KR20100061547A - Adhesive sheet, upper electrode for touch panel, and image display device - Google Patents

Abstract

Disclosed is an adhesive sheet wherein at least a polyester base film , a crosslinked silicone rubber adhesive layer having a polydimethylsiloxane skeleton, a releasing layer and a polyester film are laminated in this order through or not through another layer. This adhesive sheet is characterized in that when the hot water adhesion resistance is evaluated by the method defined in the description, the silicone rubber adhesive layer is not separated from the polyester base film (A), and the peel strength between the silicone rubber adhesive layer and the releasing layer is within the range of 0.03-1.0 N/20 mm.

Description

Adhesive sheet, upper electrode for touch panel, and image display device

The present invention has a pressure-sensitive adhesive layer excellent in adhesion and re-peelability, excellent in hot water adhesion between the pressure-sensitive adhesive layer and the base film, and an adhesive sheet in which the peel strength of the pressure-sensitive adhesive layer and the separate film is properly controlled. The present invention relates to an upper electrode for a touch panel and an image display device using the pressure sensitive adhesive sheet.

Since the adhesive sheet which made the silicone rubber layer the adhesion layer has the outstanding adhesiveness and re-peelability together, it is used in the wide field as an adhesive sheet which requires re-peelability (repairability). The present inventors etc. have already disclosed the various films which have the silicone adhesion layer which used the silicone rubber compound as a raw material (for example, refer patent documents 1-4).

The film described in each patent document is used suitably in various uses. In recent years, however, with the expansion of its use, there have been cases where market demand for quality and price has not been satisfied, and improvement thereof is required.

For example, the pressure-sensitive adhesive sheet is shipped in a form in which a separate film is laminated on the surface of the pressure-sensitive adhesive layer in order to increase its handleability, and when used in practice, the pressure-sensitive adhesive film is peeled off and adhered to a target article. There is a strong demand for reducing the power. However, if the peeling force of the separate film is too small, in the manufacturing process of the pressure-sensitive adhesive sheet, when the sheet is wound, partial lifting of the separate film occurs, and the air layer is in a direction orthogonal to the winding direction of the sheet. This so-called channeling phenomenon sometimes occurred. Moreover, although the optical use requires the high transparency and its stability to an adhesive sheet, the case where the correspondence was difficult has arisen.

Moreover, when the raw material of the silicone rubber disclosed by the said patent document is a millable type | mold silicone rubber compound, or such a compound, the solubility to a solvent falls in accordance with the storage state, and when a silicone rubber layer is coated, The appearance quality may deteriorate by unsealed seafood. In addition, the coating solution in which the silicone rubber compound is dissolved in a solvent has various problems in the stabilization of quality and stable production, such as gelation of the solution and the use of the coating solution depending on the storage condition. It has been an obstacle to responding to demands, and their problem solving is strongly urged.

On the other hand, using the double-sided adhesive sheet which formed the acrylic adhesive layer on the opposite surface of the silicone rubber layer of the adhesive sheet which made the said silicone rubber layer the adhesive layer is disclosed as a member for touch panels (for example, refer patent document 5). ).

Also in the said double-sided adhesive sheet, regarding the adhesive layer which becomes a silicone rubber layer, it has the same problem as the adhesive sheet which made the silicone rubber layer mentioned above an adhesive layer. In addition, in this patent document 5, the detailed description of the silicone rubber adhesion layer forming method is not made | formed, and the said problem solving means is not mentioned at all. Moreover, there is no specific description about adhesiveness with a base material, and the corona treatment which was illustrated was not able to provide sufficient adhesiveness under the severe use conditions mentioned above.

By the way, the touch panel is recognized as an excellent input method, and is used in various fields, such as a bank ATM, a ticket vending machine, a portable information terminal, a game machine, and a car navigation system. Since a transparent electrode is needed for a touch panel and glass was used for the board | substrate conventionally, in recent years, many transparent conductive films which provided the transparent conductive layer on the plastic film surface are proposed.

What is needed for a transparent conductive film, for example, when using it as an upper electrode, the hard-coat layer which can endure the friction at the time of input by the conductive layer used as an electrode, the base material which supports this conductive layer, and a hand or a pen. to be. For example, although the patent document 6 discloses the transparent conductive film which laminated | stacked the plastic film, the hardened | cured material layer, and the transparent conductive thin film, in this document, the film used as an input surface (hard coat layer) and a transparent conductive film are disclosed. It is bonded together using an adhesive and used for the electrode of a touchscreen. In addition, Patent Literature 7 discloses a laminate in which a plastic film provided with a hard coat layer and a transparent conductive film having a transparent conductive thin film are bonded together via a transparent adhesive layer.

Thus, when laminating | stacking each layer required as an electrode for touch panels, an adhesive layer is needed in many cases. Since many members for touch panels are expensive, the adhesive layer which is excellent in the re-peelability which can peel when an adhesion miss occurs at the time of bonding fixation by an adhesion layer, and can stick again is preferable. Moreover, it is also known that durability (pen sliding durability) with respect to repeated pressing in a touchscreen will be improved when using the cushioning adhesive layer.

From this fact, use of silicone rubber can be considered as an adhesive of a member for touch panels. In particular, when a double-sided adhesive sheet having a silicone rubber adhesive layer is used, the plastic film provided with the hard coat layer and the transparent conductive film having a transparent conductive thin film can be easily bonded together. However, the silicone rubber and the plastic film base material like polyethylene terephthalate, for example, cannot be said to have sufficient adhesiveness. When adhesiveness of an adhesive layer and a film base material is inferior, there exists a problem that peeling generate | occur | produces in a joining location and it does not become energized even if it touches. In addition, when the touch panel is used for car navigation, etc., in-vehicle environment may be very high temperature and high humidity, but it is necessary to withstand such extreme use conditions, and in particular, room for improvement in adhesion durability between the adhesive layer and the base film. There was.

On the other hand, in an image display device such as a liquid crystal display (LCD), a plasma light emitting display (PDP), an organic electroluminescence (EL), or the like, when an impact is applied to the surface thereof, the image display device is provided by the impact. The protective panel is provided on the surface of the image display panel so as not to damage the image display panel. In addition, an air layer is provided between the image display panel and the protection panel to prevent damage to the image display panel by dispersing and absorbing the shock applied to the image display device.

However, in the structure in which the air layer is provided between the image display panel and the protection panel, the reflection of light due to the difference in refractive index between the air layer and the protection panel is large, so that the sunlight and the backlight are scattered and the luminance and contrast are lowered. There was a problem of poor visibility.

In order to solve the above problem, a method of filling an elastic layer in the air layer between the image display panel and the protective panel has been proposed. For example, the image display panel and the protective panel are mediated by at least one sheet-like transparent adhesive material. The image display apparatus which adhere | attached on the surface and improved impact resistance and visibility is disclosed (for example, refer patent document 8).

However, the above-mentioned transparent adhesive material is weak in elasticity, and it may be difficult to insert a transparent adhesive material into an image display apparatus. In addition, when the transparent adhesive is adhered to the image display panel or the protective panel, air bubbles may enter, and when the entry of the bubbles occurs, the transparent adhesive may be partially fixed to the image display panel. In some cases, so-called pool remnants that remain in the protective panel were generated. In addition, the transparent adhesive material has a thick thickness, which may cause a reduction in the thickness of the image display apparatus.

Patent Document 1: Japanese Patent Application Laid-Open No. 11-320762

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-56694

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-83886

Patent Document 4: Japanese Patent Application Laid-Open No. 2001-139903

Patent Document 5: Japanese Unexamined Patent Publication No. 2003-150316

Patent Document 6: Japanese Patent Application Laid-Open No. 2007-59360

Patent Document 7: Japanese Patent Application Laid-Open No. 2007-234424

Patent Document 8: Japanese Unexamined Patent Publication No. 2003-29644

Accordingly, the present invention provides an adhesive sheet having excellent adhesion between the silicone adhesive layer and the base film, various properties, in particular, hot water adhesiveness, and a peeling force between the silicone adhesive layer and the separate film, which is suitably controlled, and such While utilizing the performance, it has been proposed as a problem to provide an adhesive sheet having various configurations suitable for the application.

The adhesive sheet of this invention which solved the said subject is a crosslinked silicone rubber adhesion layer (B), a release layer (C), and a polyester film (D) which have a polyester base film (A), a polydimethylsiloxane skeleton at least. As the pressure-sensitive adhesive sheet laminated in this order with or without another layer,

When the hot water adhesiveness was evaluated by the method defined in the specification, the silicone rubber adhesive layer (B) did not peel off from the polyester-based base film (A) side,

The peel strength of the silicone rubber adhesive layer (B) and the release layer (C) is characterized in that 0.03 ~ 1.0 N / 20 mm.

The release layer (C) is preferably a layer containing a binder resin, a polymer wax component and an antistatic agent.

It is preferable that the heat-resistant water-resistant adhesive improvement layer (E) is provided between the said polyester base film (A) and the said silicone rubber adhesion layer (B). In this case, the heat-resistant water-resistant adhesive improvement layer (E) is an embodiment containing a reaction product of at least one polymer selected from the group consisting of polyester, polyurethane and acrylic polymer and a crosslinking agent, or a self-crosslinking poly An aspect in which one or more types of self-crosslinked polymers selected from the group consisting of esters, polyurethanes, and acrylic polymers is self-crosslinked is preferable.

It is preferable that the said silicone rubber adhesion layer (B) contains the silicone rubber which bridge | crosslinked the uncrosslinked silicone compound which has the polydimethylsiloxane frame | skeleton having a number average molecular weights 50,000-500,000. In this case, it is preferable that the push elastic modulus measured by the method defined in the specification of the said silicone rubber adhesion layer (B) is 0.5-20 N / mm <2>.

In the pressure sensitive adhesive sheet of the present invention, at least one member selected from the group consisting of a scratch prevention layer, an antireflection layer, and an antifouling layer on the side opposite to the silicon rubber adhesive layer (B) forming surface of the polyester base film (A). The functional layer may be formed.

Moreover, the transparent conductive layer may be formed in the opposite surface side of the said silicone rubber adhesion layer (B) formation surface of the said polyester base film (A).

The adhesive sheet of this invention is a crosslinked silicone rubber adhesion layer (B ') which has a polydimethylsiloxane frame | skeleton on the opposite surface side of the said silicone rubber adhesion layer (B) formation surface of the said polyester base film (A), mold release The double-sided adhesive sheet laminated | stacked in this order may be sufficient as the layer (C ') and polyester film (D'), with or without another layer.

Moreover, the adhesive sheet of this invention is an acrylic adhesive layer (F), a release layer (C "), and polyester on the opposite surface side of the said silicone rubber adhesion layer (B) formation surface of the said polyester base film (A). The double-sided adhesive sheet laminated | stacked in this order may be sufficient as the film (D ") with or without another layer.

In the adhesive sheet of the present invention, the silicone rubber adhesive layer (B) may be attached to the display screen of the image display device to protect the display screen.

In addition, the adhesive sheet of this invention may be used as a member of a touchscreen. In this case, the double-sided adhesive sheet of the present invention may be used for sticking the overlay sheet of the capacitive touch panel and the coordinate detection sheet, or may be used for sticking the touch panel portion of the resistive touch panel with the display device.

In the present invention, a touch panel comprising a transparent base material of a conductive laminate in which a transparent conductive layer is laminated on a transparent base material and a silicone rubber pressure-sensitive adhesive layer (B) of the pressure-sensitive adhesive sheet of the present invention in which the functional layer is formed. The upper electrode is included.

In addition, in the present invention, a transparent substrate of a functional laminate in which at least one functional layer selected from the group consisting of a scratch prevention layer, an antireflection layer, and an antifouling layer is laminated on a transparent substrate, and a structure in which the transparent conductive layer is formed The upper electrode for touch panels in which the silicone rubber adhesion layer (B) of the adhesive sheet of this invention was bonded is also included.

The present invention also provides a functional laminate in which a transparent substrate of a conductive laminate in which a transparent conductive layer is laminated on a transparent substrate, and at least one functional layer selected from the group consisting of a scratch prevention layer, an antireflection layer, and an antifouling layer are laminated on a transparent substrate. The transparent base material of the sieve is the double-sided adhesive sheet having a silicone rubber adhesive layer (B) and a silicone rubber adhesive layer (B '), or the double-sided adhesive having a silicone rubber adhesive layer (B) and an acrylic adhesive layer (F). Also included are upper electrodes for touch panels that are bonded to each adhesive layer of the sheet.

In this invention, the silicone rubber adhesion layer (B) of the said double-sided adhesive sheet which has an image display panel and the protection panel which protects the image display panel has a silicone rubber adhesion layer (B) and a silicone rubber adhesion layer (B '). And (B ') or the image display apparatus bonded together with the silicone rubber adhesive layer (B) and the acrylic adhesive layer (F) of the double-sided adhesive sheet having a silicone rubber adhesive layer (B) and an acrylic adhesive layer (F). Included. In this case, it is preferable that push elastic modulus of the silicone rubber adhesion layer (B) and / or (B ') measured by the method defined in the specification is 0.5-5 N / mm <2>.

Since the adhesive sheet of this invention is provided with the silicone rubber adhesion layer (B) and adhesion layer (B ') containing the crosslinked silicone compound of the polydimethylsiloxane skeleton which has adhesiveness and re-peelability, for example, Even if there is an adhesion miss, it can be easily peeled off and can be fixed again. Moreover, since the transparency of the adhesive sheet of this invention is highly high, it can be used suitably as an optical member.

Moreover, the adhesive sheet of this invention is excellent also in the adhesive durability between a silicone rubber adhesion layer (B), an adhesion layer (B '), and a polyester-based base film (A), and is also suitable for a member used under severe conditions. Can be used. In addition, since the peeling force of the separate film laminated | stacked on the surface of the silicone rubber adhesion layer (B) or the adhesion layer (B ') is controlled to an appropriate range, the said channeling phenomenon arises in the process of winding up an adhesive sheet, etc. Since it is suppressed, a high quality adhesive sheet can be produced stably. Moreover, the workability at the time of bonding a member using an adhesive sheet is also excellent.

In the case of the pressure sensitive adhesive sheet of the present invention, it is preferable to form a silicone rubber adhesive layer by crosslinking an uncrosslinked body of a silicone compound of a polydimethylsiloxane skeleton, and in this case, a conventionally known millable type silicone rubber compound is formed. The transparency and clarity of the pressure-sensitive adhesive layer formed are superior to that of the silicone rubber layer used as a raw material, and also the operability in producing the pressure-sensitive adhesive sheet is excellent. For this reason, it is excellent in cost-effectiveness compared with the conventionally well-known method.

Moreover, since the adhesive sheet of this invention is rich in the deformation | transformation of the structure, it can apply to various uses. For example, in the case of a single-sided adhesive sheet, it is useful as a surface protection film of a display screen, a part of a touch panel, etc., and in the case of a double-sided adhesive sheet, it is useful for sticking of members in a touch panel or an image display apparatus. Do. In addition, an adhesive layer exists only in one side of a base film with a single-sided adhesive sheet, and an adhesive layer exists in both sides of a base film with a double-sided adhesive sheet.

For example, when the adhesive sheet of this invention is used as a film for surface protection of a display screen, even when an adhesion miss occurs, it can peel easily and reattach easily. Moreover, since the adhesive sheet of this invention has high transparency, it can be used suitably also as a surface protection film for optical members.

Since the adhesive sheet which has the silicone rubber adhesive layer which has adhesiveness and re-peelability is used for the upper electrode for touch panels of this invention, when an adhesion miss exists, an adhesive sheet can be easily peeled off and again Can be fixed Moreover, since the cushioning property could be provided to a touch panel by the elasticity which a silicone rubber adhesion layer has, the pen sliding durability of a touch panel was able to be improved.

In the image display apparatus of the present invention, by bonding the image display panel and the protective panel together using a double-sided adhesive sheet, the visibility of the image display panel and the protective panel is eliminated because air is lost. In addition, bonding or re-peeling can be easily performed, and the loss by incorrectly pasting both the surface protection panel and the image display panel can be suppressed. In particular, since the image display panel is expensive, its economic effect is large.

Moreover, as mentioned above, the adhesive sheet of this invention is excellent in the adhesive durability between a silicone rubber adhesion layer (B) or (B '), and a polyester-based base film (A), and is excessive in the said usage method. Even if used in an environment, troubles such as peeling of the silicone rubber adhesive layer (B), (B ') and the polyester base film (A) do not occur. In addition, when manufacturing a touch panel or an image display apparatus, not only the adhesion and re-peeling are easy as described above, but also when the touch panel or image display apparatus is used in an excessive environment and then disassembled into each member and recycled. , Workability is excellent.

The pressure sensitive adhesive sheet of the present invention is characterized in that at least the polyester base film (A), the crosslinked silicone rubber adhesive layer (B) having a polydimethylsiloxane skeleton, the release layer (C) and the polyester film (D) form different layers. When the heat-resistant water-adhesive property was evaluated by the method defined in the specification as an adhesive sheet laminated in this order with or without a medium, the said silicone rubber adhesion layer (B) is from the polyester-based base film (A) side. It is characterized by the fact that the peel strength of the silicone rubber adhesive layer (B) and the release layer (C) is controlled to a specific range without being peeled off. Hereinafter, each layer will be described.

[Polyester-Based Substrate Film (A) and Polyester Film (D)]

As a polyester base film (A) and a polyester film (D), as long as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, etc. are a main component (80 mass% or more), it can be used arbitrarily. The biaxially stretched thing is used preferably. Although it does not specifically limit as a manufacturing method of a biaxially-stretched polyester film, For example, after polyester is dried as needed, it is supplied to a well-known melt extruder, and it extrudes into a sheet form from a slit-shaped die, and applies electrostatic application. After contact | adhering to a casting drum, and solidifying by cooling to obtain an unstretched sheet, what is necessary is just to extend | stretch an unstretched sheet. As a method of biaxial stretching, any of simultaneous biaxial stretching and sequential biaxial stretching may be sufficient. You may perform well-known adhesive improvement processes, such as a corona treatment, a frame treatment, and a plasma treatment, to a polyester base film (A).

Although the thickness of a polyester base film (A) is not specifically limited, About 10-300 micrometers is preferable, More preferably, it is 15-260 micrometers. If it is less than 10 micrometers, it is unpreferable since mechanical strength is lacking and handling becomes difficult. On the other hand, when thickness exceeds 300 micrometers, it is too thick and it is not suitable for a mobile device.

The polyester film (D) is a film for constituting a separate film by combining with a release layer (C). As for the thickness of this polyester film (D), about 10-150 micrometers is preferable. More preferably, it is 15-75 micrometers. If the film thickness is less than 10 mu m, the mechanical strength is insufficient and the handling becomes difficult, which is not preferable. On the other hand, when thickness exceeds 150 micrometers, intensity | strength is sufficient and it is uneconomical, and the handling property at the time of peeling a film may also fall.

[Silicon Rubber Adhesive Layer (B)]

As for the adhesive sheet of this invention, the silicone rubber adhesion layer (B) is laminated | stacked. Silicone rubber is not only excellent in peelability and restickability but also excellent in elasticity and can impart cushioning properties to the used member.

The crosslinked silicone rubber adhesive layer (B) of the polydimethylsiloxane skeleton is composed of the crosslinked silicone compound of the polydimethylsiloxane skeleton as a main component (70 mass% or more, more preferably 90 mass% or more, even more preferably 100 mass%). It is to include as. In particular, as a crosslinked silicone compound having a polydimethylsiloxane skeleton, it is preferable that the uncrosslinked product having a number average molecular weight (Mn) of 50,000 to 500,000 is crosslinked. 80,000-400,000 are more preferable, and 100,000-350,000 of Mn of uncrosslinked are more preferable.

By using an uncrosslinked silicone compound, solubility and fluidity in a solvent can be ensured, and the formation of the silicone rubber adhesive layer (B) is facilitated. Since uncrosslinked Mn is 50,000 or more, since crosslinkability improves, it is preferable. In addition, the control of the push modulus becomes easy. When Mn of an uncrosslinked product is 500,000 or less, deterioration of operability at the time of production, such as the viscosity of a coating liquid becoming high too much, can be suppressed. Therefore, it is a preferred embodiment to form an uncrosslinked layer of the silicon compound and then crosslink it.

The raw material of the conventionally known silicone rubber is a millable type silicone rubber compound, but such a compound has poor solubility in a solvent depending on its storage state, and when the silicone rubber layer is coated, the appearance is not refined by unsealed products. May decrease. Moreover, there existed a problem that the coating liquid which melt | dissolved the silicone rubber compound in the solvent had the gelation of a solution, and cannot use as a coating liquid depending on the storage state. By using the uncrosslinked silicone compound, it is superior in quality, quality stability, and operability at the time of production than when using a conventionally known millable type silicone compound as a raw material.

As the uncrosslinked silicone compound which satisfies the above contents, for example, a commercially available silicone oil can be used. When using silicone oil, it is preferable to use non-reactive dimethyl silicone oil also among straight silicone oil. As a result, the silicone compound after crosslinking has a polydimethylsiloxane skeleton. The crosslinkability is lowered as the methylphenyl type silicone oil, and the reactive methylhydrogen type silicone oil is not preferable because of poor storage stability and the like, which may adversely affect the quality and operability. Preferably less than 5 mass%), you may mix | blend and use the silicone compound which does not have a polydimethylsiloxane skeleton, such as a methylphenyl type, a methyl hydrogen type, or various modified types.

In addition, if the said uncrosslinked silicone compound is less than 10 mass%, the silicone compound of a polyalkyl alkenylsiloxane skeleton may be contained, but as few as possible may be sufficient. It is most preferable to consist only of the silicone compound of the polydimethylsiloxane skeleton which does not contain the silicone compound of the polyalkyl alkenylsiloxane skeleton.

Although the silicone rubber adhesion layer (B) in this invention may contain reinforcement agents, such as a silica, as long as it is a range which does not prevent the effect of this invention, It is especially preferable that no reinforcement agent is included at all.

In the silicone rubber adhesive layer (B), the adhesive strength between the silicone rubber adhesive layer (B) and the polyester base film (A) or the water-resistant water-resistant adhesive improvement layer (E) to be described later is increased, and the silicone rubber adhesive layer ( The adhesive improving agent for making it hard to peel B) may be included. As this adhesive improving agent, it is preferable to use a compound including a reactor active against radical reaction. As this compound, a (meth) acrylic acid derivative, an allyl derivative, etc. are illustrated, Especially, the derivative which has 2 or more, especially 3 or more unsaturated bond is preferable. These compounds are widely used as a co-crosslinking agent of rubber, and examples thereof include esters of polyhydric alcohols and (meth) acrylic acid, allyl esters of polyhydric carboxylic acids, triallyl isocyanurate, triallyl cyanurate, and the like.

The ester of the polyhydric alcohol and (meth) acrylic acid is an ester compound obtained by esterifying two or more alcoholic hydroxyl groups of a polyhydric alcohol having two or more acrylic hydroxyl groups with (meth) acrylic acid. Specifically, for example, ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acryl Latex, neopentylglycol di (meth) acrylate, 2,2'-bis [4- (meth) acryloxydiethoxyphenyl] propane, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetramethylolmethane di (meth) acrylate, tetramethylolmethane Tri (meth) acrylate, tetramethylol tetra (meth) acrylate, dimerdiol di (meth) acrylate, etc. are mentioned, Especially the compound containing three or more (meth) acryloyl groups is preferable. In addition, although the said compound illustrated the single ester compound of acrylic acid and methacrylic acid, respectively, the form of the mixed ester of acrylic acid and methacrylic acid may be sufficient.

Moreover, phthalic acid diallylate, trimellitic acid diallylate, a pyromellitic acid tetraallylate, etc. are mentioned as allyl ester of polyhydric carboxylic acid.

The said adhesive improving agent may be used individually by 1 type, and may use 2 or more types together. In addition, the adhesive improving agent used for this invention is not limited to the said exemplary compound.

0.2-20 mass parts is preferable with respect to 100 mass parts of silicone compound components, and, as for the compounding quantity of the said adhesive improving agent, 0.5-10 mass parts is more preferable. When the compounding quantity of an adhesive improving agent is 0.2 mass part or more, the effect which improves the hot water adhesiveness of an adhesion layer becomes still more large. On the other hand, when the compounding quantity of an adhesive improving agent exceeds 20 mass parts, not only the effect which improves hot water adhesiveness reaches saturation, but also may worsen this effect on the contrary.

As for the minimum of the thickness of the said silicone rubber adhesion layer (B), 3 micrometers is preferable from a side of adhesive force, More preferably, it is 5 micrometers, More preferably, it is 8 micrometers. In addition, what is necessary is just to determine the upper limit of the thickness of a silicone rubber adhesion layer (B) in the range which can maintain a push elastic modulus and adhesive force stably from an economical viewpoint. For example, 200 micrometers is preferable and, as for the upper limit of thickness, 180 micrometers is more preferable.

In the present invention, the method of forming the silicone rubber adhesive layer (B) is not limited, but the above uncrosslinked silicone compound is dissolved or dispersed in a solvent to prepare a coating solution by adding an adhesive improving agent as necessary. It is a preferable embodiment to form by crosslinking after apply | coating by the coating method.

For example, since uncrosslinked silicone oil is well dissolved in aromatic hydrocarbons such as toluene, it is preferable to dissolve it in these solvents and apply the coating method. When uncrosslinked silicone oil is used, the compound plasticizing step by kneading or the like necessary when dissolving the conventional millable silicone rubber compound in a solvent is unnecessary. In addition, the storage stability of the obtained coating solution is good, and no thickening phenomenon such as gelation often occurs when the silicone rubber compound is prepared. Moreover, since generation | occurrence | production of the foreign material by undissolution of the silicone rubber compound which may generate | occur | produce in the solution of a silicone rubber compound is suppressed, there exists an advantage, such as a coating liquid with high clarity.

The silicone rubber adhesion layer (B) is heat-resistant, for example, the coating liquid containing the said silicone oil etc. formed in the surface of the polyester base film (A), or the surface of this polyester base film (A). By coating on the surface of the water-adhesive improvement layer (E) or the surface of the release layer (C) formed on the surface of the polyester film (D), and further carrying out a crosslinking treatment with or without laminating another layer. Can be formed.

The crosslinking method of the silicone compound may be, for example, thermal crosslinking such as peroxide crosslinking or addition reaction crosslinking, or may be crosslinking by high energy active rays such as electron beams or gamma rays. When the active compound is irradiated to the silicon compound, it is considered that hydrogen is extracted from the methyl group of the polydimethylsiloxane, and similarly, a crosslinking reaction occurs between adjacent silicon compounds from which hydrogen is extracted from the methyl group. Therefore, in the crosslinking method by active rays, it is not necessary to mix | blend additives, such as a peroxide for radical generation, a catalyst for crosslinking, with a silicone compound. For this reason, the contamination with respect to the to-be-adhered body by the residue of these additives is suppressed, and it is a preferable crosslinking method for the adhesive which can be re-peeled. In thermal crosslinking, the crosslinking agent is required to be blended. By blending the crosslinking agent, it is necessary to consider the problem of pot life that the curing gradually progresses even after heating, and the workability is remarkably lowered or, in some cases, gelled and cannot be processed. In the crosslinking method by active rays, such a problem does not need to be considered. In addition, the crosslinking reaction, which tends to appear in peroxide crosslinking, addition reaction crosslinking, or the like, is less likely to occur. Moreover, since bridge | crosslinking is completed efficiently in a short time, there exists an advantage that productivity increases.

Among the active rays, the electron beam crosslinking method is preferable in view of the availability of an irradiation apparatus (EB irradiation apparatus) and the control of the degree of crosslinking. As an electron beam irradiation amount in an EB irradiation apparatus, the range of 5-50 Mrad is preferable. By setting the electron beam irradiation amount to 5 Mrad or more, the crosslinking reaction of the silicone compound can be promoted, and the remaining of glue on the adherend can be reduced when re-peeling, and the repairability can be improved. On the other hand, by making the electron beam irradiation amount 50 Mrad or less, the fall of adhesiveness by the excessive progress of a crosslinking reaction, an increase of an push elastic modulus, etc. can be suppressed.

In view of reliability in the case of sticking to the adherend, the lower limit of the adhesive strength of the silicone rubber adhesive layer (B) is preferably 0.01 N / 20 mm (180-degree peeling test on glass, tensile speed 300 mm / min). More preferably, it is 0.05 N / 20 mm. On the other hand, it is preferable that the upper limit of the adhesive force of a silicone rubber adhesion layer (B) is 1.0 N / 20mm, More preferably, it is 0.5 N / 20mm from the viewpoint of improving re-peelability and ensuring favorable repair property. . In addition, it is preferable from a viewpoint of repair property that an adhesive layer does not remain in a glass surface, ie, there is no pool remaining, when it evaluates by the said evaluation method.

In the present invention, it is important that the silicone rubber adhesive layer (B) is firmly adhered to the polyester base film (A). That is, it is necessary that a silicone rubber adhesion layer (B) does not peel from the polyester base film side. For example, when a cutter knife is inserted between a polyester base film (A) and a silicone rubber adhesion layer (B), and peeled off by applying a force with a finger (interface exposure), adhesive strength is strong and an interface is carried out. It is desirable that exposure is not possible. In a preferred embodiment of the present invention, although the hot water adhesive property improving layer (E) exists between the polyester base film (A) and the silicone rubber adhesive layer (B), the thickness of the hot water adhesive property improving layer (E) Since is thin, the true interface in the said interface exposure is not analytical and it is not clear. In other words, a state in which the silicone rubber adhesive layer (B) and the polyester base film (A) are firmly adhered to each other and the interface exposure is impossible is preferable. Hereinafter, in this invention, the said characteristic may only be called adhesiveness.

Moreover, even if the adhesive sheet of this invention is preserve | saved in hot water for a long time, it is preferable that the said adhesiveness is maintained. Specifically, it is preferable that the silicone rubber adhesive layer (B) does not peel off when evaluated by the hot water adhesiveness evaluation method shown below. Hereinafter, adhesive hot water durability may be called hot water adhesive resistance.

[Heat resistant adhesiveness]

Next, the evaluation method of the hot water adhesiveness which is an important effect of the adhesive sheet of this invention is demonstrated.

When measuring the hot water adhesiveness of a silicone rubber adhesion layer (B), an adhesive sheet is cut into 50 mm x 50 mm, and the separator film of a silicone rubber adhesion layer (B) is peeled off. In a cylindrical glass container with a 500 cc lid filled with 400 cc of distilled water, the sample was sunk in water so that the silicone rubber adhesive layer (B) was lowered, and the lid was placed on the container while the whole sample was immersed in water. Cover. When only the self weight of a sample is not immersed in water, a polyester film of 60 mm x 60 mm and thickness of 188 micrometers may be put on a sample, for example, and it will be a push stone. The size and material of the pressing stone are not particularly limited, and the entire sample may be immersed in water. The container containing a sample is put in the gear oven set at 80 degreeC, and it is left to stand for 24 hours. After the heat treatment, the container was taken out of the oven, the sample was quickly taken out, and rubbed 10 times by applying a force to the end with a finger from the silicone rubber adhesive layer (B) side, the silicone rubber adhesive layer (B) was a polyester base film (A). (Circle) and peeling of the silicone rubber adhesion layer (B) were made into x that the silicone rubber adhesion layer (B) was not peeled off.

As for the evaluation method of heat-resistant water-adhesive property, an adhesive sheet is the same for both a single-sided adhesive sheet and a double-sided adhesive sheet. If a sample is a double-sided adhesive sheet, what is necessary is just to evaluate the hot water adhesiveness of the silicone rubber adhesion layer (B) side.

If the silicone rubber adhesive layer (B) is a pressure-sensitive adhesive sheet which does not peel off in this hot water adhesiveness, the silicone rubber adhesive layer (B) may be used even if exposed under high temperature and high humidity, for example, as a member such as a touch panel for car navigation. Since interfacial peeling at the interface between the polyester-based substrate film (A) can be suppressed, the reliability of the device is improved, and after being used for a long time in an harsh environment, it is decomposed into each member and recycled. Excellent workability

[Heat Resistant Adhesive Improved Layer (E)]

In evaluation of the said hot water adhesiveness of the adhesive sheet of this invention, in order to prevent a silicone rubber adhesion layer (B) from peeling off, heat-resistant water adhesion between a polyester base film (A) and a silicone rubber adhesion layer (B) It is preferable to provide the castle improvement layer (E). It is preferable that the thickness of this hot water adhesive resistance improvement layer (E) is 0.01-0.5 micrometer. If the thickness of the hot water adhesive improvement improving layer (E) is 0.01 to 0.5 µm, good hot water adhesiveness is exhibited, but outside the above range, the hot water adhesiveness is lowered (which does not become ○ in the measuring method described later). It is not desirable because there is. The range of the more preferable thickness is 0.03-0.4 micrometer, and 0.05-0.3 micrometer is still more preferable.

Preferable examples of the water-resistant water-resistant adhesive improvement layer (E) are crosslinked polymer layers (crosslinked polymer layers), which may be layers crosslinked with a crosslinking agent, or layers using a self-crosslinked polymer.

Although the polymer which can be used in the method of bridge | crosslinking with a crosslinking agent is not specifically limited, It is preferable that it is 1 or more types chosen from the group which consists of a polyester, a polyurethane, and an acrylic acid type polymer. The said polymers may be used individually, respectively, and may be used in combination of 2 types or 3 types different from each other.

[Polyester for Hot Water Adhesion Improved Layer (E)]

The said polyester has ester bond in a principal chain or a side chain, and is obtained by polycondensing polyhydric carboxylic acid and glycol.

As polyhydric carboxylic acid component which comprises polyester, aromatic, aliphatic, alicyclic dicarboxylic acid, trivalent or more polyvalent carboxylic acid, or these ester derivatives can be used.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-dimethyl terephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1 , 2-bisphenoxy ethane-p, p'-dicarboxylic acid, phenyl indane dicarboxylic acid and the like can be used. In view of the strength and the heat resistance of the heat-resistant water-resistant adhesive improvement layer (E), these aromatic dicarboxylic acids are preferably 30 mol% or more, more preferably 35 mol% or more, in 100 mol% of the polyhydric carboxylic acid component, More preferably, it is preferable to use polyester which occupies 40 mol% or more.

As aliphatic and cycloaliphatic dicarboxylic acids, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicar Acids, 1,4-cyclohexanedicarboxylic acid and the like, and ester-forming derivatives thereof can be used.

Examples of the glycol component of the polyester include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3- Diol, neopentylglycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2, 2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl -1,3-cyclobutanediol, 4,4'-thiodiphenol, bisphenol A, 4,4'-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'- Dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 4,4'-isopropylidenediol, cyclopentane-1,2-diol, cyclo Hexane-1,2-diol, c As it may be used such as hexane-1,4-diol.

In addition, when using polyester as an aqueous solution and using it as a coating liquid, in order to make water solubility or water oxidation of polyester easy, the compound containing a carboxylic acid (salt) group and the compound containing a sulfonic acid (salt) group are included. It is preferable to copolymerize a compound containing a phosphonic acid (salt) group and the like.

As a compound containing a carboxylic acid (salt) group, for example, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid , Trimesic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3- Cyclohexene-1,2-dicarboxylic acid, cyclopentanetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol bis Trimellitate, 2,2 ', 3,3'-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid and the like, or alkali metal salts thereof, Alkaline earth metal salts, ammonium salts, etc. are mentioned.

As a compound containing a sulfonic acid (salt) group, for example, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfo-p- Xylylene glycol, 2-sulfo-1, 4-bis (hydroxyethoxy) benzene, or an alkali metal salt, alkaline earth metal salt, and ammonium salt thereof can be used.

As a compound containing a phosphonic acid (salt) group, for example, phosphoterephthalic acid, 5-phosphoisophthalic acid, 4-phosphoisophthalic acid, 4-phosphonaphthalene-2,7-dicarboxylic acid, phospho -p-xylylene glycol, 2-phospho-1,4-bis (hydroxyethoxy) benzene, or the like, or alkali metal salts, alkaline earth metal salts, and ammonium salts thereof can be used.

Moreover, in this invention, modified polyester copolymers, such as a block copolymer modified with acryl, urethane, an epoxy, a graft copolymer, can also be used as said polyester, for example.

Preferred polyesters include those selected from terephthalic acid, isophthalic acid, sebacic acid, 5-sodium sulfoisophthalic acid and glycol components as ethylene glycol, diethylene glycol, 1,4-butanediol and neopentyl glycol as acid components. And copolymers. When water resistance is required, the copolymer etc. which made trimellitic acid the copolymerization component etc. can also be used instead of 5-sodium sulfoisophthalic acid.

The said polyester can be manufactured with the following manufacturing methods. For example, if the dicarboxylic acid component is a terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, and the glycol component is a ethylene glycol or neopentyl glycol, the ester of these monomers is directly esterified. Or by a second step of subjecting the reaction product or a transesterification reaction to a second step of polycondensation reaction of the reaction product of the first step.

At this time, as the reaction catalyst, for example, an alkali metal, an alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, a titanium compound, or the like can be used.

Moreover, as a method of obtaining polyester which has many carboxyl groups in a terminal and / or a side chain, Unexamined-Japanese-Patent No. 54-46294, Unexamined-Japanese-Patent No. 60-209073, and 62-240318 Japanese Patent Publication No. 53-26828, Japanese Patent Publication No. 53-26829, Japanese Patent Publication No. 53-98336, Japanese Patent Publication No. 56-116718, Japanese Patent Publication Although it can manufacture by copolymerizing the trivalent or more polyvalent carboxylic acid of Unexamined-Japanese-Patent No. 61-124684, Unexamined-Japanese-Patent No. 62-240318, etc., it is a matter of course other than these.

Moreover, as a water dispersion polyester resin, it is also possible to use the commercially available "Vironal (trademark)" series (made by Toyo Boseki Co., Ltd.).

Although the intrinsic viscosity of polyester is not specifically limited, It is preferable that it is 0.3 dl / g or more from a viewpoint of adhesiveness, More preferably, it is 0.35 dl / g or more, Most preferably, it is 0.4 dl / g or more. The glass transition temperature of the polyester (hereinafter sometimes abbreviated as Tg) is preferably 0 to 130 ° C, more preferably 10 to 85 ° C. By using polyester whose Tg is 0 degreeC or more, hot water adhesive resistance improves, Moreover, after laminating | stacking a hot water adhesive resistance improvement layer (E) on the surface of a polyester-based base film (A), etc. once The blocking phenomenon of can be suppressed. Moreover, stability and water dispersibility can be kept favorable by using polyester whose Tg is 130 degrees C or less.

[Polyurethane for Hot Water Adhesion Improved Layer (E)]

Next, a polyurethane is demonstrated. Polyurethane will not be specifically limited if it has a urethane bond, As a main component, it is a thing obtained by superposing | polymerizing a polyol compound and a polyisocyanate compound.

Examples of the polyol compound include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol and polycapro Lactone, polyhexamethylene adipate, polytetramethylene adipate, trimethylol propane, trimethylol ethane, glycerin, acrylic polyol, etc. can be used.

As the polyisocyanate compound, for example, tolylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, adduct of tolylene diisocyanate and trimethylolpropane, hexamethylene diisocyanate and trimethylol ethane Additives and the like can be used.

In the synthesis of polyurethane, in addition to the polyol compound and the polyisocyanate compound, known chain extenders, crosslinking agents and the like may be included. As the chain extender or the crosslinking agent, ethylene glycol, propylene glycol, butanediol, diethylene glycol, ethylenediamine, diethylenetriamine and the like can be used.

In order to obtain a stable polyurethane water dispersion, it is preferable to synthesize a polyurethane having high affinity with water, and specifically, anionic groups may be introduced into the appropriate polyurethane. For example, a method of using a compound having an anionic group in a polyol, a polyisocyanate, a chain extender, or the like, a method of reacting an unreacted isocyanate group of a produced polyurethane with a compound having an anionic group, or active hydrogen of a polyurethane It can manufacture using the method etc. which make group which has and a specific compound react.

The anionic group in the polyurethane is preferably used as sulfonic acid group, carboxylic acid group and ammonium salt, lithium salt, sodium salt, potassium salt or magnesium salt thereof.

The amount of the unit having an anionic group in the polyurethane is preferably 0.05% by mass to 15% by mass in terms of water dispersibility of the polyurethane.

For example, as a polyurethane water dispersion, it is also possible to use a "hydran (trademark)" series (made by Dainippon Ink and Chemicals, Inc.).

[Acrylic Polymer for Hot Water Adhesion Improved Layer (E)]

As the monomer component constituting the acrylic polymer, for example, alkyl acrylate, alkyl methacrylate (as the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl) Group, 2-ethylhexyl group, lauryl group, stearyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.); Hydroxy group-containing monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (Meth) acrylamide N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N- dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-phenyl Amide group-containing monomers such as (meth) acrylamide; Amino group-containing monomers such as N, N-diethylaminoethyl (meth) acrylate; Epoxy group-containing monomers such as glycidyl (meth) acrylate; Carboxyl groups, such as (meth) acrylic acid and its salts (lithium salt, sodium salt, potassium salt, etc.), or the monomer containing its salt, etc. can be used, These are (co) polymerized using 1 type (s) or 2 or more types. Moreover, these can be used together with another kind of monomer.

As another kind of monomer here, For example, epoxy group containing monomers, such as allyl glycidyl ether; Monomers containing sulfonic acid groups such as styrenesulfonic acid, vinylsulfonic acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt and the like) and salts thereof; Monomers containing carboxyl groups or salts thereof such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, etc.); Monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride; Vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl tris alkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid monoester, acrylonitrile, methacrylonitrile, alkyl itaconic acid monoester, vinylidene chloride , Vinyl acetate, vinyl chloride and the like can be used.

Moreover, as said acryl-type polymer, the block copolymer, graft copolymer, etc. which modified | denatured with the modified acryl-type polymer, for example, polyester, a polyurethane, an epoxy resin, etc. can also be used.

It is preferable that the minimum of Tg of the said acryl-type polymer is -10 degreeC from a viewpoint of hot water adhesiveness or blocking resistance, More preferably, a minimum is 0 degreeC and the minimum is 10 degreeC most preferable. On the other hand, it is preferable that the upper limit of Tg of an acryl-type polymer is 90 degreeC from a viewpoint of hot water adhesiveness or film-forming property, More preferable upper limit is 50 degreeC, and a most preferable upper limit is 40 degreeC. In addition, the weight average molecular weight (Mw) of the acrylic polymer is preferably 50,000 or more, and more preferably 300,000 or more, from the viewpoint of hot water adhesive resistance.

Preferable examples of the acryl-based polymers include copolymers composed of monomers selected from methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, acrylamide, N-methylol acrylamide, and acrylic acid. .

It is preferable to melt | dissolve, emulsify, or suspend an acrylic polymer in water, and to use it as an aqueous solution from the viewpoint of environmental pollution and explosion-proof property at the time of coating. Such water-based acrylic polymers include copolymerization of monomers having a hydrophilic group (acrylic acid, methacrylic acid, acrylamide, vinylsulfonic acid and salts thereof), emulsion polymerization using reactive emulsifiers and surfactants, suspension polymerization, and pre-polymerization. It can manufacture by a method.

Moreover, you may use a commercially available acrylic emulsion, For example, "John Creel (trademark)" series (made by BASF Japan company) are mentioned.

[Crosslinking Agent Used for Hot Water Adhesion Improved Layer (E)]

In this invention, it is preferable that the said polyester, a polyurethane, and an acryl-type polymer are bridge | crosslinked. When crosslinking the said polymer using a crosslinking agent, as a crosslinking agent, what can crosslink-react with the functional group which exists in the said polymer, for example, a carboxyl group, a hydroxyl group, a methylol group, an amide group, etc. may be used. For example, melamine type crosslinking agent, oxazoline type crosslinking agent, isocyanate type crosslinking agent, aziridine type crosslinking agent, epoxy type crosslinking agent, methylolated or alkylolated urea type, acrylamide type, polyamide type resin, amide epoxy compound, various silane couplers Ring agents, various titanate coupling agents, and the like can be used. In particular, a melamine type crosslinking agent and an oxazoline type crosslinking agent can be preferably used in terms of compatibility with the polymer, hot water adhesiveness, and the like.

Although it does not specifically limit as a melamine type crosslinking agent, The methylolated melamine derivative obtained by condensing melamine, melamine, and formaldehyde, the compound partially or completely etherified by making lower alcohol react with methylolated melamine, or a mixture thereof can be used. . Moreover, as a melamine type crosslinking agent, the condensate which consists of a monomer, a dimer or more multimer, a mixture thereof, etc. can be used. As lower alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol, etc. can be used. Methylolated melamine resins, such as methylated trimethylol melamine and butylated hexamethylol melamine, are preferable. Moreover, in order to promote the thermosetting of a melamine type crosslinking agent, you may use acidic catalysts, such as p-toluenesulfonic acid, for example.

The oxazoline-based crosslinking agent is not particularly limited as long as it has an oxazoline group as a functional group in the compound, but at least one or more monomers containing an oxazoline group and an oxazoline group obtained by copolymerizing one or more other monomers It is preferable to become a containing copolymer.

Examples of the monomer containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2. Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be used, and one or a mixture of two or more thereof can be used. It is also possible. Especially, 2-isopropenyl-2-oxazoline is easy to obtain industrially, and is preferable.

In the oxazoline group-containing copolymer, the one or more other monomers used together with the monomer containing the oxazoline group is not particularly limited as long as it is a monomer copolymerizable with the monomer containing the oxazoline group. For example, methyl (meth) (Meth) acrylates or methacrylates such as acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid; Unsaturated nitriles such as (meth) acrylonitrile; Unsaturated amides such as (meth) acrylamide and N-methylol (meth) acrylamide; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; Olefins such as ethylene and propylene; Halogen-containing?-,? -Unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; (Alpha), (beta)-unsaturated aromatic monomers, such as styrene and (alpha) -methylstyrene, etc. can be used, These can use 1 type, or 2 or more types of mixtures.

In addition, as an oxazoline group containing polymer, "Epoclos (trademark)" series (made by Nippon Shokubai Co., Ltd.) can be obtained, for example.

Although an isocyanate type crosslinking agent will not be specifically limited if it has an isocyanate group as a functional group in a compound, The use of the polyfunctional isocyanate compound containing two or more isocyanate groups in 1 molecule is preferable.

As the polyfunctional isocyanate compound, low molecular or high molecular aromatic, aliphatic diisocyanate, trivalent or higher polyisocyanate can be used. Examples of the polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate and their isocyanates There is a trimer of the compound. In addition, an excessive amount of these isocyanate compounds and low molecular weight active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, or polyester polyols And terminal isocyanate group-containing compounds obtained by reacting high molecular weight active hydrogen compounds such as polyether polyols and polyamides.

In addition, when using an isocyanate compound as a crosslinking agent, it is also possible to use a blocked isocyanate compound. Blocked isocyanate can be prepared by addition reaction of the isocyanate compound and the blocking agent by a conventionally known appropriate method. As an isocyanate blocking agent, For example, Phenols, such as a phenol, cresol, xylenol, a resorcinol, a nitrophenol, a chlorophenol; Thiophenols such as thiophenol and methylthiophenol; Oximes such as acetoxime, methyl ethyl ketoxime and cyclohexanone oxime; Alcohols such as methanol, ethanol, propanol and butanol; Halogen-substituted alcohols such as ethylenechlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propyllactam; Aromatic amines; Imides; Active methylene compounds such as acetylacetone, acetoacetic acid ester and malonic acid ethyl ester; Mercaptans; Imine; Urea; Diaryl compounds; Sodium bisulfite, and the like.

The epoxy crosslinking agent is not particularly limited as long as it has an epoxy group as a functional group in the compound. However, the use of a polyfunctional epoxy compound containing two or more epoxy groups in one molecule is preferable.

As a polyfunctional epoxy compound, For example, the diglycidyl ether of bisphenol A and its oligomer, the diglycidyl ether of hydrogenated bisphenol A and its oligomer, orthophthalic acid diglycidyl ester, and isophthalic acid diglycidyl ester , Terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl Ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and poly Alkylene glycol diglycidyl ether, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1, 4- diglycidyl oxybenzene, diglyl Glycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol-alkylene oxide addition of water during triglycidyl ether and the like.

As said crosslinking agent, Phenol formaldehyde resin of condensation products with formaldehyde, such as alkylated phenols and cresols; Additives of urea, melamine, benzoguanamine and the like, formaldehyde, amino resins such as alkyl ether compounds of these adducts and alcohols having 1 to 6 carbon atoms, and the like can also be used.

As the phenol formaldehyde resin, for example, alkylated (methyl, ethyl, propyl, isopropyl or butyl) phenol, p-tert-amylphenol, 4,4'-sec-butylidenephenol, p-tert-butylphenol , o-, m-, p-cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadedecylphenol, phenol, phenyl-o-cresol and condensates of phenols such as p-phenylphenol and xylenol with formaldehyde.

As an amino resin, for example, methoxylated methylol urea, methoxylated methylol N, N-ethylene urea, methylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, methyl butoxylated Olmelamine, butoxylated methylol benzoguanamine, etc. are mentioned, Preferably, methoxymethylol melamine, butoxylated methylol melamine, methylolated benzoguanamine, etc. are mentioned.

Although the said polymer (polyester, polyurethane, an acryl-type polymer) and a crosslinking agent can be mixed and used in arbitrary ratios, in order to express the effect of the heat-resistant water-adhesive property of this invention more remarkably, a crosslinking agent is with respect to 100 mass parts of polymers, 2 mass parts or more and 50 mass parts or less of addition are preferable at solid content mass ratio, More preferably, it is 3-25 mass parts. When the addition amount of a crosslinking agent is less than 2 mass parts, the addition effect is small, and when it exceeds 50 mass parts, it exists in the tendency for hot water adhesiveness to fall.

[Self-crosslinked Polymer of Hot Water Adhesion Improved Layer (E)]

In the present invention, in addition to the above-described method, for example, a hot-water-water-adhesive improved layer (E) may be formed using a self-crosslinked polymer having a crosslinkable functional group introduced into the polymer. The crosslinking method in the case of using a self-crosslinking polymer may be, for example, thermal crosslinking or may be crosslinking by high energy active rays such as ultraviolet rays, electron beams, and gamma rays.

Hereinafter, the specific method is illustrated about the case of polyester as a self-crosslinking polymer.

The self-crosslinked polyester which is preferably used in the present invention is a polyester graft copolymer obtained by grafting a compound having at least one radical polymerizable double bond to a hydrophobic copolyester. "Grafting" of the polyester type graft copolymer in this invention introduce | transduces the branched polymer which becomes a polymer different from a main chain to the stem polymer which is a main chain. Graft polymerization is normally performed by making 1 or more types of radically polymerizable monomers react using a radical initiator in the state which melt | dissolved hydrophobic copolyester in the organic solvent. Hydrophobic copolyester is essentially a water-insoluble polyester that is inherently insoluble in water, and thus heat-resistant water-adhesive bonds are compared with the case where a polyester resin dissolved in water is used as a stem polymer during graft polymerization. Excellent in sex

The hydrophobic copolyester has an aromatic dicarboxylic acid of 60 to 99.5 mol%, an aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid of 0 to 39.5 mol%, and a radical polymerizability in 100 mol% of the dicarboxylic acid component. It is preferable that dicarboxylic acid containing a double bond is 0.5-10 mol%. More preferably, 68 to 98 mol% of aromatic dicarboxylic acids, 0 to 30 mol% of aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids, and 2 to dicarboxylic acids containing a polymerizable unsaturated double bond are used. 7 mol%.

When the said aromatic dicarboxylic acid is 60 mol% or more and the said aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid is 39.5 mol% or less, hot water adhesive resistance becomes favorable. In addition, by using 0.5 mol% or more of the dicarboxylic acid containing a radically polymerizable double bond, the grafting of the radically polymerizable monomer with respect to a polyester resin can be performed efficiently. On the other hand, by setting it as 10 mol% or less, since the viscosity of a reaction solution rises remarkably in the late grafting reaction and it can advance reaction uniformly, it is preferable.

As the aromatic dicarboxylic acid, aliphatic and / or alicyclic dicarboxylic acid, all of the compounds of the above examples can be used. Examples of the dicarboxylic acid containing a radically polymerizable double bond include α, β-unsaturated dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid and citraconic acid; Alicyclic dicarboxylic acid containing unsaturated double bonds, such as 2, 5- norbornene dicarboxylic acid anhydride and tetrahydro phthalic anhydride, etc. can be illustrated. Among the dicarboxylic acids containing these polymerizable unsaturated double bonds, fumaric acid, maleic acid and 2,5-norbornenedicarboxylic acid are preferable from the viewpoint of polymerizability.

As for the glycol component, all of the above-exemplified compounds can be used. You may use together 2 or more types of glycol components. Especially, C2-C10 aliphatic glycol, C6-C12 alicyclic glycol, etc. are preferable.

0-5 mol% of trifunctional or more than trifunctional polycarboxylic acid and / or polyol can be copolymerized to the said hydrophobic copolyester. As trifunctional or more than trifunctional polycarboxylic acid, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (Anhydro trimellitate), etc. are mentioned. Moreover, as a trifunctional or more than trifunctional polyol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, etc. are used.

The trifunctional or higher polycarboxylic acid and / or polyol is copolymerized in the range of 0 to 5 mol%, preferably 0 to 3 mol%, based on the total acid component or the total glycol component. It can be suppressed.

In addition, the weight average molecular weight of the hydrophobic copolyester preferably has a lower limit of 5,000 in terms of hot water adhesive resistance. In addition, it is preferable that an upper limit is 50,000 from a viewpoint of gelation etc. at the time of superposition | polymerization,

After synthesize | combining hydrophobic copolyester, graft superposition | polymerization is performed. Graft polymerization is performed by reacting 1 or more types of radically polymerizable monomers using a radical initiator in the state which melt | dissolved hydrophobic copolyester in the organic solvent. The reaction product after the completion of the graft reaction is, in addition to the graft copolymer of the desired hydrophobic copolyester and the radical polymerizable monomer, from the radical polymerizable monomer not grafted with the hydrophobic copolyester and the hydrophobic copolyester which have not been grafted. The obtained (co) polymer is also contained. The polyester-based graft copolymer in the present invention is not only the above-described polyester-based graft copolymer, but also a (co) obtained from a hydrophobic copolymerized polyester that is not grafted and a radically polymerizable monomer that is not grafted. Also included are reaction mixtures containing polymers and monomers (remaining monomers).

In this invention, it is preferable that the acid value of the reaction material which graft-polymerized the radically polymerizable monomer to the hydrophobic co-polyester is 600 eq / 10 ⁶ g or more from a hot water adhesive property. More preferably, the acid value of the reactants is at least 1200 eq / 10 ⁶ g. When the acid value of the reactants is less than 600 eq / 10 ⁶ g, hot water adhesive resistance may be lowered.

In addition, the mass ratio of the preferred hydrophobic copolyester and the radical polymerizable monomer suitable for the purpose of the present invention is preferably in the range of polyester / radical polymerizable monomer = 40/60 to 95/5, more preferably 55 / 45-93 / 7, Most preferably, it is the range of 60 / 40-90 / 10.

By making the mass ratio of hydrophobic copolyester 40 mass% or more, the outstanding adhesiveness of polyester can be exhibited. On the other hand, by setting the mass ratio of the hydrophobic copolyester to 95% by mass or more, the blocking resistance can be improved and the acid value of the reactants can be adjusted within the above range.

The graft polymerization reactant is in the form of a solution or dispersion of an organic solvent or a solution or dispersion of an aqueous solvent. In particular, a dispersion of an aqueous solvent, that is, a form of an aqueous dispersion, is preferable in terms of working environment and applicability. Therefore, as a radically polymerizable monomer to be grafted, it is preferable to use the radically polymerizable monomer which consists essentially of a hydrophilic radically polymerizable monomer. After the graft polymerization in the organic solvent, the organic solvent is distilled off and water is added to obtain an aqueous dispersion.

The hydrophilic radical polymerizable monomer means a radical polymerizable monomer having a hydrophilic group or a group which can later be changed to a hydrophilic group. As a radically polymerizable monomer which has a hydrophilic group, the radically polymerizable monomer containing a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group, an amide group, a quaternary ammonium base group, etc. are mentioned. On the other hand, as a radically polymerizable monomer which has a group which can change with a hydrophilic group, the radically polymerizable monomer containing an acid anhydride group, glycidyl group, a chloro group etc. is mentioned. Among these, in view of water dispersibility, a carboxyl group is preferable, and a radical polymerizable monomer having a carboxyl group or a group generating a carboxyl group is preferable.

In order to make the acid value of a graft reactant into the said preferable range, it is preferable that the radical polymerizable monomer which has a carboxyl group or has the group which produces | generates a carboxyl group is contained. As such a monomer, fumaric acid and monoethyl fumarate; Maleic acid and its anhydrides, monoethyl maleate; Itaconic acid and its anhydrides, monoesters of itaconic acid; Acrylic acid, methacrylic acid; And salts thereof (sodium salt, potassium salt, ammonium salt) and the like. Preferably, it is maleic anhydride. The said monomer can be copolymerized using 1 type (s) or 2 or more types.

The radically polymerizable monomer to be grafted may contain other monomers as long as the acid value is within the above preferable range. As another kind of monomer, the monomer which can be used when synthesize | combining said acrylic polymer can be used as it is.

Examples of the graft polymerization initiator used in the present invention include organic peroxides and organic azo compounds known to those skilled in the art. As an organic peroxide, for example, benzoyl peroxide, t-butyl peroxy pivalate, and an organic azo compound, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis (2 , 4-dimethylvaleronitrile). The usage-amount of the polymerization initiator for performing graft superposition | polymerization is at least 0.2 mass% or more with respect to a radically polymerizable monomer, Preferably it is 0.5 mass% or more.

In addition to the polymerization initiator, a chain transfer agent for adjusting the chain length of the branched polymer, for example octyl mercaptan, mercaptoethanol, 3-t-butyl-4-hydroxyanisole can be used as necessary. In this case, it is preferable to add in 0-5 mass% with respect to a polymeric monomer.

It is preferable to neutralize a grafting reaction product with a basic compound, and it can be easily water-oxidized by neutralizing. As a basic compound, the compound volatilized at the time of coating film formation is preferable, and ammonia, organic amines, etc. are preferable. Preferred compounds include, for example, triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, and Nobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, etc. are mentioned.

It is preferable to use a basic compound so that pH value of an aqueous dispersion may be in the range of 5.0-9.0 by at least partial neutralization or complete neutralization according to content of the carboxyl group contained in a grafting reaction product. When the basic compound whose boiling point is 100 degrees C or less is used, there are few residual basic compounds in the coating film after drying, for example, hot water adhesive resistance in severe environments, such as high temperature and high humidity, improves.

In the case of a grafting reaction product, it is preferable that the weight average molecular weights of the polymer of a radically polymerizable monomer are 500-50,000. It is generally difficult to adjust the weight average molecular weight of the polymer of a radically polymerizable monomer to less than 500, and graft efficiency falls and there exists a tendency for the provision of a hydrophilic group to copolyester not fully performed. The graft polymer of the radical polymerizable monomer forms a hydrated layer of dispersed particles, but in order to have a hydrated layer of sufficient thickness and to obtain a stable water dispersion, the weight average molecular weight of the graft polymer of the radical polymerizable monomer is preferably 500 or more. Do.

It is preferable that the upper limit of the weight average molecular weight of the graft polymer of a radically polymerizable monomer is 50,000 from the viewpoint of the polymerizability in solution polymerization. In order to bring the weight average molecular weight of the graft polymer of the radical polymerizable monomer into the range of 500 to 50,000, an appropriate amount of an initiator amount, a monomer dropping time, a polymerization time, a reaction solvent, a monomer composition, or a chain transfer agent or a polymerization inhibitor may be appropriately combined. It is preferable to carry out by making it.

The glass transition temperature of the graft copolymer is not particularly limited, but considering the hot water adhesive resistance, the glass transition temperature is preferably 20 ° C or higher, more preferably 40 ° C or higher.

In the present invention, the reactant obtained by graft polymerizing a radically polymerizable monomer to a hydrophobic copolyester has self-crosslinking property because the hydroxyl group in the polyester and the carboxyl group present in the graft portion react. In addition, although not crosslinked at normal temperature, intermolecular reactions, such as a hydrogen extraction reaction by a thermal radical, are performed with the heat at the time of drying at the time of forming a coating film, and it crosslinks without a crosslinking agent. This exhibits a high degree of hot water adhesiveness. Although the degree of crosslinking of a coating film can be evaluated by various methods, For example, the method of measuring the insoluble content in the chloroform solvent etc. which melt | dissolve both hydrophobic copolyester and a grafted polymer, etc. are mentioned.

The insoluble content of the coating film obtained by drying at about 80 degreeC and heat-processing at 120 degreeC for 5 minutes is preferable 50 mass% or more from a viewpoint of hot water adhesiveness and blocking resistance, More preferably, it is 70 mass% or more.

As the self-crosslinked polyester resin water dispersion, for example, commercially available ones such as "Vironal (registered trademark) AGN702" (manufactured by Toyo Boseki Co., Ltd.) may be used.

In addition, the grafted polyurethane can be prepared by a method similar to the above.

[Additive of hot water adhesive improved layer (E)]

In the hot water adhesive resistance-improving layer (E), various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricating agents, and the like within the range in which the effects of the present invention are not impaired, Pigments, dyes, organic or inorganic particles, fillers, antistatic agents, nucleating agents and the like may be blended.

In particular, in which the inorganic particles are added to the hot water adhesive property improving layer (E), for example, the hot water adhesive property improving layer (E) is laminated on the surface of the polyester base film (A) and wound around one end. In this case, since this activity and blocking resistance improve, it is preferable. In this case, silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate or the like can be used as the inorganic particles to be added. As for the inorganic particle used, 0.005-5 micrometers of average particle diameters are preferable, More preferably, it is 0.01-3 micrometers, Most preferably, it is 0.05-2 micrometers. Although the usage-amount of an inorganic particle is not specifically limited, It is preferable to mix 0.05-10 mass parts with solid content with respect to 100 mass parts of polymers in a hot water adhesive resistance improvement layer (E), More preferably, it is 0.1-5 mass parts. .

[Method of Forming Hot Water Adhesion Improved Layer (E)]

The hot water adhesive resistance improving layer (E) may be formed of an aqueous dispersion of a mixture of at least one polymer selected from the group consisting of polyesters, polyurethanes, and acrylic polymers with a crosslinking agent or an aqueous dispersion of a self-crosslinking polymer. Therefore, it is easiest to form by a coating method. What is necessary is to coat the coating liquid for heat-resistant water-resistant adhesive improvement layer (E) to the surface where the silicone rubber adhesion layer (B) is going to be laminated | stacked of the polyester base film (A). Any method, such as a method of apply | coating to the unstretched film of a polyester base film (A), and then extending | stretching to at least one direction, the method of apply | coating after longitudinal stretch, and the method of apply | coating to the surface of the film in which the orientation process was complete | finished, is possible. Especially, when manufacturing a polyester base film (A), it apply | coats before the crystal orientation of a film is completed, and after extending | stretching in at least one direction after that, what is called a inline coat which completes the crystal orientation of a polyester film. Since the method can easily form a thin film, the effect of the present invention can be more markedly expressed, which is preferable. In addition, in this invention, it is preferable to form the hot-water-water-adhesive improvement layer (E) on both surfaces of a polyester-based base film (A) except the case where a transparent conductive layer is formed in the other surface. In particular, when the silicone rubber adhesive layers (B) and (B ') are formed on both surfaces of the polyester base film (A), the silicone rubber adhesive layers (B) and (B') and poly This is important because the hot water adhesiveness of the ester base film (A) is improved.

When apply | coating the coating liquid for heat-resistant water-resistant adhesive improvement layer (E) with the unstretched film of a polyester base film (A), various coating methods, for example, a reverse coat method, the gravure coat method, the rod coat Method, bar coating method, Meyer bar coating method, die coating method, spray coating method and the like can be used.

[Release layer (C)]

In order that the adhesive sheet of this invention may protect a silicone rubber adhesion layer (B), the separator film was affixed on the silicone rubber adhesion layer (B), and a separator film is the said polyester film (D) and its surface. It becomes the formed release layer (C). The peel strength of the silicone rubber adhesive layer (B) and the release layer (C) is controlled to 0.03 to 1.0 N / 20 mm. When the said peeling strength is 0.03 N / 20mm or more, it shows favorable peelability, and when winding up an adhesive sheet, the lifting of the separate film which becomes a release layer (C) and a polyester film (D) can be suppressed, The grade of an adhesive sheet can be kept high. On the other hand, the peelability of the said separator film is favorable in it being 1.0 N / 20 mm or less. In order to control peeling strength to the said range, it is preferable to provide the release layer (C) of the following structure on the surface of a polyester film (D). In addition, peeling strength is measured as follows.

First, the surface to measure the peel strength of the adhesive sheet having a length of about 200 mm and a width of 20 mm is exposed, and the adhesive sheet is divided into a laminate including one side and a laminate including the other side, and each is tensioned. Set in the chuck of the tester. That is, for example, when measuring the peeling strength of an interface of a silicone rubber adhesion layer (B) and a release layer (C), a little peeling of an adhesive sheet is carried out at the interface of a silicone rubber adhesion layer (B) and a release layer (C). Thus, each of the silicone rubber adhesive layer (B) and the release layer (C) is exposed. In this case, with one chuck, the separate film which consists of a release layer (C) and a polyester film (D) is gripped, and the laminated body containing a silicone rubber adhesion layer (B) is gripped by one chuck. And T-type peeling strength is measured by the method of JISK6854-3. The tensile tester may use, for example, a trade name "Autograph" (manufactured by Shimadzu Corporation) and the like, and performs a T-type peeling test under conditions of a distance of 50 mm between chucks, a temperature of 23 ° C, and a tensile speed of 200 mm / min. At the time of peeling, the film end is lifted with a rod so that the T shape is maintained. The maximum strength at the time of T-type peeling is called peeling strength. Hereinafter, in this invention, the said characteristic may only be called peelability.

It is preferable that a mold release layer (C) becomes a non-silicon compound in consideration of peelability with a silicone rubber adhesion layer (B). When the release layer becomes a cured product of a curable silicone compound commonly used as a release layer, since the affinity with the silicone rubber adhesive layer (B) is high, when crosslinking the silicone compound of the silicone rubber adhesive layer (B), A rubber adhesion layer (B) and a release layer (C) may crosslinking, and peelability may fall. In order to obtain stable peelability, it is preferable to form a mold release layer using the mold release agent which does not contain a silicone compound substantially. In addition, "the release layer turns into a non-silicon compound" here means that the release layer is formed from the compound (or composition) containing 10 mass% or less of a silicon compound, and more preferable silicon compound amount is 5 mass%. Below, it is most preferable that a silicon compound is 0 mass%.

In addition, although the mold release layer (C) may be a metal or an inorganic thin film, it is preferable that it is obtained from the composition containing binder resin, a polymeric wax component, and an antistatic agent from a peeling stability and a cost point.

As binder resin, it is preferable that they are 1 or more types of polymers chosen from the group which consists of a polyester, a polyurethane, and an acryl-type polymer, These polymers may be used independently, respectively, and may be used combining 2 or 3 types different from each other. do.

As the polyester, polyurethane, and acrylic polymer, the same polymer as exemplified as the constituent polymer of the hot water adhesive resistance improving layer (E) can be used. Although the necessity of bridge | crosslinking is low in binder resin, similarly to a hot water adhesive resistance improvement layer (E), you may use a crosslinking agent together, and you may use a self-crosslinking polymer.

As the polymer wax component used in the present invention, a conventionally known material can be used. For example, a wax emulsion such as polyethylene, polypropylene, acrylic, fatty acid, or the like is shown, but a polymer wax having excellent thermal decomposition stability of a hard type having no tackiness is particularly effective in improving peelability and furthermore a film. At the time of winding, it is preferable because the wax transition to the opposite surface can be suppressed. Moreover, the preferable number average molecular weights of these waxes are 1000-10000, More preferably, it is the range of 1500-6000.

It is preferable that the said polymeric wax component is contained 2-10 mass% in solid content, when the sum total with binder resin is 100 mass%. It is more preferable that 3-8 mass% is contained. By making the addition amount of a polymeric wax component into 2 mass% or more, peelability with the silicone rubber adhesion layer (B) after crosslinking process can be made favorable, and the activity of a separate film can be improved. On the other hand, by making the addition amount of a polymeric wax component into 10 mass% or less, peeling force can be maintained and generation | occurrence | production of a channeling phenomenon can be suppressed in the manufacturing process of an adhesive sheet. In addition, since migration of the polymer wax component from the release layer (C) can be suppressed, the surface of the silicone rubber adhesive layer (B) after the crosslinking treatment is less contaminated.

As an antistatic agent used in a mold release layer (C), if it can mix with binder resin, or if it is compatible, ionicity will not be specifically limited, A conventionally well-known commercially available material can be used, For example, an anion , Cationic, nonionic, amphoteric surfactants, polymeric surfactants and the like can all be used. Preferably, the polymer type antistatic agent with little bleed out to a laminated surface is preferable. As the polymer type antistatic agent, all of anionic, cationic, and nonionic types can be used. Among them, anionic and nonionic polymer type antistatic agents are preferable.

As the anionic polymer type antistatic agent, for example, a polar polymer having one or more polar groups selected from sulfonic acid groups, carboxyl groups and sulfate ester groups or salts thereof is preferable. Polar groups require at least 5 mole percent per molecule of polymer. The polar polymer which has these electroconductivity may contain hydroxyl group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, and a vinyl sulfone group as a polar group. Among these, the antistatic agent which contains styrene sulfonic acid or its salt as a repeating unit is preferable.

As such an antistatic agent, polystyrene sulfonic acid or its salt can be mentioned. As a salt, an ammonium salt, a lithium salt, a sodium salt is mentioned, for example. Polystyrene sulfonic acid or its salt is marketed under the brand name of VERSA-TL (trademark) in Japan, for example, and the neutralization and various salts from which molecular weight differs are marketed. Moreover, as an antistatic agent containing styrene sulfonic acid or its salt as a repeating unit, a styrene sulfonic acid-maleic acid copolymer can also be used and it is marketed in Japan.

On the other hand, as the nonionic polymer type surfactant, π-electron conjugated system containing aniline or derivatives thereof, pyrrole or derivatives thereof, isothianaphthene or derivatives thereof, acetylene or derivatives thereof, thiophene or derivatives thereof, and the like as a structural unit Conductive polymers are preferred. Among them, a π-electron conjugated conductive polymer containing thiophene or a derivative thereof as a structural unit is preferable in terms of less coloring. The (pi) electron-conjugated conductive polymer may be a homopolymer containing only one structural unit as a repeating unit, or may be a copolymer containing two or more structural units as a repeating unit.

As a conductive polymer which contains a thiophene or its derivative as a structural unit, for example, the "Byteron (trademark) P" series by Stark V-Tech company, "Denatrone (trademark) P-502RG" by Nagase Chemtex company ``, Denatron (registered trademark) P-502S '', Konisol F202, F205, F210, P810 (above, brand name), Shin-Etsu Polymer CPS-AS-X03 (brand name), etc. made by INSCON TECH, are marketed, have.

Since the preferable range differs according to the kind of binder resin and the kind of antistatic agent, the compounding quantity of the antistatic agent in a mold release layer (C) cannot be determined uniformly, and from the silicone rubber adhesion layer (B) of a mold release layer (C) What is necessary is just to adjust so that peeling strength of may become the said range, respectively.

For example, when using an anionic surfactant as an antistatic agent, the compounding quantity of an antistatic agent is a binder resin and a binder resin so that peeling strength from the silicone rubber adhesion layer (B) of a release layer (C) may be in the said range. When sum total is 100 mass%, it is preferable to contain 2-10 mass% as solid content, More preferably, it is 3-8 mass%. By making the compounding quantity of anionic surfactant into 2 mass% or more, peelability from the silicone rubber adhesion layer (B) after crosslinking process is made favorable, and the antistatic property of a separate film becomes also favorable. On the other hand, by making the compounding quantity of an antistatic agent into 10 mass% or less, peeling force can be maintained and generation | occurrence | production of the channeling phenomenon in the manufacturing process of a transparent conductive polyester film composite can be suppressed. In addition, since the migration of the polymer wax component from the release layer (C) can be suppressed, the surface of the silicone rubber adhesive layer (B) after the crosslinking treatment is rarely contaminated.

In order to form the release layer (C) of the said structure on a polyester film (D), other additives, such as binder resin, a polymeric wax component, an antistatic agent, and surface roughening substance as needed, What is necessary is just to mix a predetermined amount previously, to prepare a resin composition, and to coat. The resin composition can contain a surfactant, an ultraviolet ray inhibitor, an antioxidant, or the like for improving coatability. What is necessary is just to apply | coat a coating method using normal coat apparatuses, such as a gravure coater, a reverse roll coater, a reverse kiss coater, an air knife coater, a bar coater, and a method is not limited to these. As in the case of the water-resistant water-resistant adhesive improvement layer (E), when obtaining a polyester film (D), a resin composition is apply | coated to the single side | surface of the film (D) extended | stretched to the uniaxial direction, and also the direction perpendicular to the previous uniaxial stretching further The so-called in-line coat method extended | stretched by and the so-called offline coat method apply | coated after biaxial stretching etc. are illustrated.

In order to make peeling force into the appropriate range, the thickness of the said release layer (C) is preferably 0.03 to 1 µm, more preferably 0.05 to 0.5 µm in a dry state.

[Configuration of Adhesive Sheet of the Present Invention]

The simplest structure of the adhesive sheet of this invention is a single-sided adhesive sheet in which the polyester base film (A), the silicone rubber adhesive layer (B), the release layer (C), and the polyester film (D) were laminated in this order. to be. Each layer may be laminated | stacked through the other layer, As above-mentioned, the hot-water-water-adhesive improvement layer (E) is provided between polyester-based base film (A) and silicone rubber adhesion layer (B). It is preferable.

In the single-sided tape type pressure sensitive adhesive sheet, a functional layer may be formed on the opposite surface side of the silicone rubber adhesive layer (B) formation surface of the polyester base film (A). As a functional layer, 1 layer chosen from the group which consists of a scratch prevention layer, an antireflection layer, and an antifouling layer is mentioned, for example. By forming one type of these functional layers on the adhesive sheet surface, it is possible to give the adhesive sheet a scratch preventing property, an antireflection function, or an antifouling function. In addition, as long as the purpose of a functional layer is not impaired, you may laminate | stack two or more functional layers. At the time of lamination | stacking, it is preferable to set it in the order of a scratch prevention layer, an antireflection layer, and an antifouling layer from the polyester base film (A).

The anti-scratch layer is not particularly limited, but polyester-based resins, polyurethane-based resins, acrylic-based resins, melamine-based resins, epoxy-based resins, silicone-based resins, polyimide-based resins, and the like can be used for thermal crosslinking with a crosslinking agent, electron beams, ultraviolet rays, and the like. Preference is given to layers cured with actinic light. The thickness of the scratch prevention layer is preferably in the range of 1 to 50 µm, more preferably in the range of 2 to 30 µm, and in the case of thinner than 1 µm, the scratch prevention function is not sufficiently expressed, and the thickness is greater than 50 µm. The speed of the coating is significantly slowed down and it is difficult to obtain good results in terms of productivity. As a method of laminating a scratch prevention layer, after apply | coating the said resin by the gravure method, the reverse method, the die method, etc., what is necessary is just to harden | cure by applying energy, such as heat, an ultraviolet-ray, an electron beam.

Although it does not specifically limit as an antireflection layer, It is preferable to laminate | stack a single layer or two or more layers of the material which has a refractive index different from the refractive index of a polyester base film (A). In the case of a single layer, the material which has a refractive index smaller than a polyester base film (A) may be used. In the case of a multilayer structure having two or more layers, a material having a refractive index larger than that of the film (A) is used for the layer adjacent to the polyester base film (A), and the material having a refractive index smaller than this is used for the above layer. Select. The antireflection layer may be an organic material or an inorganic material. For example, CaF ₂ , MgF ₂ , SiO ₂ , ThF ₄ , ZrO ₂ , Nd ₂ O ₃ , SnO ₂ , TiO ₂ , CeO ₂ , ZnS, would a thin film or the like in ₂ O _3, as a dry coating process such as vacuum evaporation, sputtering, CVD, ion plating, and the like to a coating resin composition having a particle thereof.

Although the thickness of this anti-reflection layer is not specifically limited, 50 nm-150 nm as a single layer and 100 nm-500 nm are preferable as a multilayer.

As the material for forming the antifouling layer, any material can be used without limitation as long as it has transparency and the required performance is satisfied. For example, the compound which has hydrophobicity, More specifically, fluorocarbon, perfluorosilane, these high molecular compounds, etc. are preferable. Moreover, in order to improve fingerprint wiping property, the high molecular compound which has an oil repellent group, such as a methyl group, is preferable.

As the method for forming the antifouling layer, various coating methods such as vacuum deposition processes such as vacuum deposition, sputtering, plasma CVD, and plasma polymerization, and wet processes such as microgravure, screen, and dip can be used. The thickness of the antifouling layer is preferably set so as not to impair the function of the antireflection layer, for example, in the case of lamination on the antireflection layer, and usually 50 nm or less.

In addition, in the adhesive sheet of a single-sided tape type, you may form a transparent conductive layer in the opposite surface side of the adhesion layer (B) formation surface of a polyester base film (A).

As typical transparent conductive materials, Metals, such as Au, Ag, Cu; Metal oxides such as In ₂ O ₃ , SnO ₂ , ZnO ₂ , or composite oxides thereof; And conductive polymers such as polyaniline, polyacetylene, polythiophene, polyparaphenylene, polyparaphenylenevinylene, and polypyrrole. Of _{these, In 2 O 3, SnO 2} , a metal oxide or a composite oxide, such as ZnO ₂ is preferred. These _{include, SnO 2, ZnO 2, Sb} 2 O 3, WO 3, etc. from ZrO _2, SiO _2, may be used one or more kind of the dopant. As for content of a dopant, the range of 0.1-50 mass% is preferable with respect to a metal oxide and a composite oxide. If the content is less than 0.1% by mass, the function as a dopant cannot be sufficiently expressed. If the content is more than 50% by mass, the original characteristics of the metal oxide and the composite oxide are impaired.

When manufacturing a transparent conductive layer from the said conductive polymer, it is good to dissolve in a suitable solvent, and to use a well-known coating method.

In order to form a transparent conductive layer using the said metals, a metal oxide, and a composite oxide, the vacuum deposition method, the sputtering method, the CVD method, the ion plating method, the spray method, etc. are employable. For example, in the case of a sputtering method, the usual sputtering method using an oxide target, the reactive sputtering method using a metal target, etc. are used. At this time, oxygen, nitrogen, water vapor, or the like may be introduced as the reactive gas, or means such as ozone addition, plasma irradiation, and ion assist may be used in combination. Moreover, you may apply a bias of direct current, alternating current, high frequency, etc. to a board | substrate in the range which does not impair the objective of this invention.

In addition, it is preferable that the temperature at the time of forming a transparent conductive layer in a polyester base film (A) shall be 150 degrees C or less. In order to make the temperature at the time of film-forming into the temperature exceeding 150 degreeC, film sending speed must be made extremely slow and it is unpreferable from a productivity viewpoint.

In addition, it is preferable to perform the vacuum degree at the time of sputtering in the range of 0.01-10 Pa. At a vacuum higher than 0.01 Pa, since stable discharge is impossible, sputtering is not stabilized. Further, even at a vacuum degree lower than 10 Pa, since stable discharge is also impossible, sputtering is not stable. The same also applies to other methods such as vapor deposition and CVD.

The thickness of the transparent conductive layer is preferably in the range of 4 to 800 nm, particularly preferably 5 to 500 nm. When the thickness of the transparent conductive layer is thinner than 4 nm, it becomes difficult to form a continuous thin film and it becomes difficult to exhibit good conductivity. Moreover, when it is thicker than 800 nm, since transparency falls easily, it is not preferable.

The double-sided adhesive sheet may be sufficient as the adhesive sheet of this invention. Any structure may be sufficient as the structure of a double-sided adhesive sheet as long as it contains a polyester base film (A) and a silicone rubber adhesion layer (B). Preferred constitution is polyester film (D) / release layer (C) / silicone rubber adhesive layer (B) / hot water-resistant adhesive improvement layer (E) / polyester-based base film (A) / heat-resistant water resistance adhesive improvement layer (E) / silicone rubber adhesion layer (B ') / mold release layer (C') / polyester film (D ') or polyester film (D) / mold release layer (C) / silicone rubber adhesion layer (B) / Heat-resistant adhesiveness improvement layer (E) / polyester base film (A) / heat-resistant water-resistant adhesive improvement layer (E) / acrylic adhesion layer (F) / mold release layer (C ") / polyester film (D) to be.

The release layer (C ') may be the same composition as the release layer (C) or may have a different composition. Preferable examples of the release layer (C ') are the same as those of the release layer (C). Since the release layer (C ") is in contact with the acrylic adhesive layer (F), the crosslinking reaction as in the case of the silicone compounds between the silicone rubber adhesive layer (B) and the release layer (C) is unlikely to occur. All of the well-known compositions for mold release layers can be used.The polyester film (D ') and (D ") may be the same composition as the polyester film (D), or may be a film having a different composition. Preferable examples of the polyester film (D ') and (D ") are the same as the preferable examples of the polyester film (D).

Polyester film (D) / release layer (C) / silicone rubber adhesion layer (B) / heat-resistant water-resistant adhesive improvement layer (E) / polyester base film (A) / heat-resistant water-resistant adhesive improvement layer (E) / Silicone rubber adhesion layer (B '), release layer (C'), and polyester in the case of double-sided adhesive sheet of the structure of silicone rubber adhesion layer (B ') / mold release layer (C') / polyester film (D ') As for the film (D '), the same content or aspect as a silicone rubber adhesion layer (B), a release layer (C), and a polyester film (D) is preferable.

The pressure-sensitive adhesive constituting the acrylic pressure-sensitive adhesive layer (F) includes, for example, an acrylic pressure-sensitive adhesive containing an acrylic polymer containing (meth) acrylate having 1 to 18 carbon atoms of an alkyl group as a main monomer component. Can be.

Examples of the (meth) acrylate having 1 to 18 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth). ) Acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate , Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, Dodecyl (meth) acrylate etc. are mentioned. These (meth) acrylates can be used individually or in mixture of 2 or more types.

Moreover, the monomer component (copolymerizable monomer) which has copolymerizability with the said (meth) acrylate may be used. In particular, when crosslinking the acrylic polymer, the copolymerizable monomer is preferably a monomer for modifying an acrylic adhesive, and any of known monomers for modification may be used. The copolymerizable monomers can be used alone or in combination of two or more thereof.

Specifically, as the copolymerizable monomer, all monomers constituting the acrylic polymer for the heat-resistant water-resistant adhesive layer (E) or monomers exemplified as other types of monomers can be used, and α- such as ethylene and propylene can be used. Olefin monomers and the like.

As a monomer for modification, the said functional group containing monomer is preferable, Among these, a hydroxyl group containing monomer and a carboxyl group containing monomer are preferable, and acrylic acid is especially preferable. Moreover, an acrylic polymer can be bridge | crosslinked using the functional group (especially polar group) derived from the monomer for modification.

As a polymerization method for obtaining an acrylic polymer, a solution polymerization method performed using a polymerization initiator such as an azo compound or a peroxide, an emulsion polymerization method or a bulk polymerization method, or a polymerization method performed by irradiating light or radiation with a photoinitiator is employed. can do. In this invention, the method (radical polymerization method) of superposing | polymerizing using the polymerization initiator which decompose | disassembles and produces | generates a radical can be employ | adopted preferably. In this radical polymerization, superposition | polymerization initiators, such as peroxides, such as benzoyl peroxide and tert- butyl pamareate, azo type compounds, such as 2,2'- azobisisobutyronitrile and azobisisovaleronitrile, are used normally. Do it. The amount of the polymerization initiator to be used may be an amount usually used in the polymerization of the acrylic monomer, and is, for example, about 0.005 to 10 parts by mass, and preferably about 0.1 to 5 parts by mass based on 100 parts by weight of the total amount of the monomer components. .

As a ratio of the (meth) acrylate which has a C1-C18 alkyl group as a main monomer component of an acryl-type polymer, it is preferable that it is 50 mass% or more with respect to 100 mass% of monomer components from a viewpoint of adhesive characteristic. 80 mass% or more is more preferable, and 90 mass% or more is more preferable. Therefore, the ratio of copolymerizable monomers other than the said (meth) acrylate becomes 50 mass% or less in 100 mass% of monomer components.

The acrylic polymer obtained by superposing | polymerizing the said monomer component can be used in that state. Moreover, it is also possible to harden | cure by crosslinking an acrylic polymer. When the said polymer is crosslinked, the cohesion force of an adhesive can be enlarged further. A crosslinking agent can be used for crosslinking. That is, a crosslinking agent may be mix | blended with an acrylic adhesive with an acrylic polymer. In addition, the heat crosslinking method is preferably used for crosslinking the polymer.

As a crosslinking agent, all the crosslinking agents illustrated as a crosslinking agent which can be used in a heat-resistant water-resistant adhesive improvement layer (E) can be used. Especially as a crosslinking agent, a melamine type crosslinking agent, an epoxy type crosslinking agent, and an isocyanate type crosslinking agent are preferable. A crosslinking agent can be used individually or in mixture of 2 or more types. 0.001-10 mass parts is preferable with respect to 100 mass parts of acrylic polymers, and, as for the usage-amount of a melamine type crosslinking agent and / or an epoxy crosslinking agent, 0.01-5 mass parts is more preferable. 0.01-20 mass parts is preferable with respect to 100 mass parts of acrylic polymers, and, as for the usage-amount of an isocyanate type crosslinking agent, 0.05-15 mass parts is more preferable.

You may add various additives to an acrylic adhesive as needed. For example, in order to adjust adhesive characteristics, you may mix | blend tackifying resin (for example, rosin type resin, terpene type resin, petroleum resin, coumarone-indene resin, styrene resin, etc.). From the viewpoint of improving the colorless transparency of the double-sided adhesive sheet or suppressing the color tone change, hydrogenated tackifying resin is preferable, and the blending ratio is preferably within a range that does not increase the haze of the double-sided adhesive sheet. Moreover, as additives other than tackifying resin, it is also possible to mix | blend well-known various additives, such as fillers, such as a plasticizer and fine powder silica, a coloring agent, a ultraviolet absorber, and surfactant. All the usage-amount of these additives should just be a normal quantity applied to an acrylic adhesive.

The adhesive force of the acrylic adhesive layer (F) can be controlled by methods, such as a ratio adjustment of a monomer for modification (functional group containing copolymerizable monomer), a crosslinking agent, and the method of using surfactant. The thickness of the acrylic adhesive layer (F) is not particularly limited, and for example, 3-200 µm is preferable. 5-150 micrometers is more preferable, and 10-100 micrometers is more preferable.

Moreover, as said acrylic adhesive, it is also possible to use the "SK dyne" series by Soken Chemical Co., Ltd., for example. Especially, use of the optical adhesive brand is preferable.

The formation method of the said acrylic adhesion layer F is not limited. For example, a method of preparing a coating liquid of a solution type of an organic solvent or a coating liquid of an aqueous dispersion form and applying it by a coating method is easy. In addition, between the acrylic adhesive layer (F) and the polyester base film (A), a heat-resistant water-resistant adhesive improvement layer (D) is provided to increase the adhesion between the acrylic adhesive layer (F) and the base film (E). You may comprise so that.

The adhesive force of the acrylic adhesive layer F may be equivalent to the adhesive force of the silicone rubber adhesive layer B, may be small, or may be large. It is preferable to select and set suitably according to the usage method of the double-sided adhesive tape of this invention. For example, in order to apply to the usage method where both surfaces require re-peelability, a range equivalent to the adhesive force of the silicone rubber adhesive layer (B), that is, 0.01 to 1.0 N / 20 mm (180 degree peeling test on glass, The tensile speed is preferably in the range of 300 mm / min. On the other hand, when fixing one side firmly, it is good to set higher than the said range. For example, it is preferable that it is 5.0 N / 20 mm or more as adhesive force in the case of using for bonding together the touch panel part of a touch panel and a display apparatus part, For example, 5.0-30 N / 20 mm is a preferable range. A more preferable range is 8.0-25 N / 20 mm.

[Push Elastic Modulus of Silicone Rubber Adhesion Layers (B) and (B ') of the Present Invention

The present inventors have already disclosed a patent in which the dynamic hardness of the surface of the self-adhesive layer made of a flexible polymer is limited to a specific range (for example, Japanese Patent Laid-Open No. 2003-119434 and Japanese Patent Laid-Open No. 2001-). 139903 and Japanese Patent Laid-Open No. 2002-149341.

However, the dynamic hardness disclosed in the said document is the load at the time of pushing the indenter to the depth of 3 micrometers from the outermost surface of an adhesion layer, and only the surface hardness required for expressing adhesive force is shown. For this reason, the adhesion layer of the hardness range disclosed by the said document expressed the adhesive force by the softness of the surface, and made it possible to adhere | attach to a to-be-adhered body.

However, with the expansion of the market, for example, in the case of sticking on the surface of an adherend which is not expellable at the time of sticking or on the surface of a to-be-adhered body, the case where shape followability with respect to a surface shape has started to appear. As a result of earnestly examining the solution by the present inventors, the optimization of the push-elastic modulus of silicone rubber adhesion layer (B) and (B ') is made, in order to make them compatible with the expulsion property and shape followability of the air which entered. I found something important.

It is preferable that the push-up modulus of the said silicone rubber adhesion layer (B) and / or (B ') is 0.5-20 N / mm <2> measured by the following method. If it is less than 0.5 N / mm <2>, since the expulsion property of the entered air falls, it is unpreferable. Moreover, the cutting workability at the time of the slit processing or punching process of a double-sided adhesive sheet may fall. On the other hand, when 20 N / mm <2> is exceeded, since shape followability falls, it is not preferable. As for push elastic modulus, 0.6-15 N / mm <2> is more preferable, and 0.7-10 N / mm <2> is further more preferable.

However, when the image display panel mentioned later and the protection panel which protects an image display panel are bonded together by the double-sided adhesive sheet of this invention, and it is used in order to improve the visibility of an image display apparatus, a push elastic modulus is 0.5-. It is preferable that it is 5 N / mm <2>. Generally, as a protective panel, in order to ensure impact resistance, tempered glass, a polycarbonate resin (PC) plate, or an acrylic resin plate is used. On the rear surface thereof, a light shielding film is provided as if necessary to circumscribe the periphery of the protection panel in accordance with the screen frame. This light shielding film is formed by printing by paint, and since thickness is 5-15 micrometers normally, the back surface of a protective panel is not planar. For this reason, in the double-sided adhesive sheet in which the adhesion layer was provided on both surfaces through the base film, air bubble might generate | occur | produce without being able to absorb the step | step by a printing part. In this case, by controlling the push elastic modulus of the silicone rubber adhesive layers (B) and (B ') within the above range, the balance between appropriate elasticity and resilience against deformation is improved, for example, the protective panel on which the light shielding film is formed. Also in the case of sticking, the generation of bubbles could be suppressed.

The push elastic modulus represents the elasticity of the adhesive layer and the resilience against deformation, and can be controlled by the thickness, hardness, molecular weight, and degree of crosslinking of the silicone rubber adhesive layers (B) and (B '). That is, when the thickness of the pressure-sensitive adhesive layer becomes thick, the elasticity of the pressure-sensitive adhesive layer becomes small, so that the push elastic modulus becomes small. Moreover, since the elasticity of an adhesion layer becomes large, so that the hardness of an adhesion layer increases, a push elastic modulus becomes large. On the other hand, as the molecular weight increases, the entanglement between molecules increases, so that the stability to deformation increases, and the push modulus decreases. In addition, when the degree of crosslinking is lowered, the restorability to deformation is lowered, so the push modulus is increased.

[Measurement method of push modulus]

The sample is cut out to about 2 cm in width, and on the glass plate 1 mm or more in thickness, the opposite surface of a measurement surface is fixed with the non-carrier type acrylic adhesive (25 micrometers in thickness), or the cyanoacrylate type adhesive agent. In addition, when there exists an adhesion layer on the opposite surface of a measurement surface, it fixes to a glass plate using the adhesion layer.

After sticking and fixing a sample to a glass plate, after leaving it for 30 minutes or more, the separator film of a measurement surface is peeled off, and it measures on the following measurement conditions with dynamic ultra-micro hardness meter DUH-211 (made by Shimadzu Corporation).

"Measuring conditions"

1) Settings

Test Mode: Load-Unload Test

Working indenter: 115 degrees ridge angle, triangular indenter

: Indenter modulus: 1.140 × 10 ⁶ N / mm 2

Indent Poisson's ratio: 0.07

Soft sample measurement: Yes

Cf-Ap, As correction: Yes

2) condition

Test force: 0.50 mN

Load speed: 0.0150 mN / sec

Load holding time: 5 sec

Unloading Hold Time: 5 sec

[Optical characteristics of the pressure sensitive adhesive sheet of the present invention]

In the adhesive sheet of this invention, when the high transmittance | permeability is calculated | required, it is preferable that total light transmittance is 80% or more, and haze is 2.0% or less. It is more preferable that the total light transmittance is 85% or more, and the haze is 1.5% or less. Moreover, even after storing for 200 hours at 65 degreeC and 85 RH%, it is preferable that total light transmittance and a haze are contained in the said preferable range.

[Method of Manufacturing Adhesive Sheet of the Present Invention]

The formation method of a silicone rubber adhesion layer (B) is as above-mentioned. What is necessary is just to form another layer suitably before formation, or after formation before forming a silicone rubber adhesion layer (B). Moreover, what is necessary is just to form a separate film separately and to laminate | stack on a silicone rubber adhesion layer (B) and an acrylic adhesion layer (F). Since the peeling force of a separate film and a silicone rubber adhesion layer (B) is controlled to an appropriate range, and the adhesive sheet of this invention suppresses generation | occurrence | production of said channeling phenomenon in the process of winding up an adhesive sheet etc., The adhesive sheet can be produced stably.

[Use of adhesive sheet of the present invention]

The adhesive sheet of the present invention can be easily detached from the adhesive sheet in the case where there is an adhesive miss and can be fixed again. It is excellent in the adhesion durability between the adhesive layer and the base polyester film, and can be preferably used even when used under excessive conditions. Moreover, workability at the time of manufacturing the upper electrode for touch panels or an image display apparatus by bonding various members or various members together is also excellent.

The single-sided adhesive sheet of the present invention is useful as a protective film for protecting a display screen of an image display device. As an image display apparatus, a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescent panel (ELP), a touch panel, a CRT (cathode ray tube) display, etc. are mentioned. The single-sided adhesive sheet of the present invention is preferably used not only for the protection of the display screen at the time of their use, but also for the protection of the display screen in the manufacturing process of the apparatus.

The single-sided adhesive sheet having a functional layer is also useful as a surface layer member of a touch panel as a protective film for a display screen. Moreover, the single-sided adhesive sheet which laminated | stacked the transparent conductive layer is useful as a touch panel structural member, such as a lower electrode for touch panels, for example. When the single-sided adhesive sheet in which the transparent conductive layer is laminated is used as the lower electrode, the touch panel portion and the display device can be attached to the silicone rubber adhesive layer (B), and the space between the touch panel portion and the display device is the adhesive layer. Can be filled with As a result, since the reflection of light at the interface in the space is suppressed, the effect that the visibility of the display image is improved is exhibited. Moreover, since the silicone rubber adhesion layer (B) becomes a silicone rubber which has adhesiveness and re-peelability, both members can be easily peeled off, for example, even when there is an adhesion miss at the time of the said adhesion, It also has the effect of being reattached.

In addition, the single-sided adhesive sheet is also useful when manufacturing the upper electrode for the touch panel. For example, the upper electrode for touch panels can be manufactured by affixing the single-sided adhesive sheet which has a functional layer with respect to the transparent base material of the conductive laminated body in which the transparent conductive layer was laminated | stacked on the transparent base material. Further, by adhering a single-sided adhesive sheet in which a transparent conductive layer is laminated on a transparent substrate of a functional laminate in which at least one functional layer selected from the group consisting of a scratch prevention layer, an antireflection layer and an antifouling layer is laminated on a transparent substrate, The upper electrode for the touch panel can be manufactured. As a transparent base material in an electroconductive laminated body or a functional laminated body, it is not limited to a polyester film, Cyclic polyolefin, such as a norbornene-type polymer; Polyamide resins such as nylon 6, nylon 4, nylon 66 and nylon 12; Acrylic resins; Polycarbonate; Films, such as a triacetyl cellulose (TAC), are mentioned. The resin used for these films may be a copolymer containing a small amount of copolymerization components. In addition, these resin may be used individually or in mixture of 1 or more types other than using independently. In film-forming, what is necessary is just to be the same as the method illustrated when manufacturing a polyester base film (A). However, it is preferable to make TAC into a film by the cast method. Although the preferable thickness of a transparent base material is not specifically limited, 5-30 micrometers is preferable.

The above-mentioned double-sided adhesive sheet is suitable for bonding the structural members of a touch panel and an image display apparatus. For example, adhesion of an overlay sheet and a coordinate detection sheet of a capacitive touch panel, adhesion of a touch panel portion of a resistive touch panel and a display device, or an image display panel of an image display device and the image display panel are protected. It is suitable for sticking a protective panel. For example, the upper electrode for a touch panel can be manufactured by bonding the said electroconductive laminated body and the said functional laminated body to each adhesion layer of a double-sided adhesive sheet.

The present invention includes a touch panel upper electrode and an image display device manufactured using the pressure sensitive adhesive sheet of the present invention. The upper electrode for the touch panel of the present invention has excellent characteristics of the adhesive sheet of the present invention, and has good cushioning property due to the elasticity of the silicone rubber adhesive layer (B). Would be excellent.

The double-sided adhesive sheet described above is also suitable for bonding an image display panel and a protective panel protecting the image display panel. If there is an air layer between the image display panel and the protection panel, the reflection of light increases due to the difference in refractive index between the air layer and the protection panel, so that sunlight and backlight light are scattered. Deterioration of visibility can be suppressed because the space between an image display panel and a protective panel is filled by worsening and sticking a double-sided adhesive sheet. Moreover, also when using for manufacture of an image display apparatus, the characteristic which is excellent in adhesiveness and repair property can be utilized effectively.

In addition, the bonding method of an image display panel and a protection panel is not specifically limited. For example, after peeling one separate film of a double-sided adhesive sheet from the surface of an adhesive layer, the double-sided adhesive sheet is affixed in advance to either an image display panel or a protection panel, and then the other panel is bonded together suitably. Can be. In addition, if heat and pressure are applied by an autoclave etc. as needed, bonding will become more reliable. It is preferable to arrange the double-sided pressure-sensitive adhesive sheet so that the silicone rubber pressure-sensitive adhesive layer faces on the panel side where the re-sticking operation is required or is expected to be required. This is because the silicone rubber adhesive layer is excellent in re-peelability. Moreover, you may stick together a double-sided adhesive sheet on both a protection panel and an image display panel in the range which has no problem in a structure.

Example

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited by the following Example, of course, It is also possible to change suitably and to implement in the range suitable for the meaning of this invention, They are all the present It is included in the technical scope of the invention. In addition, the measurement and evaluation method employ | adopted in the Example is as follows. In addition, the thing described with "part" in an Example means a "mass part", and the thing described with "%" means the "mass%" unless there is particular notice.

1. Peel strength (separability) of separate film

First, about 200 mm in length and 20 mm in width, the surface to which peeling strength is to be measured are exposed, and it divides into a separate film and other laminated bodies, and sets each in the chuck of a tension tester. That is, for example, in the case of a double-sided adhesive sheet, when the peeling strength of the interface between the release layer (C) and the silicone rubber adhesive layer (B) is measured, the release layer (C) and the silicone rubber adhesive layer (B) The double-sided adhesive sheet is slightly peeled off at the interface to expose each of the release layer (C) and the silicone rubber adhesive layer (B). In this case, with one chuck, the separator film (DC) which becomes a polyester film (D) and a release layer (C) is gripped, and the other part is gripped by one chuck. And T-type peeling strength was measured by the method of JISK6854-3. The tension tester used was a T-type peeling test under the brand name "Autograph" (manufactured by Shimadzu Corporation) under conditions of a distance of 50 mm between chucks, a temperature of 23 ° C, and a tensile speed of 200 mm / min. At the time of peeling, the film end was lifted with a rod so that the T shape was maintained. The maximum strength at the time of T-type peeling was made into peeling strength. When the mold release layer (C) and silicone rubber adhesion layer (B) did not peel, it did not measure as a peeling difficulty. In this case, it shows that the release layer (C) does not function as a release layer. The measurement of the peel strength of the other interface is also performed in the same manner as above.

2. Peel strength (adhesiveness) of silicone rubber adhesive layer and polyester base film

Since the silicone rubber adhesive layer (B) or (B ') and the polyester base film (A) are firmly adhered via the hot water adhesive resistance improving layer (E), the silicone rubber adhesive layer (B) or When evaluating the peeling strength of (B '), the cutter knife was sandwiched between polyester base films (A), and it removed by applying a force with a finger (surface exposure). (Circle) and the thing which interface exposure is possible were evaluated by making into x that the peeling strength was not strong and interface exposure was impossible.

3. Hot water adhesiveness of silicone rubber adhesive layer

A sample is cut into 50 mm x 50 mm, and the separator film laminated | stacked on the silicone rubber adhesion layer (B) and / or (B ') is peeled off. In a cylindrical glass container with a 500 cc lid containing 400 cc of distilled water, the sample is submerged in water so that the adhesive layer (C) is downward, and the container is covered with a lid while the whole sample is immersed in water. When only the weight of the sample is not immersed in water, a polyester film having a thickness of 60 mm × 60 mm and a thickness of 188 μm may be placed on the sample to form a push stone, for example. The size and material of the pressing stone are not particularly limited, and the entire sample may be immersed in water. The container containing a sample is put in the gear oven set at 80 degreeC, and it is left to stand for 24 hours. After the heat treatment, the container was taken out of the oven, and the sample was taken out quickly, and rubbed 10 times by applying a force with a finger to the end portion from the silicone rubber adhesive layer (B) or (B ') side, and then the silicone rubber adhesive layer (B) or (B It evaluated that whether ") peeled from a polyester base film (A), and let (circle) and the thing which a silicone rubber adhesion layer peel that the silicone rubber adhesion layer did not peel were made into x.

4. Adhesive force of silicone rubber adhesive layer

The adhesive force with respect to the glass of a silicone rubber adhesion layer (B) or (B ') was measured by the 180 degree peeling method according to JISZ0237. The glass used the heat resistant glass of thickness 3mm and width 30mm. The sample was made into 20 mm width, and sticking to glass was performed by making two round trips at the speed of about 29 mm / sec using the roller of 2 Kg. The tensile speed was 300 mm / min, the tensile test was done in 23 degreeC atmosphere, and the maximum tensile strength was made into adhesive force (N / 20 mm).

5. Total light transmittance and haze

The total light transmittance was measured in accordance with JIS K7361-1 and haze according to JIS K7136 using a haze measuring instrument "NDH-2000" manufactured by Nippon Denshoku Industries Co., Ltd. This measurement was performed by peeling a separate film.

6. Push modulus of silicone rubber adhesive layer

The sample is cut out to about 2 cm in width and on the glass plate of 1 mm or more in thickness, and the opposite side of the measurement surface is fixed with the non-carrier type acrylic adhesive (25 micrometers in thickness) or a cyanoacrylate type adhesive agent. In addition, when there exists an adhesion layer on the opposite surface of a measurement surface, it fixes to a glass plate using the adhesion layer. In addition, in the case of the double-sided adhesive sheet of the structure which has a silicone rubber adhesion layer (B) and (B ') on both surfaces, it measured about the silicone rubber adhesion layer (B) and (B') of both surfaces.

After sticking and fixing a sample to a glass plate, after leaving it for 30 minutes or more, the separator film of a measurement surface is peeled off, and it measures on the following measurement conditions with dynamic ultra-micro hardness meter DUH-211 (made by Shimadzu Corporation).

"Measuring conditions"

1) Settings

Test Mode: Load-Unload Test

Working indenter: 115 degrees ridge angle, triangular indenter

: Indenter modulus: 1.140 × 10 ⁶ N / mm 2

Indent Poisson's ratio: 0.07

Soft sample measurement: Yes

Cf-Ap, As correction: Yes

2) condition

Test force: 0.50 mN

Load speed: 0.0150 mN / sec

Load holding time: 5 sec

Unloading Hold Time: 5 sec

7. Clarification of Coating Amount

100 cc of the coating liquid for forming the silicone rubber adhesive layer (B) or (B ') is filtered with a wire mesh of 200 mesh of 40 mm (wire diameter 0.04 mm) and visually confirmed the presence or absence of an insoluble matter. (Circle) and the case with insoluble matter were made into x for the case.

8. Solution stability of coating liquid

The coating liquid for silicone rubber adhesion layer (B) or (B ') formation was evaluated by the viscosity change of the solution when it preserve | saved at room temperature (23 degreeC) for 90 days in a sealed state, and solution stability was determined. (Circle) and the case where the viscosity change of a solution exceeded ± 20% were made into the case where the viscosity change of the solution was within +/- 20%. In addition, the viscosity was measured with the Brookfield viscometer.

9. Measurement of number average molecular weight of silicon compound

After the sample was dissolved in a solvent (toluene), molecular weight was measured by gel permeation chromatography (GPC). Measurement conditions are as follows.

(Measuring conditions)

Device: Waters410

Column: Shodex K806M + K802

Flow rate: 1.0 ml / min

Injection volume: 200 μl

Solvent: Toluene

Polystyrene conversion

Detector: Differential Refractometer

Example 1

(1) Preparation of Coating Liquid for Forming Hot Water Adhesion Improved Layer (E)

[Preparation of Water Dispersible Copolymerized Polyester Resin]

A water-dispersible copolyester was synthesized by using antimony trioxide as a polycondensation catalyst in a batch-wise manner using one pressure esterification reactor with a distillation column and two polycondensation reactors with a vacuum generator.

The copolymerization composition of the water-dispersible copolyester is terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // neopentyl glycol / ethylene glycol = 50/43/7 // 70/30 (molar ratio), and the reduced viscosity is 0.68 dl / g.

[Preparation of Coating Amount]

100 parts of crushed products of the water-dispersible copolyester were water-dispersed by a conventional method. About 100 parts of solid content of this aqueous dispersion, methylolation melamine resin "Cymel (registered trademark) 303" (made by Mitsui Cytech Co., Ltd.) as 5 parts of solid content, and a catalyst, "Calyst 600" (made by Mitsui Scitech) 0.025 parts of was added and stirred well to obtain a coating solution (E-1).

(2) Production of Polyester Base Film (A) and Lamination of Hot Water Adhesion Improved Layer (E)

Pellets of polyethylene terephthalate (high viscosity 0.65 dl / g) containing 0.04% of amorphous silica fine particles having an average particle diameter (SEM method) of 1.5 µm are sufficiently dried in vacuo, and then supplied to an extruder heated at 280 ° C to form a T-shaped mold. The sheet was extruded into a sheet form, wound around a mirror casting drum having a surface temperature of 30 ° C. and solidified by cooling using an electrostatically applied cast method. This unstretched film was stretched 3.5 times in the longitudinal direction while passing the 95 degreeC heating roll group, and it was set as the uniaxial stretched film. Corona discharge treatment was performed on both surfaces of this film, and the coating solution (E-1) was applied to both of the treated surfaces. This uniaxial stretched film was introduce | transduced into the preheating zone, holding | grip with a clip, and after drying at 110 degreeC, it extended | stretched 3.5 times in the width direction continuously in the 125 degreeC heating zone continuously. Further, at 225 ° C., heat treatment was performed for 6 seconds while relaxing 6% in the width direction. On both sides of the biaxially stretched polyethylene terephthalate base film (A), a laminate (a) having a thickness of 100 μm in which a crosslinked hot water adhesive improved layer (E) having a thickness of 0.08 μm was laminated on both sides was obtained.

(3) lamination of scratch prevention layer

On one side of the laminate (a), a solution obtained by adding 5 parts of methyl ethyl ketone to 5 parts of an ultraviolet curable hard coat paint (Deiichi Seika Industrial Co., Ltd .: "SEIKA BEAM (registered trademark) EXF-01B": solid content 100%)) It applied using the # 8 wire bar and dried at 70 degreeC for 1 minute, and removed the solvent. Subsequently, 200 mJ / cm <2> of ultraviolet-rays were irradiated with the high pressure mercury lamp at the irradiation distance of 15 cm, running this laminated body at 5 m / min. The scratch prevention layer laminated body (b) which has a scratch prevention layer of 3 micrometers in thickness was obtained.

(4) Lamination of Anti-Reflection Layer

The high refractive index coating agent obtained by the following method was apply | coated to the surface of the scratch prevention layer laminated body (b), and it dried at 150 degreeC for 2 minutes, and formed the high refractive index layer of 0.1 micrometer in film thickness. On this high refractive index layer, the low refractive index coating agent obtained by the following method was apply | coated, it dried at 150 degreeC for 2 minutes, and the low refractive index layer of 0.1 micrometer of film thickness was formed. The obtained laminated | multilayer film was irradiated with 1000 mJ / cm <2> ultraviolet-rays, the antireflection layer and the scratch prevention layer were fully hardened | cured, and the laminated body (c) which has an antireflection layer was obtained.

(4-1) Preparation of high refractive index coating agent

80 parts of methyl methacrylate, 20 parts of methacrylic acid, 1 part of azoisobutyronitrile and 200 parts of isopropyl alcohol were added to the reaction vessel, and reacted at 80 ° C. for 7 hours under a nitrogen atmosphere to obtain a polymer having a weight average molecular weight of 30,000. Isopropyl alcohol solution was obtained. The obtained polymer solution was further diluted with isopropyl alcohol to 5% of solid content, and the acrylic resin solution was obtained.

Using the obtained acrylic resin solution, it mixed according to the following formulation compositions, and obtained the high refractive index coating agent.

Acrylic resin solution: 5 parts

Bisphenol A diglycidyl ether: 0.25 parts

Titanium oxide particles with an average particle diameter of 20 nm: 0.5 parts

Triphenylphosphine: 0.05 parts

Isopropyl Alcohol: 14.25 parts

(4-2) Preparation of low refractive index coating agent

45 parts of 2,2,2-trifluoroethyl acrylate, 45 parts of perfluorooctylethyl acrylate, 10 parts of acrylic acid, 1.5 parts of azoisobutyronitrile and 200 parts of methyl ethyl ketone were added to the reaction vessel, and nitrogen atmosphere It was made to react at 80 degreeC under 7 hours, and the methyl ethyl ketone solution of the polymer of the weight average molecular weight 20,000 was obtained. The obtained polymer solution was diluted with methyl ethyl ketone to 5% of solid content, and the fluoropolymer solution was obtained.

Using the obtained fluoropolymer solution, it mixed according to the following formulation compositions, and obtained the low refractive index coating agent.

Fluoropolymer solution: 44 parts

1,10-bis (2,3-epoxypropoxy) -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro Rodecane (`` Fluorite FE-16 '' manufactured by Kyoeisha Chemical Co., Ltd.): 1 part

Triphenylphosphine: 0.1 part

Methyl ethyl ketone: 19 parts

(5) Preparation of Coating Liquid for Forming Release Layer (C)

As a binder resin, "Bironal (registered trademark) MD-1200" (manufactured by Toyo Boseki Co., Ltd.), which is a water-dispersible copolyester resin, a polyethylene emulsion wax agent as a polymer wax component, and an anionic antistatic agent (dode Styrene-benzoguanamine-based organic spherical fine particles having an average particle diameter of 2 µm as a surface roughening substance, "Eposuta (registered trademark) MS" (manufactured by Nippon Shokubai Corporation), and an average particle diameter of 0.05 µm. Colloidal silica of was used, respectively.

Using a homogenizer, the organic spherical fine particles of the surface roughening substance were sufficiently dispersed in a mixed solution of water and isopropyl alcohol (mass ratio 80/20), and then 2.5% of binder resin and polymer wax to the total mass of the coating solution. The mixing solution (C-1) for release layer formation was prepared by mixing sufficiently so that 0.13% of components, 0.13% of antistatic agent, 0.025% of organic spherical fine particles, and 0.3% of colloidal silica might be prepared.

(6) Production of Separator Film (DC) (Production of Polyester Film (D) and Lamination of Release Layer (C))

Pellets of polyethylene terephthalate (high viscosity 0.65 dl / g) are sufficiently dried in vacuo, then fed to a heated extruder at 280 ° C, extruded into a sheet from a T-shaped mold, and subjected to electrostatic applied cast method to a surface temperature of 30 ° C. It was wound around a mirror casting drum to solidify cooling. This unstretched film was stretched 3.5 times in the longitudinal direction while passing the 95 degreeC heating roll group, and it was set as the uniaxial stretched film. The coating liquid for release layer formation (C-1) was apply | coated on both surfaces of this uniaxial oriented film. The coated uniaxially stretched film was introduced into the preheating zone while being gripped with a clip, dried at 110 ° C, and subsequently stretched 3.5 times in the width direction in a heating zone at 125 ° C continuously. Further, at 225 ° C., heat treatment was performed for 6 seconds while relaxing 6% in the width direction. The 50-micrometer-thick laminated body (d) (separated film (DC-1)) by which the release layer (C) of thickness 0.15micrometer was laminated | stacked on both surfaces of the polyester film (D) was obtained.

(7) Lamination of Silicone Rubber Adhesion Layer (B)

Non-reactive silicone compound ("KF-96H-500,000 cs") which does not contain reinforcing agents, such as a silica substantially, and becomes an uncrosslinked polydimethylsiloxane skeleton whose number average molecular weight is 150,000 (measured by GPC method and polystyrene conversion); Shin-Etsu Chemical Co., Ltd.) was weighed so as to have a mass ratio of toluene of 23%, and charged into a stirrer with a vacuum degassing apparatus together with toluene, and stirred at room temperature for 15 hours to dissolve in toluene. To the obtained solution, trimethylolpropane trimethacrylate was added so as to 2 parts with respect to 100 parts of the above silicon compound, and after stirring uniformly, a vacuum degassing apparatus was driven to additionally under a vacuum having a gauge pressure of -750 mmHg. Stirred for 20 minutes and defoamed. Subsequently, the silicon compound solution after defoaming is supplied to a roll coater, and the silicon compound solution is apply | coated so that the thickness after drying may be set to 25 micrometers on the surface of the heat-resistant water-resistant adhesive improvement layer (E) of the said laminated body (c), and continue It was introduced into an oven and dried at 80 ° C. The laminated body (e) in which the uncrosslinked silicone rubber adhesion layer (B-1) was formed in the single side | surface of the laminated body (c) was obtained.

Pressing with the pressing roller (pressure 30 N / cm <2>), overlapping the laminated body d (separated film (DC-1)) on the surface of the uncrosslinked silicone rubber adhesion layer (B-1) of the said laminated body (e). , Were laminated successively. The obtained laminated body (f) was continuously introduced into an electron beam irradiation apparatus, the electron beam was irradiated with energy of 200 KV and 18 Mrad from the separator film (DC-1) side, crosslinking of the adhesion layer was carried out, and the silicone rubber adhesion after crosslinking The laminated body f 'provided with the layer (B) (protective film for display screens) was wound up in roll shape. In the manufacturing process thus far, the occurrence of the channeling phenomenon of the separator film (DC-1) was not observed.

Table 1 shows the characteristics of the protective film for display screen obtained in Example 1 and the coating liquid for forming the silicone rubber adhesive layer (B).

The protective film for display screens obtained in this example is excellent in transparency, and the silicone rubber adhesive layer (B) is firmly adhered to the polyester-based base film (A) via the hot water adhesive property improving layer (E). It was adhered and was excellent in adhesiveness and hot water adhesiveness. Moreover, the peeling force of the release layer (C) and the adhesion layer (B) was also moderate, and was excellent in peelability, and it was a high quality display screen protective film. Moreover, it was confirmed that the coating liquid for forming the adhesion layer (B) in manufacture of the protective film for display screens was also excellent in clarity and stability, and was excellent in operation property and operation stability.

Comparative Example 1

In the method of Example 1, the protective film for display screens was obtained like Example 1 except having stopped application | coating of the coating liquid (E-1) for forming a hot water adhesive improvement improvement layer (E). Table 1 shows the evaluation results.

The protective film for display screens obtained in this Comparative Example 1 was inferior in adhesiveness and hot water adhesive resistance between the silicone rubber adhesive layer (B) and the polyester base film (A) as compared with the film of Example 1. .

Comparative Example 2

In the method of Example 1, it displays similarly to Example 1 except having stopped mix | blending the methylolation melamine resin which is a crosslinking agent with the coating liquid (E-1) for formation of a hot water adhesive improvement improvement layer (E). A protective film for screens was obtained. Table 1 shows the evaluation results.

Although the protective film for display screens obtained by this comparative example 2 had favorable peeling strength between a silicone rubber adhesion layer (B) and a release layer (C), a silicone rubber adhesion layer (B) and a polyester base film ( The hot water adhesiveness between A) was inferior.

Comparative Example 3

In the method of Example 1, the protective film for a display screen in the same manner as in Example 1, except that the mixing of the polymer wax component and the antistatic agent to the coating liquid (C-1) for forming the release layer (C) was stopped. Got. Table 1 shows the evaluation results.

Although the protective film for display screens obtained by this comparative example 3 tried to peel a separator film from the silicone rubber adhesion layer (B), it could not peel, but peelability was inferior. Therefore, since it cannot use as a protective film for display screens, evaluation other than peelability was not performed.

Comparative Examples 4 and 5

In the method of Example 1, the coating liquid (C-1) for forming the release layer (C), except that the polymer wax component in Comparative Example 4, and the formulation of the antistatic agent in Comparative Example 5 respectively stopped, In the same manner as in Example 1, a protective film for a display screen was obtained. Table 1 shows the evaluation results.

In the protective film for display screens obtained by the comparative example 4, peeling of the separate film was impossible from the silicone rubber adhesion layer (B). Therefore, about the film for display screen protection of the comparative example 4, evaluation other than peelability was not performed. In Comparative Example 5, the peel strength of the separate film was large, and the peelability of the separate film was inferior.

Comparative Example 6

The method of Example 1 WHEREIN: The protective film for display screens in the same method as Example 1 except having used the releasing polyester film ("E7002"; Toyo Boseki Co., Ltd.) of thickness 38micrometer processed as a separate film. Got. In addition, the silicon rubber adhesive layer (B) was laminated so as to be in contact with the siliconized surface. Table 1 shows the evaluation results.

In the protective film for a display screen obtained in Comparative Example 6, in the same manner as in Comparative Example 3, although the separator film was to be peeled from the silicone rubber adhesive layer (B), peeling was not possible and the peelability was inferior. By EB bridge | crosslinking, it is estimated that the crosslinking adhesion phenomenon generate | occur | produced between the silicone rubber adhesion layer (B) and the release layer of a separate film. Therefore, it could not be used as a protective film for display screens. Also about the protective film for display screens of the comparative example 6, evaluation other than peelability was not performed.

Comparative Example 7

In the method of Example 1, the protective film for display screens was obtained by the same method as Example 1 except having changed the thickness of the hot water adhesive resistance improvement layer (E) so that it might become 0.7 micrometer. Table 1 shows the evaluation results.

Although the protective film for display screens obtained by this comparative example 7 had favorable adhesiveness between polyester base film (A) / silicone rubber adhesion layer (B), compared with the protective film for display screens of Example 1 The hot water adhesiveness of the silicone rubber adhesive layer (B) was inferior.

Comparative Example 8

In the method of the comparative example 2, the protective film for display screens was obtained by the method similar to the comparative example 2 except having changed the preparation of the coating liquid for silicone rubber adhesion layer (B) formation as shown below. The thickness of the silicone rubber adhesion layer was adjusted to be 25 µm after drying in the same manner as in Comparative Example 2. Table 1 shows the evaluation results.

[Preparation of Coating Liquid (B-2) for Silicon Rubber Adhesion Layer (B) Formation]

High transparency silicone rubber compound ("TSE260-3U"; rubber hardness of 30 degrees; momentum, performance) which consists of 60 parts of silicone compounds of polydimethylsiloxane skeleton, 25 parts of silicone compounds of polydimethylalkenylsiloxane skeleton, and 15 parts of silica. Materia Rouge JAPAN Co., Ltd.) was weighed so that the mass ratio to toluene was 23%, and the mixture was put into a stirrer with a vacuum degassing apparatus together with toluene, and stirred at room temperature for 15 hours to dissolve in toluene. To the obtained solution, trimethylolpropane trimethacrylate was added in an amount of 2 parts with respect to 100 parts of the rubber compound, and after stirring uniformly, a vacuum degassing apparatus was driven to additionally under vacuum having a gauge pressure of -750 mmHg. It stirred for a minute and defoamed and obtained the coating liquid (B-2) for silicone rubber adhesion layer (B) formation. In addition, the said silicone rubber compound used what passed 6 months after purchase.

In addition to the problem of the display screen protective film obtained in Comparative Example 2, the display screen protective film obtained in Comparative Example 8 was inferior in clarity and storage stability of the coating solution.

Reference Example 1

In the method of Example 1, 8 parts of organic silicones ("KS-744"; Shin-Etsu Chemical Co., Ltd.) and catalyst "PL-3" (new coating liquid) which form the hot water adhesive resistance improvement layer (E) A protective film for display screen was obtained in the same manner as in Example 1 except that 0.06 parts of STS Chemical Co., Ltd.) was changed to a solution dissolved in 100 parts by mass of toluene. Table 1 shows the evaluation results.

The protective film for display screens obtained in this Reference Example 1 had poor heat resistance water resistance between the silicone rubber adhesive layer (B) and the polyester base film (A), and was low quality.

Example 2

At the time of manufacture of the polyester base film (A) of Example 1, the polyester base film (A-2) was prepared in the same manner as in Example 1 except that the coating of the coating liquid (E-1) was stopped. Got it. Corona treatment was performed on both surfaces of this polyester base film (A-2). Separately, a copolyester resin solution ("Byron® 30SS"; manufactured by Toyo Boseki Co., Ltd.) and a polyisocyanate-based crosslinking agent ("Coronate® HX"; manufactured by Nippon Polyurethane Co., Ltd.) were each contained in a solid ratio of 100: It was mix | blended so that it might become 3 (part), and the coating liquid (E-2) for hot water adhesive improvement improvement layer (E) was prepared. This coating liquid (E-2) was apply | coated to both surfaces of the polyester base film (A-2) after corona treatment, using a coater, and it dried. The laminated body which laminated | stacked the hot-water-water adhesive improvement layer (E-2) bridge | crosslinked on both surfaces of the polyester base film (A-2) was obtained. Using this laminate, a protective film for a display screen was obtained in the same manner as in Example 1. In addition, the thickness of the hot water adhesive resistance improvement layer (E-2) after biaxial stretching was 0.31 micrometers, respectively. The evaluation results are shown in Table 2.

The protective film for display screens obtained in this example had the same characteristics as the protective film for display screens obtained in Example 1, and were of high quality.

Comparative Example 9

When preparing the coating solution (E-2) of Example 2, the formulation of the crosslinking agent "Coronate HX" was stopped and only "Byron 30SS" was used. Got. The evaluation results are shown in Table 2.

The protective film for display screens obtained by this comparative example 9 was inferior in the heat-resistant water-adhesion property of a silicone rubber adhesion layer (B) and a polyester base film (A).

Examples 3-5

A protective film for display screens was obtained in the same manner as in Example 1 except that the coating liquid (E-1) for the heat-resistant water-adhesive improved layer of Example 1 was changed to the following composition. The evaluation results are shown in Table 2.

The protective film for display screens obtained in these Examples had the same characteristics as the protective film for display screens obtained in Example 1, and were of high quality.

Coating Composition for Hot Water Adhesion Improved Layer of Example 3

To 100 parts by weight of an acrylic emulsion ("John Creel (registered trademark) PDX-7630A"; manufactured by BASF Japan), 10 parts of the "cymel 303" and 0.04 parts of the "catalyst 600" are mixed and heat-resistant. It was set as the coating liquid for water-adhesive improvement layer (E-3).

Coating Composition for Adhesive Improved Layer of Example 4

About 100 parts of solid content of polyurethane-type water dispersion ("Hylan (registered trademark AP40); Dainippon Ink Industry Co., Ltd.)," Epocross (registered trademark) WS-700 "(made by Nippon Shokubai Corporation) as an oxazoline type crosslinking agent) Was added in three parts as a solid content to obtain a coating liquid (E-4) for a hot water adhesive adhesive improved layer.

Coating Composition for Hot Water Adhesion Improved Layer of Example 5

40 parts of self-crosslinked polyester resin aqueous dispersion "Byronal (trademark) AGN702" (manufactured by Toyo Boseki Co., Ltd.), 24 parts of water and 36 parts of isopropyl alcohol were mixed, and 0.6 parts of 10% aqueous solution of anionic surfactant was added. 1 part of propionic acid, 1.8 parts of 20% aqueous dispersions of colloidal silica particles (average particle diameter 40 nm) and 1.1 parts of 4% aqueous dispersions of dry silica particles (average particle diameter 200 nm; average primary particle size 40 nm) It was set as the coating liquid for water-adhesive improvement layer (E-5).

Example 6

In the method of Example 1, the protective film for display screens was obtained by the method similar to Example 1 except having used the separate film (DC-2) manufactured by the following method. The evaluation results are shown in Table 2.

[Preparation of Separator Film (DC-2)]

The coating liquid (C-1) used for manufacture of the separator film (DC-1) of Example 1 was apply | coated on the polyester film (D: 100 micrometers) using the wire bar (No. 5). The coating amount of the coating solution (C-1) was about 8 to 10 g (wet state) per 1 m 2 of the base film. It dried for about 60 second at 160 degreeC, and obtained the separator film (DC-2).

The display screen protective film obtained in Example 6 had the same characteristics as the display screen protective film obtained in Example 1 and was of high quality. In addition, like Example 1, the generation | occurrence | production of the separator film (DC-2) was not seen at the time of manufacture of the protective film for display screens.

Example 7

In the method of Example 1, the polymeric wax component of the coating liquid (C-1) used for manufacture of the separator film (DC-1) is an acrylic wax emulsion ("ST-200"; manufactured by Nippon Shokubai Co., Ltd.). Except having changed, the protective film for display screens was obtained by the same method as Example 1. The evaluation results are shown in Table 2.

The protective film for display screens obtained in Example 7 had the same characteristics as the protective film for display screens obtained in Example 1, and were of high quality. In addition, in the same manner as in Example 1, no occurrence of separation of the separator film was observed during the manufacture of the protective film for display screen.

Example 8

The method of Example 1 WHEREIN: Except changing the antistatic agent of the coating liquid (C-1) used for manufacture of the separator film (DC-1) into an anionic antistatic agent ("TB214"; Dai-ichi Pharmaceutical Co., Ltd. product). In the same manner as in Example 1, a protective film for a display screen was obtained. Table 3 shows the results of the evaluation.

The protective film for display screens obtained in Example 8 had the same characteristics as the protective film for display screens obtained in Example 1, and were of high quality. Further, in the same manner as in Example 1, no floating of the separate film was observed during the production of the protective film for display screen.

Example 9

The method of Example 1 WHEREIN: Except having changed so that the polymeric wax component of the coating liquid (C-1) used for manufacture of the separator film (DC-1) may be 0.2%, and an antistatic agent is 0.3%. In the same manner, a protective film for a display screen was obtained. Table 3 shows the results of the evaluation.

The protective film for display screens obtained in Example 9 had the same characteristics as the protective film for display screens obtained in Example 1, and were of high quality. Further, in the same manner as in Example 1, no floating of the separate film was observed during the production of the protective film for display screen.

Comparative Example 10

In the method of Example 1, it was the same as that of Example 1 except having changed so that the polymer wax component of the coating liquid (C-1) used for manufacture of the separator film (DC-1) may be 1.3%, and an antistatic agent is 1.5%. The protective film for display screens was obtained by the method. Table 3 shows the results of the evaluation.

The peeling strength of the separator film (DC) of the protective film for display screen obtained in this Comparative Example 10 was almost 0 N / 20 mm, and the peelability was very good. There was a case.

Example 10

It carries out using the coating liquid (B-3) for silicone rubber adhesion layers (B) prepared by the following method to the surface of the laminated body (d) which is the separator film (DC-1) manufactured in the method of Example 1. The silicone rubber adhesion layer (B-3) was laminated | stacked by the method similar to Example 1, and the laminated body (g) was obtained. A compression roller (pressure 30 N) while overlapping the surface of the silicone rubber adhesive layer (B-3) of the obtained laminated body (g) with the surface of the hot water adhesive property improved layer (E) of the laminated body (c) manufactured in Example 1. / Cm 2) and laminated continuously. The obtained laminated body (h) was further continuously introduced into an electron beam irradiation apparatus, and an electron beam was irradiated with energy of 200 KV and 18 Mrad from the laminated body (d) side which is separate film (DC-1), and a silicone rubber adhesion layer ( B-3) was bridge | crosslinked and the laminated body (h ') after bridge | crosslinking was wound up in roll shape. In the manufacturing process so far, the occurrence of the channeling phenomenon of the separate film was not observed.

The protective film for display screens obtained in this example had the same characteristics as the protective film for display screens obtained in Example 1, and were of high quality. Table 3 shows the results of the evaluation.

[Preparation of Coating Liquid for Silicone Rubber Adhesion Layer (B-3)]

Non-reactive silicone compound ("KF-96H-100 million cs") which does not contain reinforcing agents, such as silica, and becomes an uncrosslinked polydimethylsiloxane skeleton whose number average molecular weight is 170,000 (measured by GPC method, polystyrene conversion). Shin-Etsu Chemical Co., Ltd.) was weighed so that the mass ratio to toluene was 23%, and the mixture was added to a stirrer with a vacuum degassing apparatus together with toluene, and stirred at room temperature for 15 hours and dissolved in toluene. To the obtained solution, trimethylolpropane trimethacrylate was added so as to 2 parts with respect to 100 parts of the above silicon compound, and after stirring uniformly, a vacuum degassing apparatus was driven to additionally under a vacuum having a gauge pressure of -750 mmHg. Stirred for 20 minutes and defoamed.

Example 11

Using the silicone compound solution prepared in Example 1, the silicone compound solution was applied to one side of the laminate (a) obtained in Example 1 so that the thickness after drying was 25 μm, and then introduced into an oven at 80 ° C. Dried. The laminated body (i) in which the uncrosslinked adhesive layer (B-1) was formed in the single side | surface of the laminated body (a) was obtained.

While laminating | stacking the laminated body (d) on the surface of the uncrosslinked adhesive layer (B-1) of the laminated body (i), it pressed by the compression roller (pressure 30N / cm <2>), and laminated | stacked continuously. The obtained laminated body (j) was further continuously introduced into an electron beam irradiation apparatus, the electron beam was irradiated with energy of 200 KV and 18 Mrad from the laminated body (d) side, the adhesion layer was bridge | crosslinked, and the silicone rubber adhesion layer after crosslinking was carried out. The laminated body j 'provided with (B) was wound up in roll shape. In the manufacturing process so far, the occurrence of the channeling phenomenon of the separate film was not observed.

(6) Lamination of Acrylic Adhesive Layer (F)

"SK Dyne 2094" (manufactured by Soken Chemical Co., Ltd.), which is an acrylic acrylic adhesive, is applied to the surface of the laminate (a ') side of the laminate (j') so that the thickness after drying is 25 µm, at 130 ° C for 3 minutes. It dried, and the acrylic adhesive layer F was formed. Silicone of a separator film (D &quot; C &quot;) (38 &quot; E &quot;) (&quot; E7002 &quot;; manufactured by Toyo Boseki Co., Ltd.) having a thickness of 38 占 퐉 made of polyethylene terephthalate (silicone processed) (release layer (C &quot;)) on the surface of the pressure-sensitive adhesive layer (F). It laminated | stacked so that the process surface side might contact, and the double-sided adhesive sheet was obtained.The occurrence of the channeling phenomenon of a separate film was not seen also in this process.

Table 4 shows the characteristics of the double-sided adhesive sheet obtained in Example 11 and the coating solution for forming the silicone rubber adhesive layer (B).

The double-sided pressure-sensitive adhesive sheet obtained in the present example is excellent in transparency, and the silicone rubber pressure-sensitive adhesive layer (B) is firmly adhered to the polyester-based base film (E) via the hot water adhesive property improving layer (E). there was. Moreover, the peeling force of the release layer (C) and silicone rubber adhesion layer (B) was also suitable, and it was a high quality double-sided adhesive sheet. Moreover, the clarity and stability of the coating liquid for forming the silicone rubber adhesion layer (B) in manufacture of a double-sided adhesive sheet were also excellent, and it was confirmed that it was excellent in operation property and operation stability.

Comparative Example 11

In the method of Example 11, the double-sided adhesive sheet was obtained by the method similar to Example 11 except having stopped mix | blending the polymeric wax component and the antistatic agent to the coating liquid (C-1) for forming a release layer (C). . Table 4 shows the results of the evaluation.

Although the double-sided adhesive sheet obtained by this comparative example 11 tried to peel a separator film from the silicone rubber adhesion layer (B), it could not peel. Therefore, it could not be used as a double-sided adhesive sheet.

Example 12

The silicone rubber adhesion layer (B-1) was formed in the same method as Example 1 in the single side | surface of the laminated body (d) manufactured in Example 1. The laminated body (a) manufactured in Example 1 was laminated | stacked on the surface of this silicone rubber adhesion layer (B-1), and the laminated body (k) was obtained. The obtained laminated body k was further continuously introduced into the electron beam irradiation apparatus, and it carried out similarly to Example 1, bridge | crosslinking the silicone rubber adhesion layer (B-1), and obtained the laminated body k '. Using this laminated body k ', the double-sided adhesive sheet was obtained by the method similar to Example 11, and it wound up in roll shape. The occurrence of channeling phenomenon of the separate film was not observed in the manufacturing process. Table 4 shows the results of the evaluation.

The double-sided adhesive sheet obtained in Example 12 had the same characteristics as the double-sided adhesive sheet obtained in Example 11, and was of high quality.

Example 13

Using the double-sided adhesive sheet obtained in Example 11 or 12, the overlay sheet and the coordinate detection sheet which are the face sheets of the capacitive touch panel were bonded together. First, the overlay sheet was stuck to the acrylic adhesive layer F side, and then the coordinate detection sheet was stuck using the silicone rubber adhesion layer (B). The workability of these sticking processes was favorable. In addition, since the silicone rubber adhesion layer (B) was excellent in repair property, even if an adhesion miss occurred, it could be repaired easily. Therefore, generation | occurrence | production of the defective article by the sticking miss was able to be eliminated. For example, when bonding together so that a silicone rubber adhesion layer (B) side might become an overlay sheet, the loss of the overlay sheet by sticking miss was similarly eliminated.

Example 14

Using the double-sided adhesive sheet obtained in Example 11 or 12, the touch panel portion of the resistive touch panel and the display device were bonded together. As in Example 13, the workability of the bonding step was good. For example, when the silicon rubber adhesive layer (B) side was bonded so as to be a display device, similarly to Example 13, the loss of the display device due to sticking miss could be eliminated.

Example 15

Using the silicone compound solution prepared in the same manner as in Example 1, the silicone compound solution was applied to both surfaces of the laminate (a) obtained in Example 1 so as to have a thickness of 25 µm after drying, and then introduced into an oven. Dried at 80 ° C. The laminated body 1 in which the uncrosslinked silicone rubber adhesion layer (B-1) and (B'-1) were formed in both surfaces of the laminated body (a) was obtained.

On the surfaces of the uncrosslinked silicone rubber adhesive layers (B-1) and (B'-1) on both sides of the laminate (l), the laminate (d) (separated films (DC and D'C) obtained in Example 1, respectively. ')) Were pressed while pressing with a crimping roller (pressure 30 N / cm 2) to stack them continuously. The obtained laminated body m was continuously introduced into an electron beam irradiation apparatus, the electron beam was irradiated with energy of 200 KV and 16 Mrad from the surface laminated body d side of (B-1), and an adhesion layer is bridge | crosslinked, The laminated body m 'provided with the adhesion layer B1 after bridge | crosslinking was wound up in roll shape. This laminated body m 'is introduce | transduced again into an electron beam irradiation apparatus, and an electron beam is irradiated with energy of 200 KV and 18 Mrad from the surface laminated body d side of (B'-1), and an adhesion layer is bridge | crosslinked, The laminated body (m ") provided with the adhesion layer (B'1) after crosslinking was wound in roll shape. In the manufacturing process to here, the occurrence of the channeling phenomenon of each separate film was not seen.

The characteristics of the double-sided adhesive sheet obtained in Example 15 and the coating liquid for forming the silicone rubber adhesive layers (B) and (B ') are shown in Table 5.

The double-sided adhesive sheet obtained by the present Example was excellent in transparency. In addition, the silicone rubber adhesive layer (B) is made of a polyester-based adhesive layer (B) through the hot water adhesiveness-improving layer (E), and the silicone rubber adhesive layer (B ') is made of a polyester-based material. It adhere | attached firmly with the base film (A), and was also excellent in adhesiveness and hot water adhesiveness. Moreover, the peeling force of the release layer (C), the silicone rubber adhesion layer (B), and the release layer (C '), and the silicone rubber adhesion layer (B') was also suitable, and it was a high quality double-sided adhesive sheet excellent in peelability. Moreover, the clarity and stability of the coating liquid for forming silicone rubber adhesion layers (B) and (B ') in manufacture of a double-sided adhesive sheet were also excellent, and it was confirmed that it was excellent in operation property and operation stability.

Comparative Example 12

In the method of Example 1, the double-sided adhesive sheet was obtained by the method similar to Example 15 except having stopped mix | blending the polymeric wax component and antistatic agent to the coating liquid (C-1) for forming a release layer (C). . Table 5 shows the results of the evaluation.

Although the double-sided adhesive sheet obtained by this comparative example 12 tried to peel a separate film from silicone rubber adhesion layer (B) and (B '), respectively, it could not peel but was inferior to peelability. Therefore, it could not be used as a double-sided adhesive sheet.

Example 16

Using the double-sided adhesive sheet obtained in Example 15, the overlay sheet and the coordinate detection sheet which are the face sheets of the capacitive touch panel were bonded together. The workability of these sticking processes was favorable. In addition, since the silicone rubber adhesion layer (B) was excellent in repair property, even if an adhesion miss occurred, it could be repaired easily. Therefore, generation | occurrence | production of the defective article by the sticking miss was able to be eliminated. In particular, since the double-sided adhesive sheet of this invention is excellent in repair property to both the adhesive layers of both surfaces, the loss by the adhesion miss of both an overlay sheet and a coordinate detection sheet was able to be eliminated.

Example 17

Using the double-sided adhesive sheet obtained in Example 15, the touch panel portion of the resistive touch panel and the display device were bonded together. As in Example 16, the workability of the bonding step was good. In addition, similarly to the sixteenth embodiment, it was possible to eliminate the loss of the display device and the panel due to the sticking miss.

Example 18

(1) Preparation of single-sided adhesive sheet having anti-scratch layer and silicone rubber adhesive layer

In the same manner as in Example 1, a coating solution (E-1) for a hot water adhesive improved layer was prepared. In the same manner as in Example 1, the polyester base film (A) and the coating solution (E-1) were laminated to each other of the biaxially stretched polyethylene terephthalate base film with a crosslinked hot water of 0.08 μm in thickness. The laminated body n of 12 micrometers in thickness which produced the adhesive improvement layer E was laminated | stacked.

The silicone compound solution prepared in the same manner as in Example 1 was applied to one side of the laminate (n) so that the thickness after drying the silicone compound solution was 25 µm, and then introduced into an oven and dried at 80 ° C. The laminated body o in which the uncrosslinked silicone rubber adhesion layer (B-1) was formed in the single side | surface of the laminated body n was obtained.

While laminating | stacking the laminated body d (separated film) manufactured in Example 1 on the surface of the uncrosslinked silicone rubber adhesion layer of the said laminated body (o), it presses continuously with a pressing roller (pressure 30N / cm <2>), and it laminates continuously It was. The obtained laminated body p was continuously introduced into an electron beam irradiation apparatus, the electron beam was irradiated with energy of 200 KV and 18 Mrad from the separator film side, the adhesion layer was bridge | crosslinked, and the silicone rubber adhesion layer B after crosslinking was made into The laminated body p 'provided was wound up in roll shape. In the manufacturing process so far, the occurrence of the channeling phenomenon of the separate film was not observed.

On the opposite side of the silicone rubber adhesive layer (B ') of the laminated body (p'), the film thickness after drying an ultraviolet curable hard-coat paint ("Seika Beam (registered trademark EXF-01B); Daiichi Seika Industries Co., Ltd.) After coating so that it might become 5 micrometers and drying a solvent, the scratch prevention layer was laminated | stacked by irradiating 800 mJ / cm <2> of ultraviolet-rays with a high pressure mercury lamp. A single-sided adhesive sheet having a scratch prevention layer was obtained. Table 6 shows the evaluation results of the single-sided adhesive sheet.

(2) Production of Transparent Conductive Laminate 2-1 with Transparent Conductive Layer Laminated on Transparent Substrate

0.533 Pa (consisting of 80% by volume of argon gas and 20% by volume of oxygen gas on a non-adhesive treated surface of a polyester film ("Cosmoshine (registered trademark) A4100"; manufactured by Toyo Boseki Co., Ltd .; 75 µm) In a 4 × 10 ^-3 Torr) atmosphere, a transparent conductive layer made of a composite oxide of indium oxide and tin oxide having a thickness of 400 kW was formed by a reactive sputtering method using an indium-tin alloy, thereby providing a transparent conductive laminate (2 -1) was obtained.

(3) Fabrication of upper electrode for touch panel

The separator film of the silicone rubber adhesion layer (B) of the single-sided adhesive sheet which has a scratch prevention layer obtained in the above is peeled, and it adheres to the opposite surface of the transparent conductive layer of the said transparent conductive laminated body 2-1, and is for touch panels An upper electrode was obtained. Workability in this sticking process was favorable. In addition, since the silicone rubber adhesion layer (B) was excellent in repair property, even if an adhesion miss occurred, it could be repaired easily. Therefore, generation | occurrence | production of the defective article by the sticking miss was able to be eliminated.

The pen sliding durability test was done using the said upper electrode for touch panels by the following method. That is, the two upper electrodes are disposed to face each other so that the transparent conductive layers face each other via a spacer having a thickness of 100 µm, and a load of 5.0 N is applied to a polyacetal pen (0.8 mmR). The linear sliding test of 100,000 times (round trip 50,000 times) was performed at 23 degreeC and 44% RH. The sliding distance at this time was 30 mm, and the sliding speed was 60 mm / second.

After the sliding durability test, first, when the sliding portion was whitened by visual observation, no whitening was observed on the electrode. In addition, when the ON resistance (resistance value when the upper and lower electrodes contacted) when the sliding portion was pressed at a pen load of 0.5 N was measured, it was maintained within three times the initial value, and it was confirmed that the pen sliding durability was excellent. .

Comparative Example 13

The scratch prevention layer was carried out similarly to Example 18 except having stopped mix | blending the polymeric wax component and the antistatic agent with the coating liquid for release layer formation (C-1) used when manufacturing a separate film in the method of Example 1. The single-sided adhesive sheet which has a was obtained. Table 6 shows the evaluation results of the single-sided adhesive sheet obtained in Comparative Example 13. Although it was trying to peel a separator film from the silicone rubber adhesion layer of this single-sided adhesive sheet, it could not peel. Therefore, the manufacturing of the upper electrode for the touch panel was stopped.

Comparative Example 14

In the method of Example 18, a single-sided adhesive sheet was obtained in the same manner as in Example 18 except that the application of the coating solution (E-1) for forming a water-resistant water-resistant adhesion-improving layer was stopped, and the upper electrode for the touch panel was obtained. Got it. Table 6 shows the evaluation results of the single-sided adhesive sheet having the scratch prevention layer obtained in Comparative Example 14. This single-sided adhesive sheet was poor in adhesiveness and hot water adhesiveness between the silicone rubber adhesive layer (B) and the polyester base film (A).

When the pen sliding durability test of the upper electrode for touch panels was performed, whitening was not confirmed in the sliding part at 23 degreeC and 44% RH, but whitening was confirmed in the sliding part at 50 degreeC and 65% RH. In addition, ON resistance was maintained within 3 times of the initial value in 23 degreeC and 44% RH, but it was 6 times the initial value in 50 degreeC and 65% RH. The single-sided adhesive sheet WHEREIN: What was bad that hot water adhesiveness was reflected was reflected.

Comparative Example 15

In the method of Example 18, except that the thickness of the water-resistant water-resistant adhesive improvement layer (E) was changed to 0.7 micrometer, the single-sided adhesive sheet which has a scratch prevention layer was obtained by the same method as Example 18, and the upper part for touch panels An electrode was obtained. Table 6 shows the evaluation results of the single-sided adhesive sheet obtained in Comparative Example 15. This single-sided adhesive sheet had poor hot water adhesiveness and was of low quality. When the upper electrode for touch panels was evaluated, the same result as the comparative example 14 was obtained.

Example 19

The laminated body (n) manufactured in Example 18 by the reactive sputtering method using the indium-tin alloy in the atmosphere of 0.533 Pa (4x10 <^-3> Torr) which becomes 80 volume% of argon gas and 20 volume% of oxygen gas. On one surface, a transparent conductive layer made of a composite oxide of indium oxide and tin oxide having a thickness of 400 kPa was formed to obtain a transparent conductive laminate (2-2).

The silicon compound solution prepared in the same manner as in Example 1 was applied to one surface of the transparent conductive laminate 2-2 so that the thickness after drying the silicon compound solution was 25 μm, and then introduced into an oven at 80 ° C. Dried at. The laminated body q in which the uncrosslinked silicone rubber adhesion layer (B-1) was formed in the single side | surface of the transparent conductive laminated body 2-2 was obtained.

While laminating | stacking the laminated body d (separated film) manufactured in Example 1 on the surface of the uncrosslinked silicone rubber adhesion layer of the said laminated body q, it presses continuously by a pressing roller (pressure 30N / cm <2>), and it laminates continuously It was. The obtained laminated body was continuously introduced into an electron beam irradiation apparatus, the electron beam was irradiated with energy of 200 KV and 18 Mrad from the separator film side, the silicone rubber adhesive layer was crosslinked, and the silicone rubber adhesive layer (B) after crosslinking was provided. The single-sided adhesive sheet having one transparent conductive layer was wound in a roll shape. In the manufacturing process so far, the occurrence of the channeling phenomenon of the separate film was not observed. Table 7 shows the characteristics evaluation results of the single-sided adhesive sheet and the coating liquid for forming the silicone rubber adhesive layer (B).

The single-sided adhesive sheet having the transparent conductive layer obtained in the present example was excellent in transparency. Moreover, the silicone rubber adhesion layer (B) was firmly adhere | attached with the polyester-based base film (A) via the heat-resistant water-resistant adhesive improvement layer (E), and was also excellent in adhesiveness and hot-water-water adhesiveness. Moreover, the peeling force of the release layer (C) and silicone rubber adhesion layer (B) was also suitable, and it was a high quality single-sided adhesive sheet excellent in peelability. In addition, the clarity and stability of the coating liquid for forming the silicone rubber adhesive layer (B) in the production of a single-sided adhesive sheet were also excellent, and it was confirmed that the operation performance and the operation stability were excellent.

Example 16

Transparent conducting in the same manner as in Example 19, except that the mixing of the polymer wax component and the antistatic agent into the release layer forming coating solution (C-1) used in the preparation of the separator film in the method of Example 1 was stopped. A single-sided adhesive sheet having a layer was obtained. Table 7 shows the evaluation results of the single-sided adhesive sheet obtained in Comparative Example 16. Although it was trying to peel a separator film from the silicone rubber adhesion layer (B) of this single-sided adhesive sheet, it could not peel. Therefore, the manufacturing of the upper electrode for the touch panel was stopped.

Example 20

(1) Production of laminate 1 having a structure in which a scratch prevention layer was laminated on a transparent substrate

An ultraviolet curable hard coat paint ("SEIKA BEAM (registered trademark) EXF-01B"; manufactured by Daiichi Seika Co., Ltd.) on one side of a polyester film ("Cosmoshine (registered trademark) A4300"; manufactured by Toyo Boseki Co., Ltd .; 75 µm)) After coating so that the film thickness after drying might be set to 5 micrometers and drying a solvent, the laminated body 1 in which the scratch prevention layer was laminated | stacked was obtained by irradiating 800 mJ / cm <2> of ultraviolet-rays with a high pressure mercury lamp.

(2) Preparation of upper electrode for touch panel

The separator film of the single-sided adhesive sheet having the transparent conductive layer obtained in the method of Example 19 was peeled off and bonded to the opposite surface of the scratch prevention layer of the laminate 1 in which the scratch prevention layer was laminated to prepare an upper electrode for a touch panel. It was. The workability of these sticking processes was favorable. In addition, since the silicone rubber adhesion layer (B) was excellent in repair property, even if an adhesion miss occurred, it could be repaired easily. Therefore, generation | occurrence | production of the defective article by the sticking miss was able to be eliminated.

Using the upper electrode for touch panels, the pen sliding durability test was done similarly to Example 18 at 23 degreeC and 44% RH. After this sliding durability test, it was observed visually whether the sliding part was whitening, and the whitening was not seen. In addition, when the ON resistance (resistance value when the upper and lower electrodes contacted) when the sliding portion was pressed at a pen load of 0.5 N was measured, it was maintained within three times the initial value, and it was confirmed that the pen sliding durability was excellent. .

Comparative Example 17

In the method of Example 20, the transparent conductive laminate 2-2 obtained in Example 19 (the laminate before laminating the silicone rubber adhesive layer C) without using a single-sided adhesive sheet having a transparent conductive layer. A pen sliding durability test was conducted in the same manner as in Example 20 except that two sheets were stacked. Whitening was observed in the sliding portion, and the value of the ON resistance was 15 times the initial value, resulting in poor pen sliding durability.

Example 21

(1) Preparation of double-sided adhesive sheet

SK dyne 2094 which is an acrylic adhesive for optics on the surface opposite to the laminated surface of the silicone rubber adhesion layer (B ') of the laminated body (p') which provided the crosslinked silicone rubber adhesion layer (B) manufactured in Example 18 on one side. (Made by Soken Chemical Co., Ltd.) was apply | coated so that the thickness after drying might be set to 25 micrometers, and it dried at 130 degreeC for 3 minutes, and formed the acrylic adhesive layer (F). On the surface of this acrylic adhesive layer F, it laminated | stacks so that the siliconization surface side of the 12 micrometer-separated separate film ("E7002"; product made by Toyo Boseki Co., Ltd.) which becomes a silicon-treated polyethylene terephthalate (D "C") may contact. , Double-sided adhesive sheet was obtained. The characteristics of the obtained double-sided adhesive sheet are shown in Table 8. Also in this process, generation | occurrence | production of the channeling phenomenon of a separate film was not seen.

(2) Preparation of upper electrode for touch panel

The separator film on the acrylic adhesive layer (F) side of the double-sided adhesive sheet obtained above was peeled off, and it stuck on the opposite surface of the transparent conductive layer of the transparent conductive laminated body 2-1 manufactured in Example 18. Next, the separator film on the side of the silicone rubber adhesive layer (B) was peeled off, adhered to the opposite surface of the scratch prevention layer of the laminate 1 in which the scratch prevention layer prepared in Example 20 was laminated, and the upper electrode for the touch panel. Got. Workability in these sticking processes was favorable. In addition, since the silicone rubber adhesion layer (B) was excellent in repair property, even if an adhesion miss occurred, it could be repaired easily. Therefore, generation | occurrence | production of the defective article by the sticking miss was able to be eliminated.

Using the upper electrode for touch panels, the pen sliding durability test was done similarly to Example 18 at 23 degreeC and 44% RH. After this sliding durability test, it was observed visually whether the sliding part was whitening, and the whitening was not seen. In addition, when the ON resistance (resistance value when the upper and lower electrodes contacted) when the sliding portion was pressed at a pen load of 0.5 N was measured, it was maintained within three times the initial value, and it was confirmed that the pen sliding durability was excellent. .

Comparative Example 18

The laminated body 3 and the transparent conductive laminated body were simply not bonded together with the laminated body 3 manufactured in Example 21, and the transparent conductive laminated body 2-1 manufactured in Example 18 with a double-sided adhesive sheet. A pen sliding durability test was conducted in the same manner as in Example 21 except that (2-1) was overlapped, and whitening was confirmed in the sliding portion. Moreover, it turned out that ON resistance is 15 times the initial value, and pen sliding durability is inferior.

Comparative Example 19

In the method of Example 18, a double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 21 except that the coating solution (E-1) for forming a water-resistant water-resistant adhesion-improving layer was stopped, thereby obtaining an upper electrode for a touch panel. Got it. Table 8 shows the evaluation results of the double-sided adhesive sheet obtained in Comparative Example 19. This double-sided adhesive sheet was inferior in the adhesiveness of the silicone rubber adhesion layer (B) and the polyester-based base film (A), and hot-water-water adhesiveness, and was low quality.

When the pen sliding durability test of the upper electrode for touch panels was performed, whitening was not confirmed in the sliding part at 23 degreeC and 44% RH, but whitening was confirmed in the sliding part at 50 degreeC and 65% RH. In addition, ON resistance was maintained within 3 times of the initial value in 23 degreeC and 44% RH, but it was 6 times the initial value in 50 degreeC and 65% RH. In the double-sided adhesive sheet obtained by this comparative example, it was the result which reflected that the hot water adhesiveness was bad.

Comparative Example 20

In the method of Example 18, a double-sided adhesive sheet was obtained in the same manner as in Example 21 except that the thickness of the hot water adhesive resistance improving layer (E) was changed to 0.7 μm, thereby obtaining an upper electrode for a touch panel. Table 8 shows the evaluation results of the double-sided adhesive sheet obtained in this comparative example. This double-sided adhesive sheet had poor hot water adhesiveness and was low quality. When the upper electrode for touch panels was evaluated, the same result as the comparative example 19 was obtained.

Comparative Example 21

The double-sided adhesion was carried out in the same manner as in Example 21 except that the mixing of the polymer wax component and the antistatic agent into the release layer forming coating liquid (C-1) used in the preparation of the separator film in the method of Example 1 was stopped. A sheet was obtained. Table 8 shows the evaluation results of the double-sided adhesive sheet obtained in this comparative example. Although it was trying to peel a separator film from the silicone rubber adhesion layer of this double-sided adhesive sheet, it could not peel. Therefore, the manufacturing of the upper electrode for the touch panel was stopped.

Example 22

In the same manner as in Example 1, a coating solution (E-1) for a hot water adhesive improved layer was prepared. In the same manner as in Example 1, the polyester base film (A) and the coating solution (E-1) were laminated to each other of the biaxially stretched polyethylene terephthalate base film with a crosslinked hot water of 0.08 μm in thickness. A laminate (r) having a thickness of 38 μm on which the adhesion improving layer (E) was laminated was prepared.

In the method for preparing the silicon compound solution of Example 1, the silicon compound solution prepared in the same manner as in Example 1 was changed to one side of the laminate (r) except that the amount of trimethylolpropane trimethacrylate was changed to 1.0 part. It apply | coated so that the thickness after drying might be set to 175 micrometers, it was introduce | transduced into the oven continuously, and it dried at 80 degreeC. The laminated body s in which the uncrosslinked silicone rubber adhesion layer (B-4) was formed in the single side | surface of the laminated body r was obtained.

While laminating | stacking the laminated body d (separated film) manufactured in Example 1 on the surface of the uncrosslinked silicone rubber adhesion layer of the said laminated body s, it presses continuously by a pressing roller (pressure 30 N / cm <2>), and it laminates continuously It was. The obtained laminated body was continuously introduced into an electron beam irradiation apparatus, the electron beam was irradiated with the energy of 700 KV and 18 Mrad from the separator film side, the adhesion layer is bridge | crosslinked, and the lamination | stacking provided with the silicone rubber adhesion layer (B) after bridge | crosslinking. The sieve t was wound up in roll shape. In the manufacturing process so far, the occurrence of the channeling phenomenon of the separate film was not observed.

SK dyne 2094 (manufactured by Soken Chemical Co., Ltd.), which is an acrylic acrylic adhesive, is applied to a surface opposite to the silicon rubber adhesive layer (B) laminated surface of the laminate (t) so that the thickness after drying is 75 μm, and at 130 ° C. It dried for 3 minutes and formed the acrylic adhesive layer (F). On the surface of this acrylic adhesive layer F, it laminated | stacks so that the siliconization surface side of the 38-micrometer-thick separator film (E7002; Toyo Boseki Co., Ltd.) which becomes a silicon-treated polyethylene terephthalate (D "C") may contact | connect, An adhesive sheet was obtained. The characteristic of the obtained double-sided adhesive sheet and the coating liquid for forming a silicone compound adhesion layer are shown in Table 9. Also in this process, generation | occurrence | production of the channeling phenomenon of a separate film was not seen.

The double-sided adhesive sheet obtained in the present Example was excellent in transparency (total light transmittance and haze value). Moreover, the silicone rubber adhesion layer (B) was firmly adhere | attached with the polyester-based base film (A) via the heat-resistant water-resistant adhesive improvement layer (E), and was also excellent in adhesiveness and hot-water-water adhesiveness. Moreover, the peeling force of the release layer (C) and silicone rubber adhesion layer (B) was also suitable, and it was a high quality double-sided adhesive sheet excellent in peelability. Moreover, the clarity and stability of the coating liquid for forming the silicone rubber adhesion layer (B) in manufacture of a double-sided adhesive sheet were also excellent, and it was confirmed that it was excellent in operation property and operation stability.

Comparative Example 22

In the method of Example 22, the double-sided adhesive sheet was obtained like Example 22 except having stopped application | coating of the coating liquid (E-1) for hot water adhesive improvement improved layer formation. Table 9 shows the evaluation results of the double-sided adhesive sheet. This double-sided adhesive sheet was inferior in the adhesiveness of the silicone rubber adhesion layer (B) and the polyester-based base film (A), and hot-water-water adhesiveness, and was low quality.

Comparative Example 23

The double-sided adhesion was carried out in the same manner as in Example 22, except that the mixing of the polymer wax component and the antistatic agent into the release layer forming coating liquid (C-1) used in the preparation of the separator film in the method of Example 1 was stopped. A sheet was obtained. Table 9 shows the evaluation results of the double-sided adhesive sheet. Although it was trying to peel a separator film from the silicone rubber adhesion layer of this double-sided adhesive sheet, it could not peel. Therefore, it could not be used as a double-sided adhesive sheet.

Example 23

[Lamination of Silicone Rubber Compound Adhesive Layer]

Non-reactive silicone compound (KF-96H-1 million cs; Shin) which is substantially free of a reinforcing agent such as silica, and becomes an uncrosslinked polydimethylsiloxane skeleton having a number average molecular weight of 170,000 (measured by GPC method and polystyrene conversion). STS Chemical Co., Ltd.) was weighed so that the mass ratio to toluene was 23%, and the mixture was put into a stirrer with a vacuum degassing apparatus together with toluene, and stirred at room temperature for 15 hours and dissolved in toluene. To the obtained solution, trimethylolpropane trimethacrylate was added so as to 2 parts with respect to 100 parts of the above silicon compound, and after stirring uniformly, a vacuum degassing apparatus was driven to additionally under a vacuum having a gauge pressure of -750 mmHg. Stirred for 20 minutes and defoamed. Subsequently, the silicon compound solution after defoaming is supplied to a roll coater, and the silicon compound solution is apply | coated so that the thickness after drying may be set to 150 micrometers on one side of the laminated body (d) (separated film) manufactured in Example 1, and then It was introduced into an oven and dried at 80 ° C. The laminated body u in which the uncrosslinked silicone rubber adhesion layer was formed in the surface of a separate film was obtained.

On both surfaces of the laminate (r) produced in Example 22, the surface of the uncrosslinked silicone rubber adhesive layer of the laminate (u) was pressed with a pressing roller (pressure 30 N / cm 2) to be laminated continuously. The obtained laminated body was further continuously introduced into the electron beam irradiation apparatus, the electron beam was irradiated with an energy of 700 KV and 18 Mrad from the separator film side to crosslink the silicon compound adhesive layer, and the crosslinked double-sided adhesive sheet after the crosslinking was wound in a roll shape. It was. The irradiation of the electron beam was produced by dividing into two and irradiating each surface. Table 9 shows the evaluation results of the properties of the obtained double-sided adhesive sheet. In the manufacturing process so far, the occurrence of the channeling phenomenon of each separate film was not observed.

The double-sided adhesive sheet obtained in Example 23 had the same properties as those of the double-sided adhesive sheet obtained in Example 22, and was of high quality.

Example 24

In the method of Example 22, the total thickness of the laminate (r) is changed to 125 µm, the thickness of the silicone rubber adhesive layer (B) is changed to 45 µm, and the electron beam irradiation conditions are changed to 200 kV and 18 Mrad. A double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 22 except the above. Table 9 shows the evaluation results of the obtained double-sided adhesive sheet.

The double-sided adhesive sheet obtained in Example 24 had the same characteristics as the double-sided adhesive sheet obtained in Example 22, and was high quality. Table 9 shows the evaluation results of the obtained double-sided adhesive sheet.

Example 25

In the method of Example 24, the double-sided adhesive sheet was obtained by the same method as Example 24 except having changed the thickness of the acryl-type adhesive layer F into 25 micrometers, and performing twice in the electron beam irradiation conditions 200 kV and 18 Mrad. . Table 9 shows the evaluation results of the obtained double-sided adhesive sheet.

Example 26

In the method of Example 22, double-sided adhesion was carried out in the same manner as in Example 22, except that the thickness of the acrylic adhesive layer (F) was changed to 25 μm and the thickness of the silicone rubber adhesive layer (B) was changed to 20 μm. A sheet was obtained. Table 9 shows the evaluation results of the obtained double-sided adhesive sheet.

Example 27

In the method of Example 22, the double-sided adhesive sheet was prepared in the same manner as in Example 22, except that the thickness of the silicone rubber adhesive layer (B) was changed to 75 µm and the electron beam irradiation conditions were changed to 200 kV and 12 Mrad. Got it. Table 9 shows the evaluation results of the obtained double-sided adhesive sheet.

The double-sided adhesive sheet obtained in Example 27 had the same properties as those of the double-sided adhesive sheet obtained in Example 22, and was of high quality.

Example 28

The separator films were peeled from each of the double-sided adhesive sheets of Examples 22 to 27, and the surface protection panel and the image display panel were bonded together. About the double-sided adhesive sheet obtained in Examples 22 and 24-27, the surface protection panel was first stuck to the acryl-type adhesive layer F side, and the image display panel was then stuck to the silicone rubber adhesion layer B side. . In the double-sided adhesive sheet obtained in Example 23, both surfaces of the silicone rubber-based adhesive layer may be attached to the surface protective panel. In this case, the surface protective panel was first adhered, and then the image display panel was adhered. After each affixation, it put into the autoclave and processed for 30 minutes on 50 degreeC and 5 atm conditions.

Workability at the time of sticking was favorable. In addition, since the silicone rubber adhesive layer (B) was excellent in repair property, the image display panel could be easily detached even after gluing occurred or after the sticking operation. Therefore, the loss of the image display panel, which is an expensive member due to incorrect pasting, can be eliminated. On the other hand, in the double-sided adhesive sheet obtained in Example 23, since both surfaces were silicone rubber adhesive layers, and both surfaces were excellent in repairability, the loss by the erroneous pasting of both the surface protection panel and the image display panel was eliminated.

Moreover, when the double-sided adhesive sheet obtained in Examples 22, 23, and 27 is used, the push-elasticity modulus of the silicone rubber adhesive layer (B) is suitable, the shape followability is excellent, and the extrudability of the air which entered In the case where a protective panel having a step of a micrometer order having a light shielding film formed by printing by paint or the like is used on the back surface of the protective panel, for example, as the circumference of the protective panel is circulated in accordance with the screen frame, Even if the step is absorbed and the bubble that enters can be extruded, bubbles do not occur in the stepped portion.

On the other hand, when the double-sided adhesive sheets obtained in Examples 24 to 26 are used, since the push elastic modulus of the silicone rubber adhesive layer (B) is large, the shape followability is slightly inferior to that of the double-sided adhesive sheets of Examples 23 and 27. For this reason, in the case where a large stepped protection panel is used, bubbles may be generated around the stepped portion.

In addition, when using the flat protective panel without a step | step, even if it uses any double-sided adhesive sheet of Examples 22-27, generation | occurrence | production of a bubble and entry | occurrence | production of a bubble are suppressed. In addition, even if bubbles are generated, for example, bubbles are lost due to the expulsion of air with time.

Example 29 and Comparative Example 24

When the surface protection panel of a commercially available cellular phone was removed, and the image display panel and the surface protection panel removed were bonded to each of the double-sided adhesive sheets of Examples 22 to 27 (Example 29), the thickness of this double-sided adhesive sheet The visibility of the image in the case of providing a space between the image display panel and the surface protection panel by the amount (Comparative Example 24) was evaluated. The same image was observed visually, respectively, and the visibility of both images was compared. As a result, the visibility of an image was favorable when it bonded together by a double-sided adhesive sheet (Example 29).

Since the adhesive sheet of this invention is provided with the silicone rubber adhesion layer (B) and adhesion layer (B ') containing the crosslinked silicone compound of the polydimethylsiloxane skeleton which has adhesiveness and re-peelability, for example, Even if there is an adhesion miss, it can be easily peeled off and can be fixed again.

Moreover, the adhesive sheet of this invention is excellent also in the adhesive durability between a silicone rubber adhesion layer (B), an adhesion layer (B '), and a polyester-based base film (A), and is also suitable for a member used under severe conditions. Can be used. In addition, since the peeling force of the separate film laminated | stacked on the surface of the silicone rubber adhesion layer (B) or the adhesion layer (B ') is controlled to an appropriate range, the said channeling phenomenon arises in the process of winding up an adhesive sheet, etc. Since it is suppressed, a high quality adhesive sheet can be produced stably. Moreover, the workability at the time of bonding a member using an adhesive sheet is also excellent.

Moreover, since the adhesive sheet of this invention is rich in the deformation | transformation of the structure, it can apply to various uses. For example, in the case of a single-sided adhesive sheet, it is useful as a surface protection film of a display screen, a part of a touch panel, etc., and in the case of a double-sided adhesive sheet, it is useful for sticking of members in a touch panel or an image display apparatus. Do.

The upper electrode for touch panels of this invention is useful for manufacture of a touch panel. Further, the image display device of the present invention can be applied to a liquid crystal display device (LCD), a plasma light emitting display device (PDP), an organic electro luminescence (organic EL), and the like.

Claims (20)

At least, the polyester-based base film (A), the crosslinked silicone rubber adhesive layer (B), the release layer (C) and the polyester film (D) having a polydimethylsiloxane skeleton are used as a medium or through another layer. As an adhesive sheet laminated in this order without
When the hot water adhesiveness was evaluated by the method defined in the specification, the silicone rubber adhesive layer (B) did not peel off from the polyester-based base film (A) side,
Adhesive sheet, characterized in that the peel strength of the silicone rubber adhesive layer (B) and the release layer (C) is 0.03 ~ 1.0 N / 20 mm. The method of claim 1,
The release sheet (C) is a pressure-sensitive adhesive sheet is a layer containing a binder resin, a polymer wax component and an antistatic agent. The method according to claim 1 or 2,
The adhesive sheet in which the heat-resistant water-resistant adhesive improvement layer (E) is provided between the said polyester base film (A) and the said silicone rubber adhesion layer (B). The method of claim 3,
The pressure-sensitive adhesive sheet, wherein the hot water adhesive resistance improving layer (E) comprises a reaction product of at least one polymer selected from the group consisting of polyester, polyurethane, and acrylic polymer and a crosslinking agent. The method according to claim 3 or 4,
The pressure-sensitive adhesive sheet, wherein the heat-resistant water-resistant adhesive improvement layer (E) is one in which one or more self-crosslinked polymers selected from the group consisting of self-crosslinked polyesters, polyurethanes, and acrylic polymers are self-crosslinked. The method according to any one of claims 1 to 5,
The said silicone rubber adhesive layer (B) is the adhesive sheet containing the silicone rubber which bridge | crosslinked the uncrosslinked silicone compound which has the polydimethylsiloxane frame | skeleton with a number average molecular weights 50,000-500,000. The method according to any one of claims 1 to 6,
The pressure-sensitive adhesive sheet having a push modulus of 0.5 to 20 N / mm 2 measured by the method defined in the specification of the silicone rubber pressure-sensitive adhesive layer (B). The method according to any one of claims 1 to 7,
A pressure-sensitive adhesive sheet having at least one functional layer selected from the group consisting of a scratch prevention layer, an antireflection layer, and an antifouling layer formed on an opposite surface side of the polyester rubber base layer (B) forming surface of the polyester base film (A). . The method according to any one of claims 1 to 7,
The adhesive sheet in which the transparent conductive layer is formed in the opposite surface side of the said silicone rubber adhesion layer (B) formation surface of the said polyester base film (A). The method according to any one of claims 1 to 7,
A crosslinked silicone rubber adhesive layer (B '), a release layer (C'), and a poly-siloxane having a polydimethylsiloxane skeleton on the side opposite to the silicone rubber adhesive layer (B) forming surface of the polyester base film (A) The adhesive sheet in which the ester film (D ') is laminated | stacked in this order, with or without another layer. The method according to any one of claims 1 to 7,
An acrylic adhesive layer (F), a release layer (C "), and a polyester film (D") are other layers on the opposite surface side of the said silicone rubber adhesion layer (B) formation surface of the said polyester base film (A). The adhesive sheet laminated | stacked in this order with or without the medium. The method according to claim 1 or 8,
And the silicone rubber adhesive layer (B) is attached to the display screen of the image display device to protect the display screen. The method according to any one of claims 8 to 11,
Adhesive sheet used as a member of a touch panel. The method according to claim 10 or 11, wherein
Adhesive sheet used for adhering the overlay sheet of the capacitive touch panel and the coordinate detection sheet. The method according to claim 10 or 11, wherein
Adhesive sheet used for adhering the touch panel portion of the resistive touch panel to the display device. A transparent base of a conductive laminate in which a transparent conductive layer is laminated on a transparent base, and a silicone rubber adhesive layer (B) of the pressure-sensitive adhesive sheet of claim 8 are bonded to each other. The transparent base of the functional laminate in which at least one functional layer selected from the group consisting of a scratch prevention layer, an antireflection layer and an antifouling layer is laminated on a transparent base material, and the silicone rubber adhesive layer (B) of the pressure-sensitive adhesive sheet of claim 9 are bonded to each other. The upper electrode for a touch panel, characterized in that. The transparent base material of the functional laminate in which the transparent base material of the conductive laminate in which the transparent conductive layer is laminated on the transparent base material and at least one functional layer selected from the group consisting of a scratch prevention layer, an antireflection layer and an antifouling layer is laminated on the transparent base material, Bonded with the silicone rubber adhesive layer (B) and silicone rubber adhesive layer (B ') of the adhesive sheet of Claim 10, or the silicone rubber adhesive layer (B) and acrylic adhesive layer (F) of the adhesive sheet of Claim 11 Upper electrode for a touch panel, characterized in that. The image display panel and the protective panel for protecting the image display panel may be a silicone rubber adhesive layer (B) and a silicone rubber adhesive layer (B ') of the pressure-sensitive adhesive sheet of claim 10, or the silicone rubber adhesion of the pressure-sensitive adhesive sheet of claim 11 An image display device comprising a layer (B) and an acrylic adhesive layer (F) bonded together. The method of claim 19,
The silicone rubber pressure-sensitive adhesive layer (B) and / or silicone rubber pressure-sensitive adhesive layer (B ') of the pressure-sensitive adhesive sheet has an push modulus of 0.5 to 5 N / mm 2 measured by a method defined in the specification.