JP2012193335A - Tacky composition, laminate and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tacky composition further suppressed in water vapor permeability compared to heretofore available ones while keeping enough peeling strength; and to provide a laminate and an image display device.SOLUTION: In this tacky composition, the mass ratio of a polyisobutylene resin and a hydrogenated petroleum resin is 70:30 to 90:10; and the viscosity-average molecular weight (Mv) of the polyisobutylene resin is 300,000-500,000. The laminate includes a tacky laminate layer where a first transparent barrier film and a second transparent barrier film are laminated via a tacky layer comprising the tacky composition. Also the image display device has such configuration that the laminate is disposed at least the surface side of the display and the end face of the laminate is not sealed.

Description

  The present invention relates to an adhesive composition, a laminate, and an image display device. More specifically, the present invention relates to a pressure-sensitive adhesive composition used to prevent water vapor from entering from the end face of the laminate toward the inside thereof, the laminate, and an image display device provided with the laminate on the surface of the display.

  Conventionally, a glass plate has been used as a surface panel member of a display. However, in recent years, electronic mobiles such as notebook computers and electronic books have become widespread, and from the viewpoint of operability and the like, thinning, lightening, and durability are required. In order to meet this demand, the surface panel member has been made into a film.

  On the other hand, it is known that display elements such as an organic EL constituting a display are deteriorated by water vapor. For this reason, when forming a surface panel member into a film, a high-level water vapor barrier close to glass is required. As such a water vapor barrier film, for example, a transparent barrier laminate is known in which a plurality of transparent barrier films obtained by depositing an inorganic oxide such as silica on a transparent film are bonded together. In this case, a pressure sensitive adhesive or an adhesive is used for bonding the transparent barrier films. In such a transparent barrier laminate, a general water vapor barrier property in a direction perpendicular to the laminate surface is very high.

  As the pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive is common and conventionally used. However, since the acrylic pressure-sensitive adhesive has a low water vapor barrier property, it is necessary to consider water vapor intrusion from a surface parallel to the laminated surface, that is, from the end surface side of the pressure-sensitive adhesive layer. Specifically, after water vapor intrusion from the end face of the adhesive layer, water vapor enters the element side through a path through which water vapor passes through the vapor deposition surface, causing deterioration of the display elements, circuits, and the like. In this way, in the high water vapor barrier region, the influence of water vapor intrusion from the end face of the adhesive layer becomes large, so even if a plurality of barrier films are laminated, the barrier property beyond a certain level cannot be obtained due to the presence of the adhesive layer. There's a problem. For this reason, a display including a transparent barrier laminated film and a display element is usually provided with an outer frame made of a sealant on the outer periphery so as to cover an end surface exposed around the display. However, the outer frame leads to a complicated manufacturing process of the display and an increase in manufacturing cost. In order to eliminate the need for the outer frame, it is required to reduce the water vapor permeability of the adhesive itself to prevent water vapor intrusion from the end face.

As an encapsulant having a reduced water vapor permeability as compared with the prior art, an adhesive encapsulating composition containing a hydrogenated cyclic olefin polymer and a polyisobutylene resin having a weight average molecular weight exceeding 500,000 has been proposed (for example, , See Patent Document 1). There has also been proposed an encapsulating film comprising an adhesive film containing the adhesive encapsulating composition and a backing provided on the adhesive film. Furthermore, an image display device having this adhesive film has also been proposed. According to the composition, the encapsulating film and the image display device described in Patent Document 1, the water vapor transmission rate per 100 μm of the encapsulating film coated with the composition is 11 g / m ² · in JISZ0204 method, 60 ° C. × 90% RH. (Comparative example is 16 g / m ² · day).

JP 2009-524705 A

  However, even in the composition, the encapsulating film and the image display device described in Patent Document 1, the composition still has water vapor permeability, and it is required to further reduce this water vapor permeability. Moreover, in the usage method called the interlayer adhesive of a transparent barrier laminated body, in addition to water vapor permeability, the peel strength between layers is also required, but Patent Document 1 does not describe the peel strength.

  This invention is made | formed in view of the above situations, and makes it a subject to provide the adhesive composition, laminated body, and image display apparatus which hold | suppress water vapor permeability further further and are excellent in peeling strength.

  As a result of intensive studies to solve the above problems, the present inventors have made the mass ratio of the polyisobutylene resin and the hydrogenated petroleum resin of the pressure-sensitive adhesive composition 70:30 to 90:10, and the polyisobutylene resin It has been found that by setting the viscosity average molecular weight (Mv) to 300,000 to 500,000, the water vapor permeability can be further reduced, and the present invention has been completed. Specifically, the present invention provides the following.

  (1) In the present invention, the mass ratio of the polyisobutylene resin to the hydrogenated petroleum resin is 70:30 to 90:10, and the viscosity average molecular weight (Mv) of the polyisobutylene resin is 300,000 to 500,000. It is the adhesive composition which is.

  (2) In the present invention, the hydrogenated petroleum resin is a copolymer resin of dicyclopentadiene and an aromatic vinyl monomer, and the number average molecular weight (Mn) of the hydrogenated petroleum resin is from 660 to 1,000. The pressure-sensitive adhesive composition according to (1).

(3) Further, in the present invention, the water vapor permeability per 25 μm of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition according to (1) or (2) is 15 g / m ² · day in JIS K7129A method, 40 ° C. × 90% RH. It is the adhesive composition which is less than.

  (4) Moreover, this invention contains organic clay further, and the mass ratio of the said polyisobutylene resin and the said hydrogenated petroleum resin, and the said organic clay is 99: 1-90: 10, (1) or (2 ).

  (5) Moreover, this invention is an adhesion composition as described in (4) which is the montmorillonite which the said organic clay modified the quaternary ammonium.

(6) Further, in the present invention, the water vapor permeability per 25 μm of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition according to (4) or (5) is 6 g / m ² · day in JIS K7129A method, 40 ° C. × 90% RH. It is the adhesive composition which is less than.

  (7) Moreover, this invention laminated | stacked the adhesive layer 25 micrometers and the soda glass of thickness 1mm which consist of an adhesive composition in any one of (4) to (6) on the optical PET film of thickness 100 micrometers. The adhesive composition has a total light transmittance of 85% or more in the JIS K7361 method and a haze of the laminate of 1% or less in the JIS K7136 method.

  (8) Moreover, this invention contains a styrene-type elastomer further, and the said styrene-type elastomer is a styrene-isobutylene-styrene triblock copolymer whose styrene content is 10 mass%-40 mass%, (1) To (7).

  (9) Moreover, this invention mix | blends the said styrene-type elastomer so that the ratio of the said styrene content may be 1 mass%-5 mass% in the total mass of the said polyisobutylene resin and the said styrene-type elastomer. The pressure-sensitive adhesive composition according to (8).

  (10) Moreover, this invention is the adhesion lamination by which the 1st transparent barrier film and the 2nd transparent barrier film are laminated | stacked through the adhesion layer which consists of an adhesion composition as described in (1) to (9). A laminate including at least a body layer.

  (11) In the present invention, the pressure-sensitive adhesive layer is 15 μm or more, and the peel strength in a 180-degree T-shaped peel test between the first transparent barrier film and the second transparent barrier film is 2 N / 15 mm. This is the laminate as described in (10).

(12) In the present invention, the first transparent barrier film and the second transparent barrier film are each a transparent inorganic oxide vapor deposition film, and the water vapor permeability of each transparent inorganic oxide vapor deposition film is JIS. It is a laminated body as described in (10) or (11) which is less than 1 g / m < ² > * day in K7129A method and 40 degreeC x 90% RH.

  (13) Further, in the present invention, the laminate according to any one of (10) to (12) is disposed at least on the surface side of the display, and the end face of the laminate is unsealed. It is a display device.

  According to the present invention, a pressure-sensitive adhesive composition having excellent peel strength while suppressing water vapor permeability further lower than that of a conventional pressure-sensitive adhesive composition, and a laminate and an image display device using the pressure-sensitive adhesive composition are also provided. Provided.

It is a figure which shows the schematic sectional drawing of the sealing film 1 arrange | positioned at the image display apparatus which concerns on this embodiment. It is the figure which showed typically the evaluation method of the bonding in this embodiment.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

[Adhesive composition]
The pressure-sensitive adhesive composition of the present invention contains a polyisobutylene resin and a hydrogenated petroleum resin, the mass ratio of these is 70:30 to 90:10, and the viscosity average molecular weight (Mv) of the polyisobutylene resin is 300,000 to 500,000. The pressure-sensitive adhesive composition of the present invention is characterized in that a polyisobutylene resin and a hydrogenated petroleum resin are selected as constituent components, the mass ratio thereof is adjusted, and the viscosity average molecular weight (Mv) of the polyisobutylene resin is optimized. There is. According to the pressure-sensitive adhesive composition of the present invention, the water vapor transmission rate can be kept low as compared with conventional pressure-sensitive adhesive compositions. As a result, even when two or more transparent barrier films are bonded to each other with the pressure-sensitive adhesive composition of the present invention and the bonded transparent barrier laminated film is provided as a surface panel member on the surface of a display such as an electronic mobile, the pressure-sensitive adhesive layer It is possible to prevent water vapor from entering the inside of the electronic mobile from the end face and causing trouble to the display element and the circuit. Hereinafter, the pressure-sensitive adhesive composition of the present invention will be specifically described.

<Polyisobutylene resin>
The pressure-sensitive adhesive composition of the present invention contains a polyisobutylene resin. The polyisobutylene resin is a synthetic resin composed of long-chain hydrocarbons obtained by polymerization of isobutene and is characterized by high water vapor barrier properties and adhesiveness. The viscosity average molecular weight (Mv) of polyisobutylene is preferably in the range of 300,000 to 500,000. In order to keep the water vapor transmission rate low, a polymer having a high molecular weight in this range should be used. preferable. This viscosity average molecular weight is measured by ASTM D1601 method. As a commercially available product of the above polyisobutylene, for example, Opanol B50SF (manufactured by BASF) is suitable.

  The viscosity average molecular weight (Mv) of the polyisobutylene resin is related to the water vapor transmission rate and the peel strength when it is made into a laminate. The higher the molecular weight, the higher the water vapor barrier property (the lower the water vapor transmission rate). As a result, the tackiness decreases. For this reason, when the molecular weight is less than 300,000, the water vapor barrier property is lowered, which is not preferable. On the other hand, if the molecular weight exceeds 500,000, the peel strength (adhesive strength) when the laminate is formed is not preferred.

  The present invention is used as an interlayer pressure-sensitive adhesive layer in a transparent barrier laminated film (hereinafter also simply referred to as a laminate) described later. For this reason, unlike the sealing agent like patent document 1, high peeling strength is required for a laminated body. In this respect, the selection of the molecular weight is important in terms of both water vapor barrier properties and peel strength. That is, in the examples of Patent Document 1, a polyisobutylene resin having a viscosity average molecular weight of 1,100,000 or 4,000,000 is used, but this is for use as a sealant, and in the present invention used as an adhesive layer, The present invention is characterized in that a lower molecular weight is selected in consideration of prevention of a decrease in peel strength.

<Hydrogenated petroleum resin>
The pressure-sensitive adhesive composition of the present invention contains a hydrogenated petroleum resin. The hydrogenated petroleum resin used in the present embodiment is obtained by adding hydrogen to a petroleum resin used as a tackifier (tackifier). Petroleum resin mainly consists of the remaining C4 to C5 fraction (mainly C5 fraction) or C5 to C9 fraction (mainly C9 fraction) obtained by pyrolyzing naphtha and removing useful compounds such as ethylene, propylene and butadiene. Although it refers to a resin obtained by polymerization as a raw material, in the present invention, it is preferably a copolymer resin of dicyclopentadiene and an aromatic vinyl monomer. As a commercial item of the above hydrogenated petroleum resin, for example, Imabe P-100, P-125 and P-140 (all manufactured by Idemitsu Kosan Co., Ltd.) are suitable. The hydrogenation rate is preferably higher from the viewpoint of tackiness, and the amount of unsaturated residues is preferably less than 5 g / 100 g in terms of bromine number according to JIS K2605.

  Further, the number average molecular weight (Mn) of hydrogenated petroleum resin by vapor pressure absolute molecular weight measurement method (VPO method) is preferably from 660 to 1,000. The softening point in JISK2207 is preferably 100 ° C or higher and 150 ° C or lower. When the number average molecular weight is less than 660, it is not preferable from the point that the heat resistant temperature does not increase, and when it exceeds 1000, flexibility at the time of attachment is impaired, and the function as a tackifier may be impaired.

<Mass ratio of polyisobutylene resin and hydrogenated petroleum resin>
The mass ratio between the polyisobutylene resin and the hydrogenated petroleum resin is preferably 70:30 to 90:10. As described above, in the present invention, this quantity ratio is important because it is necessary to satisfy both the water vapor barrier property and the peel strength. When the mass ratio of polyisobutylene is less than 70%, it is not preferable because the water vapor barrier property is lowered. On the contrary, when the mass ratio of polyisobutylene is more than 90%, the peel strength is lowered and the initial adhesiveness is inferior. In addition, there are cases where subsequent peeling occurs, such being undesirable.

  As described above, since the present invention is an interlayer pressure-sensitive adhesive that is used differently from the sealing agent of Patent Document 1, it is provided with a water vapor barrier property on the premise of maintaining a predetermined peel strength. Originally, it is preferable that the amount of the tackifier is large from the viewpoint of improving the peel strength, but this will deteriorate the water vapor barrier property. For this reason, by lowering the molecular weight of the polyisobutylene resin from Patent Document 1 to an extent that does not affect the water vapor barrier, a part of the tackifying property is also borne on the polyisobutylene resin side. For this reason, it has succeeded in obtaining an excellent peel strength even with a small amount of hydrogenated petroleum resin of 10% to 30% with little decrease in water vapor barrier property.

<Water vapor barrier property>
The pressure-sensitive adhesive composition has a water vapor permeability per 25 μm of the pressure-sensitive adhesive layer of less than 15 g / m ² · day, more preferably 10 g or less in JIS K7129A method, 40 ° C. × 90% RH. The pressure-sensitive adhesive layer per 25 μm means that even when measured at other thicknesses, the water vapor permeability is inversely proportional to the thickness, so that a value converted per 25 μm can be adopted. In this respect, the water vapor permeability per unit thickness is a physical property unique to the material. The water vapor permeability of the adhesive layer may be measured by sandwiching the adhesive layer single film between supporting substrates that do not affect the measured value such as filter paper.

<Organic clay>
By the way, the pressure-sensitive adhesive composition of the present invention contains a polyisobutylene resin and a hydrogenated petroleum resin, and further contains an organic clay, contains a polyisobutylene resin and a hydrogenated petroleum resin, and contains water vapor as compared with a case where no organic clay is contained. The barrier property is further improved and good T-peel strength can be secured. The organic clay is a clay in which an organic agent is inserted between layers by utilizing the cation exchange property of the clay, thereby enabling dispersion in an organic solvent or resin. It is not preferable to add clay before putting the organic agent between the layers, because when clay is dispersed in an organic solvent as a diluting solvent, it is not uniformly dispersed and precipitation occurs. In addition, when an inorganic filler such as calcium carbonate or hydrophobic fumed silica is added instead of clay, the pressure-sensitive adhesive composition formed by mixing the polyisobutylene resin and hydrogenated petroleum resin with the inorganic filler turns white and has sufficient transparency. It is not preferable because it cannot be secured.

  As the clay, montmorillonite, hectorite, saponite, beidellite, stevensite, smectite clay minerals such as nontronite, swelling mica, vermiculite, halloysite, and the like are used. Among these, one selected from the group consisting of montmorillonite, hectorite (especially synthetic hectorite), swellable mica, and vermiculite is preferably used. Clay may be used independently and 2 or more types may be used together.

  As the organic agent, quaternary ammonium salts are generally used, but quaternary phosphonium salts, imidazolium salts, and the like may be used instead of ammonium salts.

  Examples of the quaternary ammonium salt include dimethyl distearyl ammonium salt and trimethyl stearyl ammonium salt, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl. Ammonium salt, N-polyoxyethylene-N-lauryl-N, N-dimethylammonium salt, trimethylalkylammonium salt, triethylalkylammonium salt, tributylalkylammonium salt, dimethyldialkylammonium salt, dibutyldialkylammonium salt, methylbenzyldialkylammonium salt Salt, dibenzyldialkylammonium salt, trialkylmethylammonium salt, trialkylethylan Quaternary ammonium salt having an aromatic ring such as nium salt, trialkylbutylammonium salt; benzylmethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl} ammonium chloride Quaternary ammonium salts with aromatic amines such as trimethylphenylammonium; quaternary ammonium salts with heterocycles such as alkylpyridinium salts and imidazolium salts; dialkyl quaternary ammonium salts with two polyethylene glycol chains, polypropylene glycol chains A dialkyl quaternary ammonium salt having two polyethylene glycol chains, a trialkyl quaternary ammonium salt having one polyethylene glycol chain, a trialkyl quaternary ammonium salt having one polypropylene glycol chain, and the like. These quaternary ammonium salts may be used independently and 2 or more types may be used together.

  Examples of the quaternary phosphonium salt include dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzylphosphonium salt, etc. Is used. These quaternary phosphonium salts may be used alone or in combination of two or more.

  In the present embodiment, it is preferable to use montmorillonite modified with quaternary ammonium as the organic clay, and examples of commercially available products include Kunifil-D36 (manufactured by Kunimine Industries) and Sven NX (manufactured by Hojun Co.). Moreover, it is also preferable to use smectite modified with quaternary ammonium as the organic clay, and as a commercial product, Lucentite SPN (manufactured by Coop Chemical Co., Ltd.) can be mentioned. It is preferable to use a synthetic material in that it contains almost no foreign matter / impurities and has a constant quality. Lucentite SPN is an organically modified synthetic smectite.

  On the other hand, it is not preferable to use mica (including synthetic mica) modified with an organic agent as the organic clay because sufficient water vapor barrier properties cannot be secured and sufficient T-peeling strength cannot be secured.

<Dispersion of organic clay in dilute solvent>
The pressure-sensitive adhesive composition is prepared by mixing a resin solution obtained by dissolving the polyisobutylene resin and hydrogenated petroleum resin in a diluting solvent (organic solvent) and a dispersion obtained by dispersing the organic clay in a diluting solvent (organic solvent). Is done. Here, the process of preparing a dispersion by dispersing organoclay in a diluent solvent will be described.

  When montmorillonite modified with quaternary ammonium is used as the organic clay, this montmorillonite may be dispersed as it is in a diluting solvent, regardless of whether a dispersant is used. On the other hand, when using smectite modified with quaternary ammonium as the organic clay, it is necessary to use a dispersing agent in dispersing the smectite in the diluting solvent. When a dispersant is not used, it is not preferable because sufficient T-peel strength cannot be ensured when an adhesive composition is prepared. As a commercially available dispersant, DA-7301 (manufactured by Enomoto Kasei Co., Ltd., a dispersant obtained by dissolving an amide amine salt of high molecular weight polyester acid in a dearomatic solvent) can be mentioned.

<Mass ratio of polyisobutylene resin and hydrogenated petroleum resin to organic clay>
Subsequently, a process of mixing the resin solution and the dispersion liquid will be described. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the organic clay is preferably 99: 1 to 90:10. As described above, in the present invention, this quantity ratio is important because it is necessary to satisfy both the water vapor barrier property and the peel strength. If the mass ratio of the organic clay is less than 1%, it is not preferable because a significant difference in water vapor barrier properties is not observed as compared with the case where the organic clay is not added. On the contrary, the mass ratio of the organic clay is 10%. On the other hand, when the resin solution and the dispersion liquid are mixed, it becomes a gel and is not preferable because sufficient transparency cannot be secured.

<Water vapor barrier property of adhesive composition to which organic clay is added>
The pressure-sensitive adhesive composition added with the organic clay has a water vapor permeability per 25 μm of the pressure-sensitive adhesive layer of less than 6 g / m ² · day in JIS K7129A method, 40 ° C. × 90% RH. As described above, the pressure-sensitive adhesive composition to which no organic clay is added has a water vapor permeability of less than 15 g / m ² · day. Therefore, when the organic clay is added, better water vapor barrier properties than when no organic clay is added. Is obtained.

<Total light transmittance and haze of adhesive composition to which organic clay is added>
The adhesive composition to which the above organic clay is added is a total light transmission of a laminate in which an adhesive layer made of the adhesive composition having a thickness of 25 μm and a soda glass having a thickness of 1 mm are laminated on an optical PET film having a thickness of 100 μm. The rate is 85% or more in the JIS K7361 method, and the haze (cloudiness) is 1% or less in the JIS K7136 method. The thickness of the adhesive layer is 25 μm, but the total light transmittance and haze per unit thickness are physical properties specific to the material. In addition, what is necessary is just to measure the total light transmittance and haze of an adhesion layer using the haze meter according to said JIS specification.

<Styrene elastomer>
In addition to the polyisobutylene resin and hydrogenated petroleum resin, the pressure-sensitive adhesive composition of the present invention contains a polystyrene resin and hydrogenated petroleum resin and further contains no styrene elastomer. , Heat resistance is improved.

  The styrenic elastomer is preferably a styrene-isobutylene-styrene triblock copolymer. It is not preferable that the styrene elastomer is a styrene-isobutylene diblock copolymer because heat resistance may not be sufficiently obtained.

  The styrene content is preferably 10% by mass to 40% by mass, and the ratio of the styrene content in the total mass of the polyisobutylene resin and the styrene elastomer is 1% by mass to 5% by mass. More preferably, a styrene-based elastomer is blended. When the styrene content is less than 10% by mass, sagging occurs at a high temperature, which is not preferable because there is a possibility that sufficient adhesive performance cannot be obtained. If it exceeds 40% by mass, it is not preferable because sufficient transparency may not be ensured.

  For example, SIBSTAR 102T and 103T (both manufactured by Kaneka Corporation) are suitable as commercial products of the styrene-based elastomer.

<Adhesive film>
As will be described later, the pressure-sensitive adhesive composition of the present invention is formed as a pressure-sensitive adhesive layer on a protective film by a conventionally known method for the convenience of lamination as an interlayer pressure-sensitive adhesive between two or more films. The protective film may be a release film that is easily peeled with silicone or the like, or a polyethylene terephthalate film (hereinafter also referred to as “PET film”) or a triacetyl cellulose film (hereinafter also referred to as “TAC film”). Etc. A commercially available release film that can be easily peeled with silicone or the like can be used. For example, SP-PET-01 and SP-PET-03 (both manufactured by Mitsui Chemicals, Inc.) are suitable. .

  The thickness of the pressure-sensitive adhesive layer is not particularly limited, and can be appropriately selected depending on the application. Usually, it is 10-30 micrometers, Preferably it is 15-25 micrometers. If the thickness is less than 10 μm, sufficient adhesive strength may not be obtained, and if it exceeds 30 μm, the cost is increased for performance, and sufficient adhesiveness is exhibited depending on the processing conditions. The amount of heat and pressure may be insufficient.

  The formation method of an adhesion layer is not specifically limited, A conventionally well-known method can be used. For example, a coating liquid for forming an adhesive layer is obtained by dissolving and dispersing the polyisobutylene resin and the hydrogenated petroleum resin in an organic solvent. Next, the entire surface of the coating solution is coated on the release-treated surface of the peelable protective film with an applicator or the like to form an adhesive layer. Then, the pressure-sensitive adhesive layer can be dried, and a pressure-sensitive adhesive layer can be formed by laminating a peelable protective film (release film). The organic solvent is not particularly limited, and for example, toluene, methyl ethyl ketone (MEK), ethyl acetate, dimethylacetamide, N-methyl-2-pyrrolidone, a mixed solution thereof and the like can be preferably used. . The method for coating the coating liquid on the peelable protective film layer is not particularly limited, and a conventionally known method can be used. Examples thereof include a roll coating method, a gravure coating method, a reverse coating method, a spray coating method, an air knife coating method, a curtain coating method, a die coating method, and a comma coating method.

  Various modes of supplying the adhesive film can be considered. For example, the embodiment may be a release film / adhesive layer / release film, or a protective film (PET film, TAC film, etc.) / Adhesive layer / release film.

[Laminate]
The laminated body of this invention is sufficient if the 1st transparent barrier film and the 2nd transparent barrier film contain the adhesion laminated body layer laminated | stacked through the adhesion layer which consists of the said adhesion composition.
That is, another layer may be laminated with the two adhesive laminate layers as a basic configuration.

Here, the transparent barrier film in the present invention has a haze value of 5.0% or less according to JISK7361 as a single film, and a water vapor permeability of 3 g / m ² · day in the JISK7129A method, 40 ° C. × 90% RH. Means less than. Specifically, an inorganic oxide vapor deposition film obtained by forming a thin film of an inorganic oxide such as silica or alumina on a transparent substrate film such as PET by a conventionally known vapor deposition method can be exemplified.

  In the laminating method, for example, the first transparent barrier film and the above-mentioned pressure-sensitive adhesive film are stacked and pressure-bonded with the pressure-sensitive adhesive layer interposed therebetween, whereby the pressure-sensitive adhesive layer is transferred to the first transparent barrier film side. A second transparent barrier film may be further pressure-bonded on the adhesive layer transferred thereafter.

  In addition, you may supply to a market with the form of the adhesive film which consists of a 1st transparent barrier film / adhesion layer / release film which is an intermediate product.

[Image display device]
The pressure-sensitive adhesive layer constituting the laminate of the present invention not only exhibits good adhesion and adhesion to the adherend, but also can keep the water vapor permeability from the end face low, The laminate of the present invention can be applied to the surface side of a small electronic mobile display such as a mobile phone or an electronic book, which is an example of an image display device, without providing a frame with a sealant along the surface.

  FIG. 1 is a schematic cross-sectional view of an image display apparatus 1 according to an embodiment of the present invention. The image display device 1 includes a first stacked body 2, a second stacked body 3, and a storage unit 4 surrounded by the first stacked body 2 and the second stacked body 3. A display element 5 is stored in the storage unit 4. The display element 5 includes a driving electrode 6 for driving a display, a display body 7 made of microcapsules in which particles moving by application of an electric field are dispersed in a dispersion medium, and an ITO film formed on a PET film. These ITO-PET films 8 are laminated from the second laminated body 3 toward the first laminated body 3.

  In this image display device 1, at least the first laminate 2 is constituted by the transparent laminate of the present invention. The first laminated body 2 is arranged in front of the display as viewed from the front side, and has a substantially horizontal shape. On the other hand, the 2nd laminated body 3 is arrange | positioned in the back seeing from the surface side of a display, and has the shape bent along the shape of the accommodating part 4. FIG. The peripheral portions of the first laminate 2 and the second laminate 3 are joined with a material having a water vapor barrier property.

  In this image display device 1, the end surface 2a of the first laminated body 2 is exposed, and the sealing process of the frame or the like is not performed. As described above, in the present invention, since the water vapor barrier property of the adhesive layer is excellent, the end surface sealing process of the laminated body with a frame body or a sealing material is unnecessary, and thus the structure of the image display device is simplified. be able to. Note that the end face of the laminate in the present invention is not sealed, and includes not only those in which the end face of the laminate is exposed, but also all aspects in which sealing treatment for securing a water vapor barrier is not substantially performed. Meaning.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention does not receive a restriction | limiting at all in these description.

[First embodiment]
The first example shows an example in which a polyisobutylene resin having a viscosity average molecular weight (Mv) of 300,000 to 500,000 and a hydrogenated petroleum resin are added at a mass ratio of 70:30 to 90:10. .

<Example 1>
70 parts by mass of polyisobutylene resin (trade name: Opanol B50SF, viscosity average molecular weight (Mv): 400,000, manufactured by BASF) and hydrogenated petroleum resin (trade name: Imabu P-140, dicyclopentadiene and aromatic vinyl monomer And 30 parts by mass of a copolymer resin, number average molecular weight (Mn): 900, manufactured by Idemitsu Kosan Co., Ltd., dissolved in 400 parts by mass of a diluting solvent (trade name: Reagent special grade toluene, manufactured by Wako Pure Chemical Industries, Ltd.) A coating solution was obtained.

  And a middle release sheet (trade name: SP-PET-03, a polyester film having a release treatment with a silicone-based release agent on one side, a film thickness: 38 μm, manufactured by Mitsui Chemicals, Inc. The coating solution was applied on the entire surface with an applicator so that the film thickness after drying was 15 μm and 25 μm, and then dried at 120 ° C. for 2 minutes in a drying oven. Next, a light release sheet (trade name: SP-PET-01, a polyester film that has been subjected to a release treatment with a silicone-based release agent on one side, a film thickness: 38 μm, manufactured by Mitsui Chemicals, Inc. And an adhesive film of Example 1 was obtained.

<Example 2>
A pressure-sensitive adhesive film of Example 2 was obtained in the same manner as in Example 1 except that the polyisobutylene resin was 80 parts by mass and the hydrogenated petroleum resin was 20 parts by mass.

<Example 3>
A pressure-sensitive adhesive film of Example 3 was obtained in the same manner as in Example 1 except that the polyisobutylene resin was 90 parts by mass and the hydrogenated petroleum resin was 10 parts by mass.

<Example 4>
The hydrogenated petroleum resin has a number average molecular weight (Mn) of 820 (trade name: Imabu P-125, copolymer resin of dicyclopentadiene and aromatic vinyl monomer, number average molecular weight (Mn): 820, Idemitsu Kosan The pressure-sensitive adhesive film of Example 4 was obtained in the same manner as in Example 1 except that the polyisobutylene resin was 80 parts by mass and the hydrogenated petroleum resin was 20 parts by mass.

<Example 5>
Number average molecular weight (Mn) of hydrogenated petroleum resin is 660 (trade name: Imabu P-100, copolymer resin of dicyclopentadiene and aromatic vinyl monomer, number average molecular weight (Mn): 660, Idemitsu Kosan The pressure-sensitive adhesive film of Example 5 was obtained in the same manner as in Example 1 except that the polyisobutylene resin was 80 parts by mass and the hydrogenated petroleum resin was 20 parts by mass.

<Comparative Example 1>
A pressure-sensitive adhesive film of Comparative Example 1 was obtained in the same manner as in Example 1 except that the polyisobutylene resin was 60 parts by mass and the hydrogenated petroleum resin was 40 parts by mass.

<Comparative example 2>
A pressure-sensitive adhesive film of Comparative Example 2 was obtained in the same manner as in Example 1 except that the polyisobutylene resin was 100 parts by mass and the hydrogenated petroleum resin was 0 parts by mass.

<Comparative Example 3>
The viscosity average molecular weight (Mv) of the polyisobutylene resin is 200,000 (Opanol B30SF, viscosity average molecular weight (Mv): 200,000, manufactured by BASF), and the number average molecular weight (Mn) of the hydrogenated petroleum resin is 660. Except for the above (Imabe P-100), a pressure-sensitive adhesive film of Comparative Example 3 was obtained in the same manner as in Example 1.

<Comparative example 4>
The viscosity average molecular weight (Mv) of the polyisobutylene resin is 85,000 (Opanol B15SFN, viscosity average molecular weight (Mv): 85,000, manufactured by BASF), number average molecular weight (Mn) of hydrogenated petroleum resin Was obtained in the same manner as in Example 1 except that No. 660 (Imabe P-100).

<Comparative Example 5>
The viscosity average molecular weight (Mv) of the polyisobutylene resin is 85,000 (the above-mentioned Opanol B15SFN), the number average molecular weight (Mn) of the hydrogenated petroleum resin is 660 (the above-mentioned Imabe P-100), polyisobutylene A pressure-sensitive adhesive film of Comparative Example 5 was obtained in the same manner as in Example 1 except that the resin was 90 parts by mass and the hydrogenated petroleum resin was 10 parts by mass.

<Comparative Example 6>
100 parts by mass (solid content) of acrylic pressure-sensitive adhesive (trade name: SK-2094, manufactured by Soken Chemical Co., Ltd.) and 0.3 part by mass of a crosslinking agent (trade name: E-AX, manufactured by Soken Chemical Co., Ltd.) A comparative coating solution was obtained by mixing.

  And two release sheets were laminated | stacked through the adhesion layer which consists of the said comparison coating liquid by the method similar to Example 1, and it aged at 40 degreeC for 3 days, and obtained the adhesion film of the comparative example 6.

  The light release sheet of the adhesive film of Examples and Comparative Examples was peeled off, and the adhesive layer surface was laminated with the corona surface side of a 12 μm thick single-sided corona-treated PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.). After pressure bonding with a roller, the intermediate release sheet was peeled off, and the adhesive layer was transferred to the PET film side to form PET 12 μm (corona surface) / adhesive layer 15 μmor 25 μm. Then, the corona surface of the same PET film was laminated | stacked on the adhesion layer, and it pressure-bonded similarly, and produced the laminated body of PET12micrometer (corona surface) / adhesion layer 15micrometer25micrometer / (corona surface) PET12micrometer.

Moreover, the light release sheet | seat of the adhesive film of an Example and a comparative example was peeled off, and the adhesive layer surface 12-micrometer-thick single-sided silica vapor deposition processing PET film (Brand name: IB-PET-PXB, Dai Nippon Printing Co., Ltd. water vapor permeability 0.1g / m ² · day) layered on the alumina vapor deposition surface side, after pressing with a 45mm width 2kg roller, peel off the intermediate release sheet and transfer the adhesive layer to the PET film side, PET 12μm (inorganic vapor deposition surface) / Adhesive layer 15 μm was formed. Then, the inorganic material vapor deposition surface of the same PET film was laminated | stacked on the adhesion layer, and it pressure-bonded similarly, and the barrier laminated body of PET12micrometer (inorganic substance vapor deposition surface) / adhesion layer 15micrometer / (inorganic substance vapor deposition surface) PET12micrometer was created.

[Evaluation of T-peel strength]
The evaluation of the T-shaped peel strength was performed according to a 180-degree T-shaped peel test. The laminates obtained in Examples 1 to 5 and Comparative Examples 1 to 3 having an adhesive layer of 15 μm were cut into a length of 100 mm and a width of 15 mm, a test piece was created, and a tensile tester (product) Name: Tensilon RTF-1150H, manufactured by A & D Co., Ltd.) (speed: 50 mm / min, peel angle: 180 °), and the strength at that time was defined as T-shaped peel strength. The results are shown in Table 2. The unit is N / 15mm. 2N / 15 mm or more was set as “◯”, and less than 2N / 15 mm was set as “x”.

[Evaluation of water vapor permeability]
The water vapor permeability was evaluated according to JIS K7129A method. The pressure-sensitive adhesive layers obtained in Examples 1 to 5 and Comparative Examples 1 to 3 having a pressure-sensitive adhesive layer of 25 μm were peeled from both release sheets, and the pressure-sensitive adhesive layer 25 μm was sandwiched between filter papers for measurement. The test measured the water vapor transmission rate in JIS K7129A method, 40 degreeC, 90% RH using the water vapor transmission rate measuring machine L80-5000 (made by PBI Dunsensor). The results are shown in Table 2. The unit was g / m ² · day, and less than 15 g / (m ² · day) was “◯”, and 15 g / (m ² · day) or more was “x”.

  Although it is difficult to directly measure the water vapor transmission rate from the end surface, as described above, the water vapor transmission rate is an intrinsic property of the composition. Therefore, if the normal water vapor transmission rate is low, the water vapor transmission rate from the end surface is low. It can be said that it is low. For this reason, there is no problem in discussing the end face water vapor permeability with a relative comparison of normal water vapor permeability.

  Example 1 Adhesive composition in which the mass ratio of polyisobutylene resin to hydrogenated petroleum resin is 70:30 to 90:10, and the viscosity average molecular weight (Mv) of the polyisobutylene resin is 300,000 to 500,000 (Example 1) ~ 5) all showed good T-shaped peel strength and water vapor permeability.

  On the other hand, if the polyisobutylene resin is less than 70 parts by mass, the water vapor permeability may not be sufficiently suppressed even if the viscosity average molecular weight (Mv) of the polyisobutylene resin is 300,000 to 500,000. It was confirmed (Comparative Example 1). Further, when the polyisobutylene resin is added in an amount of more than 90 parts by mass, even if the viscosity average molecular weight (Mv) of the polyisobutylene resin is 300,000 to 500,000, sufficient T-peel strength cannot be secured, and the initial It was confirmed that the adhesiveness is inferior or the subsequent peeling may occur (Comparative Example 2).

  Further, when the viscosity average molecular weight (Mv) of the polyisobutylene resin is smaller than 300,000, even if the mass ratio of the polyisobutylene resin to the hydrogenated petroleum resin is 70:30 to 90:10, a sufficient T-shape is obtained. It was confirmed that the peel strength could not be ensured and the initial adhesiveness was inferior or that subsequent peeling occurred (Comparative Examples 3 to 5).

[Second Embodiment]
The second embodiment shows an example in which an organic clay is further added in addition to the polyisobutylene resin and the hydrogenated petroleum resin.

<Preparation of resin solution A>

  80 parts by mass of polyisobutylene resin (trade name: Opanol B50SF, viscosity average molecular weight (Mv): 400,000, manufactured by BASF), hydrogenated petroleum resin (trade name: Imabu P-140, dicyclopentadiene and aromatic vinyl monomer And 20 parts by mass of a copolymer resin and a number average molecular weight (Mn): 900, manufactured by Idemitsu Kosan Co., Ltd. are dissolved in 300 parts by mass of a diluting solvent (trade name: reagent special grade toluene, manufactured by Wako Pure Chemical Industries, Ltd.) A resin solution A was obtained.

<Preparation of dispersion B>

<Dispersion B-1>
As clay, 10 parts by mass of organic montmorillonite A (trade name: Kunifil D36, manufactured by Kunimine Kogyo Co., Ltd.) was dissolved in 90 parts by mass of a diluent solvent (trade name: reagent special grade toluene, manufactured by Wako Pure Chemical Industries, Ltd.). As a result, a uniformly dispersed dispersion B-1 was obtained.

<Dispersion B-2>
As clay, 10 parts by mass of organic montmorillonite B (trade name: Sven NX, manufactured by Hojun Co., Ltd.) was dissolved in 90 parts by mass of the dilution solvent. As a result, a uniformly dispersed dispersion B-2 was obtained.

<Dispersion B-3>
As clay, 10 parts by mass of organically modified synthetic smectite (trade name: Lucentite SPN, manufactured by Co-op Chemical Co., Ltd.) was dissolved in 90 parts by mass of the dilution solvent. As a result, a uniformly dispersed dispersion B-3 was obtained.

<Dispersion B-4>
As clay, 10 parts by mass of synthetic mica (trade name: Somasif MPE, manufactured by Co-op Chemical Co.) was dissolved in 90 parts by mass of the dilution solvent. As a result, a uniformly dispersed dispersion B-4 was obtained.

<Dispersion B-5>
As clay, 10 parts by mass of montmorillonite (trade name: Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) was dissolved in 90 parts by mass of the dilution solvent. As a result, Dispersion B-5 was obtained in which the precipitate remained without being uniformly dispersed.

<Dispersion B-6>
As clay, 10 parts by mass of the above organic montmorillonite A was dissolved in 89.5 parts by mass of the diluting solvent together with 0.5 parts by mass of dispersant A (trade name: DA-7301, manufactured by Enomoto Kasei Co., Ltd.). As a result, a uniformly dispersed dispersion B-6 was obtained.

<Dispersion B-7>
As a clay, 10 parts by mass of the synthetic smectite was dissolved in 89.5 parts by mass of the dilution solvent together with 0.5 part by mass of the dispersant A. As a result, a uniformly dispersed dispersion B-7 was obtained.

<Dispersion B-8>
In place of clay, 10 parts by mass of calcium carbonate (trade name: SCP-E # 2010, manufactured by Sankyo Flour Mills) as an inorganic filler is diluted with 0.5 parts by weight of dispersant B (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.). It was dissolved in 89.5 parts by mass of the solvent. As a result, a uniformly dispersed dispersion B-8 was obtained.

<Dispersion B-9>
Instead of clay, 10 parts by mass of hydrophobic fumed silica (trade name: AEROSIL R7200, manufactured by Nippon Aerosil Co., Ltd.) as an inorganic filler was dissolved in 89.5 parts by mass of the diluent together with 0.5 part by mass of the dispersant B. As a result, a uniformly dispersed dispersion B-9 was obtained.

<Preparation of Examples 11-17, Comparative Examples 11-16, and Control>

<Example 11>
100 parts by mass of the resin solution A and 7.5 parts by mass of the dispersion B-1 were mixed to obtain a light brown transparent coating solution. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (in this example, organic montmorillonite) in this coating solution is 97: 3.

  And a middle release sheet (trade name: SP-PET-03, a polyester film having a release treatment with a silicone-based release agent on one side, a film thickness: 38 μm, manufactured by Mitsui Chemicals, Inc. The coating solution was applied on the entire surface with an applicator so that the film thickness after drying was 15 μm and 25 μm, and then dried at 120 ° C. for 2 minutes in a drying oven. Next, a light release sheet (trade name: SP-PET-01, a polyester film that has been subjected to a release treatment with a silicone-based release agent on one side, a film thickness: 38 μm, manufactured by Mitsui Chemicals, Inc. And an adhesive film of Example 11 was obtained. This adhesive film was colorless and transparent.

<Example 12>
An adhesive film of Example 12 was obtained in the same manner as in Example 11 except that the dispersion B-1 was 12.5 parts by mass. The coating liquid was a light brownish transparent liquid, and the adhesive film was colorless and transparent. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (organic montmorillonite in this example) in the coating solution is 95: 5.

<Example 13>
An adhesive film of Example 13 was obtained in the same manner as in Example 11 except that the dispersion B-1 was 25 parts by mass. The coating liquid was a light brownish transparent liquid, and the adhesive film was colorless and transparent. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (in this example, organic montmorillonite) in the coating solution is 90:10.

<Example 14>
An adhesive film of Example 14 was obtained in the same manner as in Example 11 except that 12.5 parts by mass of the above dispersion B-2 was used instead of the above dispersion B-1. The coating liquid was a light brownish transparent liquid, and the adhesive film was colorless and transparent. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (organic montmorillonite in this example) in the coating solution is 95: 5.

<Example 15>
A pressure-sensitive adhesive film of Comparative Example 12 was obtained in the same manner as in Example 11 except that 12.5 parts by mass of Dispersion B-3 was used instead of Dispersion B-1. The coating solution is colorless and transparent,
The adhesive film was also colorless and transparent. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (organically modified synthetic smectite in this example) in the coating solution is 95: 5.

<Example 16>
An adhesive film of Example 15 was obtained in the same manner as in Example 11 except that 12.5 parts by mass of the above dispersion B-6 was used instead of the above dispersion B-1. The coating liquid was a light brownish transparent liquid, and the adhesive film was colorless and transparent. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (organic montmorillonite in this example) in the coating solution is 95: 5.

<Example 17>
An adhesive film of Example 16 was obtained in the same manner as in Example 11 except that 12.5 parts by mass of the above dispersion B-7 was used instead of the above dispersion B-1. The coating solution is colorless and transparent,
The adhesive film was also colorless and transparent. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (organically modified synthetic smectite in this example) in the coating solution is 95: 5.

<Comparative Example 11>
A pressure-sensitive adhesive film of Comparative Example 11 was obtained in the same manner as in Example 11 except that the dispersion B-1 was 37.5 parts by mass. The coating solution was in the form of a gel and the adhesive film had deposits. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (organic montmorillonite in this example) in the coating solution is 85:15.

<Comparative Example 12>
A pressure-sensitive adhesive film of Comparative Example 13 was obtained in the same manner as in Example 11 except that 7.5 parts by mass of Dispersion B-4 was used instead of Dispersion B-1. The coating solution is colorless and transparent,
The adhesive film was also colorless and transparent. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (synthetic mica in this example) in the coating solution is 97: 3.

<Comparative Example 13>
A pressure-sensitive adhesive film of Comparative Example 14 was obtained in the same manner as in Example 11 except that 12.5 parts by mass of Dispersion B-4 was used instead of Dispersion B-1. The coating solution is colorless and transparent,
The adhesive film was also colorless and transparent. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (synthetic mica in this example) in the coating solution is 95: 5.

<Comparative example 14>
A pressure-sensitive adhesive film of Comparative Example 15 was obtained in the same manner as in Example 11 except that 25 parts by mass of Dispersion B-4 was used instead of Dispersion B-1. The coating solution is colorless and transparent,
The adhesive film was also colorless and transparent. The mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (synthetic mica in this example) in the coating solution is 90:10.

<Comparative Example 15>
A pressure-sensitive adhesive film of Comparative Example 16 was obtained in the same manner as in Example 11 except that 7.5 parts by mass of Dispersion B-8 was used instead of Dispersion B-1. The coating solution was white and the adhesive film was also white. In addition, the mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (in this embodiment, calcium carbonate) in the coating solution is 97: 3.

<Comparative Example 16>
A pressure-sensitive adhesive film of Comparative Example 16 was obtained in the same manner as in Example 11 except that 7.5 parts by mass of Dispersion B-9 was used instead of Dispersion B-1. The coating solution was white and the adhesive film was also white. In addition, the mass ratio of the polyisobutylene resin and hydrogenated petroleum resin to the filler (in this embodiment, calcium carbonate) in the coating solution is 97: 3.

<Control example>
A control adhesive film was obtained in the same manner as in Example 11 except that the dispersion B-1 was not used. The coating solution was colorless and transparent, and the adhesive film was also colorless and transparent. The composition of the control example is the same as that of Example 2 above.

  Thereafter, a laminate of PET 12 μm (corona surface) / adhesive layer 15 μm 25 μm / (corona surface) PET 12 μm was prepared for each of the Examples, Comparative Examples, and Control Examples. The laminate was produced in the same manner as in the first example.

[Evaluation of T-peel strength]
Evaluation of the T-shaped peel strength was performed in the same manner as in the first example according to the 180-degree T-shaped peel test. The results are shown in Table 6. In addition, 2N / 15mm or more was made into "(circle)", and less than 2N / 15mm was made into "x".

[Evaluation of water vapor permeability]
The evaluation of water vapor permeability was performed in the same manner as in the first example according to JIS K7129A method. The results are shown in Table 6. The unit is g / m ² · day, and less than 6 g / (m ² · day) is “◯”, and 6 g / (m ² · day) or more is “x”. In the first embodiment, “◯” is less than 15 g / (m ² · day), whereas in the second embodiment, less than 6 g / (m ² · day) is “◯”. In this respect, the second embodiment is a stricter standard than the first embodiment.

[Evaluation of total light transmittance and haze]
Evaluation of total light transmittance was performed according to JIS K7361 method. An optical PET film having a thickness of 100 μm (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd., having a total light transmittance of 90% and haze of 0.5%) and 25 μm in the above Examples 11 to 11. 16, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition obtained in Comparative Examples 11 to 17 and the control example, and soda glass having a thickness of 1 mm (S7213 manufactured by Matsunami Glass Industrial Co., Ltd. Was measured using a haze meter NDH-200 (manufactured by Nippon Denshoku Co., Ltd.). The results are shown in Table 6. The unit is%, and 89% or more is “◯”, and less than 89% is “×”.

  The haze was evaluated according to JIS K7136 method. About the laminated body used by evaluation of said total light transmittance, the haze when using a D65 fluorescent lamp as a light source was measured using the said haze meter NDH-200. The results are shown in Table 6. The unit is%, and less than 1.5% is “◯”, and 1.5% or more is “x”.

  Example 1 Adhesive composition in which the mass ratio of polyisobutylene resin to hydrogenated petroleum resin is 70:30 to 90:10, and the viscosity average molecular weight (Mv) of the polyisobutylene resin is 300,000 to 500,000 (Example 1) To 5), montmorillonite or smectite modified with an organic agent is added as an organic clay so that the mass ratio of polyisobutylene resin, hydrogenated petroleum resin and organic clay is 99: 1 to 90:10. As compared with the case where no organic clay was added, the T-peeling strength and water vapor permeability were even better (Examples 11-14, 16 and 17). However, when the organic clay is a smectite modified with quaternary ammonium, when dispersing the smectite without using a dispersant when dispersing the smectite in a diluting solvent, sufficient T There may be a case where the character peel strength cannot be ensured and the initial adhesiveness is inferior, or the subsequent peeling occurs (Example 15). The adhesive compositions according to Examples 11 to 14, 16 and 17 have good total light transmittance and haze. Therefore, a laminated body can be formed by laminating the first transparent barrier film and the second transparent barrier film via the adhesive composition, and this laminated body can be disposed on the surface side of the display.

  On the other hand, when the organic clay is mica modified with an organic agent, even if the added material is an organic clay, the water vapor permeability and the T-shaped peel strength may be inferior compared to the case where the organic clay is not added. Was confirmed (Comparative Examples 12 to 14). Moreover, when adding an inorganic filler instead of organic clay, it was confirmed that water vapor permeability and T-peeling strength may be inferior compared with the case where an inorganic filler is not added (Comparative Examples 15 and 16).

[Third embodiment]
The third example shows an example in which a styrene elastomer is further added in addition to the polyisobutylene resin and the hydrogenated petroleum resin.

<Preparation of resin solution A>

<Example 21>
90 parts by mass of the above-mentioned “Opanol B50SF” as a polyisobutylene resin, 30 parts by mass of the above-mentioned “Imabe P-140” as a hydrogenated petroleum resin, and a styrene elastomer (trade name: SIBSTAR 102T, styrene-isobutylene-styrene triblock copolymer) 10 parts by mass of coalesced, weight average molecular weight (MW): 112,000, styrene content: 12%, manufactured by Kaneka Corporation) was dissolved in 400 parts by mass of the dilution solvent to obtain a transparent coating solution.

  And after coating the said coating liquid with the applicator so that the film thickness after drying may be set to 15 micrometers and 25 micrometers on the peeling process surface of the said inside peeling sheet "SP-PET-03", after drying, Dry at 120 ° C. for 2 minutes. Subsequently, the light release sheet “SP-PET-01” was laminated to obtain an adhesive film of Example 21.

<Example 22>
A pressure-sensitive adhesive film of Example 22 was obtained in the same manner as in Example 21 except that the polyisobutylene resin was 80 parts by mass and the styrene-based elastomer was 20 parts by mass.

<Example 23>
An adhesive film of Example 23 was obtained in the same manner as in Example 21, except that the polyisobutylene resin was 75 parts by mass and the styrene elastomer was 25 parts by mass.

<Example 24>
10 mass of styrene elastomer (trade name: SIBSTAR 103T, styrene-isobutylene-styrene triblock copolymer, number average molecular weight (Mn): 100,000, styrene content: 30%, manufactured by Kaneka Corporation) instead of the above styrene elastomer A pressure-sensitive adhesive film of Example 24 was obtained in the same manner as in Example 21, except that the part was used.

<Comparative Example 21>
A pressure-sensitive adhesive film of Comparative Example 21 was obtained in the same manner as in Example 21, except that the polyisobutylene resin was 50 parts by mass and the styrene elastomer “SIBSTAR 102T” was 50 parts by mass.

<Comparative Example 22>
A pressure-sensitive adhesive film of Comparative Example 22 was obtained in the same manner as in Example 21, except that the polyisobutylene resin was 25 parts by mass and the styrene elastomer “SIBSTAR 102T” was 75 parts by mass.

<Comparative Example 23>
A pressure-sensitive adhesive film of Comparative Example 23 was obtained in the same manner as in Example 21 except that the polyisobutylene resin was 80 parts by mass and the styrene elastomer “SIBSTAR 103T” was 20 parts by mass.

<Control example>
A comparative adhesive film was obtained in the same manner as in Example 21 except that the polyisobutylene resin was 78 parts by mass, the hydrogenated petroleum resin was 22 parts by mass, and no styrene elastomer was added.

  Examples 21-24, Comparative Examples 21-23 and the light release sheet of the adhesive film of the control example were peeled off, and the corona of the PET film having a thickness of 12 μm (trade name: Toyobo Ester Film E5100, manufactured by Toyobo Co., Ltd.) After laminating with the treated surface side and pressing with a 2 kg roller having a width of 45 mm, the intermediate release sheet was peeled off and the adhesive layer was transferred to the PET film side to form PET 12 μm (corona treated surface) / adhesive layer 15 μm. Then, the inorganic material vapor deposition surface of the same PET film was laminated | stacked on the adhesion layer, and it pressure-bonded similarly, and produced the laminated body of PET12micrometer (corona treatment surface) / adhesion layer 15micrometer / (corona treatment surface) PET12micrometer.

[Evaluation of peel strength]
Evaluation of peel strength is carried out on the corona-treated surface side of a SUS plate and a PET film having a thickness of 12 μm (trade name: Toyobo Ester Film E5100, manufactured by Toyobo Co., Ltd.) in Examples 21-24, Comparative Examples 21-23, and Comparative Examples. The pressure-sensitive adhesive layer having a thickness of 25 μm was pressure-bonded with a 2 kg roller having a width of 45 mm and then subjected to JIS K6854 method. The results are shown in Table 8. The unit is N / 15mm. 1.5 N / 15 mm or more was set as “◯”, and less than 1.5 N / 15 mm was set as “x”.

[Evaluation of water vapor permeability]
The water vapor permeability was evaluated in the same manner as in the first and second examples according to the JIS K7129A method. The results are shown in Table 8. The unit was g / m ² · day, and less than 15 g / (m ² · day) was “◯”, and 15 g / (m ² · day) or more was “x”.

[Evaluation of total light transmittance and haze]
Evaluation of the total light transmittance was performed in the same manner as in the second example according to the JIS K7361A method. The results are shown in Table 8. The unit is%, and 89% or more is “◯”, and less than 89% is “×”.
The haze was evaluated according to JIS K7136 method, and was performed in the same manner as in the second example. The results are shown in Table 8. The unit is%, and less than 1.5% is “◯”, and 1.5% or more is “x”.

[Evaluation of coated surface condition]
Evaluation of the coated surface state was performed by visually confirming whether the coated surface was rough when the light release sheet of the adhesive film was peeled off. The results are shown in Table 8. When there was no roughness, “◯” was assigned, and when there was roughness, “X” was assigned.

[Evaluation of dynamic viscoelasticity]
Evaluation of dynamic viscoelasticity was performed from three viewpoints of glass transition temperature Tg, storage elastic modulus E ′, and loss elastic modulus E ″. The dynamic viscoelasticity is measured by using a solid viscoelasticity analyzer RSA-III manufactured by TA Instruments Inc., and a dynamic viscoelasticity measurement method (attachment mode: compression mode, frequency: compliant with JIS K7244-1). 1 Hz, temperature: −50 to 150 ° C., heating rate: 5 degrees / minute). The glass transition temperature Tg was determined from the temperature showing the maximum value of the loss tangent tan δ obtained by this measurement. Values obtained by this measurement were adopted as they were for the storage elastic modulus E ′ and the loss elastic modulus E ″. Table 8 shows the measurement results. Regarding the storage elastic modulus E ′, the case where the value of E ′ (100 ° C.) is 2.0 × 10 ⁵ or more and 5.0 × 10 ⁵ or less is “◯”, and the case where it is not is “×”. Regarding the loss elastic modulus E ″, when the value of E ″ (100 ° C.) is 0.9 × 10 ⁵ or more and 2.3 × 10 ⁵ or less, “◯” is indicated, and otherwise, “×” is indicated. did.

[Evaluation of pasting after standing at high temperature]
FIG. 2 is a diagram schematically showing a bonding evaluation method in the present embodiment. Two SUS plates 11 having a width of 60 mm, a thickness of 2 mm, and a weight of 70 g were prepared, and an adhesive layer having a width of 60 mm, a length of 25 mm, and a thickness of 25 μm was formed on the bonding surface 11 a of one SUS plate 11. Then, the bonding surfaces 11a of the two SUS plates 11 were bonded to each other, and then bonded in a 40 ° C. oven for 24 hours while applying a load of 500 g. Then, the pressed SUS plate 11 was suspended in an oven at 80 ° C. for 24 hours, and the subsequent displacement of the SUS plate 11 was measured. The results are shown in Table 8. When the deviation was less than 5 mm, “◯” was given, and when it was not, “x” was given.

  Example 1 Adhesive composition in which the mass ratio of polyisobutylene resin to hydrogenated petroleum resin is 70:30 to 90:10, and the viscosity average molecular weight (Mv) of the polyisobutylene resin is 300,000 to 500,000 (Example 1) To 5), a styrene-isobutylene-styrene triblock copolymer having a styrene content of 10% by mass to 40% by mass as a styrene-based elastomer in the total mass of the polyisobutylene resin and the styrene-based elastomer, By blending so that the ratio of the styrene content is 1% by mass to 5% by mass, the bonding is good even after standing at high temperature, compared to the case where no styrene elastomer is added, and high heat resistance is achieved. It was confirmed to have (Examples 21 to 24). The adhesive compositions according to Examples 21 to 24 have good total light transmittance and haze. Therefore, a laminated body can be formed by laminating the first transparent barrier film and the second transparent barrier film via the adhesive composition, and this laminated body can be disposed on the surface side of the display.

  On the other hand, when the ratio of the styrene content in the total mass of the polyisobutylene resin and the styrene-based elastomer exceeds 5% by mass, it was confirmed that haze is inferior and sufficient transparency cannot be secured ( Comparative Examples 21-23). In particular, when it exceeds 9 parts by mass, it was confirmed that the pressure-sensitive adhesive layer becomes too hard and the coated surface becomes rough (Comparative Example 22).

DESCRIPTION OF SYMBOLS 1 Image display apparatus 2 1st laminated body 3 2nd laminated body 4 Storage part 5 Display element 6 Drive electrode 7 Display body 8 ITO-PET film

Claims (13)

The mass ratio of the polyisobutylene resin and the hydrogenated petroleum resin is 70:30 to 90:10,
The pressure-sensitive adhesive composition, wherein the polyisobutylene resin has a viscosity average molecular weight (Mv) of 300,000 to 500,000.   The pressure-sensitive adhesive according to claim 1, wherein the hydrogenated petroleum resin is a copolymer resin of dicyclopentadiene and an aromatic vinyl monomer, and the number average molecular weight (Mn) of the hydrogenated petroleum resin is 660 or more and 1000 or less. Composition. A pressure-sensitive adhesive composition having a water vapor permeability per 25 μm of the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to claim 1 or 2 of less than 15 g / m ² · day in JIS K7129A method, 40 ° C. × 90% RH. In addition, containing organic clay,
The pressure-sensitive adhesive composition according to claim 1 or 2, wherein a mass ratio of the polyisobutylene resin, the hydrogenated petroleum resin, and the organic clay is 99: 1 to 90:10.   The pressure-sensitive adhesive composition according to claim 4, wherein the organic clay is montmorillonite modified with quaternary ammonium. A pressure-sensitive adhesive composition having a water vapor transmission rate per 25 μm of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition according to claim 4 or 5 is less than 6 g / m ² · day in JIS K7129A method, 40 ° C. × 90% RH.   The total light transmittance of a laminate obtained by laminating an adhesive layer of 25 µm made of the adhesive composition according to any one of claims 4 to 6 and soda glass having a thickness of 1 mm on an optical PET film having a thickness of 100 µm is JIS K7361. The adhesive composition is 85% or more in the method and the haze of the laminate is 1% or less in the JIS K7136 method. In addition, including a styrenic elastomer,
The pressure-sensitive adhesive composition according to any one of claims 1 to 7, wherein the styrene-based elastomer is a styrene-isobutylene-styrene triblock copolymer having a styrene content of 10% by mass to 40% by mass.   The said styrene-type elastomer is mix | blended so that the ratio of the said styrene content in the total mass of the said polyisobutylene resin and the said styrene-type elastomer may be 1 mass%-5 mass%. Adhesive composition.   A laminate characterized in that the first transparent barrier film and the second transparent barrier film include at least an adhesive laminate layer laminated through an adhesive layer made of the adhesive composition according to claim 1. body.   The said adhesion layer is 15 micrometers or more, Comprising: The peeling strength in the 180 degree | times T-shaped peeling test between the said 1st transparent barrier film and a 2nd transparent barrier film is 2 N / 15mm or more. Laminated body. Each of the first transparent barrier film and the second transparent barrier film is a transparent inorganic oxide vapor-deposited film, and the water vapor permeability of each transparent inorganic oxide vapor-deposited film is JIS K7129A method, 40 ° C. × 90% RH. The laminate according to claim 10 or 11, which is less than 3 g / m ² · day.   An image display device, wherein the laminate according to any one of claims 10 to 12 is disposed at least on a surface side of a display, and an end surface of the laminate is unsealed.

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