JP2018151637A - Transparent resin layer, polarizing film with adhesive layer, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent resin layer that does not degrade reliability of a polarizing film disposed on the most viewer side in an image display device and can impart an antistatic function at such level as not to cause sensitivity degradation of a touch panel.SOLUTION: A transparent resin layer is placed further on a viewer side than a polarizing film disposed on the most viewer side in an image display device. The transparent resin layer has a surface resistivity value of not greater than 1.0×10Ω/sq.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transparent resin layer disposed on the viewing side rather than the polarizing film provided on the most viewing side in the image display device. Moreover, this invention relates to the polarizing film with an adhesive layer formed on the polarizing film by using the said transparent resin layer as a transparent adhesive layer. Further, the present invention provides an image display in which the transparent resin layer (or the transparent adhesive layer of the polarizing film with the adhesive layer) is arranged on the viewing side rather than the polarizing film provided on the most viewing side in the image display device. Relates to the device. Examples of the image display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and electronic paper.

  The transparent resin layer of the present invention can be formed of a transparent adhesive, a transparent liquid resin, and the like. For example, an input device such as a touch panel applied on the viewing side of an image display device, a transparent substrate such as a cover glass and a plastic cover It can apply suitably between members, such as, and a polarizing film. As a touch panel, it can use suitably for touch panels, such as an optical system, an ultrasonic system, an electrostatic capacitance system, and a resistive film system. In particular, it is suitably used for a capacitive touch panel. Although the said touch panel is not specifically limited, For example, it is used for a mobile telephone, a tablet computer, a portable information terminal, etc.

  In recent years, an input device using an image display device such as a liquid crystal display device such as a mobile phone or a portable music player in combination with a touch panel has become widespread. In particular, capacitive touch panels are rapidly spreading due to their functionality.

  Currently, many transparent conductive films used for touch panels are known in which a transparent conductive thin film (ITO film) is laminated on a transparent plastic film substrate or glass. A transparent conductive film is laminated | stacked on another member through an adhesive layer. Various types of pressure-sensitive adhesive layers have been proposed (see Patent Documents 1 to 5).

  When the transparent conductive film is used for an electrode substrate of a capacitive touch panel, a film obtained by patterning the transparent conductive thin film is used. A transparent conductive film having such a patterned transparent conductive thin film is used by being laminated with an adhesive layer together with other transparent conductive films and the like. These transparent conductive films are suitably used for multi-touch type input devices that can be operated simultaneously with two or more fingers. In other words, the capacitive touch panel has a mechanism for sensing when the output signal of the position changes when the touch panel is touched with a finger or the like, and the amount of change of the signal exceeds a certain threshold.

JP 2003-238915 A JP 2003-342542 A JP 2004-231723 A JP 2002-363530 A JP 2012-246477 A

  Static electricity is generated during the manufacture of image display devices. In such a case, for example, in a liquid crystal display device, the orientation of the liquid crystal inside the device is affected, leading to defects. Further, display unevenness due to static electricity may occur when the liquid crystal display device is used. In order to suppress the generation of static electricity generated in the liquid crystal display device, for example, an antistatic function is imparted to the pressure-sensitive adhesive layer provided between the polarizing film on the viewing side and the liquid crystal cell, or an antistatic layer is provided. However, when a surfactant or an ionic compound is added to the pressure-sensitive adhesive layer in order to impart an antistatic function, there is a concern that reliability of the polarizing film may be reduced in a heating test or a heating / humidification test.

  Moreover, in an image display apparatus, a touch panel may be arrange | positioned further on the visual recognition side rather than the polarizing film by the visual recognition side. The touch panel is required to have an antistatic function at a level that does not cause a decrease in sensitivity of the touch panel in order to suppress the generation of static electricity. For example, in an image display device (liquid crystal display device), when an antistatic layer (ITO layer or the like) is provided on the surface on the viewing side of the liquid crystal panel, unevenness in static electricity can be suppressed to some extent. However, the antistatic layer provided on the surface on the viewing side of the liquid crystal panel is likely to cause problems such as a decrease in optical properties such as depolarization or generation of bright spots due to impurities depending on the antistatic agent to be added. The reliability of the polarizing film was not sufficient. In addition, in an in-cell type liquid crystal display device with a built-in touch sensor, an antistatic layer for suppressing static electricity unevenness is not formed on the surface on the viewing side of the liquid crystal panel. Although the antistatic layer is formed on the surface on the side, since the antistatic layer is patterned for grounding, there is a part where the antistatic layer is partially absent. The built-in liquid crystal display device cannot be said to have a sufficient antistatic function.

  Therefore, the present invention provides a transparent resin layer that can impart an antistatic function at a level that does not cause a decrease in sensitivity of the touch panel without impairing the reliability of the polarizing film provided on the most visible side in the image display device. For the purpose.

  Moreover, this invention aims at providing the polarizing film with an adhesive layer formed on the polarizing film by using the said transparent resin layer as a transparent adhesive layer. Furthermore, this invention aims at providing the image surface apparatus which has the said polarizing film with a transparent resin layer or an adhesive layer.

  As a result of intensive studies to solve the above problems, the present inventors have found the following transparent resin layer and have completed the present invention.

That is, the present invention is a transparent resin layer disposed on the viewing side rather than the polarizing film provided on the most viewing side in the image display device,
The transparent resin layer relates to a transparent resin layer having a surface resistance value of 1.0 × 10 ¹³ Ω / □ or less.

In the transparent resin layer, the transparent resin layer preferably has a thickness of 5 μm to 1 mm. The transparent resin layer preferably has a surface resistance value (Ω / □) multiplied by a thickness (cm) (volume resistance value) of 1.0 × 10 ¹² Ω · cm or less.

  The material for forming the transparent resin layer preferably contains an acrylic polymer as a base polymer.

  The material for forming the transparent resin layer can contain an ionic compound.

  A transparent adhesive can be used as a material for forming the bright resin layer. A transparent liquid resin can be used as a material for forming the transparent resin layer.

  The transparent resin layer can be suitably applied to a touch panel. In particular, it can be suitably applied to a liquid crystal display device with a built-in touch sensor such as an in-cell type or an on-cell type.

Further, the present invention is a polarizing film with a pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer disposed on the viewing side than the polarizing film provided on the most viewing side in the image display device and the polarizing film,
The said adhesive layer is related with the polarizing film with an adhesive layer characterized by being a transparent resin layer which uses the said transparent adhesive layer as a forming material.

The present invention is also an image display device having at least one polarizing film,
The present invention relates to an image display device comprising at least one transparent resin layer on the viewing side of a polarizing film provided on the most viewing side in the image display device. The said image display apparatus WHEREIN: The said transparent resin layer can be provided as an adhesive layer in the said polarizing film with an adhesive layer.

The transparent resin layer of the present invention has a surface resistance value of 1.0 × 10 ¹³ Ω / □ or less and has an antistatic function. Moreover, the said transparent resin layer is arrange | positioned at the visual recognition side rather than the polarizing film provided in the visual recognition side most in the image display apparatus (for example, liquid crystal display device) which has arrange | positioned the touch panel. Therefore, there are problems such as depolarization that may occur when an antistatic layer (low surface resistance layer) is provided between the polarizing film on the viewing side and the liquid crystal panel, and deterioration of optical properties such as generation of bright spots due to impurities. It can be greatly reduced, and the reliability of the polarizing film provided on the most visible side is not impaired. Thus, the transparent resin layer of the present invention can impart an antistatic function to the touch panel at an appropriate level without impairing the performance of the image display device.

  In particular, the transparent resin layer of the present invention is effective when applied to an in-cell type or on-cell type liquid crystal display device with a built-in touch sensor. For example, by providing the transparent resin layer of the present invention as a pressure-sensitive adhesive layer or the like on a polarizing film provided on the most visible side, an in-cell type or on-cell type liquid crystal display device with a built-in touch sensor can be improved in quality.

  Moreover, when using the said transparent resin layer as an adhesive layer, durability is favorable when a polarizing film with an adhesive layer is produced beforehand and applied to an image display apparatus. The polarizing film with an adhesive layer is preferable in terms of the reliability of the polarizing film provided on the most visible side.

It is a conceptual diagram of the arrangement | positioning location where the transparent resin layer of this invention is applied in an image display apparatus. It is a conceptual diagram which shows typically the state by which the image display apparatus and the member are bonded through the transparent resin layer of this invention. It is sectional drawing which shows typically one Embodiment of an image display apparatus. It is sectional drawing which shows typically one Embodiment of an image display apparatus. It is sectional drawing which shows typically one Embodiment of an image display apparatus. It is sectional drawing which shows typically one Embodiment of a touchscreen. It is sectional drawing which shows typically one Embodiment of a touchscreen.

  Hereinafter, embodiments of the transparent resin layer of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the embodiments shown in the drawings.

  As shown in FIG. 1, the transparent resin layer A of the present invention is applied more on the viewing side than the polarizing film 1 provided on the most viewing side in the image display device B having at least one polarizing film 1.

  FIG. 2 is a conceptual diagram schematically showing a state in which the polarizing film 1 provided on the most viewing side of the image display device B and the member C are bonded via the transparent resin layer A. In FIG. 2, the transparent resin layer A can be used as a transparent adhesive layer or a transparent liquid resin layer. Moreover, when the transparent resin layer A is a transparent adhesive layer, it can be used as a polarizing film with an adhesive layer provided in the polarizing film 1 in advance. Examples of the member C include an input device such as a touch panel applied on the viewing side of the image display device, a transparent substrate such as a cover glass and a plastic cover, and the like.

  The image display device B has at least one polarizing film 1, and examples of the image display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and electronic paper. . As the image display device B, a liquid crystal display device having the polarizing film 1 on both sides of the liquid crystal layer 5 can be suitably used. Cross-sectional views schematically showing a typical embodiment of an image display device (liquid crystal display device) are shown in FIGS. 3a to 3c. In the image display devices (liquid crystal display devices) shown in FIGS. 3a to 3c, the upper polarizing film 1 is located on the most visible side.

  The image display device (liquid crystal display device) shown in FIG. 3a has a polarizing film 1 (viewing side) / adhesive layer 2 / antistatic layer 3 / glass substrate 4 / liquid crystal layer 5 / drive electrode 6 / glass substrate 4 / adhesive. It has the structure of layer 2 / polarizing film 1. The antistatic layer 3 and the drive electrode 6 can be formed of a transparent conductive layer. The antistatic layer 3 can be arbitrarily formed.

  The image display device (liquid crystal display device) shown in FIG. 3b is a case where the transparent conductive layer is used as an electrode for a touch panel (in-cell type touch panel), and polarizing film 1 (viewing side) / adhesive layer 2 / antistatic layer. It has the configuration of cum sensor layer 7 / glass substrate 4 / liquid crystal layer 5 / driving electrode / sensor layer 8 / glass substrate 4 / adhesive layer 2 / polarizing film 1. The antistatic layer / sensor layer 7, the drive electrode / sensor layer 8, and the drive electrode 6 can be formed of a transparent conductive layer.

  The image display device (liquid crystal display device) shown in FIG. 3c is a case where the transparent conductive layer is used as an electrode for a touch panel (on-cell type touch panel). Polarizing film 1 / adhesive layer 2 / antistatic layer / sensor layer 7 / Sensor layer 9 / glass substrate 4 / liquid crystal layer 5 / drive electrode 6 / glass substrate 4 / adhesive layer 2 / polarizing film 1 The antistatic layer / sensor layer 7, the sensor layer 9, and the drive electrode 6 can be formed of a transparent conductive layer.

  As the polarizing film, one having a transparent protective film on one or both sides of a polarizer is generally used. The transparent protective film in the polarizing film can be provided with a functional layer such as a hard coat layer. In addition, an optical film used for forming an image display device such as a liquid crystal display device or an organic EL display device is appropriately used. Examples of the optical film include liquid crystal display devices such as a reflection plate, an anti-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), an optical compensation film, a visual compensation film, and a brightness enhancement film. What becomes an optical layer which may be used for formation of is mentioned. These can be used alone as an optical film, or can be laminated on the polarizing film for practical use to use one layer or two or more layers.

  A pressure-sensitive adhesive layer (corresponding to the pressure-sensitive adhesive layer 2 in FIGS. 3a to 3c) can be formed on the polarizing film and the optical film in order to adhere to other members such as a liquid crystal cell (glass substrate). For the pressure-sensitive adhesive layer, for example, an acrylic polymer, a silicone-based polymer, polyester, polyurethane, polyamide, polyether, a fluorine-based polymer, a rubber-based polymer, or the like can be used by appropriately selecting a base polymer and various pressure-sensitive adhesives. In particular, an acrylic pressure-sensitive adhesive having excellent optical transparency, moderate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and excellent weather resistance and heat resistance is preferable.

  Attaching the pressure-sensitive adhesive layer to one side or both sides of the polarizing film or the optical film can be performed by an appropriate method. For example, a pressure sensitive adhesive solution of about 10 to 40% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of a suitable solvent alone or a mixture such as toluene and ethyl acetate is prepared. A method in which it is directly attached on a polarizing film or an optical film by an appropriate development method such as a casting method or a coating method, or an adhesive layer is formed on a separator according to the above, and this is applied to a polarizing film or an optical film. Examples include a method of transferring onto a film.

  The pressure-sensitive adhesive layer can be provided on one side or both sides of a polarizing film or an optical film as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers, such as a different composition, a kind, and thickness, in the front and back of a polarizing film or an optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 500 μm, preferably 5 to 200 μm, and particularly preferably 10 to 100 μm.

  Generally, a liquid crystal display device incorporates a drive circuit by appropriately assembling components such as a liquid crystal cell (glass substrate / liquid crystal layer / glass substrate), polarizing films disposed on both sides thereof, and an illumination system as required. And so on. As the liquid crystal cell, any type such as a TN type, STN type, π type, VA type, IPS type, or the like can be used. In addition, an appropriate liquid crystal display device such as a lighting system using a backlight or a reflecting plate can be formed. Further, when forming a liquid crystal display device, for example, a single layer or a suitable part such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.

  Cross-sectional views schematically showing a typical embodiment of the touch panel C are shown in FIGS. 4a to 4b. The touch panel C in FIG. 4a is a capacitive touch panel, and a transparent substrate 11, a transparent resin layer A, and a transparent conductive film 12 are laminated in this order. Moreover, the transparent conductive film 12 can be laminated in two or more layers. In FIG. 4b, as the capacitive touch panel C, two transparent conductive films 12 are laminated. The transparent base 11, the transparent resin layer A, the transparent conductive film 12, the transparent resin layer A, and the transparent conductive The film 12 is laminated in this order. Thus, the transparent resin layer A of the present invention can be applied as an internal member of a touch panel. The transparent substrate 11 can have a sensor layer. The transparent substrate 11 can be applied alone to an image display device (liquid crystal display device) as a cover glass or a plastic cover. In addition, a hard coat film can be provided on the transparent conductive film 12 on the side opposite to the transparent substrate 11 of the touch panel C represented by FIGS. 4a to 4b (not shown).

  Examples of the transparent substrate include a glass plate and a transparent acrylic plate (PMMA plate). The transparent substrate is a so-called cover glass and can be used as a decorative panel. The transparent conductive film is preferably a glass plate or a transparent plastic film (particularly a PET film) provided with a transparent conductive film. Examples of the transparent conductive film include a thin film made of a metal, a metal oxide, or a mixture thereof, and examples thereof include a thin film of ITO (indium tin oxide), ZnO, SnO, and CTO (cadmium tin oxide). The thickness of the transparent conductive film is not particularly limited, but is about 10 to 200 nm. A typical example of the transparent conductive film is an ITO film in which an ITO film is provided on a PET film. The transparent conductive film can be provided via an undercoat layer. A plurality of undercoat layers can be provided. An oligomer migration preventing layer can be provided between the transparent plastic film substrate and the pressure-sensitive adhesive layer. The hard coat film is preferably one obtained by subjecting a transparent plastic film such as a PET film to a hard coat treatment.

The structure of the example which applied the transparent resin layer A of this invention to the image display apparatus is shown below. As a configuration,
Transparent substrate 11 / transparent resin layer (adhesive layer) A / transparent conductive film 12 / adhesive layer (or adhesive sheet) / transparent conductive film / transparent resin layer (adhesive layer) A / liquid crystal display (LCD) B;
Transparent substrate 11 (with transparent conductive thin film such as ITO: with sensor) / transparent resin layer (adhesive layer) A / transparent conductive film 12 / transparent resin layer (adhesive layer) A / liquid crystal display (LCD) B ;
Transparent substrate 11 (with transparent conductive thin film such as ITO: with sensor) / transparent resin layer (adhesive layer) A / liquid crystal display (LCD) B;
Transparent substrate 11 / transparent resin layer (adhesive layer) A / circularly polarizing film / transparent resin layer (adhesive layer) A / touch sensor / organic EL display device (OLED) B;
Transparent substrate 11 / transparent resin layer (adhesive layer) A / touch sensor / transparent resin layer (adhesive layer) A / touch sensor / liquid crystal display (LCD) B;
Transparent substrate 11 / transparent resin layer (adhesive layer) A / touch sensor / liquid crystal display (LCD) B:
Transparent substrate 11 / transparent resin layer (adhesive layer) A / touch sensor / transparent resin layer (adhesive layer) A / liquid crystal display (LCD) B;
Transparent substrate 11 / transparent resin layer (adhesive layer) A / in-cell type liquid crystal display device (in-cell type liquid crystal display device with a built-in touch sensor: LCD) B / polarizing film 1;
Transparent substrate 11 / transparent resin layer (adhesive layer) A / on-cell liquid crystal display device (on-cell liquid crystal display device with built-in touch sensor: LCD) B; and the like.
The above is an example of a preferable layer structure, and is not limited to these structures. In the above configuration, the transparent resin layer A of the present invention is used as at least one transparent resin layer A. In addition, although the case where it was the adhesive layer as the transparent resin layer A was illustrated in the said structure, the transparent resin layer A can also be formed from transparent liquid resin.

The transparent resin layer of the present invention will be described below. The transparent resin layer of the present invention satisfies a surface resistance value of 1.0 × 10 ¹³ Ω / □ or less. The surface resistance value is preferably 1.0 × 10 ⁸ Ω / □ to 1.0 × 10 ¹³ Ω / □, more preferably 1.0 × 10 ⁹ Ω / □ to 1.0 × 10 ¹² Ω / □, More preferably, it is 5.0 × 10 ⁹ Ω / □ to 5.0 × 10 ¹¹ Ω / □. By disposing the transparent resin layer that satisfies the surface resistance value on the image display device (viewing side more than the polarizing film on the most viewing side), it is possible to charge the touch panel appropriately without degrading the performance of the image display device. A prevention function can be added.

  In addition, it can be satisfied that the transparent resin layer of the present invention is “transparent” because the haze value measured at a thickness of 25 μm is 2% or less. The haze value is preferably 0 to 1.5%, and more preferably 0 to 1%.

  Moreover, it is preferable that the thickness of the transparent resin layer of this invention is 5 micrometers-1 mm. The thickness of the transparent resin layer can be appropriately designed depending on the location where the transparent resin layer is applied. The thickness of the transparent resin layer is preferably 10 μm to 500 μm, more preferably 20 μm to 300 μm.

Further, the transparent resin layer of the present invention preferably has a value (volume resistance value) obtained by multiplying the surface resistance value (Ω / □) by the thickness (cm) of 1.0 × 10 ¹² Ω · cm or less, Furthermore, it is preferably 1.0 × 10 ⁷ Ω · cm or less, more preferably 1.0 × 10 ⁶ Ω · cm or less.

  As the material for forming the transparent resin layer, materials containing various base polymers can be used. There are no particular restrictions on the type of base polymer, but examples include rubber polymers, (meth) acrylic polymers, silicone polymers, urethane polymers, vinyl alkyl ether polymers, polyvinyl alcohol polymers, polyvinyl pyrrolidone polymers, poly polymers. Various polymers such as acrylamide polymer and cellulose polymer are listed.

  Among these base polymers, those excellent in optical transparency, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties and excellent in weather resistance and heat resistance are preferably used. A (meth) acrylic polymer is preferably used as such a feature. Hereinafter, the case where a transparent resin layer is used as an adhesive layer is demonstrated as a representative example of a transparent resin layer.

  The (meth) acrylic polymer can be obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having an alkyl group having 4 to 24 carbon atoms at the terminal of the ester group. Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.

  Examples of the alkyl (meth) acrylate include those having a linear or branched alkyl group having 4 to 24 carbon atoms. Alkyl (meth) acrylate can be used individually by 1 type or in combination of 2 or more types.

  As said alkyl (meth) acrylate, the alkyl (meth) acrylate which has the said C4-C9 branch can be illustrated, for example. The alkyl (meth) acrylate is preferable in terms of easily balancing the adhesive properties. For example, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, isohexyl (meth) ) Acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and the like. The carbon number of the acrylic group in the alkyl (meth) acrylate having a branched chain having 6 to 9 carbon atoms is more preferably 7 to 9, and further preferably 8 to 9.

  In the present invention, the alkyl (meth) acrylate having an alkyl group having 4 to 24 carbon atoms at the ester end is 40% by weight or more based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. It is preferably 50% by weight or more, more preferably 60% by weight or more. It is preferable to use 40% by weight or more because it is easy to balance the adhesive properties.

  The monomer component forming the (meth) acrylic polymer of the present invention can contain a copolymerizable monomer other than the alkyl (meth) acrylate as a monofunctional monomer component. A copolymerization monomer can be used as the remainder of the said alkyl (meth) acrylate in a monomer component.

  As the copolymerization monomer, for example, a cyclic nitrogen-containing monomer can be included. As the cyclic nitrogen-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a cyclic nitrogen structure can be used without particular limitation. The cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure. Examples of cyclic nitrogen-containing monomers include lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinyl Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as imidazole, vinyl oxazole and vinyl morpholine. Moreover, the (meth) acryl monomer containing heterocyclic rings, such as a morpholine ring, a piperidine ring, a pyrrolidine ring, a piperazine ring, is mentioned. Specific examples include N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like. Among the cyclic nitrogen-containing monomers, lactam vinyl monomers are preferable from the viewpoint of dielectric constant and cohesiveness.

  In the present invention, the cyclic nitrogen-containing monomer is preferably 0.5 to 50% by weight, more preferably 0.5 to 40% by weight, based on all monomer components forming the (meth) acrylic polymer. More preferably, it is 0.5 to 30% by weight. Use of the cyclic nitrogen-containing monomer in the above range is preferable in terms of control of the surface resistance value, particularly compatibility with the ionic compound when using the ionic compound, and durability of the antistatic function.

  The monomer component forming the (meth) acrylic polymer of the present invention can contain a hydroxyl group-containing monomer as a monofunctional monomer component. As the hydroxyl group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and the like; And hydroxyalkylcycloalkane (meth) acrylates such as 4-hydroxymethylcyclohexyl) methyl (meth) acrylate. Other examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. These can be used alone or in combination. Of these, hydroxyalkyl (meth) acrylate is preferred.

  In the present invention, the hydroxyl group-containing monomer is preferably 1% by weight or more from the viewpoint of enhancing adhesive force and cohesive force with respect to the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, Further, it is preferably 2% by weight or more, and more preferably 3% by weight or more. On the other hand, if the amount of the hydroxyl group-containing monomer is too large, the pressure-sensitive adhesive layer becomes hard and the adhesive strength may decrease, and the viscosity of the pressure-sensitive adhesive may become too high or gel. The hydroxyl group-containing monomer is preferably 30% by weight or less, more preferably 27% by weight or less, and further 25% by weight with respect to the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. The following are preferable.

  In addition, the monomer component forming the (meth) acrylic polymer of the present invention can contain other functional group-containing monomers as monofunctional monomers, such as having a carboxyl group-containing monomer and a cyclic ether group. Monomer.

  As the carboxyl group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Can be used alone or in combination. These anhydrides can be used for itaconic acid and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable. In addition, a carboxyl group-containing monomer can be arbitrarily used for the monomer component used for manufacture of the (meth) acrylic-type polymer of this invention, On the other hand, it is not necessary to use a carboxyl group-containing monomer. A pressure-sensitive adhesive containing a (meth) acrylic polymer obtained from a monomer component not containing a carboxyl group-containing monomer can form a pressure-sensitive adhesive layer in which metal corrosion caused by a carboxyl group is reduced.

  As the monomer having a cyclic ether group, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and a cyclic ether group such as an epoxy group or an oxetane group. It can be used without particular limitation. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Examples of the oxetane group-containing monomer include 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, and 3-butyl-oxetanylmethyl (meth) acrylate. , 3-hexyl oxetanylmethyl (meth) acrylate, and the like. These can be used alone or in combination.

  In the present invention, the carboxyl group-containing monomer and the monomer having a cyclic ether group are preferably 30% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. It is preferably 27% by weight or less, more preferably 25% by weight or less.

The monomer component forming the (meth) acrylic polymer of the present invention includes, for example, CH ₂ ═C (R ¹ ) COOR ² (wherein R ¹ is hydrogen or a methyl group, and R ² is the number of carbon atoms). And an alkyl (meth) acrylate represented by 1 to 3 unsubstituted alkyl groups, substituted alkyl groups, or cyclic cycloalkyl groups.

Here, the unsubstituted alkyl group having 1 to 3 carbon atoms or the substituted alkyl group as R ² represents a linear or branched alkyl group. In the case of a substituted alkyl group, the substituent is preferably an aryl group having 3 to 8 carbon atoms or an aryloxy group having 3 to 8 carbon atoms. The aryl group is not limited, but is preferably a phenyl group.

Examples of such a monomer represented by CH ₂ ═C (R ¹ ) COOR ² include methyl (meth) acrylate, ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. These can be used alone or in combination.

In the present invention, the (meth) acrylate represented by CH ₂ ═C (R ¹ ) COOR ² is 50% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. 45% by weight or less is preferable. Furthermore, it is preferably 40% by weight or less, and more preferably 35% by weight or less.

  Other copolymer monomers include vinyl acetate, vinyl propionate, styrene, α-methylstyrene; (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) Glycol acrylic ester monomers such as methoxypolypropylene glycol acrylate; Acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate; Monomers, amino group-containing monomers, imide group-containing monomers, N-acryloylmorpholine, vinyl ether monomers and the like can also be used. Moreover, as a copolymerization monomer, the monomer which has cyclic structures, such as terpene (meth) acrylate and dicyclopentanyl (meth) acrylate, can be used.

  Furthermore, the silane type monomer containing a silicon atom, etc. are mentioned. Examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane. , 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.

  The monomer component that forms the (meth) acrylic polymer of the present invention contains a polyfunctional monomer as necessary in order to adjust the cohesive strength of the pressure-sensitive adhesive, in addition to the monofunctional monomer exemplified above. be able to.

  The polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, such as (poly) ethylene glycol di (meth) acrylate, (Poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methanetri (meth) acrylate Ester compounds of polyhydric alcohols such as carbonate and (meth) acrylic acid; allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di (meth) acrylate, hexyl di ( And (meth) acrylate. Among these, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.

  The amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but it is preferably used at 3 parts by weight or less, more preferably 2 parts by weight or less, with respect to a total of 100 parts by weight of monofunctional monomers 1 part by weight or less is more preferable. Moreover, it does not specifically limit as a lower limit, However It is preferable that it is 0 weight part or more, and it is more preferable that it is 0.001 weight part or more. Adhesive force can be improved when the usage-amount of a polyfunctional monomer exists in the said range.

  The production of such a (meth) acrylic polymer can be appropriately selected from known production methods such as radiation polymerization such as solution polymerization and ultraviolet polymerization, various radical polymerizations such as bulk polymerization and emulsion polymerization. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

  The polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, The usage-amount is suitably adjusted according to these kinds.

  For example, in solution polymerization or the like, for example, ethyl acetate, toluene or the like is used as a polymerization solvent. As a specific example of solution polymerization, the reaction is performed under an inert gas stream such as nitrogen, and a polymerization initiator is added, and the reaction is usually performed at about 50 to 70 ° C. under reaction conditions of about 5 to 30 hours.

  Examples of the thermal polymerization initiator used for solution polymerization include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis (2 -Methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (N, N′-dimethyleneisobutyl) Amidine), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057) Any azo initiator, persulfate such as potassium persulfate, ammonium persulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxy Dicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3 -Tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-hexylperoxy) cyclohexane , Peracids such as t-butyl hydroperoxide and hydrogen peroxide Physical initiators, combinations of persulfates and sodium bisulfite, redox initiators combining peroxides and reducing agents, such as combinations of peroxides and sodium ascorbate, etc. It is not limited.

  The polymerization initiator may be used alone or in combination of two or more, but the total content is 0.005 to 1 part by weight with respect to 100 parts by weight of the monomer. Is preferably about 0.02 to 0.5 parts by weight.

  In order to produce the (meth) acrylic polymer having the weight average molecular weight using, for example, 2,2′-azobisisobutyronitrile as the polymerization initiator, the amount of the polymerization initiator used is a monomer. The amount is preferably about 0.06 to 0.2 part by weight, more preferably about 0.08 to 0.175 part by weight with respect to 100 parts by weight of the total amount of the components.

  Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. The chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to

  Examples of the emulsifier used in emulsion polymerization include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, and polyoxy Nonionic emulsifiers such as ethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer are exemplified. These emulsifiers may be used alone or in combination of two or more.

  Further, as reactive emulsifiers, as emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Soap SE10N (manufactured by ADEKA), and the like. Reactive emulsifiers are preferable because they are incorporated into the polymer chain after polymerization and thus have improved water resistance. The amount of the emulsifier used is more preferably 0.3 to 5 parts by weight and 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability with respect to 100 parts by weight of the total amount of monomer components.

  Moreover, when manufacturing a (meth) acrylic-type polymer by radiation polymerization, it can superpose | polymerize and manufacture the said monomer component by irradiating radiation, such as an electron beam and an ultraviolet-ray. When the radiation polymerization is performed with an electron beam, it is not particularly necessary to include a photopolymerization initiator in the monomer component. However, when the radiation polymerization is performed with ultraviolet polymerization, the polymerization time is particularly shortened. For example, a photopolymerization initiator can be contained in the monomer component because of the advantages that can be achieved. A photoinitiator can be used individually by 1 type or in combination of 2 or more types.

  The photopolymerization initiator is not particularly limited, but is not particularly limited as long as it initiates photopolymerization, and a commonly used photopolymerization initiator can be used. For example, benzoin ether photopolymerization initiator, acetophenone photopolymerization initiator, α-ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator Agents, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, thioxanthone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and the like can be used.

  Specifically, examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- 1-one [trade name: Irgacure 651, manufactured by BASF Corporation], anisole methyl ether and the like can be mentioned. Examples of the acetophenone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone [trade name: Irgacure 184, manufactured by BASF], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [trade name: Irgacure 2959, manufactured by BASF Corp.], 2-hydroxy-2-methyl-1-phenyl-propane- 1-one [trade name: Darocur 1173, manufactured by BASF Corporation], methoxyacetophenone, and the like can be given. Examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) -phenyl] -2-hydroxy-2-methylpropane-1- ON etc. are mentioned. Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalene sulfonyl chloride. Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.

  The benzoin photopolymerization initiator includes, for example, benzoin. Examples of the benzyl photopolymerization initiator include benzyl. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexyl phenyl ketone, and the like. Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone and the like are included.

Examples of the acylphosphine photopolymerization initiator include bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, bis ( 2,6-dimethoxybenzoyl) -n-butylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1- Methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -t-butylphosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2,6-dimethoxybenzoyl) octylphosphine Oxides, bis (2-mes Xylbenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-methoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (2-methyl Propan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-dibutoxybenzoyl) (2-methylpropane-1- Yl) phosphine oxide, bis (2,4-dimethoxybenzoyl)
(2-methylpropan-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) (2,4-dipentoxyphenyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, Bis (2,6-dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylethylphosphine oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, bis (2 , 6-Dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzo Rubenzyloctylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-diisopropylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2-methylphenylphosphine oxide, bis (2, 4,6-trimethylbenzoyl) -4-methylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-diethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2, 3,5,6-tetramethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Limethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) isobutylphosphine oxide, 2,6-dimethyloxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis (2,4,4) 6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dibutoxyphenylphosphine oxide, 1,10-bis [bis (2,4,6-trimethylbenzoyl) phosphine oxide Decane, tri (2-methylbenzoyl) phosphine oxide, and the like.

  Although the usage-amount of a photoinitiator is not restrict | limited in particular, For example, 0.01-5 weight part with respect to 100 weight part of said monomer components, Preferably it is 0.05-3 weight part, More preferably, it is 0.05- The amount is 1.5 parts by weight, more preferably 0.1 to 1 part by weight.

  If the amount of the photopolymerization initiator used is less than 0.01 parts by weight, the polymerization reaction may be insufficient. When the usage-amount of a photoinitiator exceeds 5 weight part, a photoinitiator may absorb an ultraviolet-ray and an ultraviolet-ray may not reach the inside of an adhesive layer. In this case, the polymerization rate is lowered, or the molecular weight of the produced polymer is reduced. And thereby, the cohesive force of the pressure-sensitive adhesive layer to be formed becomes low, and when the pressure-sensitive adhesive layer is peeled off from the film, a part of the pressure-sensitive adhesive layer may remain on the film and the film may not be reused. . In addition, a photopolymerization initiator can be used individually by 1 type or in combination of 2 or more types.

  The weight average molecular weight of the (meth) acrylic polymer of the present invention is preferably 400,000 to 2,500,000, more preferably 600,000 to 2,200,000. By making the weight average molecular weight larger than 400,000, it is possible to satisfy the durability of the pressure-sensitive adhesive layer, or to suppress the occurrence of adhesive residue due to the reduced cohesive force of the pressure-sensitive adhesive layer. On the other hand, when the weight average molecular weight is larger than 2.5 million, the bonding property and the adhesive strength tend to be lowered. Furthermore, in the solution system, the viscosity becomes too high, and coating may be difficult. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene. In addition, it is difficult to measure the molecular weight of the (meth) acrylic polymer obtained by radiation polymerization.

<Measurement of weight average molecular weight>
The weight average molecular weight of the obtained (meth) acrylic polymer was measured by GPC (gel permeation chromatography). The sample used was a filtrate obtained by dissolving the sample in tetrahydrofuran to make a 0.1 wt% solution, which was allowed to stand overnight, and then filtered through a 0.45 μm membrane filter. Analytical apparatus: manufactured by Tosoh Corporation, HLC-8120GPC, column: manufactured by Tosoh Corporation, (meth) acrylic polymer: GM7000H _XL + GMH _XL + GMH _XL
Aromatic polymer: G3000HXL + 2000HXL + G1000HXL, column size; each 7.8 mmφ × 30 cm, total 90 cm, eluent: tetrahydrofuran (concentration 0.1 wt%), flow rate: 0.8 ml / min, inlet pressure: 1.6 MPa, detector: Differential refractometer (RI), column temperature: 40 ° C
・ Injection volume: 100 μl
・ Eluent: Tetrahydrofuran ・ Detector: Differential refractometer ・ Standard sample: Polystyrene

  The forming material (transparent adhesive) of the transparent resin layer (adhesive layer) of the present invention can contain a crosslinking agent. Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents, metal chelate crosslinking agents, Crosslinkers such as oxides are included. A crosslinking agent can be used alone or in combination of two or more. As said crosslinking agent, an isocyanate type crosslinking agent and an epoxy-type crosslinking agent are used preferably.

  The crosslinking agent may be used alone or in combination of two or more, but the total content is based on 100 parts by weight of the (meth) acrylic polymer. It is preferable to contain the said crosslinking agent in 0.01-5 weight part. The content of the crosslinking agent is preferably 0.01 to 4 parts by weight, more preferably 0.02 to 3 parts by weight.

  The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups in a molecule (including isocyanate-regenerating functional groups in which isocyanate groups are temporarily protected by a blocking agent or quantification).

  Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.

More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2,4-tolylene diisocyanate, Aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), tri Methylolpropane / hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Coronate HL), hexamethylene diisocyanate Isocyanurate of anate (made by Nippon Polyurethane Industry Co., Ltd., trade name Coronate HX), etc., xylylene diisocyanate trimethylolpropane adduct (Mitsui Chemicals, trade name D110N), hexamethylene diisocyanate trimethylolpropane Additives (Mitsui Chemicals, trade name D160N); polyether polyisocyanate, polyester polyisocyanate, adducts of these with various polyols, polyfunctionalized polyisocyanate, burette, allophanate, etc. An isocyanate etc. can be mentioned. Of these, it is preferable to use an aliphatic isocyanate because of its high reaction rate.

  The isocyanate-based crosslinking agent may be used alone or in combination of two or more, but the total content is 100 parts by weight of the (meth) acrylic polymer. On the other hand, it is preferable to contain 0.01-5 weight part of the said isocyanate type crosslinking agent, Furthermore, it is preferable to contain 0.01-4 weight part, Furthermore, it is preferable to contain 0.02-3 weight part. . It can be appropriately contained in consideration of cohesive force and prevention of peeling in a durability test.

  In addition, in the aqueous dispersion of the modified (meth) acrylic polymer prepared by emulsion polymerization, it is not necessary to use an isocyanate-based crosslinking agent. However, if necessary, it is blocked because it easily reacts with water. Isocyanate-based crosslinking agents can also be used.

  The said epoxy type crosslinking agent says the polyfunctional epoxy compound which has 2 or more of epoxy groups in 1 molecule. Examples of the epoxy crosslinking agent include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, diamine glycidylamine, 1 , 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether Glycerin diglycidyl ether, glycerin triglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris (2-hydroxy Ethyl) isocyanurate, resorcin diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule. Examples of the epoxy-based crosslinking agent include commercially available products such as trade names “Tetrad C” and “Tetrad X” manufactured by Mitsubishi Gas Chemical Company.

  The epoxy crosslinking agent may be used alone or in combination of two or more. However, the total content is 100 parts by weight of the (meth) acrylic polymer. On the other hand, it is preferable to contain 0.01-5 weight part of the said epoxy type crosslinking agent, Furthermore, it is preferable to contain 0.01-4 weight part, Furthermore, it is preferable to contain 0.02-3 weight part. . It can be appropriately contained in consideration of cohesive force and prevention of peeling in a durability test.

  The peroxide crosslinking agent can be used as appropriate as long as it generates radical active species by heating to cause the crosslinking of the base polymer of the pressure-sensitive adhesive, but in consideration of workability and stability, 1 It is preferable to use a peroxide having a minute half-life temperature of 80 ° C to 160 ° C, and it is more preferable to use a peroxide having a temperature of 90 ° C to 140 ° C.

  Examples of peroxides that can be used include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 Minute half-life temperature: 92.1 ° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butyl peroxyneodecanoate (1 minute half-life temperature: 103 0.5 ° C), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C), dilauroyl peroxide ( 1 minute half-life temperature: 116.4 ° C.), di-n-octanoyl peroxide (1 minute half-life temperature: 117.4 ° C.), 1,1,3,3-tetramethylbutyl Oxy-2-ethylhexanoate (1 minute half-life temperature: 124.3 ° C), di (4-methylbenzoyl) peroxide (1 minute half-life temperature: 128.2 ° C), dibenzoyl peroxide (half-minute for 1 minute) Period temperature: 130.0 ° C.), t-butyl peroxyisobutyrate (1 minute half-life temperature: 136.1 ° C.), 1,1-di (t-hexylperoxy) cyclohexane (1 minute half-life temperature: 149.2 ° C.). Especially, since the crosslinking reaction efficiency is excellent, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.), dilauroyl peroxide (1 minute half-life temperature: 116. 4 ° C), dibenzoyl peroxide (1 minute half-life temperature: 130.0 ° C) and the like are preferably used.

  The peroxide half-life is an index representing the decomposition rate of the peroxide, and means the time until the remaining amount of peroxide is reduced to half. The decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic peroxide catalog 9th edition by Nippon Oil & Fats Co., Ltd.” (May 2003) ".

  The peroxide may be used alone or as a mixture of two or more, but the total content is based on 100 parts by weight of the (meth) acrylic polymer. The peroxide is 0.02 to 2 parts by weight, preferably 0.05 to 1 part by weight. In order to adjust processability, reworkability, cross-linking stability, peelability, and the like, it is appropriately selected within this range.

In addition, as a measuring method of the peroxide decomposition amount remaining after the reaction treatment, for example, HPLC
It can be measured by (high performance liquid chromatography).

  More specifically, for example, about 0.2 g of the pressure-sensitive adhesive after the reaction treatment is taken out, immersed in 10 ml of ethyl acetate, and extracted by shaking at 25 ° C. and 120 rpm for 3 hours with a shaker. Let stand for days. Next, 10 ml of acetonitrile was added, shaken at 120 rpm at 25 ° C. for 30 minutes, and about 10 μl of the extract obtained by filtration through a membrane filter (0.45 μm) was injected into the HPLC for analysis. The amount of peroxide can be set.

  Moreover, you may use together an organic type crosslinking agent and a polyfunctional metal chelate as a crosslinking agent. A polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinately bonded to an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be mentioned. Examples of the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.

  In order to improve the adhesive force, the (meth) acrylic oligomer can be contained in the forming material (pressure-sensitive adhesive) of the transparent resin layer (pressure-sensitive adhesive layer) of the present invention. The (meth) acrylic oligomer is preferably a polymer having a Tg higher than that of the (meth) acrylic polymer of the present invention and a small weight average molecular weight. Such a (meth) acrylic oligomer functions as a tackifying resin and has the advantage of increasing the adhesive force without increasing the dielectric constant.

  The (meth) acrylic oligomer preferably has a Tg of about 0 ° C. or higher and 300 ° C. or lower, preferably about 20 ° C. or higher and 300 ° C. or lower, more preferably about 40 ° C. or higher and 300 ° C. or lower. When the Tg is less than about 0 ° C., the cohesive force of the pressure-sensitive adhesive layer at room temperature or higher is lowered, and the holding characteristics and the adhesiveness at high temperature may be lowered. The Tg of the (meth) acrylic oligomer is a theoretical value calculated based on the Fox equation, similar to the Tg of the (meth) acrylic polymer.

  The weight average molecular weight of the (meth) acrylic oligomer is 1000 or more and less than 30000, preferably 1500 or more and less than 20000, and more preferably 2000 or more and less than 10,000. If the weight average molecular weight is 30000 or more, the effect of improving the adhesive strength may not be sufficiently obtained. On the other hand, if the molecular weight is less than 1000, the molecular weight may be low, which may cause a decrease in adhesive strength and retention characteristics. In this invention, the measurement of the weight average molecular weight of a (meth) acrylic-type oligomer can be calculated | required in polystyrene conversion by GPC method. Specifically, TSKgelGMH-H (20) × 2 columns are used in HPLC 8020 manufactured by Tosoh Corporation, and the measurement is performed with a tetrahydrofuran solvent at a flow rate of about 0.5 ml / min.

Examples of the monomer constituting the (meth) acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , S-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undeci Alkyl (meth) acrylates such as (meth) acrylate and dodecyl (meth) acrylate; (meth) acrylic acid and alicyclic such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate An ester with a group alcohol; an aryl (meth) acrylate such as phenyl (meth) acrylate and benzyl (meth) acrylate; a (meth) acrylate obtained from a terpene compound derivative alcohol; and the like. Such (meth) acrylates can be used alone or in combination of two or more.

  Examples of (meth) acrylic oligomers include alkyl (meth) acrylates in which alkyl groups such as isobutyl (meth) acrylate and t-butyl (meth) acrylate have a branched structure; cyclohexyl (meth) acrylate and isobornyl (meth) Esters of (meth) acrylic acid and alicyclic alcohols such as acrylate dicyclopentanyl (meth) acrylate; cyclic structures such as aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate It is preferable that an acrylic monomer having a relatively bulky structure represented by (meth) acrylate possessed as a monomer unit. By giving such a bulky structure to the (meth) acrylic oligomer, the adhesiveness of the pressure-sensitive adhesive layer can be further improved. In particular, those having a ring structure in terms of bulkiness are highly effective, and those having a plurality of rings are more effective. In addition, when ultraviolet rays are employed in the synthesis of a (meth) acrylic oligomer or in the production of a pressure-sensitive adhesive layer, those having a saturated bond are preferred in that they are less likely to cause polymerization inhibition. An alkyl (meth) acrylate having a branched structure or an ester with an alicyclic alcohol can be suitably used as a monomer constituting the (meth) acrylic oligomer.

From this point, suitable (meth) acrylic oligomers include, for example, a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), and a copolymer of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA). Polymer, copolymer of cyclohexyl methacrylate (CHMA) and acryloylmorpholine (ACMO), copolymer of cyclohexyl methacrylate (CHMA) and diethylacrylamide (DEAA), copolymer of 1-adamantyl acrylate (ADA) and methyl methacrylate (MMA) Polymer, copolymer of dicyclopentanyl methacrylate (DCPMA) and isobornyl methacrylate (IBXMA), dicyclopentanyl methacrylate (DCPMA), cyclohexane Xyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), a copolymer of cyclopentanyl methacrylate (DCPMA) and methyl methacrylate (MMA), dicyclopentanyl acrylate (DCPA), 1 -Adamantyl methacrylate (ADMA), 1-adamantyl acrylate (ADA) homopolymers, and the like. In particular, an oligomer containing CHMA as a main component is preferable.

  In the forming material (adhesive) of the transparent resin layer (adhesive layer) of the present invention, when the (meth) acrylic oligomer is used, its content is not particularly limited, but it is 100 parts by weight of the (meth) acrylic polymer. It is preferable that it is 70 weight part or less with respect to it, More preferably, it is 1-70 weight part, More preferably, it is 2-50 weight part, More preferably, it is 3-40 weight part. When the added amount of the (meth) acrylic oligomer exceeds 70 parts by weight, there is a problem that the elastic modulus is increased and the adhesiveness at low temperature is deteriorated. In addition, it is effective from the point of the improvement effect of adhesive force, when mix | blending 1 weight part or more of (meth) acrylic-type oligomers.

  Furthermore, the forming material (adhesive) of the transparent resin layer (adhesive layer) of the present invention includes silane for increasing the water resistance at the interface when applied to a hydrophilic adherend such as glass of the adhesive layer. A coupling agent can be contained. The amount of the silane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0 parts per 100 parts by weight of the (meth) acrylic polymer. .6 parts by weight. If the amount of the silane coupling agent is too large, the adhesion to the glass increases and the removability is poor, and if it is too small, the durability decreases, which is not preferable.

  Examples of the silane coupling agent that can be preferably used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4 epoxy cyclohexyl). ) Epoxy group-containing silane coupling agent such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1 , 3-dimethylbutylidene) propylamine, amino group-containing silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. (Meta) Acry Group-containing silane coupling agents, such as isocyanate group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane and the like.

  In order to control the surface resistance value of the transparent resin layer within the range of the present invention, the transparent resin layer (adhesive layer) forming material (adhesive layer) of the present invention contains an ionic compound in addition to the base polymer. can do. As the ionic compound, an alkali metal salt and / or an organic cation-anion salt can be preferably used. As the alkali metal salt, an organic salt or inorganic salt of an alkali metal can be used. The “organic cation-anion salt” in the present invention refers to an organic salt whose cation part is composed of an organic substance, and the anion part may be an organic substance or an inorganic substance. There may be. “Organic cation-anion salt” is also called an ionic liquid or ionic solid.

<Alkali metal salt>
Examples of the alkali metal ions constituting the cation part of the alkali metal salt include lithium, sodium, and potassium ions. Of these alkali metal ions, lithium ions are preferred.

The anion part of the alkali metal salt may be composed of an organic material or an inorganic material. Examples of the anion part constituting the organic salt include CH ₃ COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , and C ₄ F ₉ SO _{3. ^{-, C 3 F 7 COO -}} , (CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 -, PF 6 -, CO 3 2-, or the following general formula ( 1) to (4),
(1): (C _n F _{2n + 1} SO ₂ ) ₂ N ⁻ (where n is an integer of 1 to 10),
_{(2): CF 2 (C} m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10),
^{_{(3): - O 3 S}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
^{_{(4) :( C p F 2p}} + 1 SO 2) N - (C q F 2q + 1 SO 2), ( where, p, q is an integer of from 1 to 10), in represented by ones like. In particular, an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained. The anion part constituting the inorganic salt includes Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , AsF ₆ ⁻ , SbF. ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , (CN) ₂ N ⁻ , and the like are used. As the anion moiety, (perfluoroalkylsulfonyl) imide represented by the general formula (1) such as (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , and the like is preferable. (Trifluoromethanesulfonyl) imide represented by CF ₃ SO ₂ ) ₂ N ⁻ is preferable.

Specific examples of the alkali metal organic salt include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluenesulfonate, LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C, KO ₃ S (CF ₂ ) ₃ SO ₃ K, _{LiO 3 S (CF 2) 3} SO 3 K , and the like, among these _{LiCF 3 SO 3, Li (CF} 3 SO 2) 2 N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F ₉ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C and the like are preferable, and Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO _{2) 2} Fluorine-containing lithium imide salt is more preferably equal, particularly (perfluoroalkyl sulfonyl) imide lithium salts are preferred.

  Examples of the alkali metal inorganic salt include lithium perchlorate and lithium iodide.

<Organic cation-anion salt>
The organic cation-anion salt used in the present invention is composed of a cation component and an anion component, and the cation component is composed of an organic substance. As the cation component, specifically, pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, Examples include pyrazolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, and tetraalkylphosphonium cation.

Examples of the anion component include Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , and CF ₃ COO. ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , (CN) ₂ N ⁻ , C ₄ F _{^{9 SO 3 -, C 3 F}} 7 COO -, ((CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 -, or the following general formula (1) to (4 ),
(1): (C _n F _{2n + 1} SO ₂ ) ₂ N ⁻ (where n is an integer of 1 to 10),
_{(2): CF 2 (C} m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10),
_{^{(3): - O 3 S}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
^{_{(4) :( C p F 2p}} + 1 SO 2) N - (C q F 2q + 1 SO 2), ( where, p, q is an integer of from 1 to 10), in represented by ones like. Among these, an anion component containing a fluorine atom is particularly preferably used because an ionic compound having good ion dissociation properties can be obtained.

As a specific example of the organic cation-anion salt, a compound composed of a combination of the cation component and the anion component is appropriately selected and used.
For example, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium Bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-hexylpyridinium tetrafluoroborate, 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2 -Phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-ethyl-3-methylimidazo Um tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methyl Imidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1- Ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3- Methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium bromide, 1 -Hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3 -Methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, Diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanes Phonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, N, N-diethyl-N-methyl-N -(2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N -(2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyl trime Ruammonium bis (pentafluoroethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (Trifluoromethanesulfonyl) trifluoroacetamide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (trifluoromethanesulfonyl) trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, glycidyl Trimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N-dimethyl-N-ethyl-N-pro Pyrammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethane Sulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N , N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N- Propi -N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide N, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, , N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) Imido, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N- Diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (Trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl- N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoro) (Romethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-hexylammonium bis (g Fluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridine Examples include -1-ium trifluoromethanesulfonate. As these commercially available products, for example, “CIL-314” (manufactured by Nippon Carlit Co., Ltd.), “ILA2-1” (manufactured by Koei Chemical Co., Ltd.) and the like can be used.
Also, for example, tetramethylammonium bis (trifluoromethanesulfonyl) imide, trimethylethylammonium bis (trifluoromethanesulfonyl) imide, trimethylbutylammonium bis (trifluoromethanesulfonyl) imide, trimethylpentylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptyl Ammonium bis (trifluoromethanesulfonyl) imide, trimethyloctylammonium bis (trifluoromethanesulfonyl) imide, tetraethylammonium bis (trifluoromethanesulfonyl) imide, triethylbutylammonium bis (trifluoromethanesulfonyl) imide, tetrabutylammonium bis (trifluoromethanesulfonyl) Imide, tetrahex Le ammonium bis (trifluoromethanesulfonyl) imide, and the like.
Further, for example, 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethane) Sulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl- -Butyl pyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (trifluoromethane) Sulfonyl) imide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-pentylpiperidinium bis (trifluoromethane) Sulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis ( Trifluoromethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpi Peridinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1- Ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) Imido, 1-ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoro) Lomethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium (Pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl -1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoro) Ethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentyl Pyrrolidine Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1, 1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) Imido, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) i 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl -1 heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethane) Sulfonyl) imi , 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpi Peridinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1, Examples include 1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide.
Also, instead of the cation component of the above compound, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium Examples thereof include compounds using a cation, a tetrabutylphosphonium cation, and a tetrahexylphosphonium cation.
Further, instead of the above bis (trifluoromethanesulfonyl) imide, bis (pentafluorosulfonyl) imide, bis (heptafluoropropanesulfonyl) imide, bis (nonafluorobutanesulfonyl) imide, trifluoromethanesulfonyl nonafluorobutanesulfonylimide, And compounds using heptafluoropropanesulfonyl trifluoromethanesulfonylimide, pentafluoroethanesulfonylnonafluorobutanesulfonylimide, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide anion, and the like.

  Examples of the ionic compound include inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate in addition to the alkali metal salts and organic cation-anion salts. . These ionic compounds can be used alone or in combination.

  As for the ratio of the ionic compound in the formation material (adhesive) of the transparent resin layer (adhesive layer) of this invention, 0.0001-5 weight part is preferable with respect to 100 weight part of (meth) acrylic-type polymers. If the ionic compound is less than 0.0001 part by weight, the effect of improving the antistatic performance may not be sufficient. The ionic compound is preferably 0.01 parts by weight or more, and more preferably 0.1 parts by weight or more. On the other hand, if the amount of the ionic compound is more than 5 parts by weight, the durability may not be sufficient. The ionic compound is preferably 3 parts by weight or less, more preferably 1 part by weight or less. The ratio of the ionic compound can be set within a preferable range by adopting the upper limit value or the lower limit value.

  Furthermore, the material (adhesive) for forming the transparent resin layer (adhesive layer) of the present invention may contain other known additives, for example, a polyether compound of polyalkylene glycol such as polypropylene glycol, Powders such as colorants, pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization Inhibitors, inorganic or organic fillers, metal powders, particles, foils, and the like can be added as appropriate according to the intended use. Moreover, you may employ | adopt the redox system which added a reducing agent within the controllable range.

  The transparent resin layer (pressure-sensitive adhesive layer) can be formed, for example, by applying the forming material (pressure-sensitive adhesive) to a member such as a transparent substrate and / or a polarizing film and drying and removing a polymerization solvent or the like. In applying the forming material, one or more solvents other than the polymerization solvent may be added as appropriate.

  Various methods are used as a method of applying the forming material. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.

  The heating and drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and particularly preferably 70 ° C to 170 ° C. By setting the heating temperature within the above range, a transparent resin layer having excellent adhesive properties can be obtained. As the drying time, an appropriate time can be adopted as appropriate. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

  The transparent resin layer can be formed by polymerizing the forming material (adhesive) by irradiating active energy rays such as ultraviolet rays. For ultraviolet irradiation, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or the like can be used. In addition, when the said forming material is a transparent adhesive, while manufacturing a (meth) acrylic-type polymer from a monomer component, a transparent resin layer (adhesive layer) can be formed. A crosslinking agent or the like can be appropriately blended with the monomer component. As the monomer component, a part of the monomer component previously polymerized into a syrup can be used for ultraviolet irradiation.

  When the forming material is a transparent adhesive, the transparent resin layer (adhesive layer) can be transferred to a polarizing film or the like after being formed on a support. As the support, for example, a release-treated sheet can be used. A silicone release liner is preferably used as the release-treated sheet.

  A pressure-sensitive adhesive sheet in which a transparent resin layer (pressure-sensitive adhesive layer) is formed on a release-treated sheet is a sheet (separator) that is peeled until practical use when the transparent resin layer (pressure-sensitive adhesive layer) is exposed. The transparent resin layer (adhesive layer) may be protected. In practical use, the peeled sheet is peeled off.

  Examples of the constituent material of the separator include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. Although a thin leaf body etc. can be mentioned, a plastic film is used suitably from the point which is excellent in surface smoothness.

  The plastic film is not particularly limited as long as it can protect the transparent resin layer (adhesive layer). For example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride Examples thereof include a film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.

  The thickness of the separator is usually about 5 to 200 μm, preferably about 5 to 100 μm. For the separator, if necessary, mold release and antifouling treatment with a silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to carry out antistatic treatment such as. In particular, when the surface of the separator is appropriately subjected to release treatment such as silicone treatment, long-chain alkyl treatment, and fluorine treatment, the peelability from the transparent resin layer (adhesive layer) can be further enhanced.

The transparent resin layer can be formed of a transparent liquid resin. As the transparent liquid resin, for example, an active energy ray-curable resin composition containing a bifunctional (meth) acrylate compound (component A) having two (meth) acryloyl groups represented by the following general formula (A): Is mentioned.

Formula ^{(A): R 1 -O (} X 1 -O) m -Y- (X 2 -O) n -R 2
(In General Formula (A), R ¹ and R ² are each an acryloyl group or a methacryloyl group, and may be the same or different from each other. X ¹ and X ^{2 each} have 2 to 4 carbon atoms. An alkylene group which may be the same or different from each other, m and n are positive integers and m + n = 3 to 40, Y is a single bond, -Ph-C (CH ₃ ); _{2 -Ph-O -, - Ph} -CH 2 -Ph-O-, or -C (CH _{3) 2} -O-, a, -Ph- represents a para-phenylene group.

In particular, in the general formula (A), it is preferable that R ¹ and R ² are methacryloyl groups from the viewpoint of good active energy ray curability. Similarly, the general formula (A), the possible X ¹ and X ² is an alkylene group of 3-4 carbon atoms, from the viewpoint of optical transparency is improved. Furthermore, in the said general formula (A), it is preferable that it is m + n = 10-20 from the point from which a light transmittance becomes favorable.

Furthermore, the general formula (A), ^{X 1} and ^{X 2} _-CH (CH 3) -CH ₂ - and is, that Y is a single bond, from the viewpoint of optical transparency is improved.

  The amount of the specific (meth) acrylate compound (component A) is preferably set in the range of 0.1 to 50% by weight, more preferably 1 to 40% by weight of the entire active energy ray-curable resin composition. % Range. That is, if the blending amount of the specific (meth) acrylate compound is too small, the active energy ray curability tends to be inferior. On the other hand, if the blending amount is too large, the low curing shrinkage tends to be inferior.

  The active energy ray-curable resin composition containing the specific (meth) acrylate compound (component A) can be cured by irradiation with radiation such as an electron beam or ultraviolet rays. When the radiation irradiation is performed with an electron beam, it is not particularly necessary to include a photopolymerization initiator in the composition. However, when the radiation irradiation is performed with ultraviolet rays, a photopolymerization initiator (component B) is used. ) Can be contained. The photopolymerization initiator (component B) acts as an ultraviolet curing agent, and various photopolymerization initiators such as a radical photopolymerization initiator are used. In the present invention, when a touch panel on which a transparent electrode such as ITO (indium tin oxide) is formed is used in the liquid crystal display device, ITO corrosion caused by ions (particularly counter anions) derived from the photopolymerization initiator is avoided. For the purpose, a radical photopolymerization initiator is more preferably used.

  As said radical photopolymerization initiator, the thing similar to radical photopolymerization initiator used when manufacturing the acrylic polymer which forms the said transparent resin layer (adhesive layer) by ultraviolet polymerization can be used. The blending amount of the photopolymerization initiator is preferably set in the range of 0.1 to 20% by weight, more preferably in the range of 0.2 to 20% by weight, based on the entire ultraviolet curable resin composition. That is, when the blending amount of the photopolymerization initiator is too small, the ultraviolet curable property is inferior, and conversely when it is too large, the light transmittance tends to be inferior.

  The active energy ray-curable resin composition of the present invention contains the specific (meth) acrylate compound (component A), but if necessary, has an average of one or more (meth) acryloyl groups per molecule. It is preferable to contain a conjugated diene polymer (C component) from the viewpoint of improving light transmittance. The blending amount of the component C is preferably set in the range of 0.1 to 50% by weight of the entire active energy ray-curable resin composition.

  The conjugated diene polymer (component C) is composed of at least one selected from the group consisting of polybutadiene, polyisoprene, and a copolymer of butadiene and isoprene, and has an average of 1 or more per molecule ( A polymer having a (meth) acryloyl group is preferable from the viewpoint of good light transmittance.

  Furthermore, the active energy ray-curable resin composition of the present invention can contain a monofunctional monomer other than the above components. The monofunctional monomer is a monomer having one polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. The monofunctional monomer is preferably a (meth) acrylate monomer having a (meth) acryloyl group.

Examples of the (meth) acrylate monomer include 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, and alkyl. (Meth) acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate , Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hydroxyethyl (meth) acrylate, 1,3-butylene glycol (Meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, norbornene A (meth) acrylate can be illustrated. These (meth) acrylate phenoxyethyl (meth) acrylate (PO), phenoxy polyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate (CH), nonylphenol EO adduct Examples include (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. These may be used alone or in combination of two or more.

  The blending amount of the monofunctional monomer is preferably set in the range of 0 to 50% by weight of the entire active energy ray-curable resin composition of the present invention. That is, if the amount of the monofunctional monomer is too large, a tendency to be inferior in low curing shrinkage is observed.

In addition, the transparent liquid resin that forms the transparent resin layer includes a crosslinking agent in the same manner as the transparent adhesive.
It can contain compounds such as (meth) acrylic oligomers, silane coupling agents, ionic compounds, and other known additives. In addition, in the said transparent adhesive, although the ratio of the said compound is described with respect to 100 weight part of (meth) acrylic-type polymers, about transparent liquid resin, transparent liquid resin (active energy ray hardening-type resin composition) is described. Product) It is preferable to contain the above compound in the same proportion as the transparent adhesive based on 100 parts by weight as a whole.

  Furthermore, the active energy ray-curable resin composition of the present invention includes an antifoaming agent, a surfactant, a colorant, an organic filler, various spacers, adhesives / adhesives in addition to the above-described components, depending on the application. An imparting agent or the like can be appropriately blended as necessary. These may be used alone or in combination of two or more.

  The active energy ray-curable resin composition of the present invention is, for example, blended with a specific (meth) acrylate compound (component A) and other blending components, and stirred by a revolving planetary stirring mixer or a glass stirring container. It can be produced by mixing and kneading.

  The active energy ray-curable resin composition of the present invention thus obtained is provided as a cured body by, for example, ultraviolet irradiation using a UV lamp or the like. Further, after the light irradiation such as the ultraviolet irradiation, post-curing at a predetermined temperature may be performed as necessary.

  As described above, the active energy ray-curable resin composition of the present invention includes an input device such as a touch panel applied on the viewing side of an image display device, a member such as a transparent substrate such as a cover glass and a plastic cover, and a polarizing film ( It is suitably applied between the image display panel) and used to fill a gap between the member and the polarizing film (image display panel). Specifically, for example, a necessary amount of the active energy ray-curable resin composition of the present invention is applied to the member side, and is aligned and bonded to a polarizing film (image display panel) under normal pressure or vacuum. At this time, by controlling the laminating pressure and height, the active energy ray is partially irradiated while the distance between the member and the polarizing film (image display panel) is maintained, and temporary fixing is performed. Then, after performing an appearance inspection as necessary, the active energy ray curable resin composition is cured by irradiating active energy rays again, whereby a target image display device can be manufactured.

  As described above, after the gap between the polarizing film (image display panel) and the member disposed on the image display panel is filled with the active energy ray-curable resin composition of the present invention, active energy ray irradiation is performed. By curing the active energy ray-curable resin composition by the above, a target image display device can be produced. When a touch sensor is provided in the image display device, a touch sensor is disposed between the image display panel and a protective cover plate (a transparent substrate such as a cover glass or a plastic cover), and the image display panel After burying at least one of the space between the touch sensor and the protective cover plate and the touch sensor with the active energy ray-curable resin composition of the present invention, the active energy ray-curable resin composition is irradiated by active energy ray irradiation. The target image display device can be manufactured by curing the object.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, all the parts and% in each example are based on weight. Evaluation items in Examples and the like were measured as follows.

Example 1
<Preparation of monomer components used for UV polymerization>
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 70 parts by weight of 2-ethylhexyl acrylate (2EHA), 15 parts by weight of N-vinylpyrrolidone (NVP), 4-hydroxybutyl acrylate ( 4 HBA) 15 parts by weight, two types of photopolymerization initiator (trade name: Irgacure 184, manufactured by BASF) 0.05 part by weight and photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF) 0.05 part by weight Was put into a four-necked flask to prepare a monomer mixture. Next, the monomer mixture was partially photopolymerized by exposing it to ultraviolet rays under a nitrogen atmosphere to obtain a partially polymerized product (acrylic polymer syrup) having a polymerization rate of about 10% by weight.

  After adding 0.01 parts by weight of trimethylolpropane triacrylate (TMPTA) to 100 parts by weight of the above-mentioned acrylic polymer syrup, these were uniformly mixed to prepare a monomer component.

<Preparation of material for forming transparent resin layer>
Furthermore, 1 part by weight of bistrifluoromethanesulfonylamide lithium (LiTFSA) was added as an ionic compound to 100 parts by weight of the acrylic polymer syrup to prepare a transparent resin layer forming material.

<Creation of transparent resin layer by UV polymerization>
Next, the transparent resin layer forming material prepared above was applied to the release-treated surface of a polyethylene terephthalate film (separator film) treated on one side with a silicone-based release agent so that the final thickness was 20 μm. A coating layer was formed. Next, a polyethylene terephthalate film (separator film) whose one surface was treated with a silicone-based release agent was coated on the surface of the applied monomer component so that the release treatment surface of the film was on the coating layer side. Thereby, the coating layer of the monomer component was shielded from oxygen. Using a chemical light lamp (manufactured by Toshiba Corporation) on the sheet having the coating layer thus obtained, ultraviolet rays having an illuminance of 5 mW / cm ² (measured with Topcon UVR-T1 having a maximum sensitivity at about 350 nm) are applied for 360 seconds. Irradiated to cure the coating layer to create a transparent resin layer.

≪Creation of polarizing film≫
A polyvinyl alcohol film having a thickness of 80 μm was stretched up to 3 times while being dyed for 1 minute in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the total draw ratio was stretched to 6 times while being immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 20 μm. A saponified 40 μm thick triacetyl cellulose film was bonded to both surfaces of the polarizer with a polyvinyl alcohol adhesive (hereinafter referred to as a polarizing film P1).

<Creation of pressure-sensitive adhesive layer (viewing side) polarizing film P1>
The obtained transparent resin layer was used as an adhesive layer. After peeling off the separator film on one side from the obtained transparent resin layer, the transparent resin layer (adhesive layer) formed on the separator film on the other side is transferred to the polarizing film P1 prepared above and adhered. A polarizing film P1 with an agent layer (viewing side) was prepared.

Examples 2 to 15 and Comparative Examples 1 to 5
In Example 1, the type and composition ratio of the monofunctional monomer used for the preparation of the monomer component, the type and addition amount of the ionic compound, and the thickness of the transparent resin layer to be formed were changed as shown in Table 1. Except for the above, the same operation as in Example 1 was performed to prepare a transparent resin layer. Moreover, it carried out similarly to Example 1, and created the polarizing film P1 with an adhesive layer (viewing side).

  The following evaluation was performed about polarizing film P1 with a transparent resin layer (adhesive layer) or an adhesive layer (visual recognition side) obtained by the said Example and comparative example. The evaluation results are shown in Table 1.

<Surface resistance value>
After removing the separator film on one side from the transparent resin layer obtained in each of the above examples, the surface resistance value (Ω / □) of the exposed transparent resin layer surface was measured using MCP-HT450 manufactured by Mitsubishi Chemical Analytech. did.

<Durability>
The separator film of the polarizing film P1 with the pressure-sensitive adhesive layer (viewing side) obtained in each of the above examples was peeled off and attached to a non-alkali glass (Corning Corp., 1737) having a thickness of 0.7 mm using a laminator. Subsequently, the autoclave process for 15 minutes was performed at 50 degreeC and 0.5 MPa, and the said polarizing film with an adhesive layer was completely stuck to the alkali free glass. Next, vacuum bonding was performed using a vacuum bonding apparatus manufactured by LANTECH under a pressure of 0.2 MPa and a degree of vacuum of 30 Pa. This was put in the conditions of a heating oven (heating) at 80 ° C. and a constant temperature and humidity machine (humidification) at 60 ° C./90% RH, respectively, and the presence or absence of peeling of the polarizing film after 500 hours was determined according to the following criteria. evaluated.
A: No peeling was observed.
○: Peeling that was not visually confirmed was observed.
(Triangle | delta): The small peeling which can be confirmed visually is recognized.
X: Clear peeling was recognized.

<Measurement of haze>
The transparent resin layer obtained in each of the above examples was pasted on one side of an alkali-free glass having a total light transmittance of 93.3% and a haze of 0.1%, and a haze meter (Murakami Color Research Laboratory, MR-100). Thus, haze was measured. In measuring with a haze meter, the transparent resin layer was disposed on the light source side. Since the haze value of the alkali-free glass is 0.1%, the haze value is defined as a value obtained by subtracting 0.1% from the measured value. The measured value was adopted as the total light transmittance (%).

<ESD gun test / Evaluation of static electricity unevenness>
≪Creation of polarizing film P1 with adhesive layer (cell side) ≫
A monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was charged into a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device. Furthermore, 0.1 part of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged with ethyl acetate to 100 parts of the monomer mixture (solid content), and nitrogen gas was introduced while gently stirring. Then, the temperature of the liquid in the flask was kept at around 60 ° C., and a polymerization reaction was carried out for 7 hours. Then, ethyl acetate was added to the obtained reaction liquid, and the solution of the acrylic polymer (A) with a weight average molecular weight of 1.6 million adjusted to solid content concentration 30% was prepared. As a crosslinking agent, 0.1 part of trimethylolpropane xylylene diisocyanate (manufactured by Mitsui Chemicals: Takenate D110N) and 0.1 part of dibenzoyl peroxide are added to 100 parts of the solid content of the resulting acrylic polymer (A) solution. 3 parts and 0.2 part of γ-glycidoxypropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403) were blended to obtain a solution of an adhesive composition.
Next, after the pressure-sensitive adhesive composition prepared above was uniformly applied to the release-treated surface of a polyethylene terephthalate film (separator film) treated on one side with a silicone-based release agent so that the final thickness was 20 μm. The adhesive layer X having a thickness of 20 μm was formed by drying for 60 seconds in an air circulation type thermostatic oven at 150 ° C.
Next, the pressure-sensitive adhesive layer X formed on the separator film was transferred to the polarizing film P1 to obtain a polarizing film P1 with a pressure-sensitive adhesive layer (cell side).

<< Examples 1-15, Comparative Examples 1-5 >>
What peeled off the cover glass C and the viewing side polarizing film P2 (the polarizing film P2 also peeled off together with the adhesive layer on the liquid crystal cell side) from the liquid crystal panel (Apple iPod touch in-cell touch sensor built-in liquid crystal display device) Sample 1 was designated. The pressure-sensitive adhesive layer (cell side) -attached polarizing film P1 created above was bonded to the release surface of Sample 1. On the other hand, the cover film C was used after being cleaned from the polarizing film P2. The transparent resin layer (adhesive layer) prepared in Examples 1 to 15 and Comparative Examples 1 to 5 was transferred to the cleaned cover film C. Thereafter, the transparent resin layer (adhesive layer) formed on the cover film C was bonded to the polarizing film P1 provided on the sample 1 to prepare an evaluation sample 2.

<< Examples 16 and 17 >>
The transparent resin layer (pressure-sensitive adhesive layer) created in Examples 2 and 5 is attached to the opposite side (viewing side) of the pressure-sensitive adhesive layer (cell side) in the polarizing film P1 with the pressure-sensitive adhesive layer (cell side) created above. In addition, a polarizing film P1 with a double-sided pressure-sensitive adhesive layer was prepared. The pressure-sensitive adhesive layer (cell side) side of the double-sided pressure-sensitive adhesive layer-attached polarizing film P1 was bonded to the release surface of Sample 1. On the other hand, the cover film C was used after being cleaned from the polarizing film P1. The cleaned cover film C was bonded to the pressure-sensitive adhesive layer (viewing side) in the polarizing film P1 provided in the sample 1 to prepare an evaluation sample 2.

<< Comparative Example 6 >>
The pressure-sensitive adhesive layer (viewing side) -attached polarizing film P1 prepared in Example 5 was bonded to the release surface of Sample 1. On the other hand, the cover film C was used after being cleaned from the polarizing film P1. The adhesive layer X created above was transferred to the cleaned cover film C. Thereafter, the pressure-sensitive adhesive layer X formed on the cover film C was bonded to the polarizing film P1 provided on the sample 1 to prepare an evaluation sample 2.

In addition, the said polarizing film with an adhesive layer was cut | disconnected and used for the magnitude | size of 100 mm x 100 mm.
The evaluation sample 2 (liquid crystal panel) is placed on a backlight having a luminance of 10000 cd, and 5 kv of static electricity is generated using ESD (SANKI, ESD-8012A) which is a static electricity generating device. Disturbed. The display failure recovery time (seconds) due to the alignment failure was measured using an instantaneous multiphotometric detector (manufactured by Otsuka Electronics Co., Ltd., MCPD-3000) and evaluated according to the following criteria.
A: Display failure disappeared in less than 1 second.
○: Display failure disappeared in 1 second or more and less than 10 seconds.
X: Display defect disappeared in 10 seconds or more.

In Table 1,
2EHA is 2-ethylhexyl acrylate;
NVP is N-vinylpyrrolidone;
4HBA is 4-hydroxybutyl acrylate;
MEA is methoxyethyl acrylate;
TMPTA is trimethylolpropane triacrylate;
LiTFSA is bistrifluoromethanesulfonylamidolithium;
KTFSA is potassium bistrifluoromethanesulfonylamide;
The liquid salt is methylpropylpyrrolidinium bistrifluoromethanesulfonylamide salt (melting point 12 ° C.);
The solid salt represents ethylmethylpyrrolidinium bistrifluoromethanesulfonylamide salt (melting point 90 ° C.).

A transparent resin layer B image display device C member (touch panel or transparent substrate)
DESCRIPTION OF SYMBOLS 1 Polarizing film 2 Adhesive layer 3 Transparent conductive layer (antistatic layer)
4 Glass substrate 5 Liquid crystal layer 6 Drive electrode 7 Antistatic layer / sensor layer 8 Drive electrode / sensor layer 9 Sensor layer 11 Transparent substrate 12 Transparent conductive film

Claims (12)

Than the polarizing film provided on the most viewing side in the image display device, is a transparent resin layer disposed on the viewing side,
The transparent resin layer has a surface resistance value of 1.0 × 10 ¹³ Ω / □ or less.   The transparent resin layer according to claim 1, wherein the transparent resin layer has a thickness of 5 μm to 1 mm. The transparent resin layer has a value (volume resistance value) obtained by multiplying a surface resistance value (Ω / □) by a thickness (cm) of 1.0 × 10 ¹² Ω · cm or less. Or the transparent resin layer of 2.   The transparent resin layer according to any one of claims 1 to 3, wherein the material for forming the transparent resin layer contains an acrylic polymer as a base polymer.   The transparent resin layer according to claim 1, wherein the material for forming the transparent resin layer contains an ionic compound.   The transparent resin layer according to claim 1, wherein a material for forming the transparent resin layer is a transparent adhesive.   The transparent resin layer according to claim 1, wherein a material for forming the transparent resin layer is a transparent liquid resin.   The transparent resin layer according to claim 1, wherein the transparent resin layer is applied to a touch panel.   The transparent resin layer according to claim 1, which is applied to an in-cell type or on-cell type liquid crystal display device with a built-in touch sensor. More than the polarizing film provided on the most visible side in the image display device and the polarizing film, the polarizing film with the pressure-sensitive adhesive layer having the pressure-sensitive adhesive layer disposed on the visual recognition side,
The said adhesive layer is a transparent resin layer formed with the transparent adhesive in any one of Claims 1-9, The polarizing film with an adhesive layer characterized by the above-mentioned. An image display device having at least one polarizing film,
An image display device comprising at least one transparent resin layer according to any one of claims 1 to 9 on the viewing side of a polarizing film provided on the most viewing side in the image display device. The image display device according to claim 11, wherein the transparent resin layer is provided as an adhesive layer in the polarizing film with an adhesive layer according to claim 10.

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