WO2015194523A1

WO2015194523A1 - Polarizer, polarizer plate with adhesive, and image display device

Info

Publication number: WO2015194523A1
Application number: PCT/JP2015/067242
Authority: WO
Inventors: 誠田崎; 耕太村野
Original assignee: 住友化学株式会社
Priority date: 2014-06-18
Filing date: 2015-06-16
Publication date: 2015-12-23
Also published as: CN106489086A; TWI662102B; TW201604261A; CN106489086B; JPWO2015194523A1; KR20170020452A; KR102347401B1

Abstract

Even with an antistatic agent-containing adhesive layer formed on at least one surface of this polarizer, when exposed to a high temperature environment or a high heat and high humidity environment, degradation and color loss, common in polarizers, are suppressed. This polarizer comprises an adhesive layer which is formed on at least one side and which is formed from an adhesive composition which contains an antistatic agent that includes a polyether and a salt having a negative ion that has a fluoro group and a sulfonyl group. One or more types of polyethers can be selected from the group consisting of polyether esters having 2 types of specific structures, and polyalkylene glycol (di- or mono-)alkyl ethers.

Description

Polarizer, polarizing plate with adhesive, and image display device

The present invention relates to a polarizer applied to an image display device such as a liquid crystal display device, a polarizing plate with an adhesive provided with a transparent protective layer on one surface of the polarizer and an adhesive layer on the other surface, and this The present invention relates to an image display device to which a polarizing plate with an adhesive is applied.

In recent years, the use of liquid crystal display devices has been rapidly expanding, and has been used from mobile devices such as mobile phones to large televisions regardless of screen size. In addition to liquid crystal display devices, organic electroluminescence (organic EL) display devices also tend to increase mainly in mobile applications. The polarizing plates used in these image display apparatuses are not only in increasing demand but also required to have performance suitable for each application.

The above polarizing plate is generally a retardation having optical properties in a state where a transparent protective layer is laminated on both sides of a polarizer having a dichroic dye adsorbed and oriented on a polyvinyl alcohol (PVA) resin film, or if necessary. An optical display device such as a liquid crystal cell or an organic EL display device is bonded to an image display device in a form in which an optical layer such as a film or an optical compensation film is bonded.

By the way, in recent years, in an image display device for mobile use such as a mobile phone, the entire module has been made thinner in terms of design and the like. Accordingly, further reduction in thickness and weight has been demanded for the polarizing plate. For example, JP-A-2003-185842 (Patent Document 1) discloses a polarizing plate in which a protective layer is formed on at least one side of a polarizer instead of a transparent protective film. In 2), polarizing plates each having a protective layer with improved durability under a high temperature or high humidity environment are proposed. In order to provide antistatic performance in addition to thinning and light weight, JP 2012-247574A (Patent Document 3) provides a transparent protective layer only on one side of the polarizer and transparent protection on the other side. There is disclosed a polarizing plate provided with an adhesive layer containing an alkali metal salt as an antistatic agent without providing a layer.

JP 2003-185842 A JP 2010-9027 A JP 2012-247574 A

However, when the polarizer is provided with a pressure-sensitive adhesive layer having a conventional antistatic property directly as described above, color loss of dichroic dyes such as iodine adsorbed and oriented on the polyvinyl alcohol resin film constituting the polarizer ( Degradation of the polarizer) may occur, and the method described in Patent Document 3 has room for improvement in optical durability.

The object of the present invention is to provide color loss that is likely to occur in a polarizer when it is exposed to a high temperature or high humidity environment even when an adhesive layer containing an antistatic agent is formed on at least one surface of the polarizer. Another object of the present invention is to provide a polarizer with a pressure-sensitive adhesive in which deterioration is suppressed.

Another object of the present invention is to provide a polarizing plate with an adhesive in which a transparent protective layer is laminated on the polarizer with an adhesive, and an image display device in which the polarizing plate is applied to an image display element.

The present invention has been made to solve the above problems. Specifically, the present invention has the following configuration.

[1] An antistatic material comprising a salt having an anion having a fluoro group and a sulfonyl group, and at least one polyether selected from the group consisting of a polyether ester, a polyalkylene glycol monoalkyl ether and a polyalkylene glycol dialkyl ether A polarizer with an adhesive in which an adhesive layer formed from an adhesive composition containing an adhesive is laminated on at least one surface of the polarizer.
[2] The polyether has the following formula (I)

(Wherein, m and n are each an integer, and R ¹ and R ² represent an alkyl group)
A compound represented by the following formula (II)

(Wherein p is an integer and R ³ and R ⁴ represent an alkyl group)
And a compound of the following formula (III)
R ⁵ (OCH ₂ CH ₂ ) _n OR ⁶ (III)
(Wherein R ⁵ represents an alkyl group having 1 to 12 carbon atoms, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n represents an integer of 3 to 6)
The polarizer with an adhesive according to [1], which is at least one selected from the group consisting of compounds represented by:
[3] The polyether has the following formula (I)

(Wherein, m and n are each an integer, and R ¹ and R ² represent an alkyl group)
And a compound of the following formula (II)

(Wherein p is an integer and R ³ and R ⁴ represent an alkyl group)
The polarizer with an adhesive according to [2], which is at least one selected from the group consisting of compounds represented by:
[4] The polyether has the following formula (III)
R ⁵ (OCH ₂ CH ₂ ) _n OR ⁶ (III)
(Wherein R ⁵ represents an alkyl group having 1 to 12 carbon atoms, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n represents an integer of 3 to 6)
The polarizer with an adhesive according to [2], which is a compound represented by:
[5] The pressure-sensitive adhesive composition is a copolymer of a monomer mixture containing at least a (meth) acrylic acid ester monomer having an alkyl group having 1 to 18 carbon atoms, and has a weight average molecular weight of 400,000 to 250. The polarizer with pressure-sensitive adhesive according to any one of [1] to [4], which contains 100 parts by weight of acrylic resin (A), and 0.001 to 10 parts by weight of crosslinking agent (B).
[6] The acrylic resin (A) is a copolymer of a monomer mixture containing at least a carboxyl group-containing monomer in addition to a (meth) acrylic acid ester monomer having an alkyl group having 1 to 18 carbon atoms [ 5] A polarizer with an adhesive.
[7] The acrylic resin (A) contains, in addition to the (meth) acrylic acid ester monomer having an alkyl group having 1 to 18 carbon atoms, one olefinic double bond and at least one reactivity in the molecule. The polarizer with an adhesive according to [5], which is a copolymer of a monomer mixture containing at least a monomer having a functional group (excluding a carboxyl group).
[8] The anion having a fluoro group and a sulfonyl group is at least one anion selected from the group consisting of a bis (fluoroalkylsulfonyl) imide ion, a tris (fluoroalkylsulfonyl) methide ion, and a fluoroalkylsulfonic acid ion. [1]-[7] polarizer with adhesive.
[9] The salt having an anion having a fluoro group and a sulfonyl group is any cation selected from the group consisting of alkali metal ions, group 2 element ions, transition metal ions, and amphoteric metal ions, and the fluoro group. And a pressure-sensitive adhesive polarizer according to any one of [1] to [8], which is a salt composed of an anion having a sulfonyl group.
[10] The salt having an anion having a fluoro group and a sulfonyl group is an alkali metal salt of bis (fluoroalkylsulfonyl) imide, an alkali metal salt of tris (fluoroalkylsulfonyl) methide, or an alkali metal of trifluoroalkylsulfonic acid. The polarizer with an adhesive according to any one of [1] to [9], which is at least one salt selected from the group consisting of salts.
[11] In the polarizer with an adhesive according to any one of [1] to [10], a first transparent protective layer is laminated on one surface of the polarizer, and the adhesive layer is formed on the other surface of the polarizer. Is a polarizing plate with an adhesive.
[12] The pressure-sensitive adhesive-attached polarizing plate according to [11], wherein the first transparent protective layer is laminated on the polarizer via an adhesive layer.
[13] The polarizing plate with an adhesive according to [11] or [12], which has a second transparent protective layer between the polarizer and the adhesive layer.
[14] The polarizing plate with an adhesive according to any one of [11] to [13], wherein an optical layer is laminated on the surface of the first transparent protective layer opposite to the polarizer.
[15] The polarizer with an adhesive according to any one of [1] to [10], wherein a release film is adhered to the surface of the adhesive layer, or any one of [11] to [14]. Polarizing plate with adhesive.
[16] The polarizer with an adhesive according to any one of [1] to [10] or the polarizing plate with an adhesive according to any one of [11] to [14] is interposed via the adhesive layer. An image display device bonded to the image display element.

According to the present invention, even if a pressure-sensitive adhesive layer containing an antistatic agent is directly formed on the surface of the polarizer, color loss and deterioration of the polarizer can be suppressed under a high temperature or high humidity environment. Further, by laminating the pressure-sensitive adhesive layer on the polarizer, the polarizing plate and the image display device to which this is applied can be made thinner and lighter. Since the polarizing plate with the pressure-sensitive adhesive of the present invention exhibits good durability even in a high temperature or high humidity environment, an image display device combining this polarizing plate with an image display element is also thinned and durable. Excellent in properties.

It is a cross-sectional schematic diagram which shows the example of the preferable layer structure of the polarizing plate with an adhesive of this invention. It is a cross-sectional schematic diagram which shows the other example of the preferable layer structure of the polarizing plate with an adhesive of this invention. It is a cross-sectional schematic diagram which shows the example of the preferable layer structure of the image display apparatus of this invention.

The polarizer with a pressure-sensitive adhesive of the present invention has at least one polyether selected from the group consisting of polyether ester, polyalkylene glycol monoalkyl ether and polyalkylene glycol dialkyl ether, and an anion having a fluoro group and a sulfonyl group. An adhesive layer formed from an adhesive composition containing an antistatic agent containing a salt is laminated on at least one surface of a polarizer. This polarizer can be made into a polarizing plate with an adhesive by laminating a first transparent protective layer on one surface and an adhesive layer on the other surface. Moreover, it can also be set as the polarizing plate with an adhesive which has a 2nd transparent protective layer between the polarizer and adhesive layer of the said polarizing plate with an adhesive. This polarizing plate with an adhesive is bonded to an image display element including a liquid crystal cell to become an image display device. Hereinafter, the present invention will be described in detail with appropriate reference to the drawings. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments.

[Adhesive composition (adhesive layer)]
In the present invention, the pressure-sensitive adhesive layer is laminated on at least one surface of the polarizer. This pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing an antistatic agent. Here, the antistatic agent includes a polyether and a salt having an anion having a fluoro group and a sulfonyl group.

(Antistatic agent)
The antistatic agent in the present invention contains a polyether and a salt having an anion having a fluoro group and a sulfonyl group. For example, a salt having an anion having a fluoro group and a sulfonyl group is dissolved in the polyether. It is distributed in the state where it was done. In the present invention, by employing such an antistatic agent, it is possible to prevent color loss of the polarizer even when the pressure-sensitive adhesive composition is directly attached to the polarizer. In this specification, “dispersion” means a state in which a salt having an anion having a fluoro group and a sulfonyl group is dispersed or dissolved in a polyether.

As such an antistatic agent, a commercially available product can be used. For example, “Sanconol (registered trademark) AD2326”, “Sanconol (registered trademark) AD2600”, sold by Sanko Chemical Industries, Ltd., “Sanconol (registered trademark) TGR” (all are trade names).

When a pressure-sensitive adhesive composition containing a conventional ionic compound is directly attached to a polarizer, the cation bleeds out or blooms due to the poor flowability of the ionic compound or compatibility with the acrylic resin, and the iodine of the polarizer. A pseudo bond is formed with the ions (I ³⁻ , I ⁵⁻ ), and the color loss of the polarizer is caused. On the other hand, when the antistatic agent used in the present invention is dispersed in a state of being dissolved in a polyether having a high affinity with an acrylic resin, it is more suppressed from causing bleeding out and blooming. preferable. Furthermore, the cation constituting the antistatic agent forms a Lewis acid / base complex ion with the polyether, and therefore does not form a chemical bond with the iodine ion of the polarizer.

The content of the antistatic agent is preferably from 0.01 to 30% by weight, more preferably from 0.1 to 10% by weight, based on 100 parts by weight of the solid content of the pressure-sensitive adhesive composition. By setting the content of the antistatic agent within the above range, sufficient antistatic performance can be exhibited, and problems such as precipitation of the antistatic agent under a low temperature environment can be suppressed.

In the present invention, at least one compound selected from the group consisting of polyether esters, polyalkylene glycol monoalkyl ethers and polyalkylene glycol dialkyl ethers is employed as the polyether. In the present invention, only the polyether ester may be employed, or only the polyalkylene glycol (di or mono) alkyl ether may be employed, or two or more may be used in combination. These polyethers act as plasticizers. In the present specification, the term “polyether” refers to the specific compound contained in the antistatic agent.

(Polyether ester)
The polyether ester contains a polyether structure and an ester bond, and can prevent the resin from being regularly oriented by entering the gap between the resins as the main component of the pressure-sensitive adhesive composition. Moreover, what maintains an amorphous state is preferable even if a polyetherester is below a glass transition point. When adopting a polyether ester as the polyether contained in the antistatic agent, it is preferable to contain at least one compound represented by the following formula (I) or (II).

In the above formula (I), m and n are each an integer, and R ¹ and R ² each represents an alkyl group. m is preferably an integer of 1 to 40, and n is preferably an integer of 1 to 20. More preferably, m and n are integers of 2 or more. In particular, m is preferably an integer of 2 or more. R ¹ and R ² are preferably alkyl groups having 1 to 14 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, An n-nonyl group, an isononyl group, an n-decyl group, an n-lauryl group and the like are preferable.

In the above formula (II), p is an integer, and R ³ and R ⁴ represent an alkyl group. p is preferably an integer of 1 to 40, and more preferably an integer of 2 or more. R ³ and R ⁴ are preferably alkyl groups having 1 to 14 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n -Nonyl group, isononyl group, n-decyl group, n-lauryl group and the like are preferable.

Commercially available products can be used as the polyether ester. For example, Adeka Sizer (registered trademark) manufactured by Adeka Co., Ltd., HA-5 manufactured by Kao, D620, D623N, D643 manufactured by J Plus Co., Ltd., Polycizer (registered trademark) W-230-H manufactured by DIC Co., Ltd., DIC Monosizer (registered trademark) W-262 manufactured by Co., Ltd. may be mentioned.

(Polyalkylene glycol (di or mono) alkyl ether)
Polyalkylene glycol (di or mono) alkyl ether has a property of being easily dissolved in a resin as a main component of the pressure-sensitive adhesive composition. As the polyalkylene glycol (di or mono) alkyl ether contained in the antistatic agent, it is preferable to employ a compound represented by the following formula (III).
R ⁵ (OCH ₂ CH ₂ ) _n OR ⁶ (III)

In formula (III), R ⁵ represents an alkyl group having 1 to 12 carbon atoms, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. n represents an integer of 3 to 6.

Examples of the polyalkylene glycol (di or mono) alkyl ether include triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, heptaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ( And (dodecyloxy) triethylene glycol monomethyl ether and (dodecyloxy) tetraethylene glycol monomethyl ether.

The above polyethers preferably have a molecular weight of 250 to 2000, more preferably 500 to 1500. The viscosity (25 ° C.) is preferably 30 to 600 mPa · s.

The polyether described above has low viscosity, good workability, low temperature flexibility, and a balance between flexibility and durability, heat aging resistance, non-volatility, non-migration, oil resistance Excellent in safety and safety (PL conformance).

(Other plasticizers)
In addition to the above-described polyether, the antistatic agent may contain a further plasticizer. As such a plasticizer, an ester formed from a mono- or dicarboxylic acid having a saturated or unsaturated chain hydrocarbon group and an alcohol having a chain hydrocarbon group having 1 to 20 carbon atoms, or unsaturated And a plasticizer comprising an ester in which an unsaturated group in the chain hydrocarbon group is epoxidized. By using such an ester, the wettability of the pressure-sensitive adhesive layer to the adherend can be improved, and it is possible to make it difficult for air bubbles to be involved at the time of sticking, and the plasticizer bleed out from the pressure-sensitive adhesive layer. It becomes difficult to occur and adherend contamination can be suitably reduced.

As the saturated or unsaturated chain hydrocarbon group in the mono- or dicarboxylic acid component constituting the ester, an alkyl group or an alkylene group can be used, and among them, an alkyl group or alkylene group having 1 to 20 carbon atoms is preferable. An alkyl group having 4 to 18 carbon atoms is more preferable, and an alkyl group having 4 to 14 carbon atoms is particularly preferable. The chain hydrocarbon group may be branched or linear as long as it has 3 or more carbon atoms. Such a mono- or dicarboxylic acid having a saturated or unsaturated chain hydrocarbon group has a carbon number close to the carbon number of the acrylic monomer constituting the acrylic resin used in the pressure-sensitive adhesive composition, thereby Since the compatibility with the adhesive composition is improved and the adhesive composition is suitably held in the adhesive composition, bleeding out is suppressed.

Examples of the dicarboxylic acid having a saturated or unsaturated chain hydrocarbon group include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid. Examples include mono- or polyesters of linear aliphatic dicarboxylic acids such as acids, itaconic acid and dodecanedioic acid. Examples of monocarboxylic acids having a saturated chain hydrocarbon group include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, isocaproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, Examples include pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, nonadecylic acid, and arachidic acid. Examples of monocarboxylic acids having an unsaturated chain hydrocarbon group include crotonic acid, angelic acid, Linderic acid, myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid , Unsaturated fatty acids such as linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, elaidic acid and docosahexaenoic acid Is mentioned.

As the chain hydrocarbon group having 1 to 20 carbon atoms in the alcohol constituting the ester, an alkyl group or alkylene group having 1 to 20 carbon atoms, particularly an alkyl group, can be preferably used. Are preferred, and alkyl groups having 4 to 14 carbon atoms are particularly preferred. The alcohol having such a saturated or unsaturated chain hydrocarbon group has a carbon number close to the carbon number of the acrylic monomer constituting the acrylic resin contained in the pressure-sensitive adhesive composition. The compatibility is improved, and the bleed-out is suppressed because it is suitably retained in the pressure-sensitive adhesive composition. Compared with the carboxylic acid component constituting the ester, the carbon number of the hydrocarbon group of the alcohol component is set to be close to the carbon number of the acrylic monomer constituting the acrylic resin used in the pressure-sensitive adhesive composition. In particular, it becomes easy to suppress adherend contamination.

Examples of the alcohol having such a chain hydrocarbon group include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, 3 -Pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, 3,3,5-trimethyl-1-hexanol, decanol, undecyl alcohol, Examples include linear and branched alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, and arachidyl alcohol. Among them, alcohols having 4 to 10 carbon atoms such as 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, 3-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 3 -Hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, 3,3,5-trimethyl-1-hexanol and decanol are particularly preferably used.

More preferably, an ester formed from the above mono- or dicarboxylic acid and an alcohol is used as a plasticizer. The ester may have a skeleton composed of a saturated or unsaturated hydrocarbon group, but is preferably an ester not having a skeleton composed of an unsaturated hydrocarbon group. Moreover, an epoxidized ester in which an unsaturated bond of an ester having a skeleton composed of an unsaturated hydrocarbon group is epoxidized can also be preferably used. Of these, adipic acid monoester, sebacic acid monoester, and epoxidized fatty acid monoester can be particularly preferably used.

The ester used as the plasticizer may be either a monoester or a polyester, but it is easy to control the solubility parameter (SP value) to a suitable range and to improve the compatibility with the pressure-sensitive adhesive composition. An ester having a weight average molecular weight in terms of PS of 1000 or less is preferable, and an ester having a molecular weight of 300 to 800 is particularly preferable.

As the plasticizer, it is preferable to use a plasticizer having a solubility parameter (SP value) of 8.5 or less. Among these, 7.0 to 8.4 is preferable. When the plasticizer has an SP value of 8.5 mm or less, it is excellent in compatibility with an acrylic resin, and therefore, when the adhesive composition is stuck on a polarizer and left in a high humidity environment for a long time. However, fogging hardly occurs on the surface of the polarizer when it is peeled off from the surface of the polarizer. As the SP value of the plasticizer, a plasticizer larger than 7 is generally used. The SP value is a value calculated by the Small formula [P.A.J.Small: J.Appl.Chem., 3, 71 (1953)] proposed by J. Small.

The plasticizer is preferably added in an amount of 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the solid content of the (meth) acrylic copolymer constituting the acrylic resin. Addition of 1 to 10 parts by weight is particularly preferable. When the addition amount of the plasticizer is more than 0.5 parts by weight, bubbles are easily removed when pasted. On the other hand, when the amount is less than 30 parts by weight, fogging hardly occurs on the display surface even in a high humidity heat environment.

(Salt having an anion having a fluoro group and a sulfonyl group)
A salt having an anion having a fluoro group and a sulfonyl group is easily dissolved in the polyether, and the salt concentration in the plasticizer can be increased. By dispersing this solution in the pressure-sensitive adhesive composition, a large amount of a salt having an anion having a fluoro group and a sulfonyl group can be incorporated into the pressure-sensitive adhesive composition in a large amount.
Since a solution containing a salt having an anion having a fluoro group and a sulfonyl group and a polyether, in combination with the plasticity of the polyether in the pressure-sensitive adhesive composition, imparts plasticity while exhibiting antistatic properties. is there. Moreover, since the polyether can be close to the solubility parameter (SP value) of the pressure-sensitive adhesive composition, it has excellent affinity and does not bleed. As a result, it is possible to obtain a pressure-sensitive adhesive composition that does not cause migration contamination, does not depend on humidity, has excellent rapidity, and maintains excellent antistatic properties.

The salt having an anion having a fluoro group and a sulfonyl group exhibits antistatic properties while maintaining the adhesive properties in the adhesive composition. Furthermore, since the salt having an anion having a fluoro group and a sulfonyl group is excellent in compatibility with the constituents of the pressure-sensitive adhesive composition, bleeding, blooming, and migration contamination do not occur, and it does not depend on humidity and is effective immediately. It is possible to obtain a pressure-sensitive adhesive composition that is excellent in properties and maintains excellent antistatic properties.

The anion having a fluoro group and a sulfonyl group is preferably an anion selected from the group consisting of a bis (fluoroalkylsulfonyl) imide ion, a tris (fluoroalkylsulfonyl) methide ion, and a fluoroalkylsulfonic acid ion.

The salt having an anion having a fluoro group and a sulfonyl group is a salt comprising an anion having an alkali metal, a group 2 element, a transition metal or an amphoteric metal and the anion having the fluoro group and the sulfonyl group. Is preferred. Further, salts having an anion having a fluoro group and a sulfonyl group include alkali metal salts of bis (fluoroalkylsulfonyl) imide ions, alkali metal salts of tris (fluoroalkylsulfonyl) methide ions, and alkali metal salts of fluoroalkylsulfonate ions. Preferably there is. Lithium salts are particularly preferred.

There are many salts composed of the above anions and cations, and among them, those composed of bis (fluoroalkylsulfonyl) imide ion, tris (fluoroalkylsulfonyl) methide ion, and fluoroalkylsulfonic acid ion are preferable. Specifically, bis (trifluoromethanesulfonyl) imide lithium [Li N (SO ₂ CF ₃ ) ₂ ], bis (trifluoromethanesulfonyl) imide potassium [K N (SO ₂ CF ₃ ) ₂ ], bis (trifluoromethanesulfonyl) ) Imido sodium [Na N (SO ₂ CF ₃ ) ₂ ], tris (trifluoromethanesulfonyl) methide lithium [Li C (SO ₂ CF ₃ ) ₃ ], tris (trifluoromethanesulfonyl) methide potassium [K C (SO ₂ CF ₃₎ _3], tris (trifluoromethanesulfonyl) methide sodium [Na C (SO ₂ CF ₃₎ _3], lithium trifluoromethanesulfonate [Li SO ₃ CF _3], potassium trifluoromethanesulfonate [K SO ₃ CF _3] , Sodium trifluoromethanesulfonate [Na SO ₃ CF ₃ ] is preferred. Of these, lithium bis (trifluoromethanesulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methide, and lithium trifluoromethanesulfonate are more preferable. In particular, lithium bis (trifluoromethanesulfonyl) imide and lithium trifluoromethanesulfonate are preferable.

For example, bis (trifluoromethanesulfonyl) imide lithium [Li N (SO ₂ CF ₃ ) ₂ ] is used as a salt, and the state dissolved in a polyether composed of diethylene glycol and adipic acid is converted to an ether oxygen atom in polyethylene glycol. Lithium ions are coordinated. When the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer in which lithium ions are uniformly dispersed is formed in a state where lithium ions are coordinated to ether oxygen atoms, and an electric field is applied to the pressure-sensitive adhesive layer from the outside. Then, in the pressure-sensitive adhesive layer, lithium ions move toward the corresponding pole (ion transport) and express ionic conductivity.

The state in which bis (trifluoromethanesulfonyl) imide lithium [Li N (SO ₂ CF ₃ ) ₂ ] is dissolved in tetraethylene glycol dimethyl ether is the state in which the polar ether group is coordinated to the Li ⁺ ion. And is dispersed in the composition in this state. Since Li ⁺ ions are surrounded by ether oxygen and away from N (SO ₂ CF ₃ ) ₂ ⁻ ions, they greatly contribute to antistatic properties. In particular, a mixture of a lithium salt and a polyether forms a Lewis acid / base type complex ion, and thus contributes greatly to antistatic properties. Moreover, since lithium salt forms a Lewis acid / base complex ion with a polyether, it cannot form a chemical bond with the iodine ion of the polarizer. Therefore, the color loss of the polarizer is not caused.

The salt having an anion having a fluoro group and a sulfonyl group is preferably contained in an amount of 0.1 to 200 parts by weight, more preferably 1 to 180 parts by weight, based on 100 parts by weight of the polyether. More preferably, 150 parts by weight is contained.

The salt having an anion having a fluoro group and a sulfonyl group is preferably contained in an amount of 0.01 to 30 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive composition. By setting the content of the salt having an anion having a fluoro group and a sulfonyl group within the above range, sufficient antistatic performance can be exhibited.

(Polymer type antistatic agent)
The antistatic agent may further contain a polymer type antistatic agent. The polymer type antistatic agent can stabilize a salt having an anion. In addition, since the salt having an anion is dispersed in a state dissolved in the polyether, the salt gathers in the presence of a polymer type antistatic agent having an affinity for the polyether and is stabilized by the affinity of both. It is thought to do. Examples of such a polymer type antistatic agent include a polyether block polyolefin copolymer, a polyoxyalkylene copolymer, and an ethylene oxide-propylene oxide-allyl glycidyl copolymer.

The polymer type antistatic agent is preferably contained in an amount of 0.1 to 65 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive composition.

(Acrylic resin)
The pressure-sensitive adhesive composition in the present invention is preferably composed mainly of an acrylic resin crosslinked with a crosslinking agent. “Main component” means that it is contained in an amount of 50% by weight or more based on the whole pressure-sensitive adhesive.

In the present invention, the acrylic resin (A) contained in the pressure-sensitive adhesive composition is a copolymer of a monomer mixture containing at least a (meth) acrylic acid ester monomer having an alkyl group having 1 to 18 carbon atoms. The weight average molecular weight is preferably 400,000 to 2.5 million. “(Meth) acrylic acid” indicates acrylic acid or methacrylic acid.
The same applies to other cases of “(meta)”.

As the (meth) acrylic acid ester monomer having an alkyl group having 1 to 18 carbon atoms (hereinafter referred to as a non-crosslinking acrylic monomer), for example, the hydrogen atom of the carboxyl group of (meth) acrylic acid is substituted with a hydrocarbon group. (Meth) acrylic acid esters. The hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms. Moreover, the hydrocarbon group may have a substituent. Any substituent that does not contain a crosslinkable group may be used, and examples thereof include alkoxy groups such as a methoxy group and an ethoxy group. Specific examples of such (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n- Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid n-octyl, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n- (meth) acrylate Undecyl, n-dodecyl (meth) acrylate, stearyl, methoxyethyl (meth) acrylate, (meth) acrylic Le acid ethoxyethyl, (meth) cyclohexyl acrylate include benzyl (meth) acrylate. These may be used individually by 1 type and may use 2 or more types together. Among these, n-butyl acrylate, 2-ethylhexyl acrylate, and methyl acrylate are preferable from the viewpoint of adhesiveness.

The content of the structural unit derived from the non-crosslinkable acrylic monomer in the acrylic resin (A) is preferably 60 to 99.99% by weight, and more preferably 65 to 99.9% by weight. If this content is not less than the above lower limit value, sufficient adhesive force can be exhibited, and if it is not more than the above upper limit value, it is sufficiently crosslinked by a crosslinking agent.

The acrylic resin (A) is a co-polymer of a monomer mixture containing at least a monomer having one olefinic double bond and at least one reactive functional group in the molecule in addition to the non-crosslinkable acrylic monomer. A polymer is preferred. A monomer having one olefinic double bond and at least one reactive functional group in the molecule (hereinafter referred to as a crosslinkable monomer) is an acrylic monomer as long as it can be polymerized with a non-crosslinkable acrylic monomer. Although it may be a monomer or a non-acrylic monomer, it is preferably an acrylic monomer. Examples of reactive functional groups include carboxyl groups, hydroxyl groups, amino groups, epoxy groups, glycidyl groups, and the like.

Examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and grataconic acid, and anhydrides thereof. .

Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth And (meth) acrylic acid lactone such as (meth) acrylic acid [(mono, di or poly) alkylene glycol] such as mono (diethylene glycol) acrylic acid and monocaprolaclone (meth) acrylic acid.

Examples of amino group-containing monomers include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, and allylamide.

Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate.

These crosslinkable monomers may be used alone or in combination of two or more.

In addition, the content of the structural unit derived from the crosslinkable monomer in the acrylic resin (A) is preferably 0.01 to 40% by weight, and more preferably 0.5 to 35% by weight. If this content is not less than the above lower limit value, it can be sufficiently cross-linked, and if it is not more than the above upper limit value, the adhesive force tends to be controlled and the reworkability of the resulting adhesive tends to be good.

When a carboxyl group-containing monomer is copolymerized as a crosslinkable monomer, heat resistance tends to be improved. When the carboxyl group-containing monomer is copolymerized, the content of structural units derived from the carboxyl group-containing monomer in the acrylic resin (A) is preferably from 0.01 to 20% by weight, and preferably from 0.05 to 10% by weight. % Is more preferable. When the content of the carboxyl group-containing monomer is 0.05% by weight or more, the heat resistance under a high temperature or high humidity heat environment or an environment where heating and cooling are repeated is improved. If the content of the carboxyl group-containing monomer is not more than the above upper limit value, the adhesive force can be easily controlled, and the rework property of re-peeling and reusing the glass is good. As the carboxyl group-containing monomer, (meth) acrylic acid is preferable.

On the other hand, when a carboxyl group-containing monomer is not employed as the crosslinkable monomer, the resulting pressure-sensitive adhesive layer can be substantially free of an acid component. Thereby, for example, even if the pressure-sensitive adhesive composition or the pressure-sensitive adhesive layer is in contact with a corrosive film such as a tin-doped indium oxide film or a metal film, these films are not corroded. Therefore, when this pressure-sensitive adhesive composition or pressure-sensitive adhesive layer is placed in direct contact with a transparent conductive film such as a capacitive touch panel that employs these corrosive films, the transparent conductive film is corroded. Without increasing the electrical resistance value of the conductive film. From the viewpoint of corrosion prevention, the amount of the carboxyl group-containing monomer used for the polymerization of the (meth) acrylic copolymer (A) is preferably less than 0.5% by weight, and 0.05% by weight. More preferably, it is less than%.

In order to form such a pressure-sensitive adhesive layer, it is possible to form a hydroxyl group as a crosslinkable monomer from the viewpoint of adhesiveness, crosslinkability, polymerizability and durability, and reworkability that allows re-peeling and reuse of glass. Containing monomers or amino group-containing monomers are preferred, and these may be used in combination. As the hydroxyl group-containing monomer, hydroxyalkyl (meth) acrylate is more preferable, and 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferable. As the amino group-containing monomer, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-butyl (meth) acrylamide are preferable.

The acrylic resin (A) may have a structural unit derived from a monomer other than the non-crosslinkable acrylic monomer and the crosslinkable monomer. Examples of such a monomer include (meth) acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinyl pyrrolidone, vinyl pyridine and the like.

The content of structural units derived from other monomers in the acrylic resin (A) is preferably 0 to 20% by weight, and more preferably 0.5 to 10% by weight. If this content is not less than the lower limit, the physical properties can be easily adjusted, and if it is not more than the upper limit, yellowing due to deterioration over time can be prevented.

The acrylic resin (A), which is a copolymer of monomers described above, preferably has a weight average molecular weight Mw of 400,000 to 2,500,000, more preferably 500,000 to 2,000,000. More preferably, it is 1 million to 2 million, and particularly preferably 1.5 to 2 million. By setting the weight average molecular weight within the above range, a sufficient cohesive force can be exhibited and durability can be enhanced. Furthermore, an increase in the viscosity of the coating liquid containing the pressure-sensitive adhesive composition can be suppressed, and the pressure-sensitive adhesive layer can be easily formed by coating. In addition, a weight average molecular weight can be measured using a gel permeation chromatography (GPC), and is a weight average molecular weight converted into standard polystyrene (PS).

(Crosslinking agent)
As the crosslinking agent, it is preferable to use a crosslinking agent capable of reacting with a monomer having a reactive functional group. For example, an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound, a butylated melamine compound, and the like can be given. Among these crosslinking agents, an isocyanate compound, an epoxy compound, and a metal chelate compound are preferable because the acrylic resin can be easily crosslinked. In particular, when only a hydroxyl group-containing monomer is used as the crosslinkable monomer, it is preferable to use an isocyanate compound because of the reactivity of the hydroxyl group.

Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diester. Glycidyl ether, tetraglycidyl xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexanone, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. Can be mentioned. It is preferable that the content of the crosslinking agent is appropriately selected according to the desired pressure-sensitive adhesive properties. These crosslinking agents can be used alone or in combination of two or more.

The content of the crosslinking agent is preferably from 0.001 to 10 parts by weight, more preferably from 0.01 to 5 parts by weight, based on 100 parts by weight of the solid content of the acrylic resin (A). If it is more than the said lower limit, foaming can be suppressed, and if it is below the said upper limit, sufficient stress relaxation performance can be given.

(Additive)
In the pressure-sensitive adhesive composition of the present invention, components other than the acrylic resin (A), the crosslinking agent and the antistatic agent may be contained. For example, in addition to the acrylic resin (A), a polyester resin, an amino resin, an epoxy resin, or a polyurethane resin may be used in combination.

In addition, the pressure-sensitive adhesive composition in the present invention includes an antioxidant, a metal corrosion inhibitor, a tackifier, a silane coupling agent, an ultraviolet absorber, a light stabilizer such as a hindered amine compound, and a filler as necessary. An additive may be contained. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, lactone antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. These antioxidants may be used alone or in combination of two or more. As the metal corrosion inhibitor, a benzotriazole-based resin is preferable because of the compatibility and high effect of the pressure-sensitive adhesive. Examples of the tackifier include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, and petroleum resin. Examples of the silane coupling agent include mercaptoalkoxysilane compounds (for example, mercapto group-substituted alkoxy oligomers). Examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, triazine compounds, and the like.

The content of these additives is usually preferably from 0.01 to 10 parts by weight, more preferably from 0.05 to 5 parts by weight, based on 100 parts by weight of the solid content of the pressure-sensitive adhesive composition. The amount is particularly preferably 0.1 to 3 parts by weight.

(Method for producing pressure-sensitive adhesive composition)
The pressure-sensitive adhesive composition is produced by dispersing a salt having an anion having a fluoro group and a sulfonyl group in a composition containing a pressure-sensitive resin such as an acrylic resin (A). The production method comprises preparing a salt solution having a polyether and a salt having an anion having a fluoro group and a sulfonyl group, kneading the salt solution (first component) and the adhesive resin (second component) A step of forming a product, and a step of kneading or blending the composition and the adhesive resin (second component). By kneading the first component and the second component, the salt solution is dispersed or dissolved in the composition in the form of fine droplets. In addition, the salt is further kneaded or blended with the adhesive resin (second component) in a state where the salt is dissolved in the composition, so that the salt is dispersed in a state more evenly compatible with the adhesive resin (second component). Is done.

(Adhesive layer)
The thickness of the pressure-sensitive adhesive layer formed from the above pressure-sensitive adhesive composition can be 100 μm or less, preferably about 5 to 50 μm. When the pressure-sensitive adhesive layer is applied to a polarizer, a polarizing plate or the like, it is desirable to form the pressure-sensitive adhesive layer thinly within a range not impairing properties such as workability and durability. For example, the thickness is set to 3 to 25 μm. It is suitable for obtaining good durability while maintaining good processability.

Also, the above-mentioned pressure-sensitive adhesive composition can be formed into a sheet to form a pressure-sensitive adhesive sheet. The pressure-sensitive adhesive sheet can be produced, for example, by dissolving the pressure-sensitive adhesive in a solvent, removing the solvent after coating. As a coating method, a knife coater, a micro bar coater, an air knife coater, a reverse roll coater, a reverse gravure coater, a bario gravure coater, a die coater, a curtain coater and the like can be appropriately selected. If an adhesive sheet is used, there is no need to apply an adhesive at the bonding stage, and a drying step is required. is there.

This pressure-sensitive adhesive sheet preferably has a structure in which a release film (also referred to as a separator) provided with a release agent on a substrate is provided on one or both sides of the pressure-sensitive adhesive sheet. For example, in a double-sided pressure-sensitive adhesive sheet with a release sheet in which a release film is provided on both sides of the pressure-sensitive adhesive layer, a pressure-sensitive adhesive coating solution is applied to the release layer surface of a first release film in which a release film is provided on a polymer film and dried. After that, the release layer surface of the second release film composed of a release agent layer having a different release force from that of the first release film can be obtained by bonding and pressure-bonding to the pressure-sensitive adhesive layer. When the release force of the first release film and the second release film is close, when the release film on the light release force side is peeled off, there is a tearing phenomenon in which the adhesive floats from the release film on the heavy release force side. appear. Therefore, the peel force of the release film on the heavy peel force side is preferably 0.05 to 0.15 N, and the peel force of the peel film on the light peel force side is preferably 0.01 to 0.04 N.

Moreover, at this time, when the difference of the peeling force of two peeling films can be maintained, after apply | coating an adhesive coating liquid previously to a 2nd peeling film, a 1st peeling film may be bonded and pressure-bonded. . The pressure-sensitive adhesive sheet may have a sheet shape or may be wound up in a roll shape.

[Polarizer]
The polarizer is a film having a function of extracting linearly polarized light from incident natural light, and a film obtained by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film can be used. As a raw material for producing a polarizer, for example, a polyvinyl alcohol resin film or a polyvinyl alcohol resin described in JP 2012-159778 A is obtained by adsorbing and orienting a dichroic dye. The polyvinyl alcohol resin constituting the polarizer can be obtained by saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group. The saponification degree of the polyvinyl alcohol resin is usually 85 mol% or more, preferably 98 mol% or more. This polyvinyl alcohol-based resin may be further modified, and for example, polyvinyl formal and polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol resin is usually about 1,000 to 10,000, preferably about 1,500 to 5,000.

In the present invention, an appropriate commercially available product can be used as the polyvinyl alcohol-based resin. Examples of suitable commercial products are trade names, “PVA124”, “PVA117”, “PVA624” and “PVA617” manufactured by Kuraray Co., Ltd., “N-300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. And “NH-18”, “AH-22”, “AH-26”, “JC-33”, “JF-17”, “JF-17L”, “JF-20” of Nippon Vinegar Poval Co., Ltd. ”,“ JM-26 ”,“ JM-33 ”,“ JP-45 ”, and the like.

A film obtained by forming such a polyvinyl alcohol resin is used as an original film of a polarizer. A polyvinyl alcohol-type resin can be formed into a film by a well-known method. The film thickness of the raw film made of polyvinyl alcohol resin is, for example, about 1 to 150 μm. In consideration of easiness of stretching, the film thickness is preferably 3 μm３ or more.

A polarizer is a step of uniaxially stretching a polyvinyl alcohol-based resin film as described above or a polyvinyl alcohol-based resin described in JP 2012-159778A, and dyeing the polyvinyl alcohol-based resin or film with a dichroic dye. After the step of adsorbing the dichroic dye, the step of treating the polyvinyl alcohol resin or film adsorbed with the dichroic dye with an aqueous boric acid solution, and the step of washing with water after the treatment with the aqueous boric acid solution, and finally drying Manufactured.

In addition, the polarizer can also be produced by a method in which a solution of a polyvinyl alcohol resin is applied to a substrate or the like and dried, and then stretched together with the substrate to remove the substrate. Examples of the substrate include a polyethylene terephthalate film, a polycarbonate film, a triacetyl cellulose film, a norbornene film, a polyester film, and a polystyrene film. In this manufacturing method, it becomes easy to manufacture a polarizer layer having a thickness of 7 μm or less.

The transmittance Ty of the polarizer or polarizing plate is preferably 40% to 44%, more preferably 42% to 44%, and even more preferably 42.5% to 44%.
Further, the degree of polarization Py of the polarizer or the polarizing plate is 99% or more, and preferably 99.9% or more.

In the present invention, the thickness of the polarizer layer is preferably 1 to 50 μm, more preferably 2 to 30 μm from the viewpoint of thinning.

In the present invention, the pressure-sensitive adhesive layer formed from the above-mentioned pressure-sensitive adhesive composition is laminated on at least one surface of the polarizer made of the polyvinyl alcohol-based resin described above. By adopting such a pressure-sensitive adhesive composition, the present invention can flexibly adhere the polarizer and the pressure-sensitive adhesive layer, and suppress color loss and deterioration of the polarizer under high temperature and high humidity environment. it can.

The pressure-sensitive adhesive layer is formed on the polarizer by, for example, applying a pressure-sensitive adhesive composition on the polarizer and drying it, or preparing a double-sided pressure-sensitive adhesive sheet with a release sheet as described above. It can carry out by the method of bonding to a polarizer through the adhesive layer exposed by peeling. As for an adhesive layer, it is preferable that the peeling film is laminated | stacked on the surface on the opposite side to a polarizing film.

[Polarizing plate with adhesive]
In the polarizer with an adhesive of the present invention, the above-mentioned adhesive layer is laminated on one surface of the polarizer, and the first transparent protective layer is laminated on the other surface to form a polarizing plate with an adhesive. it can.

(Transparent protective layer)
The 1st transparent protective layer laminated | stacked on the single side | surface of a polarizer can be comprised with the hardened | cured material of a suitable transparent resin film or active energy ray curable resin composition. As the transparent resin film, a film formed from a resin excellent in transparency, uniformity of optical properties, mechanical strength, thermal stability and the like is preferably used. For example, cellulose resin films such as triacetyl cellulose and diacetyl cellulose; polyester resin films such as polyethylene terephthalate, polyethylene isophthalate and polybutylene terephthalate; acrylic resin films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Examples thereof include polycarbonate-based resin films, polyethersulfone-based resin films, polysulfone-based resin films, polyimide-based resin films, polyolefin-based resin films, and cyclic olefin-based resin films having a cyclic olefin as a monomer such as norbornene. Especially, a cellulose resin film, an acrylic resin film, and a cyclic olefin resin film are preferable.

When a cellulose resin film is used as the transparent protective layer, a cellulose acetate resin in which at least a part of cellulose is esterified is suitable. For example, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate and the like can be mentioned. As such a cellulose acetate-based resin film, an appropriate commercially available product can be used. For example, “Fujitac (registered trademark) TD80”, “Fujitac (registered trademark) TD80UF” and “Fujitac (registered trademark) TD80UZ”, sold by FUJIFILM Corporation, are sold by Konica Minolta Opt. “KC8UX2M” and “KC8UY” (both are trade names) are preferable examples.

The acrylic resin film is a film formed from an acrylic resin obtained by mixing and melting and kneading a methacrylic resin and additives added as necessary. Methacrylic resin is a polymer mainly composed of methacrylic acid ester. The methacrylic resin may be a homopolymer of one kind of methacrylic acid ester or a copolymer of methacrylic acid ester with other methacrylic acid ester or acrylic acid ester. Examples of the methacrylic acid esters include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, and the alkyl group usually has about 1 to 4 carbon atoms. The acrylic ester that can be copolymerized with a methacrylic ester is preferably an alkyl acrylate, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. The group usually has about 1 to 8 carbon atoms. In addition to these, the copolymer contains an aromatic vinyl compound such as styrene and a vinylcyan compound such as acrylonitrile, which are compounds having at least one polymerizable carbon-carbon double bond in the molecule. Also good.

The acrylic resin may have a ring structure in the polymer main chain because the durability of the film can be improved. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure, or a lactone ring structure. Specific examples include cyclic acid anhydride structures such as glutaric anhydride structure and succinic anhydride structure, cyclic imide structures such as glutarimide structure and succinimide structure, and lactone ring structures such as butyrolactone and valerolactone.

The acrylic resin film preferably contains acrylic rubber particles from the viewpoint of impact resistance and film-forming property of the film. The amount of the acrylic rubber particles that can be contained in the acrylic resin is preferably 5% by weight or more, more preferably 10% by weight or more with respect to 100% by weight of the acrylic resin. The upper limit of the amount of the acrylic rubber particles is not critical, but if the amount of the acrylic rubber particles is too large, the surface hardness of the film is lowered, and when the film is subjected to surface treatment, it is resistant to the organic solvent in the surface treatment agent. Solvent property decreases. Therefore, the amount of acrylic rubber particles that can be contained in the acrylic resin is preferably 80% by weight or less, and more preferably 60% by weight or less.

The cyclic olefin-based resin is a thermoplastic resin having a cycloolefin monomer unit represented by, for example, norbornene, tetracyclododecene (also known as dimethanooctahydronaphthalene) or a derivative thereof. In addition to the ring-opened polymer of the present invention and the hydrogenated product of the ring-opened copolymer using two or more kinds of cycloolefins, addition copolymerization of cycloolefin with a chain olefin or an aromatic compound having a vinyl group It may be a coalescence. In addition, a polar group may be introduced.

Examples of commercially available cyclic olefin resins include “ARTON” (registered trademark) 販売 sold by JSR Co., Ltd. and “ZEONEX” (registered trademark) sold by Nippon Zeon Co., Ltd. ) And “ZEONOR” (registered trademark), produced in TOPAS ADVANCED POLYMERS GmbH, and sold in Japan from Polyplastics, Mitsui Chemicals, Inc. "Apel" (registered trademark) and the like (all are trade names) sold by

When forming such a cycloolefin-based resin into a film, a known film forming method such as a solvent casting method or a melt extrusion method is appropriately used for film formation. A formed cycloolefin-based resin film and a cycloolefin-based resin film further stretched and provided with a phase difference are also commercially available. For example, "Arton Film" ("Arton" is a registered trademark of the company) sold by JSR Corporation, "Zeonor Film" (registered trademark), sold by Nippon Zeon Corporation, Sekisui Chemical Co., Ltd. "Essina" (registered trademark) and "SCA40" bags (both are trade names), which can be suitably used.

The above transparent resin film is laminated on the polarizer using an appropriate adhesive or pressure-sensitive adhesive. Examples of the adhesive include an active energy ray-curable adhesive and a water-based adhesive. As the active energy ray-curable adhesive, the curing component may be cationically polymerizable, radically polymerizable, or may include both. Examples of the water-based adhesive include an adhesive composition using a polyvinyl alcohol resin or a urethane resin as a main component.

When the transparent protective layer is a cured product of the active energy ray-curable resin composition, the active energy ray-curable component contained in the composition may be cationically polymerizable or radically polymerizable It may be one or both of these components may be included. Examples of active energy rays include ultraviolet rays, visible light, electron beams, and X-rays.

In the polarizing plate with an adhesive of the present invention, the first transparent protective layer is laminated on one side of the polarizer, and the second transparent protective layer and the adhesive layer are provided in this order on the other side of the polarizer. But you can. As the second transparent protective layer, those mentioned as the first transparent protective layer can be used.

(Other optical layers)
The polarizing plate with the pressure-sensitive adhesive of the present invention can be laminated with an optical layer having another optical function, if necessary, on the first transparent protective layer. For example, when this polarizing plate with an adhesive is disposed on the display surface (viewing side) of the image display element, a surface treatment layer such as a hard coat layer, an antireflection layer, or an antiglare layer is formed on the transparent protective layer. It may be provided. These optical layers correspond to the optical layer 13 shown in FIG.

The hard coat layer is formed to prevent the surface of the polarizing plate from being scratched. The hard coat layer is mainly made of an ultraviolet curable resin, for example, an acrylic resin or a silicone resin, so that the adhesion and hardness with the transparent protective layer are increased. An excellent material is appropriately selected and can be formed on the surface of the transparent protective layer.

The antireflection layer is formed for the purpose of preventing reflection of external light on the surface of the polarizing plate, and can be formed by a known method. The anti-glare layer is formed to prevent disturbance of visibility caused by external light reflected on the surface of the polarizing plate, for example, a roughening method such as a sand blast method or an embossing method, In general, the surface of the transparent protective layer is formed to have a concavo-convex structure by a method of applying and curing a coating liquid in which transparent fine particles are mixed with an ultraviolet curable resin.

On the other hand, when this polarizing plate is disposed on the side opposite to the display surface of the liquid crystal cell (back side), on the transparent protective layer, a reflective layer, a transflective layer, a light diffusion layer, a light collector, a brightness enhancement film Etc. can be laminated. These optical layers correspond to the optical layer 15 shown in FIG.

The reflective polarizing plate is used in a liquid crystal display device of a type that reflects external light incident from the viewing side and displays a light source such as a backlight, so that the liquid crystal display device can be easily thinned. The transflective polarizing plate is used in a liquid crystal display device that displays as a reflective type in a bright place and as a transmissive type using a light source such as a backlight in a dark place. The reflective layer for forming a reflective polarizing plate can be formed, for example, by attaching a foil or a vapor deposition film made of a metal such as aluminum to a protective layer on the polarizer. The semi-transmissive reflective layer for making a semi-transmissive reflective polarizing plate is a method of using the reflective layer as a half mirror, or a reflective plate containing a pearl pigment or the like and exhibiting light transmittance is adhered to the polarizing plate. It can be formed by a method or the like.

A diffusion type polarizing plate has a function of diffusing incident light. The light diffusing layer used for this purpose is formed using various methods such as a method of applying a mat treatment to the transparent protective layer on the polarizer, a method of applying a resin containing fine particles, and a method of adhering a film containing fine particles. Is done.

Further, the reflection / diffusion polarizing plate is obtained by providing a diffusion reflection layer by a method of providing a reflection layer reflecting the uneven structure on the fine uneven structure surface of the diffusion type polarizing plate, for example. The reflective layer having a fine concavo-convex structure has advantages such that incident light is diffused by irregular reflection, directivity and glare can be prevented, and unevenness in brightness and darkness can be suppressed. In addition, the resin layer or film containing fine particles has an advantage that incident light and its reflected light are diffused when passing through the layer, and brightness unevenness can be further suppressed. The reflective layer reflecting the surface fine concavo-convex structure can be formed, for example, by directly attaching a metal to the surface of the fine concavo-convex structure by a method such as vapor deposition such as vacuum deposition, ion plating, sputtering, or plating. The fine particles to be blended to form the surface fine concavo-convex structure include, for example, silica, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, cadmium oxide, oxide having an average particle diameter of 0.1 to 30 μm. Inorganic fine particles made of antimony or the like, organic fine particles made of a crosslinked or uncrosslinked polymer, or the like can be used.

The light collecting plate is attached for the purpose of optical path control and can be formed as a prism array sheet, a lens array sheet, or a dot attached sheet.

The brightness enhancement film has a function of transmitting a part of incident natural light as linearly polarized light or circularly polarized light and reflecting the remaining light for reuse, and is used for the purpose of improving brightness in a liquid crystal display device or the like. . Examples include a reflective linearly polarized light separation sheet, a cholesteric liquid crystal polymer alignment film designed to produce anisotropy in reflectance by laminating a plurality of thin film films having different refractive index anisotropies, and the like. Examples include a reflective circularly polarized light separating sheet in which an oriented liquid crystal layer is supported on a film substrate.

The various optical layers as described above can be integrated with the transparent protective layer using a pressure-sensitive adhesive or an adhesive, but the pressure-sensitive adhesive or the adhesive used for this purpose is not particularly limited and is appropriate. Can be selected and used. It is preferable to use a pressure-sensitive adhesive from the viewpoint of easy bonding work and prevention of optical distortion. As an example of an adhesive, the thing similar to an above-described adhesive layer can be mentioned. Moreover, when the formed adhesive layer is exposed on the surface, it is good to arrange | position a peeling film in order to prevent contamination. As a peeling film, the thing similar to what was demonstrated previously can be used.

Hereinafter, the polarizing plate with an adhesive of the present invention will be described with reference to the drawings. In FIG. 1, the example of the preferable layer structure of the polarizing plate with an adhesive of this invention was shown with the cross-sectional schematic diagram. Referring to FIG. 1, a polarizing plate 10 with an adhesive is obtained by laminating a first transparent protective layer 3 on one side of a polarizer 1 and providing an adhesive layer 5 on the other side of the polarizer 1. is there. And the adhesive layer 5 is a composition containing a polyether and a salt having an anion containing a fluoro group and a sulfonyl group as an antistatic agent. It is customary to place a release film 7 on the exposed surface of the pressure-sensitive adhesive layer 5 and temporarily protect the surface until it is bonded to another member.

FIG. 2 is a schematic cross-sectional view showing another example of a preferable layer configuration of the polarizing plate with an adhesive of the present invention. Referring to FIG. 2, a pressure-sensitive adhesive polarizing plate 10 includes a first transparent protective layer 3 laminated on one side of a polarizer 1, and a second transparent protective layer 4 and a pressure-sensitive adhesive on the other side of the polarizer 1. The layer 5 is provided in this order.

The polarizing plate with an adhesive of the present invention has a structure in which a transparent protective layer is laminated on one surface of a polarizer and an adhesive layer is laminated on the other surface, for example, as shown in FIG. The thin polarizing plate is achieved. In addition, even with a polarizing plate having a transparent protective layer only on one side as described above, by providing the above-mentioned pressure-sensitive adhesive layer, it is excellent in heat resistance under a high temperature or high humidity environment or an environment where heating and cooling are repeated, Furthermore, color loss of the polarizer caused by the transfer of the pressure-sensitive adhesive component (mainly antistatic component) can be suppressed.

In addition, the polarizing plate with an adhesive of the present invention has a structure in which a transparent protective layer is laminated on both sides of a polarizer and an adhesive layer is laminated on one transparent protective layer, for example, as shown in FIG. is doing. Thus, when the polarizing plate has a transparent protective layer on both sides, by providing the above-mentioned pressure-sensitive adhesive layer, it is excellent in heat resistance under a high temperature or high humidity environment or an environment where heating and cooling are repeated, and further a pressure-sensitive adhesive. Color loss of the polarizer caused by component transfer can be further suppressed.

The polarizing plate with an adhesive of the present invention can be applied to an image display element such as a liquid crystal cell or a touch panel. Therefore, it is preferable that a release film subjected to a release treatment is laminated on the pressure-sensitive adhesive layer until use.

[Image display element]
The polarizing plate with an adhesive of the present invention can be disposed in various image display elements to form an image display device. In FIG. 3, the example of the preferable layer structure of the image display apparatus of this invention was shown with the cross-sectional schematic diagram.
With reference to FIG. 3, polarizing plate 10 with an adhesive is bonded to both surfaces of image display element (liquid crystal cell) 20 through adhesive layer 5 exposed by peeling release film 7 (see FIG. 1). . FIG. 3 shows an example in which the polarizing plate with the adhesive of the present invention is bonded to both surfaces of the liquid crystal cell, but the

polarizing plates

17 and 19 with the adhesive to be bonded to both surfaces of the liquid crystal cell are the same. It may be different or different.

The polarizing plate with a pressure-sensitive adhesive of the present invention can be arranged, for example, on one or both sides of a liquid crystal cell to form a liquid crystal display device. The liquid crystal cell used is arbitrary, for example, an active matrix drive type represented by VA (Vertical Allignment), IPS (In-plane Switching), ECB (Electrically Controlled Birefringence), OCB (Optically Compensated Birefringence) mode, etc. Liquid crystal display devices using various liquid crystal panels, such as simple matrix drive type represented by STN (Super Twisted Nematic) mode and static drive type represented by TN (Twisted Nematic) mode Can be formed. When providing the polarizing plate with an adhesive of this invention in the both sides of a liquid crystal cell, both may be the same and may differ.

Furthermore, the polarizing plate with an adhesive of the present invention is also effectively used in a circularly polarized or elliptically polarized mode having an antireflection function in an image display device other than a liquid crystal display device, for example, a flat display such as an organic EL display device. . Those skilled in the art will easily understand that when the image display element is an organic EL display element, the polarizing plate of the present invention may be bonded to one side thereof, that is, the viewing side display surface. Of course, the image display device to which the polarizing plate with an adhesive of the present invention is applied is not limited to the one exemplified here.

Hereinafter, the features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. In the examples, “parts” and “%” are “parts by weight” and “% by weight”, respectively, unless otherwise specified.

[Production Example 1: Preparation of acrylic resin A]
80 parts of ethyl acetate was added to a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a stirrer, and a thermometer, and 65 parts of butyl acrylate, 30 parts of 2-ethylhexyl acrylate and 2-hydroxy acrylate were used as monomer components. The internal temperature was raised to 55 ° C. while charging 5 parts of ethyl and filling it with nitrogen gas so as not to contain oxygen. Thereafter, a total solution of 0.06 part of azobisisobutyronitrile (polymerization initiator) dissolved in 10 parts of ethyl acetate was added. Then, after stirring for 12 hours while maintaining the temperature, the polymerization reaction was stopped by cooling to prepare an acrylic resin A. The weight average molecular weight Mw in terms of polystyrene by GPC of the acrylic resin A was 1,500,000.

[Production Example 2: Preparation of acrylic resin B]
80 parts of ethyl acetate was added to a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a stirrer and a thermometer, and 71 parts of butyl acrylate, 24 parts of methyl acrylate, 2-hydroxyethyl acrylate 4 as monomer components And 1 part of acrylic acid were charged and the internal temperature was raised to 55 ° C. while nitrogen gas was sealed and oxygen was not contained. Thereafter, a total amount of a solution obtained by dissolving 0.06 part of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. Then, after stirring for 12 hours while maintaining the temperature, the polymerization reaction was stopped by cooling to prepare an acrylic resin B. The weight average molecular weight Mw in terms of polystyrene by GPC of the acrylic resin B was 15.1 million.

[Production Example 3: Preparation of acrylic resin C]
80 parts of ethyl acetate was added to a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a stirrer and a thermometer, and 71 parts of butyl acrylate, 24 parts of methyl acrylate and 2-hydroxyethyl acrylate 5 as monomer components The internal temperature was increased to 55 ° C. while nitrogen gas was charged and oxygen free. Thereafter, a total solution of 0.06 part of azobisisobutyronitrile (polymerization initiator) dissolved in 10 parts of ethyl acetate was added. Then, after stirring for 12 hours while maintaining the temperature, the polymerization reaction was stopped by cooling to prepare an acrylic resin C. The weight average molecular weight Mw in terms of polystyrene by GPC of the acrylic resin C was 15.1 million.

[Production Example 4: Preparation of acrylic resin D]
80 parts of ethyl acetate was added to a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a stirrer and a thermometer, and 71 parts of butyl acrylate, 24 parts of methyl acrylate, 2-hydroxyethyl acrylate 4 as monomer components .93 parts and 0.07 parts of acrylic acid were charged, and the internal temperature was raised to 55 ° C. while nitrogen gas was sealed and no oxygen was contained. Thereafter, a total amount of a solution obtained by dissolving 0.06 part of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. Then, after stirring for 12 hours while maintaining the temperature, the polymerization reaction was stopped by cooling to prepare an acrylic resin D. The weight average molecular weight Mw in terms of polystyrene by GPC of the acrylic resin D was 1,500,000.

[Production Example 5: Preparation of acrylic resin E]
80 parts of ethyl acetate was added to a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a stirrer and a thermometer, and 71 parts of butyl acrylate, 24 parts of methyl acrylate, 2-hydroxyethyl acrylate 4 as monomer components .85 parts and 0.15 parts of acrylic acid were charged, and the internal temperature was raised to 55 ° C. while nitrogen gas was sealed and no oxygen was contained. Thereafter, a total amount of a solution obtained by dissolving 0.06 part of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. Then, after stirring for 12 hours while maintaining the temperature, the polymerization reaction was stopped by cooling to prepare an acrylic resin system E. The polymerization average molecular weight Mw in terms of polystyrene by GPC of the acrylic resin E was 1,500,000.

About each acrylic resin prepared above, these weight average molecular weight Mw measured the sample melt | dissolved in THF (tetrahydrafuran) by GPC (gel permeation chromatography).

[Production Example 6: Production of polarizing plate 1]
A 75 μm thick polyvinyl alcohol film (trade name “Kuraray Vinylon VF-PS # 7500” obtained from Kuraray Co., Ltd., average polymerization degree of about 2,400, saponification degree of 99.9 mol% or more) was obtained by dry stretching. The film was uniaxially stretched about 5 times and further immersed in pure water at 60 ° C. for 1 minute while maintaining the tension state, and then dissolved in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.05 / 5/100. Immersion at 60 ° C. for 60 seconds. Then, it was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 8.5 / 8.5 / 100 at 72 ° C. for 300 seconds. Next, after washing with pure water at 26 ° C. for 20 seconds, it was dried at 65 ° C. to obtain a 28 μm thick polarizer in which iodine was adsorbed and oriented on the polyvinyl alcohol film. When the polarization degree Py and transmittance Ty of this polarizer were measured using a spectrophotometer [product name “V-7100” of JASCO Corporation], Py = 99.995%, Ty = 42.6. %Met. Next, a water-soluble epoxy resin was added to an aqueous solution in which 3 parts of carboxyl group-modified polyvinyl alcohol [trade name “KL-318” obtained from Kuraray Co., Ltd.] was dissolved in 100 parts of water on one side of the polarizer. Epoxy adhesive added with 1.5 parts of a certain polyamide epoxy additive [trade name “Smiles Resin (registered trademark) 650 (30)” obtained from Taoka Chemical Co., Ltd., aqueous solution with a solid content of 30%]. Agent A was applied, and a polarizing plate 1 was prepared by laminating a 40 μm thick triacetylcellulose film (TAC) [trade name “KC4UY” obtained from Konica Minolta Opto Co., Ltd.] as a transparent protective layer.

[Production Example 7: Production of polarizing plate 2]
A polyvinyl alcohol aqueous solution was applied on a base film [a polypropylene film having a melting point of 163 ° C., a thickness of 110 μm] and dried to prepare a laminated film as a raw material for producing a polarizer. Next, an acetoacetyl group-modified polyvinyl alcohol powder having an average degree of polymerization of 1,100 and a saponification degree of 99.5 mol% [trade name “GOHSEFIMAR (registered trademark) Z-200 obtained from Nippon Synthetic Chemical Industry Co., Ltd.” ”] Was dissolved in 95 ° C. hot water to prepare a 3% strength aqueous solution.
As a crosslinking agent in this aqueous solution, a water-soluble polyamide epoxy resin (trade name “Smiles Resin (registered trademark) 650” obtained from Taoka Chemical Industry Co., Ltd., aqueous solution with a solid content of 30%) The mixture was mixed at a ratio of 5 parts per 6 parts to prepare a primer coating solution. Then, the coated surface of the base film made of polypropylene is subjected to corona treatment, and the primer coating solution is coated on the corona treated surface with a micro gravure coater, and then dried at 80 ° C. for 10 minutes to have a thickness of 0.2 μm. A primer layer was formed. Next, polyvinyl alcohol powder (trade name “PVA124” obtained from Kuraray Co., Ltd.) having an average polymerization degree of 2,400 and a saponification degree of 98.0 to 99.0 mol% was dissolved in 95 ° C. hot water. An aqueous 8% polyvinyl alcohol solution was prepared. The obtained aqueous solution was applied onto the primer layer of the above-mentioned base film using a lip coater at room temperature and dried at 80 ° C. for 20 minutes to form a laminated film consisting of the base film / primer layer / polyvinyl alcohol layer. Produced. This laminated film was subjected to 5.8 times free end longitudinal uniaxial stretching at a temperature of 160 ° C. to obtain a laminated stretched film. The laminated stretched film had an overall thickness of 28.5 μm, and the polyvinyl alcohol layer had a thickness of 4.2 μm.

The laminated stretched film was dyed by immersing it in an aqueous solution of water / iodine / potassium iodide in a weight ratio of 100 / 0.35 / 10 at 26 ° C. for 90 seconds and then washed with pure water at 10 ° C. Next, this laminated film was immersed in an aqueous solution of water / boric acid / potassium iodide in a weight ratio of 100 / 9.5 / 5 at 76 ° C. for 300 seconds to crosslink the polyvinyl alcohol. Next, it was washed with pure water at 10 ° C. for 10 seconds, and finally was dried at 80 ° C. for 200 seconds. By the above operation, a polarizing laminated film in which a polarizer composed of a polyvinyl alcohol layer on which iodine was adsorbed and oriented was formed on a polypropylene base film was produced. The same epoxy adhesive A as used in Production Example 6 is applied to the surface (polarizer surface) opposite to the base film of this polarizing laminated film, and a triacetyl having a thickness of 40 μm is used as a transparent protective layer. After bonding the cellulose film (TAC) [trade name “KC4UY” obtained from Konica Minolta Opto Co., Ltd.], only the base film was peeled off to produce a polarizing plate 2 made of a TAC / polyvinyl alcohol polarizer. . When the polarization degree Py and transmittance Ty of the polarizing plate 2 were measured using a spectrophotometer [product name “V-7100” manufactured by JASCO Corporation], Py = 99.995%, Ty = 41.9. %Met.

A polarizing plate with an adhesive was prepared using these polarizing plates. In the following examples and comparative examples, the following were used as the antistatic agent blended in the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer.

<Antistatic agent>
Antistatic agent 1: Trade name “Monocizer (registered trademark) W-262” of DIC Corporation having the structure of chemical formula (II) and “Polysizer (registered trademark) W-230- having the structure of chemical formula (I) A composition obtained by dissolving 20 parts of bis (trifluoromethanesulfonyl) imidolithium in 100 parts of a polyether ester mixed with H ″ at a ratio of 1: 1. In Table 1 described later, “antistatic agent 1” is described.
Antistatic agent 2: A composition in which 50 parts of bis (trifluoromethanesulfonyl) imide lithium is dissolved in 50 parts of polyalkylene glycol (di / mono) alkyl ether. In Table 2 described later, “antistatic agent 2” is described.
Ionic compound 1: N-hexyl-4-methylpyridinium hexafluorophosphate, solid (25 ° C.). In Tables 1 and 2 below, it is described as “ionic compound 1”.
Ionic compound 2: glycidyltrimethylammonium trifluoromethanesulfonate, liquid (25 ° C.). In Tables 1 and 2 below, it is described as “ionic compound 2”.
Ionic compound 3: 1-decyl-3-methylimidazolium hexafluorophosphate, solid (25 ° C.). In Tables 1 and 2 below, “Ionic Compound 3” is described.

[Example 1]
(Preparation of acrylic adhesive solution)
0.1 part of xylylene diisocyanate (trade name “Takenate (registered trademark) 500” obtained from Mitsui Chemicals, Inc.) as a crosslinking agent with respect to 100 parts of the solid content of the acrylic resin A prepared in Production Example 1, and Add 0.1 part of 3-glycidoxypropylmethoxysilane (product name “KBM-403” obtained from Shin-Etsu Chemical Co., Ltd.) and then add 2.5 parts of antistatic agent 1 as an antistatic agent. Ethyl acetate was added to dilute the solution to a solid content concentration of 15% to prepare an acrylic pressure-sensitive adhesive solution.

(Preparation of adhesive sheet)
A polyethylene terephthalate film with a thickness of 38 μm having a release agent layer treated with a silicone release agent (product name “38RL-07 (2)” obtained from Oji F-Tex Co., Ltd.) The separator is coated on the surface of the release agent layer uniformly with an applicator so that the coating amount after drying is 20 μm / m ² , and dried in a 100 ° C. air-circulating constant temperature oven for 3 minutes. An adhesive layer was formed on the surface of the film. Next, it was bonded to the surface of this pressure-sensitive adhesive layer on a separator film having a thickness of 38 μm (product name “38RL-07 (L)” obtained from Oji F-Tex Co., Ltd.). An adhesive sheet having a configuration of separator film / adhesive layer / separator film sandwiched between a pair of separator films was obtained. This pressure-sensitive adhesive sheet was cured for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 50%.

(Preparation of polarizing plate with adhesive)
The separator film provided with a release agent layer with a light release force is released from the adhesive sheet after curing, and the exposed adhesive layer is directly transferred to the polarizer side of the polarizing plate 1 obtained in Production Example 6 ( A polarizing plate with an adhesive was prepared.

[Example 2]
An acrylic pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that the acrylic resin B was used instead of the acrylic resin A used in Example 1. Next, using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 1.

[Example 3]
An acrylic pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that the acrylic resin C was used instead of the acrylic resin A used in Example 1. Next, using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 1.

[Example 4]
An acrylic pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that the acrylic resin D was used instead of the acrylic resin A used in Example 1. Next, using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 1.

[Example 5]
In the same manner as in Example 1, an acrylic pressure-sensitive adhesive solution was prepared and a pressure-sensitive adhesive sheet was prepared. A polarizing plate with an adhesive was prepared in the same manner as in Example 1 except that the polarizing plate 2 obtained in Production Example 7 was used.

[Example 6]
An acrylic pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that the antistatic agent 2 was used.
Next, using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 1.

[Example 7]
An acrylic pressure-sensitive adhesive solution was prepared in the same manner as in Example 6 except that the acrylic resin B was used instead of the acrylic resin A used in Example 6. Next, a pressure-sensitive adhesive sheet and a polarizing plate with a pressure-sensitive adhesive were produced in the same manner as in Example 6 using this acrylic pressure-sensitive adhesive solution.

[Example 8]
An acrylic pressure-sensitive adhesive solution was prepared in the same manner as in Example 6 except that the acrylic resin C was used instead of the acrylic resin A used in Example 6. Next, a pressure-sensitive adhesive sheet and a polarizing plate with a pressure-sensitive adhesive were produced in the same manner as in Example 6 using this acrylic pressure-sensitive adhesive solution.

[Example 9]
An acrylic pressure-sensitive adhesive solution was prepared in the same manner as in Example 6 except that the acrylic resin D was used instead of the acrylic resin A used in Example 6. Next, a pressure-sensitive adhesive sheet and a polarizing plate with a pressure-sensitive adhesive were produced in the same manner as in Example 6 using this acrylic pressure-sensitive adhesive solution.

[Comparative Example 1]
An acrylic pressure-sensitive adhesive solution was obtained in the same manner as in Example 1 except that the ionic compound 1 was used as the antistatic agent. Next, using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 1.

[Comparative Example 2]
An acrylic pressure-sensitive adhesive solution was obtained in the same manner as in Example 1 except that the ionic compound 2 was used as the antistatic agent. Next, using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 1.

[Comparative Example 3]
An acrylic pressure-sensitive adhesive solution was obtained in the same manner as in Example 2 except that the ionic compound 3 was used as the antistatic agent. Next, using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 1.

[Comparative Example 4]
An acrylic pressure-sensitive adhesive solution was obtained in the same manner as in Example 3 except that the ionic compound 3 was used as the antistatic agent. Next, using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 1.

[Comparative Example 5]
An acrylic pressure-sensitive adhesive solution was obtained in the same manner as in Example 4 except that the ionic compound 3 was used as the antistatic agent. Next, using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 1.

[Comparative Example 6]
An acrylic pressure-sensitive adhesive solution was prepared and a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the ionic compound 1 was used as the antistatic agent. A polarizing plate with an adhesive was prepared in the same manner as in Example 5 using the polarizing plate 2 obtained in Production Example 7.

[Comparative Example 7]
An acrylic pressure-sensitive adhesive solution was prepared in the same manner as in Example 6 except that the ionic compound 1 was used as the antistatic agent. Next, a pressure-sensitive adhesive sheet and a polarizing plate with a pressure-sensitive adhesive were produced in the same manner as in Example 6 using this acrylic pressure-sensitive adhesive solution.

[Comparative Example 8]
An acrylic pressure-sensitive adhesive solution was prepared in the same manner as in Example 6 except that the ionic compound 2 was used as the antistatic agent. Next, a pressure-sensitive adhesive sheet and a polarizing plate with a pressure-sensitive adhesive were produced in the same manner as in Example 6 using this acrylic pressure-sensitive adhesive solution.

[Comparative Example 9]
An acrylic pressure-sensitive adhesive solution was obtained in the same manner as in Example 8 except that the ionic compound 3 was used as the antistatic agent. Next, a pressure-sensitive adhesive sheet and a polarizing plate with a pressure-sensitive adhesive were produced in the same manner as in Example 6 using this acrylic pressure-sensitive adhesive solution.

[Comparative Example 10]
An acrylic pressure-sensitive adhesive solution was obtained in the same manner as in Example 9 except that the ionic compound 3 was used as the antistatic agent. Next, using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 1.

[Reference Example 1]
An acrylic pressure-sensitive adhesive solution was obtained in the same manner as in Example 1 except that the antistatic agent 1 used in Example 1 was not added. Using this acrylic adhesive solution, an adhesive sheet and a polarizing plate with an adhesive were prepared in the same manner as in Example 1.

[Reference Example 2]
Acrylic adhesive in the same manner as in Example 1 except that the acrylic resin E was used in place of the acrylic resin A used in Example 1 and the antistatic agent 1 used in Example 1 was not added. An agent solution was obtained. Using this acrylic adhesive solution, an adhesive sheet and a polarizing plate with an adhesive were prepared in the same manner as in Example 1.

[Reference Example 3]
An acrylic pressure-sensitive adhesive solution was obtained in the same manner as in Example 6 except that the antistatic agent 2 used in Example 6 was not added. Using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 6.

[Reference Example 4]
Acrylic adhesive in the same manner as in Example 6 except that the acrylic resin E was used in place of the acrylic resin A used in Example 6 and the antistatic agent 2 used in Example 6 was not added. An agent solution was obtained. Using this acrylic pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive-attached polarizing plate were produced in the same manner as in Example 6.

The following evaluation was performed using each polarizing plate with an adhesive produced above. The results of Examples 1 to 5, Comparative Examples 1 to 6 and Reference Examples 1 and 2 are shown in Table 1, and the results of Examples 6 to 9, Comparative Examples 7 to 10 and Reference Examples 3 and 4 are shown in Table 2. Shown respectively.

[Evaluation]
<Measurement of surface resistance value>
After removing the separator film of the adhesive-coated polarizing plate cut to 100 mm x 100 mm, the surface resistance value (Ω / □) of the pressure-sensitive adhesive surface was measured using a resistance meter [trade name “Hiresta-UP” (Mitsubishi Chemical Corporation) Hiresta is a registered trademark) Model: MCP-HT450 "].

<Evaluation of polarizing plate durability>
After peeling off the separator film of the polarizing plate with the adhesive, the adhesive surface is attached to one side of a 0.7 mm-thick alkali-free glass [trade name “EAGLE XG (registered trademark)” manufactured by Corning] A laminate was produced. Subsequently, an autoclave treatment was performed at 50 ° C. and 0.5 MPa for 20 minutes to completely adhere the polarizing plate with an adhesive to the glass to produce an optical laminate. The optical laminate produced above was treated at 85 ° C. (heat resistance test) for 500 hours in a constant temperature and humidity chamber, and the optical laminate after the test was visually observed.

(Evaluation criteria)
○: No change in appearance such as floating, peeling or foaming.
Δ: Appearance changes such as floating, peeling and foaming are slightly noticeable.
X: Appearance changes such as floating, peeling and foaming are noticeable.

<Evaluation of optical durability (transmission hue)>
After peeling off the separator film of the polarizing plate with pressure-sensitive adhesive, the pressure-sensitive adhesive surface was adhered to one side of a 0.7 mm-thick alkali-free glass (trade name “EAGLE XG (registered trademark)” manufactured by Corning) An optical laminate was produced. Subsequently, an autoclave treatment was performed at 50 ° C. and 0.5 MPa for 20 minutes to completely adhere the polarizing plate with an adhesive to the glass to produce an optical laminate, and the transmission hue b ^* value was measured. Then, the transmission hue b ^* value after processing the optical laminated body for 100 hours at a temperature of 60 ° C. and a relative humidity of 90% (moisture heat resistance test) in a constant temperature and humidity chamber was measured. Here, b ^* is a color value expressed in the L ^* a ^* b ^* color system. A spectral color difference meter [Nippon Denshoku Co., Ltd. product name “SE6000”] was used for the measurement. Using this measured value, the amount of change Δb ^{* in} the transmitted hue before and after the test was calculated.
Δb ^* = measured value after test-measured value before test

<Measurement of polarization degree>
After peeling off the separator film of the polarizing plate with adhesive, the adhesive surface is attached to one side of a 0.7 mm-thick alkali-free glass [trade name “EAGLE XG (registered trademark)” manufactured by Corning Inc.] and optical A laminate was produced. Subsequently, an autoclave treatment was performed at 50 ° C. and 0.5 MPa for 20 minutes, and the polarizing plate with the adhesive was completely adhered to the glass to produce an optical laminate. The optical laminate produced above was treated at a temperature of 60 ° C. and a relative humidity of 90% (moisture heat resistance test) for 100 hours, and the polarization degree Py of the polarizing plate before and after the treatment for 100 hours was measured with a spectrophotometer [JASCO Product name “V-7100”] was used to calculate the change ΔPy.
ΔPy = (measured value after treatment) − (initial value)

<Verification of visual color change>
After peeling off the separator film of the polarizing plate with adhesive, the adhesive surface is attached to one side of a 0.7 mm-thick alkali-free glass [trade name “EAGLE XG (registered trademark)” manufactured by Corning Inc.] and optical A laminate was produced. Subsequently, an autoclave treatment was performed at 50 ° C. and 0.5 MPa for 20 minutes to completely adhere the polarizing plate with an adhesive to the glass to produce an optical laminate. The optical laminate produced above was treated for 500 hours at 60 ° C. and 90% relative humidity (moisture and heat resistance test) in a constant temperature and humidity chamber, and the presence or absence of a color change was visually confirmed.

From the results shown in Table 1 and Table 2, in Examples 1 to 9 satisfying the provisions of the present invention, the surface resistance value of the pressure-sensitive adhesive layer is sufficiently small, and the optical durability is excellent in addition to the polarizing plate durability. I understand.
That is, in any embodiment, even when left in a high humidity environment for a long time, the hue change (polarizer deterioration) is sufficiently suppressed, the change in the degree of polarization is small, and the high degree of polarization is maintained. Yes. On the other hand, it can be seen that in Comparative Examples 1 to 10 that are outside the scope of the present invention, the optical durability is low. In particular, in Comparative Examples 1 and 2, the durability of the polarizing plate was low and the function as a polarizing plate was poor. In addition, it is understood from the comparison between the reference example and the example that the surface resistance value is sufficiently reduced in the present invention by the antistatic agent defined in the present invention.

The polarizing plate with an adhesive of the present invention is excellent in durability under a high humidity and heat environment. In particular, the present invention is useful for various image display devices for mobile use in which the module itself is thin and light and the durability is improved.

1 ... Polarizer,
3 …… First transparent protective layer,
4 ... Second transparent protective layer,
5 ... Adhesive layer (has antistatic performance),
7: Release film (separator film)
10: Polarizing plate with adhesive,
13: Optical layer (viewing side),
15: Optical layer (back side),
17: Polarizing plate with adhesive on the viewing side,
19 …… Back polarizing plate with adhesive,
20: Image display element (liquid crystal cell).

Claims

Contains an antistatic agent comprising a salt having an anion having a fluoro group and a sulfonyl group, and at least one polyether selected from the group consisting of polyether esters, polyalkylene glycol monoalkyl ethers and polyalkylene glycol dialkyl ethers A polarizer with an adhesive in which an adhesive layer formed from an adhesive composition is laminated on at least one surface of the polarizer.
The polyether has the following formula (I)

(Wherein, m and n are each an integer, and R 1 and R 2 represent an alkyl group)
A compound represented by the following formula (II)

(Wherein p is an integer and R 3 and R 4 represent an alkyl group)
And a compound of the following formula (III)
R 5 (OCH 2 CH 2 ) n OR 6 (III)
(Wherein R 5 represents an alkyl group having 1 to 12 carbon atoms, R 6 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n represents an integer of 3 to 6)
The polarizer with pressure-sensitive adhesive according to claim 1, which is at least one selected from the group consisting of compounds represented by:
The polyether has the following formula (I)

(Wherein, m and n are each an integer, and R 1 and R 2 represent an alkyl group)
And a compound of the following formula (II)

(Wherein p is an integer and R 3 and R 4 represent an alkyl group)
The polarizer with a pressure-sensitive adhesive according to claim 2, which is at least one selected from the group consisting of compounds represented by:
The polyether has the following formula (III)
R 5 (OCH 2 CH 2 ) n OR 6 (III)
(Wherein R 5 represents an alkyl group having 1 to 12 carbon atoms, R 6 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n represents an integer of 3 to 6)
The polarizer with an adhesive according to claim 2, which is a compound represented by the formula:
The pressure-sensitive adhesive composition is a copolymer of a monomer mixture containing at least a (meth) acrylic acid ester monomer having an alkyl group having 1 to 18 carbon atoms, and has a weight average molecular weight of 400,000 to 2.5 million. The polarizer with an adhesive according to any one of claims 1 to 4, comprising 100 parts by weight of the acrylic resin (A) and 0.001 to 10 parts by weight of the crosslinking agent (B).
6. The acrylic resin (A) is a copolymer of a monomer mixture containing at least a carboxyl group-containing monomer in addition to a (meth) acrylic acid ester monomer having an alkyl group having 1 to 18 carbon atoms. The polarizer with adhesive as described.
The acrylic resin (A) contains, in addition to the (meth) acrylic acid ester monomer having an alkyl group having 1 to 18 carbon atoms, one olefinic double bond and at least one reactive functional group ( The polarizer with an adhesive according to claim 5, which is a copolymer of a monomer mixture containing at least a monomer having a carboxyl group).
2. The anion having a fluoro group and a sulfonyl group is at least one anion selected from the group consisting of a bis (fluoroalkylsulfonyl) imide ion, a tris (fluoroalkylsulfonyl) methide ion, and a fluoroalkylsulfonic acid ion. 8. A polarizer with an adhesive according to any one of 7 to 7.
The salt having an anion having a fluoro group and a sulfonyl group is any cation selected from the group consisting of alkali metal ions, group 2 element ions, transition metal ions and amphoteric metal ions, and the fluoro group and sulfonyl group. The polarizer with a pressure-sensitive adhesive according to any one of claims 1 to 8, which is a salt composed of an anion having an anion.
The salt having an anion having a fluoro group and a sulfonyl group comprises an alkali metal salt of bis (fluoroalkylsulfonyl) imide, an alkali metal salt of tris (fluoroalkylsulfonyl) methide, and an alkali metal salt of trifluoroalkylsulfonic acid. The polarizer with a pressure-sensitive adhesive according to any one of claims 1 to 9, which is at least one salt selected from the group.
The first transparent protective layer is laminated on one surface of the polarizer in the polarizer with an adhesive according to any one of claims 1 to 10, and the adhesive layer is laminated on the other surface of the polarizer. A polarizing plate with an adhesive.
The polarizing plate with an adhesive according to claim 11, wherein the first transparent protective layer is laminated on the polarizer via an adhesive layer.
The polarizing plate with an adhesive according to claim 11 or 12, which has a second transparent protective layer between the polarizer and the adhesive layer.
The polarizing plate with an adhesive according to any one of claims 11 to 13, wherein an optical layer is laminated on a surface of the first transparent protective layer opposite to the polarizer.
The polarizer with an adhesive according to any one of claims 1 to 10 or the polarizing plate with an adhesive according to any one of claims 11 to 14, wherein a release film is adhered to the surface of the adhesive layer.
The polarizer with an adhesive according to any one of claims 1 to 10 or the polarizing plate with an adhesive according to any one of claims 11 to 14 is bonded to an image display element through the adhesive layer. Image display device.