strength of the measurement sample was measured under the following conditions using a tensile tester (Tensilon made by Orientec Co., Ltd.).

Peeling speed: 300 mm / min

Peeling angle: 180 °

On the other hand, similarly, measurement of the adhesive strength was carried out in the case where the measurement sample was stuck to an alkali-free glass and then left under the conditions of 23 ° C and 50% RH for 14 days (336 hours).

The obtained results are shown in Table 4.

(2) Durability

The durability of the polarizing plate with a pressure-sensitive adhesive layer under predetermined conditions was evaluated.

That is, the obtained polarizing plate with a pressure-sensitive adhesive layer was cut into a size of 233 mm 309 mm using a cutting device (Super Cutter, manufactured by Oginosei Shoji Co., Ltd.) to obtain a measurement sample.

Then, the release film was peeled off from the obtained measurement sample, and then the glass plate was bonded to alkali-free glass (Eagle XG, manufactured by Corning Incorporated).

Subsequently, the alkali-free glass to which the measurement sample was bonded was placed in an autoclave (manufactured by Kurarasa Seisakusho Co., Ltd.) and pressurized at 5 kg / cm ² at 50 ° C for 20 minutes, then 85 (Or 200 (or 200) hours after being charged under the respective endurance conditions of a temperature of 60 ° C / dry, 60 ° C / 90% RH, and a heat shock (HS) condition (one cycle is -20 ° C Cycle).

Then, the state of the sample to be measured was observed using a 10-fold loupe, and the durability was evaluated according to the following criteria. The obtained results are shown in Table 4.

&Amp; cir &: No defects such as foaming, streaking or peeling were observed in the sample

?: No defects such as foaming, streaking or peeling occurred on the four sides of the sample (0.6 mm or more from the outer peripheral end)

?: Defects such as foaming, streaking, and peeling occurred on four sides of the sample (0.6 mm or more from the outer peripheral end)

X: Defects such as foaming, streaking, and peeling occurred on the four sides of the sample (1.0 mm or more from the peripheral edge)

(3) Surface resistivity

The surface resistivity of the pressure-sensitive adhesive layer was measured in accordance with JIS K6911.

That is, under the following conditions, a value after 30 seconds from the start of the measurement was read and determined as the surface resistivity (? /?) Of the pressure-sensitive adhesive layer. The obtained results are shown in Table 4.

Measurement sample form: 50 mm x 50 mm sheet-like pressure sensitive adhesive layer with polarizer

Thickness of the pressure-sensitive adhesive layer: 25 m

Measurement environment: 23 ± 2 ℃, 50 ± 2% RH

Measuring instrument: HIRESTA-UP MCP-HT450 manufactured by Mitsubishi Kagaku Co., Ltd.

Applied voltage: 100V

(4) Storage modulus

Quot; 2. Applying the pressure-sensitive adhesive composition onto the release layer of the release film and applying heat treatment at 90 占 폚 for 1 minute in accordance with the step of "application of the pressure-sensitive adhesive composition". Then, instead of the polarizing plate, a polyethylene terephthalate (SP-PET3801, manufactured by LINTEC CO., LTD.) Was bonded so that the release layer was in contact with the release layer.

Then, a pressure-sensitive adhesive sheet was obtained by seasoning under the same conditions as those in the case of obtaining a polarizing plate with a pressure-sensitive adhesive layer.

Subsequently, the obtained pressure-sensitive adhesive sheet was peeled off from both sides of the release film, and the pressure-sensitive adhesive layer was laminated so as to have a thickness of 3 mm. In addition, the lowest and uppermost surfaces of the laminated pressure-sensitive adhesive layer did not peel off the release film until the storage elastic modulus was measured.

Subsequently, the laminated pressure-sensitive adhesive layer was cut into a circle having a diameter of 8 mm to obtain a measurement sample.

The obtained measurement sample was peeled off from both sides of the release film, and the storage elastic modulus G 'of the pressure-sensitive adhesive was measured using the twist shearing method according to JIS K7244-6 under the following conditions. The obtained results are shown in Table 4.

Measuring device: Automatic viscoelasticity measuring device manufactured by Rheometric Co., Ltd. DYNAMIC ANALYZER RDAII

Frequency: 1Hz

Temperature: 23 ° C

[Example 16]

A polarizing plate with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 15, except that the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester polymer as the component (A) I appreciated.

(A): BA / HEA / AA (97.5 / 0.5 / 2) Mw = 1.7 million

[Example 17]

In Example 17, the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester polymer as the component (A) was changed as follows, and the mixing ratio of the potassium / fluorine-containing sulfonylimide salt as the component (B) A pressure-sensitive adhesive sheet with a pressure-sensitive adhesive layer was prepared and evaluated in the same manner as in Example 15, except that the ratio (dispersion preparation is the same) was reduced to 1 part by weight.

(A): BA / HEA / AA (96.5 / 0.5 / 3) Mw = 1.7 million

[Example 18]

A polarizing plate with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 15, except that the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester polymer as the component (A) I appreciated.

(A): BA / HEA / AA (96.5 / 0.5 / 3) Mw = 1.7 million

[Example 19]

The mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester polymer as the component (A) in Example 19 was as follows, and the mixing ratio of the potassium / fluorine-containing sulfonylimide salt as the component (B) A pressure-sensitive adhesive sheet with a pressure-sensitive adhesive layer was prepared and evaluated in the same manner as in Example 15 except that the ratio (dispersion preparation is the same) was increased to 5 parts by weight.

(A): BA / HEA / AA (96.5 / 0.5 / 3) Mw = 1.7 million

[Example 20]

The mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester polymer as the component (A) in Example 20 was changed as follows, and the mixing ratio of the potassium / fluorine-containing sulfonylimide salt as the component (B) Sensitive adhesive layer-containing polarizing plate was prepared and evaluated in the same manner as in Example 15, except that the ratio (the same also for the dispersion aid) was further increased to 7.5 parts by weight.

(A): BA / HEA / AA (96.5 / 0.5 / 3) Mw = 1.7 million

[Example 21]

In the same manner as in Example 15 except that the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester polymer as the component (A) was as follows and the dispersion aid was not used, Layered polarizer was produced and evaluated.

(A): BA / HEA / AA (96.5 / 0.5 / 3) Mw = 1.7 million

[Example 22]

In the same manner as in Example 22, except that the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester polymer as the component (A) was changed as follows, and the potassium / fluorine-containing sulfonylimide salt as the component (B) And the amount thereof was adjusted to 3 parts by weight, and a polarizing plate with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 15 except that no dispersing aid was used.

(A): BA / HEA / AA (96.5 / 0.5 / 3) Mw = 1.7 million

Component (B): Potassium bis (trifluoromethylsulfonyl) imide (hereinafter sometimes referred to as KTFSI)

[Example 23]

A polarizing plate with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 15, except that the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester polymer as the component (A) was changed as follows. I appreciated.

(A): BA / HEA / AA (95.5 / 0.5 / 4) Mw = 1.7 million

[Example 24]

A polarizing plate with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 15 except that the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester polymer as the component (A) was changed as follows, I appreciated.

(A): BA / HEA / AA (94.5 / 0.5 / 5) Mw = 1.7 million

[Example 25]

The procedure of Example 25 was repeated except that the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester polymer as the component (A) was changed to 0.2 parts by weight as the crosslinking agent of the component (C) , And a silane coupling agent was used as the following compound, a polarizing plate with a pressure-sensitive adhesive layer was produced and evaluated.

(A): BA / HEA (99/1) Mw = 1.7 million

Component (C): trimethylolpropane adduct xylylene diisocyanate (Takenate D-110N, solid content 75%, hereinafter referred to as TMPXDI, manufactured by Mitsui Takeda Chemical Co., Ltd.)

Silane coupling agent: 3-isocyanate propyltriethoxysilane (KBE9007, hereinafter referred to as KBE9007, made by Shin-Etsu Chemical Co., Ltd.)

[Example 26]

The procedure of Example 26 was repeated except that the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester copolymer as the component (A) was changed to 0.2 parts by weight as the crosslinking agent of the component (C) A polarizing plate with a pressure-sensitive adhesive layer was prepared and evaluated in the same manner as in Example 15 except that the following compounds were used as the silane coupling agent.

(A): BA / HEA (95/5) Mw = 1.7 million

(C) Component: TMPXDI

Silane coupling agent: KBE9007

[Example 27]

The mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester copolymer as the component (A) in Example 27 was set as follows, and as a dispersion aid of the potassium / fluorine-containing sulfonylimide salt, A polarizing plate with a pressure-sensitive adhesive layer was produced and evaluated as in Example 15, except that the compound was used.

(A): BA / HEA / AA (96.5 / 0.5 / 3) Mw = 1.7 million

Dispersion aid: polyoxyethylene glycol-polyoxypropylene glycol block copolymer (hereinafter sometimes referred to as polyether polyol)

[Comparative Example 2]

In Comparative Example 2, the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester copolymer as the component (A) was set as follows, and the following alkali metal salt as the component (B) By weight, and 6 parts by weight of the following compound was used as a dispersing aid for the alkali metal salt, and a crosslinking agent as the component (C) was used as the following compound and a silane coupling agent was used as the following compound. , A polarizing plate with a pressure-sensitive adhesive layer was prepared and evaluated.

(A): BA / HEA (99/1) Mw = 1.7 million

(B): Lithium bis (trifluoromethylsulfonium) imide (hereinafter sometimes referred to as LiTFSI)

Dispersion preparation: adipic acid ester

(C) Component: TMPXDI

Silane coupling agent: KBE9007

[Referential Example 3]

A polarizing plate with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 15, except that the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester copolymer as the component (A) was changed as follows , Respectively.

(A): BA / AA (99/1) Mw = 170 million

[Reference Example 4]

A polarizing plate with a pressure-sensitive adhesive layer was produced in the same manner as in Example 15 except that the mixing ratio of the monomer components in the polymerization of the (meth) acrylic acid ester copolymer as the component (A) was changed as follows , Respectively.

(A): BA / HEA / AA (92.5 / 0.5 / 7) Mw = 1.7 million

[Table 3]

[Table 4]

[Example 28]

1. Adjustment of the pressure-sensitive adhesive composition

100 parts by weight of a mixture (90 parts by weight of the first (meth) acrylic acid ester polymer and 10 parts by weight of the second (meth) acrylic acid ester polymer) of the (meth) acrylic acid ester polymer as component (A) 2.5 parts by weight of a fluorine-containing sulfonylimide salt as a potassium salt, 5 parts by weight of a photocuring component as a component (D), 0.5 part by weight of a photopolymerization initiator, 0.5 part by weight of a crosslinking agent as a component (C) By weight, a pressure-sensitive adhesive composition was prepared. Separately from the fluorine-containing sulfonylimide salt as the cationic potassium salt, 2.5 parts by weight of the dispersion aid for improving the dispersibility was mixed with other components in the pressure-sensitive adhesive composition.

The values in Table 5 indicate values converted to solid contents.

(1) For the component (A)

(1) -1 The first (meth) acrylic acid ester polymer

98.5 parts by weight of butyl acrylate (BA) and 1.5 parts by weight of 2-hydroxyethyl acrylate (HEA) were polymerized in accordance with a conventional solution polymerization method (solvent: ethyl acetate) to obtain a copolymer having a weight average molecular weight of 170 (Meth) acrylic acid ester polymer 1 was obtained.

(A) -1 component: BA / HEA (98.5 / 1.5) Mw = 1.7 million

Then, the solid content concentration of the (meth) acrylic acid ester polymer 1 obtained using the ethyl acetate solution was adjusted to obtain a 20 wt% (meth) acrylic acid ester polymer solution.

The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer 1 was measured by a gel permeation chromatography method (hereinafter abbreviated as GPC method).

That is, first, a calibration curve was prepared using polystyrene. Hereinafter, the weight average molecular weight is represented by a polystyrene reduced value. Then, (meth) the concentration of the object to be measured, such as acrylic ester polymer to prepare a tetrahydrofuran (THF) solution of 1% by weight, Tosoh Corporation (Ltd.), GEL PERMEATION CHROMATOGRAPH HLC-8020 (TSK _GEL GMH _XL, TSK _GEL GMH _XL , and TSK _GEL G2000 _HXL ), the weight average molecular weight was measured at 40 ° C in a THF solvent at 1 ml / min. As a guard column, TSK GUARD COLUMN made by Tosoh Corporation was used.

(1) -2 Polymerization of (meth) acrylic acid ester polymer 2

Subsequently, 95 parts by weight of butyl acrylate (BA) and 5 parts by weight of acrylic acid (AA) were polymerized by a solution polymerization method (solvent: ethyl acetate), which is a conventional method, ) Acrylic acid ester polymer 2 was obtained.

(A) -2 component: BA / AA (95/5) Mw = 170 million

Subsequently, the solid content concentration of the (meth) acrylic acid ester polymer 2 obtained by using the ethyl acetate solution was adjusted to 20 wt% of the (meth) acrylic acid ester polymer solution 2, .

The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer 2 was also measured by the GPC method.

Further, when the amount of the hydroxyl group in the first (meth) acrylic acid ester polymer is H1 and the amount of the carboxyl group in the second (meth) acrylic acid ester polymer is C1, the equivalent ratio expressed by C1 / H1 in Example 28 Was specifically calculated according to the following calculation formula (1). Other embodiments are also the same.

(2) Potassium / fluorine-containing sulfonylimide salt and its dispersion preparation

(Mixing ratio 90:10) of (meth) acrylic acid ester polymer 1 and 2 as component (A), using the following potassium / fluorine-containing sulfonylimide salt as component (B).

However, the potassium / fluorine-containing sulfonylimide salt and the following dispersion auxiliary were separately mixed in the (meth) acrylic acid ester polymer.

Component (B): Potassium bis (fluorosulfonyl) imide (hereinafter sometimes referred to as KFSI)

Dispersion aid: tetraethylene glycol dimethyl ether (hereinafter sometimes referred to as TG)

(3) For the component (D)

(Mixing ratio 90:10) of the (meth) acrylic acid ester polymers 1 and 2 as the component (A) was used as the photo-curing component (containing the photopolymerization initiator) of the component (D) did.

(D) Component: Tris (acryloxyethyl) isocyanurate (sometimes referred to as M-315)

(Aronix M-315, manufactured by Toagosei Co., Ltd.)

Photopolymerization initiator: a mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone (weight ratio 1: 1) (sometimes referred to as IRG500)

(Product name: Irgacure 500, manufactured by Chiba Specialty Chemicals Co., Ltd.)

(4) Isocyanate-based crosslinking agent

The following compounds were used as the isocyanate-based crosslinking agent of the component (C), and they were mixed in a mixture (mixing ratio: 90:10) of the (meth) acrylic acid ester polymers 1 and 2 as the component (A).

Component (C): trimethylolpropane adduct Toluene diisocyanate (sometimes referred to as TMPTDI)

(Trade name: Coronate L, Mw: 657, solid content: 75%, manufactured by Nippon Polyurethane Industry Co., Ltd.)

(5) Silane coupling agent

Further, as the silane coupling agent, the following compounds were mixed in a mixture (mixing ratio: 90:10) of (meth) acrylic acid ester polymer 1 and 2 as component (A).

Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (sometimes referred to as KBM403)

(KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.)

2. Application of pressure-sensitive adhesive composition

Subsequently, toluene was added to a release layer of a polyethylene terephthalate release film (SP-PET3811, manufactured by LINTEC CORPORATION) having a thickness of 38 mu m as a release film to dilute the pressure-sensitive adhesive composition so as to have a solid content of 15 wt% Was 25 占 퐉, using a knife-type coater.

Subsequently, the film was dried at 90 DEG C for 1 minute, and then laminated on a polarizing plate having a thickness of 180 mu m.

3. Curing of the pressure-sensitive adhesive composition

(1) Photocuring of the pressure-sensitive adhesive composition

Subsequently, the pressure-sensitive adhesive composition was irradiated with ultraviolet rays (UV) under the following conditions from the application layer of the pressure-sensitive adhesive composition obtained as described above and the release film side of the laminate composed of the polarizing plate under the following conditions.

Lamp: High-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.)

Light quantity: 300 mJ / cm ²

Illumination: 300 mW / cm ²

UV light intensity and illuminometer: UVF-PFA1 (manufactured by EI Graphics Corporation)

(2) Seasoning process

Subsequently, the polarizing plate with a pressure-sensitive adhesive layer after photo-curing was left (seasoned) under the conditions of 23 占 폚 and 50% RH for 14 days to thermally crosslink the pressure-sensitive adhesive layer sufficiently to obtain a polarizing plate with a pressure- .

4. Evaluation

(1) Adhesion

The adhesive strength of the polarizing plate with a pressure-sensitive adhesive layer after 1 day and 14 days after the application to the adherend (alkali-free glass) was measured.

That is, the obtained polarizing plate with a pressure-sensitive adhesive layer was cut into a size of 25 mm in width × 100 mm in length using a cutting device (Super Cutter, manufactured by Oginosei Shoji Co., Ltd.), and a measurement sample was obtained.

Then, the release film was peeled off from the obtained measurement sample, and then the glass plate was bonded to alkali-free glass (Eagle XG, manufactured by Corning Incorporated).

Subsequently, an alkali-free glass to which a measurement sample was bonded was placed in an autoclave (manufactured by Kuraray Seisakusho Co., Ltd.), and the mixture was pressurized at 0.5 MPa, 50 ° C for 20 minutes, Under the conditions of relative humidity of 50% RH for one day.

Subsequently, the adhesive strength of the measurement sample was measured under the following conditions using a tensile tester (Tensilon made by Orientec Co., Ltd.).

Peeling speed: 300 mm / min

Peeling angle: 180 °

On the other hand, in the same manner, the measurement of the adhesive strength in the case where the measurement sample was allowed to adhere to the alkali-free glass and left to stand for 14 days (336 hours) under conditions of 23 캜 and 50% RH were performed.

The obtained results are shown in Table 6.

(2) Durability

The durability of the polarizing plate with a pressure-sensitive adhesive layer under predetermined conditions was evaluated.

That is, the obtained polarizing plate with a pressure-sensitive adhesive layer was cut into a size of 233 mm 309 mm using a cutting device (Super Cutter, manufactured by Oginosei Shoji Co., Ltd.) to obtain a measurement sample.

Then, the release film was peeled off from the obtained measurement sample, and then the glass plate was bonded to alkali-free glass (Eagle XG, manufactured by Corning Incorporated).

Subsequently, the alkali-free glass to which the measurement sample was bonded was placed in an autoclave (manufactured by Kuraray Seisakusho Co., Ltd.), pressurized at 5 kg / cm ² at 50 ° C for 20 minutes, Lt; 0 > C / dry and 60 [deg.] C / 90% RH, and left for 200 hours.

Then, the state of the sample to be measured was observed using a 10-fold loupe, and the durability was evaluated according to the following criteria. The obtained results are shown in Table 6.

&Amp; cir &: No defects such as foaming, streaking or peeling were observed in the sample

?: No defects such as foaming, streaking or peeling occurred on the four sides of the sample (0.6 mm or more from the outer peripheral end)

?: Defects such as foaming, streaking, and peeling occurred on four sides of the sample (0.6 mm or more from the outer peripheral end)

X: Defects such as foaming, streaking, and peeling occurred on the four sides of the sample (1.0 mm or more from the peripheral edge)

(3) Surface resistivity

The surface resistivity of the pressure-sensitive adhesive layer was measured in accordance with JIS K6911.

That is, under the following conditions, a value after 30 seconds from the start of the measurement was read and determined as the surface resistivity (? /?) Of the pressure-sensitive adhesive layer. The obtained results are shown in Table 6.

Measurement sample form: 50 mm x 50 mm sheet-like pressure sensitive adhesive layer with polarizer

Thickness of the pressure-sensitive adhesive layer: 25 m

Measurement environment: 23 ± 2 ℃, 50 ± 2% RH

Measuring instrument: HIRESTA-UP MCP-HT450 manufactured by Mitsubishi Kagaku Co., Ltd.

Applied voltage: 100V

(4) Storage modulus

Quot; 2. Applying the pressure-sensitive adhesive composition onto the release layer of the release film and applying heat treatment at 90 占 폚 for 1 minute in accordance with the step of "application of the pressure-sensitive adhesive composition". Then, instead of the polarizing plate, a polyethylene terephthalate (SP-PET3801, manufactured by LINTEC CO., LTD.) Was bonded so that the release layer was in contact with the release layer.

Subsequently, a pressure-sensitive adhesive sheet was obtained by photo-curing and seasoning under the same conditions as when a polarizing plate with a pressure-sensitive adhesive layer was obtained.

Subsequently, the obtained pressure-sensitive adhesive sheet was peeled off from both sides of the release film, and the pressure-sensitive adhesive layer was laminated so as to have a thickness of 3 mm. In addition, the lowest and uppermost surfaces of the laminated pressure-sensitive adhesive layer did not peel off the release film until the storage elastic modulus was measured.

Subsequently, the laminated pressure-sensitive adhesive layer was cut into a circle having a diameter of 8 mm to obtain a measurement sample.

The obtained measurement sample was peeled off from both sides of the release film, and the storage elastic modulus G 'of the pressure-sensitive adhesive was measured using the twist shearing method according to JIS K7244-6 under the following conditions. The obtained results are shown in Table 6.

Measuring device: Automatic viscoelasticity measuring device manufactured by Rheometric Co., Ltd. DYNAMIC ANALYZER RDAII

Frequency: 1Hz

Temperature: 23 ° C

[Example 29]

The content of the photocuring component and the photopolymerization initiator as the component (D) in Example 29 was adjusted to 10 parts by weight based on 100 parts by weight of the mixture of the (meth) acrylic acid ester polymers 1 and 2 (mixing ratio 90:10) By weight, and 1.0 part by weight, a pressure-sensitive adhesive sheet with a pressure-sensitive adhesive layer was produced and evaluated as in Example 28. [

[Example 30]

The content of the photocuring component and the photopolymerization initiator as the component (D) in Example 30 was adjusted to 15 parts by weight based on 100 parts by weight of the mixture of the (meth) acrylic acid ester polymers 1 and 2 (mixing ratio 90:10) By weight, and 1.5 parts by weight, a pressure-sensitive adhesive sheet with a pressure-sensitive adhesive layer was produced and evaluated.

[Example 31]

The mixing ratio of the monomers in the polymerization of the (meth) acrylic acid ester copolymers 1 and 2 as the component (A) in Example 31 was set as follows, and the content of the antistatic agent and the dispersion aid as the component (B) (Meth) acrylic acid ester polymers 1 and 2 (mixing ratio: 90:10), the content of the photocuring component and the photopolymerization initiator as the component (D) were respectively 15 parts by weight and 100 parts by weight, A pressure-sensitive adhesive sheet with a pressure-sensitive adhesive layer was prepared and evaluated in the same manner as in Example 28. [

(A) -1 component: BA / HEA (95/5) Mw = 1.7 million

(A) -2 component: BA / AA (90/10) Mw = 170 million

[Example 32]

Except that the content of the antistatic agent and the dispersion aid as the component (B) was changed to 2.5 parts by weight with respect to 100 parts by weight of the mixture (mixing ratio: 90:10) of the (meth) acrylic acid ester polymer 1 and 2 , A polarizing plate with a pressure-sensitive adhesive layer was prepared and evaluated as in Example 31. [

[Example 33]

Except that the content of the antistatic agent and the dispersing aid as the component (B) was changed to 5.0 parts by weight with respect to 100 parts by weight of the mixture (mixing ratio: 90:10) of the (meth) acrylic acid ester polymer 1 and 2 , A polarizing plate with a pressure-sensitive adhesive layer was prepared and evaluated as in Example 31. [

[Example 34]

Except that the content of the antistatic agent and the dispersing aid as the component (B) was changed to 7.5 parts by weight with respect to 100 parts by weight of the mixture (mixing ratio 90:10) of the (meth) acrylic acid ester polymer 1 and 2 , A polarizing plate with a pressure-sensitive adhesive layer was prepared and evaluated as in Example 31. [

[Example 35]

In Example 35, the content of the antistatic agent as the component (B) was changed to 2.5 parts by weight based on 100 parts by weight of the mixture of the (meth) acrylic acid ester polymers 1 and 2 (mixing ratio 90:10) , A polarizing plate with a pressure-sensitive adhesive layer was prepared and evaluated in the same manner as in Example 31.

[Example 36]

A polarizing plate with a pressure-sensitive adhesive layer was prepared and evaluated in the same manner as in Example 35 except that the following compounds were used as the antistatic agent as the component (B) in Example 36. [

Component (B): Potassium bis (trifluoromethylsulfonyl) imide (hereinafter sometimes referred to as KTFSI)

[Example 37]

(Meth) acrylic acid ester polymer 1 as a component (A) and a mixture of (meth) acrylic acid ester polymers 1 and 2 (mixing ratio 90: 1) in the same manner as in Example 37, 10), the polarizing plate with a pressure-sensitive adhesive layer was prepared and evaluated in the same manner as in Example 28 except that the content of the photocuring component and the photopolymerization initiator as the component (D) was 15 parts by weight and 1.5 parts by weight, respectively did.

(A) -1 component: BA / HEA (90/10) Mw = 1.7 million

(A) -2 component: BA / AA (90/10) Mw = 170 million

[Example 38]

The procedure of Example 38 was repeated except that the crosslinking agent as the component (C) was not blended and the content of the photocuring component and the photopolymerization initiator as the component (D) was 15 parts by weight and 1.5 parts by weight, respectively. Similarly, a polarizer with a pressure-sensitive adhesive layer was prepared and evaluated.

[Example 39]

In Example 39, the following compounds were used as a dispersing aid for the potassium / fluorine-containing sulfonylimide salt, and the content of the photocuring component and the photopolymerization initiator as the component (D) was changed to 15 parts by weight and 1.5 parts by weight, respectively Except for this, as in Example 28, a polarizer with a pressure-sensitive adhesive layer was produced and evaluated.

Dispersion aid: Polyether polyol (polyoxyethylene glycol-polyoxypropylene glycol block copolymer)

[Comparative Example 5]

In Comparative Example 5, 1.5 parts by weight of the following lithium-containing imide salt was used as the alkali metal salt as the component (B), 6 parts by weight of the adipic acid ester was used as the dispersion aid of the alkali metal salt, A polarizing plate with a pressure-sensitive adhesive layer was prepared and evaluated in the same manner as in Example 28 except that the content of the photocuring component and the content of the photopolymerization initiator as the components were changed to 15 parts by weight and 1.5 parts by weight, respectively.

(B): Lithium bis (trifluoromethanesulfonium) imide (hereinafter sometimes referred to as LiTFSI)

[Referential Example 6]

In the same manner as in Reference Example 6 except that the mixing ratio of the monomers when the (meth) acrylic acid ester polymer 1 as the component (A) was polymerized was as follows, and the contents of the antistatic agent and the dispersion aid as the component (B) , And the content of the photo-curing component and the photopolymerization initiator as the component (D) was 15 parts by weight and 1.5 parts by weight, respectively, as in Example 28, and evaluated.

(A) -1 component: BA / HEA (70/30) Mw = 1.7 million

[Table 5]

[Table 6]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, a pressure-sensitive adhesive composition is prepared by containing a (meth) acrylic acid ester polymer as the component (A) and an antistatic agent as the component (B) A pressure-sensitive adhesive composition excellent in adhesion and durability under a predetermined environment can be obtained, while the occurrence of static electricity can be effectively suppressed even when the pressure-sensitive adhesive sheet such as the optical film used is peeled from the adherend.

Therefore, the pressure-sensitive adhesive composition or the like of the present invention is expected to remarkably contribute to the enhancement of various films including optical films such as liquid crystal display, plasma display, organic electroluminescence and inorganic electroluminescence devices .

1: a coating layer of a pressure-sensitive adhesive composition, 2: a release film, 10: a pressure-sensitive adhesive (layer), 100: an adhesive sheet, 101:

Claims (15)

A pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer as component (A) and an antistatic agent as component (B)
Wherein the antistatic agent as the component (B) is at least one member selected from the group consisting of potassium bis (fluorosulfonyl) imide or potassium bis (perfluoroalkylsulfonyl) imide, Is set to a value within a range of 0.05 to 15 parts by weight based on 100 parts by weight of the ester polymer,
Wherein the dispersion aid further comprises a dispersion aid of an antistatic agent as the component (B), and the dispersion aid is an alkylene glycol dialkyl ether,
The number of repeating units of the polyoxyalkylene chain in the alkylene glycol dialkyl ether is set to a value within the range of 2 to 10,
(Molar ratio) of the potassium bis (fluorosulfonyl) imide or potassium bis (perfluoroalkylsulfonyl) imide to the alkylene glycol dialkyl ether in the range of 30:70 to 70:30 By weight based on the total weight of the pressure-sensitive adhesive composition. The method according to claim 1,
Wherein the (meth) acrylic acid ester polymer as the component (A) contains a structural moiety derived from a (meth) acrylic acid ester monomer, a structural moiety derived from a hydroxyl group-containing vinyl monomer, and a structural moiety derived from a carboxyl group- The content of the hydroxyl group-containing vinyl monomer is within a range of 0.1 to 20% by weight, the proportion of the carboxyl group-containing vinyl monomer is 0 or 0 to 6% by weight, % Is not included), and also contains a crosslinking agent as the component (C). 3. The method of claim 2,
Wherein the content of the crosslinking agent as the component (C) is set to a value within a range of 0.01 to 10 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A). 3. The method of claim 2,
Wherein the crosslinking agent as the component (C) comprises an isocyanate crosslinking agent. The method according to claim 1,
The (meth) acrylic acid ester polymer as the component (A)
(Meth) acrylic acid ester monomer and a structural moiety derived from a hydroxyl group-containing vinyl monomer, wherein the mixing ratio of the hydroxyl group-containing vinyl monomer to the total amount of the monomer components in copolymerization is from 1 to 20% by weight, Of the first (meth) acrylic acid ester polymer,
A second (meth) acrylic acid ester polymer containing a structural part derived from a (meth) acrylic acid ester monomer and a structural part derived from a carboxyl group-containing vinyl monomer,
Wherein an equivalent ratio represented by C1 / H1 is set to 0.01 to 1.0 (where H1 represents the amount of the hydroxyl group in the first (meth) acrylic acid ester polymer and C1 represents the amount of the carboxyl group in the second (meth) acrylic acid ester polymer , And contains a photo-curing component as the component (D). 6. The method of claim 5,
In the (meth) acrylic acid ester polymer as the component (A), the compounding ratio (by weight) expressed by the first (meth) acrylic acid ester polymer / the second (meth) acrylic acid ester polymer is from 99/1 to 60/40 Sensitive adhesive composition of the present invention. 6. The method of claim 5,
In the second (meth) acrylic acid ester polymer contained in the (meth) acrylic acid ester polymer as the component (A), the total amount of the monomer components in the polymerization of the second (meth) acrylic acid ester polymer, Containing vinyl monomer is in the range of 1 to 30% by weight based on the total weight of the pressure-sensitive adhesive composition. 6. The method of claim 5,
Wherein the photo-curable component as the component (D) is a polyfunctional (meth) acrylate monomer having an isocyanurate structure. 6. The method of claim 5,
Wherein the content of the photocurable component as the component (D) is set to a value within a range of 1 to 25 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A). delete delete A pressure-sensitive adhesive which is formed as a pressure-sensitive adhesive through a process including the following steps (1) to (3).
(1) A pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer as the component (A) and an antistatic agent as the component (B), wherein the antistatic agent as the component (B) is potassium bis (fluorosulfonyl) Or potassium bis (perfluoroalkylsulfonyl) imide, the content is within a range of 0.05 to 15 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester polymer as the component (A) Wherein the dispersion aid is an alkylene glycol dialkyl ether and the number of repeating units of the polyoxyalkylene chain in the alkylene glycol dialkyl ether, (Fluorosulfonyl) imide or potassium bis (perfluoroalkylsulfonyl) imide and the alkylene glycol dialkyl ether is in the range of 2 to 10, ) In the range of 30:70 to 70:30 Step of preparing a pressure-sensitive adhesive composition in a proportion of
(2) a step of applying the pressure-sensitive adhesive composition to a release film to form a pressure-sensitive adhesive composition layer
(3) a step of curing the pressure-sensitive adhesive composition layer to form a pressure-sensitive adhesive layer A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive according to claim 12 on a substrate. 14. The method of claim 13,
Wherein the base material is an optical film base material and the pressure-sensitive adhesive layer is provided on at least one side of the optical film base material. 14. The method of claim 13,
Wherein the substrate is a release film and another release film is laminated on the opposite side of the release film in the pressure-sensitive adhesive layer.

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