TWI500727B - Adhesive sheet, upper electrode for touch panel and image display device - Google Patents

Description

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

The present invention relates to an adhesive layer having excellent adhesion and removability, and the adhesive layer and the base film are excellent in heat-resistant water adhesion, and the adhesive strength of the adhesive layer and the separation film can be appropriately controlled, and The upper electrode for an touch panel and an image display device using the adhesive sheet.

In order to provide the adhesive layer of the adhesive layer as an adhesive layer with excellent adhesion and re-peelability, the adhesive sheet of repeel which is required by us is being used in a wide range of fields. Here, the inventors of the present invention have disclosed various films having a polyoxyalkylene adhesive layer using a polyoxyalkylene rubber compound as a raw material (see, for example, Patent Documents 1 to 4).

The film described in each patent document can be suitably used for various uses. However, in recent years, there has been a situation in which the market demand for quality or price cannot be satisfied at the same time as its use is expanded, and improvement has been gradually sought.

For example, in order to improve the handleability of the above-mentioned adhesive sheet, the separator film is deposited on the surface of the adhesive layer, and the separator film is peeled off and attached to the target article for use in actual use, but there is a strong demand depending on the use. The peeling force should be reduced. However, when the peeling force of the separator film is too small, in the step of manufacturing the pressure-sensitive adhesive sheet, the film is floated at the portion where the film is wound, and the air layer enters in a direction orthogonal to the sheet winding direction. There is a so-called channeling phenomenon. Further, in optical applications, although it is highly transparent to the adhesive sheet and its stability, it is difficult to cope with it.

Moreover, although the polyoxyalkylene rubber raw material disclosed in the above patent document is a millable polyoxyalkylene rubber compound, such a compound has a low solubility in a storage state with respect to a solvent, and is coated. In the case of a polyoxyalkylene rubber layer, the appearance of the product may be lowered due to the undissolved material. In addition, the coating liquid obtained by dissolving the polyoxane rubber compound in a solvent causes gelation of the solution depending on the storage state, and it cannot be used as a coating liquid, and has various problems in quality stabilization or stable production. The obstacles to the response to the reduced cost requirements, and the resolution of these issues is strongly expected.

On the other hand, in the patent document, there is disclosed a double-sided adhesive sheet in which an acrylic adhesive layer is formed on the opposite side of a polyoxyalkylene rubber layer in which the polyoxyalkylene rubber layer is used as an adhesive layer of an adhesive layer as a touch type. The panel member is used (see, for example, Patent Document 5).

In the above-mentioned two-sided adhesive sheet, the adhesive layer formed of the polyoxyalkylene rubber layer has the same problem as the adhesive sheet in which the polyoxyalkylene rubber layer is used as the adhesive layer. Further, in Patent Document 5, there is no detailed description of the method for forming the adhesive layer of the polyoxyalkylene rubber, and there is no mention of any means for solving the problem. Further, the adhesion to the substrate is not specifically described, and the corona treatment exemplified does not provide sufficient adhesion under the above-mentioned excessive use conditions.

However, the touch panel has been recognized as an excellent input method, and is used in various aspects such as bank ATMs, vending machines for ticket sales, portable information terminals, game machines, and car navigation systems. In the touch panel, a transparent electrode is necessary. It is conventionally used for glass on a substrate. However, recently, a transparent conductive film having a transparent conductive layer on the surface of a plastic film has been proposed.

For the transparent conductive film, if it is used as the upper electrode, for example, it is a conductive layer that serves as an electrode and a substrate that supports the conductive layer, and then is resistant to friction when input by a hand or a dedicated pen. Hard coating layer. For example, Patent Document 6 discloses a transparent conductive film in which a plastic film, a cured layer, and a transparent conductive film are laminated. However, in this document, a film which is an input surface (hard coating layer) and transparent conductive are used. The film is bonded to the electrode of the touch panel by an adhesive. Further, Patent Document 7 discloses a laminate in which a plastic film having a hard coating layer and a transparent conductive film having a transparent conductive film are bonded together by a transparent adhesive layer.

In this case, in the case where layers which are necessary for the electrode for a touch panel are laminated, it is often necessary to use an adhesive layer. Since the components for the touch panel are expensive, they are peeled off when the adhesive layer is bonded and fixed, and the adhesive layer which is re-peelable again can be desired. . Further, when an adhesive layer having a cushioning property is used, it is also known that the durability (pen sliding resistance) with respect to the pressing force of the touch panel can be improved.

From this, it is known that we have considered the use of polyoxyalkylene rubber as an adhesive for a member for a touch panel. In particular, when a double-sided adhesive sheet having a polyoxyalkylene rubber adhesive layer is used, a plastic film having a hard coat layer can be easily bonded to a transparent conductive film having a transparent conductive film. However, the adhesion of the polyoxyalkylene rubber to a plastic film substrate such as polyethylene terephthalate is not sufficient. If the adhesion between the adhesive layer and the film substrate is poor, peeling occurs at the joint, and there is a problem that power cannot be supplied even if it is touched. Moreover, in the case where the touch panel is used in a car navigation system or the like, the environment inside the vehicle may be under a relatively high temperature and high humidity, and it is necessary to withstand the harsh conditions, especially in the adhesive layer. There is room for improvement in adhesion durability to the substrate film.

On the one hand, in an image display device such as a liquid crystal display device (LCD), a plasma light-emitting display device (PDP), or an organic electroluminescence (EL), in the case where any impact is applied to the surface thereof, in order to cause an impact The image display panel provided with the image display device is not damaged, and a protective panel is provided on the surface of the image display panel. Further, an air layer is provided between the image display panel and the protective panel, and the impact applied to the image display device is dispersed/absorbed to prevent damage of the image display panel.

However, since the air layer is disposed between the image display panel and the protective panel, since the light reflection due to the difference in refractive index between the air layer and the protective panel is large, light scattering by sunlight or backlight reduces brightness or contrast. There will be problems with poor visibility.

In order to solve the above problems, there is a method of filling an elastic layer of an air layer between an image display panel and a protective panel. For example, it is disclosed that the image display panel and the protective panel are made of at least one layer or more of a sheet-like transparent adhesive. An image display device in which impact resistance and visibility are improved by close contact (see, for example, Patent Document 8).

However, the above-mentioned transparent adhesive material is not elastic, and it may be difficult to assemble a transparent adhesive material in an image display device. Further, when the transparent display material of the image display panel or the protective panel is stuck, there is a case where a bubble is bite into, and when the penetration of the bubble occurs, the transparent adhesive is reapplied. When a part of the transparent adhesive remains on the image display panel or the protective panel, there is a case where a so-called residual glue occurs. Further, the transparent adhesive material may have a problem of thinning the image display device due to its thickness.

[Patent Document 1] Japanese Patent Publication No. 11-320762

[Patent Document 2] JP-A-2000-56694

[Patent Document 3] JP-A-2001-83886

[Patent Document 4] JP-A-2001-139903

[Patent Document 5] JP-A-2003-150316

[Patent Document 6] JP-A-2007-59360

[Patent Document 7] JP-A-2007-234424

[Patent Document 8] JP-A-2003-29644

Therefore, in the present invention, the adhesiveness or various characteristics of the adhesive layer of the polyoxyalkylene oxide and the substrate film are provided, especially the hot water adhesive property is excellent, and the peeling force of the adhesive layer of the polyoxynethane and the separation film can be appropriately controlled. Adhesive sheets, and particularly the subject of the present invention, disclose an adhesive sheet which can utilize such properties while having various configurations suitable for the purpose.

The adhesive sheet of the present invention which solves the above problems is a crosslinked polyoxyalkylene rubber adhesive layer (B) having a polydimethylsiloxane skeleton at least in accordance with a polyester base film (A), and a release mold The order of the layer (C) and the polyester film (D) is laminated with or without other layers, and is characterized in that

When the hot water adhesion is evaluated by the method defined in the present specification, the polyoxyalkylene rubber adhesive layer (B) is not peeled off from the polyester base film (A) side, and

The peeling strength of the polyoxyalkylene rubber adhesive layer (B) and the release layer (C) is 0.03 to 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 to provide a hot water resistant adhesion improving layer (E) between the polyester base film (A) and the polyoxyalkylene rubber adhesive layer (B). In this case, the hot water-resistant water-improving layer (E) contains one or more polymers selected from the group consisting of polyesters, polyurethanes, and acrylic polymers, and a crosslinking agent. The self-crosslinking is carried out by containing one or more kinds of self-crosslinking polymers selected from the group consisting of self-crosslinking type polyesters, polyurethanes, and acrylic polymers. The situation is better.

The polyoxyalkylene rubber adhesive layer (B) is a crosslinked polyoxyxene containing an uncrosslinked body of a polyoxyalkylene compound having a polydimethylsiloxane skeleton having a number average molecular weight of 50,000 to 500,000. Alkane rubber is preferred. In this case, the polyadoxane rubber adhesive layer (B) preferably has a embossing modulus of 0.5 to 20 N/mm ² as measured by the method defined in the present specification.

The adhesive sheet of the present invention may be formed on the opposite side of the surface on which the polyoxyalkylene rubber adhesive layer (B) of the polyester-based base film (A) is formed, and may be formed of an anti-damage layer and an anti-reflection layer. One or more functional layers of the group formed by the layer and the anti-contamination layer.

Further, a transparent conductive layer may be formed on the side opposite to the surface on which the polyoxyalkylene rubber adhesive layer (B) is formed on the polyester base film (A).

The adhesive sheet of the present invention may have a polydimethyl siloxane skeleton on the opposite side to the surface on which the polyoxyalkylene rubber adhesive layer (B) is formed on the polyester base film (A). The crosslinked polyoxyalkylene rubber adhesive layer (B'), the release layer (C') and the polyester film (D') are adhered to each other in this order with or without other layers interposed therebetween.

Moreover, the adhesive sheet of the present invention may be on the opposite side to the surface on which the polyoxyalkylene rubber adhesive layer (B) is formed on the polyester base film (A), and may be in accordance with the acrylic adhesive layer (F). The order of the release layer (C") and the polyester film (D") is adhered to both sides of the laminate with or without the other layers interposed therebetween.

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

Moreover, the adhesive sheet of the present invention can also be used as a member of a touch panel. In this case, the double-sided adhesive sheet of the present invention can be used for attaching the facing sheet of the electrostatic capacitive touch panel to the coordinate detecting sheet, and can also be used for the touch panel portion and display of the resistive film type touch panel. The device is attached.

In the present invention, the upper electrode for a touch panel is bonded, and the upper electrode is bonded to a transparent substrate in which a conductive laminate of a transparent conductive layer is laminated on a transparent substrate, and the present invention in which the functional layer is formed. Adhesive sheet of polyoxyalkylene rubber adhesive layer (B).

Further, the present invention also includes an upper electrode for a touch panel, wherein the upper electrode is laminated on the transparent substrate, and one layer selected from the group consisting of a damage prevention layer, an antireflection layer, and an antifouling layer The transparent substrate of the functional laminate obtained from the above functional layer, and the polyoxyalkylene rubber adhesive layer (B) of the adhesive sheet of the present invention having the transparent conductive layer formed thereon.

Further, the present invention relates to an upper electrode for a touch panel, characterized in that the double-sided adhesive sheet having a polyoxyalkylene rubber adhesive layer (B) and a polyoxyalkylene rubber adhesive layer (B'), or The adhesive layer of the two-sided adhesive sheet having the polyoxyalkylene rubber adhesive layer (B) and the acrylic adhesive layer (F) is bonded to the conductive laminated body in which the transparent conductive layer is laminated on the transparent substrate. The transparent substrate is a transparent substrate in which a functional layered body of one or more functional layers selected from the group consisting of a damage prevention layer, an antireflection layer, and an antifouling layer is laminated on the transparent substrate.

In the present invention, there is provided an image display device which is a polyoxyalkylene rubber adhesive layer having the above-mentioned two-sided adhesive sheet of a polyoxyalkylene rubber adhesive layer (B) and a polyoxyalkylene rubber adhesive layer (B'). (B) and (B'), or a polyoxyalkylene rubber adhesive layer (B) having an adhesive layer of a polyoxyalkylene rubber (B) and an acrylic adhesive layer (F), and an acrylic adhesive layer (F), the image display panel is attached to the protective panel that protects the image display panel. In this case, the polyoxyalkylene rubber adhesive layer (B) and/or (B') preferably has a embossing modulus of 0.5 to 5 N/mm ² as measured by the method defined in the specification.

The adhesive sheet of the present invention can be formed, and comprises a polyoxyalkylene rubber adhesive layer (B) of a crosslinked polyoxyalkylene compound having both a tacky and releasable polydimethyloxane skeleton or Since the adhesive layer (B') is adhered to, for example, even if it is missed, it can be easily peeled off and can be reattached again. Moreover, since the adhesive sheet of the present invention has high transparency, it can be suitably used as an optical member.

Further, the adhesive sheet of the present invention has excellent adhesion durability between the polyoxyalkylene rubber adhesive layer (B) or the adhesive layer (B') and the polyester base film (A), even as a severe condition The components used can also be used as appropriate. Further, the peeling force of the separator film laminated on the surface of the adhesive layer of the polyoxyalkylene rubber (B) or the adhesive layer (B') is controlled to an appropriate range, and the step of winding the adhesive sheet or the like is suppressed. The occurrence of channeling phenomenon enables stable production of high quality adhesive sheets. Moreover, the workability at the time of bonding a member using an adhesive sheet is also excellent.

Further, in the adhesive sheet of the present invention, it is preferred that the uncrosslinked body of the polyoxymethane compound of the polydimethylsiloxane skeleton is crosslinked to form a polyoxyalkylene rubber adhesive layer, in which case, Comparing the case of a polyoxyalkylene rubber compound having a conventionally rollable polyoxyalkylene rubber compound as a raw material, the adhesive layer formed is excellent in transparency or clarity, and is operated in the case of producing an adhesive sheet. Sex is also excellent. Therefore, the cost efficiency is superior to the well-known method.

Further, since the adhesive sheet of the present invention is rich in variations in its constitution, it can be applied to various uses. For example, if it is a single-sided adhesive sheet, it is useful as a surface protection film or a touch panel of a display screen. If it is a double-sided adhesive sheet, the members are in the touch panel or the image display device. It is useful to stick to each other. Further, the one-sided adhesive sheet means that the adhesive layer is present only on one side of the base film, and the double-sided adhesive sheet means that the adhesive layer exists on both sides of the base film.

For example, when the adhesive sheet of the present invention is used as a film for surface protection of a display screen, it is easy to peel off even if it is accidentally lost, and it is possible to stick it again. Moreover, since the adhesive sheet of the present invention has high transparency, the surface protective film for an optical member can also be suitably used.

In the upper electrode for a touch panel of the present invention, since an adhesive sheet having a polyoxyalkylene rubber adhesive layer having both adhesiveness and re-peelability is used, it may be missed. The adhesive sheet is easily removed and can be reattached again. Moreover, by having the elasticity of the adhesive layer of the polyoxyalkylene rubber, since the touch panel can be provided with good cushioning properties, the pen sliding resistance of the touch panel can be improved.

In the image display device of the present invention, the image display panel and the protective panel are bonded together by the double-sided adhesive sheet, whereby the air in the space of the image display panel and the protective panel is eliminated, so that the visibility can be improved. Moreover, it is easy to attach or re-peel, and it is possible to suppress the loss due to incorrect sticking of both the surface protection panel and the image display panel. In particular, since the image display panel is expensive, its economic effect is extremely large.

Further, as described above, the adhesive sheet of the present invention is excellent in adhesion durability between the polyoxyalkylene rubber adhesive layer (B) or (B') and the polyester base film (A), and even in the above-described use method The use of a problem in which the polyoxyalkylene rubber adhesive layer (B) or (B') is peeled off from the polyester base film (A) or the like is caused in an excessively harsh environment. Further, when manufacturing a touch panel or an image display device, it is easy to adhere and re-peel as described above, and the touch panel or the image display device is decomposed into components after use in an excessively harsh environment, even if In the case of recycling, etc., workability is also excellent.

The best form of implementing the invention

The adhesive sheet of the present invention is characterized in that it is at least a polyester-based base film (A), a crosslinked polyoxyalkylene rubber adhesive layer (B) having a polydimethylsiloxane skeleton, and a release mold. The layer (C) and the polyester film (D) are laminated, and the laminated sheets are laminated with or without other layers, wherein the above-mentioned polymerization is evaluated when the heat-resistant water adhesion is evaluated by the method defined in the present specification. The silicone rubber adhesive layer (B) is not peeled off from the polyester base film (A) side, and the peel strength of the above-mentioned polyoxyalkylene rubber adhesive layer (B) and the above release layer (C) is controlled. Specific range. In the following, each layer will be described separately.

[Polyester base film (A) and polyester film (D)]

In the case of the polyester base film (A) and the polyester film (D), polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate (PBT), etc. The main component (80% by mass or more) can be used arbitrarily. The use of biaxially stretched compounds is desired. The method for producing the biaxially stretched polyester film is not particularly limited. For example, the polyester is supplied to a known melt extruder after being dried as needed, and is extruded into a sheet shape by a slit-like mold, and electrostatically applied. The film is adhered to the casting drum in the same manner, and is cooled and solidified to obtain an unstretched sheet, and the unstretched sheet can also be stretched. In the method of biaxial stretching, it may be either a simultaneous biaxial stretching or a sequential biaxial stretching. In the polyester base film (A), a known adhesion improving treatment such as corona treatment, flame treatment, or plasma treatment can be performed.

The thickness of the polyester base film (A) is not particularly limited, and is preferably about 10 to 300 μm, more preferably 15 to 260 μm. When the hardness is less than 10 μm, the mechanical strength is insufficient, which is not preferable because of difficulty in handling. On the other hand, when the thickness exceeds 300 μm, it is too thick, and it is not suitable for carrying a portable device or the like.

The polyester film (D) is combined with the release layer (C) to form a film for a separator film. The thickness of the polyester film (D) is preferably about 10 to 150 μm. More preferably, it is 15 to 75 μm. When the film thickness is less than 10 μm, the mechanical strength is insufficient, and it is not preferable because the treatment becomes difficult. On the other hand, when the thickness exceeds 150 μm, the strength is sufficiently uneconomical, and when the film is peeled off, the handleability is also lowered.

[Polyoxyalkylene rubber adhesive layer (B)]

The adhesive sheet of the present invention has a polyoxyalkylene rubber adhesive layer (B). The polyoxyalkylene rubber is excellent in removability and re-adhesiveness, and is excellent in elasticity, and can impart cushioning properties to the member to be used.

The crosslinked polyoxyalkylene rubber adhesive layer (B) of the polydimethyl siloxane skeleton is a crosslinked polyoxy siloxane compound containing a polydimethyl siloxane skeleton as a main component (70% by mass) The above is more preferably 90% by mass or more, and still more preferably 100% by mass. In particular, as the crosslinked polyoxyalkylene compound having a polydimethylsiloxane skeleton, it is preferred to crosslink an uncrosslinked body having a number average molecular weight (Mn) of 50,000 to 500,000. The Mn of the uncrosslinked body is preferably from 80,000 to 400,000, more preferably from 100,000 to 350,000.

The solubility or fluidity to the solvent can be ensured by using the uncrosslinked body of the polyoxyalkylene compound, so that the formation of the polyoxyalkylene rubber adhesive layer (B) is easy. It is appropriate that the Mn of the uncrosslinked body is 50,000 or more because crosslinking property can be improved. Moreover, the control of the indentation modulus is easy. When the Mn of the uncrosslinked body is 500,000 or less, it is possible to suppress deterioration of workability during production such as excessive increase in viscosity of the coating liquid. Therefore, the formation of a layer of the uncrosslinked body of the polyoxyalkylene compound, followed by crosslinking is an appropriate embodiment.

The raw material of the conventional polyoxyalkylene rubber is a rollable polyoxyalkylene rubber compound, and such a compound has a reduced solubility in a solvent due to its storage state, and when the polyoxyalkylene rubber layer is coated, there is a A situation in which the appearance quality is lowered due to undissolved matter. Further, the coating liquid obtained by dissolving the polyoxyalkylene rubber compound in a solvent may cause gelation of the solution depending on the state of storage, and may not be used as a coating liquid. In the case where the above-mentioned uncrosslinked polyoxyalkylene compound is used and a conventionally-rollable polysiloxane compound is used as a raw material, quality, quality stability, and workability at the time of production are dominant.

In the case of the uncrosslinked polyoxyalkylene compound which satisfies the above, for example, a commercially available product of polyoxyxylene oil can be used. In the case of using polyoxyxylene oil, it is preferred to use a non-reactive dimethylpolyphthalic acid oil in the pure polyoxyxene oil. Thereby, the crosslinked polyoxyalkylene compound has a polydimethylsiloxane skeleton. Since the cross-linking property of the methyl phenyl type polyoxo-oxygen oil is lowered, the storage stability of the reactive methyl hydrogen-containing polyoxo-oxygen oil is poor, and the quality or workability is adversely affected, and if not When it is 30% by mass (more preferably, it is less than 5% by mass), it may be used in combination with a methyl phenyl form or a methyl hydrogen form or various modified forms, and does not have a polydimethyl siloxane skeleton. A siloxane compound.

Further, the above-mentioned uncrosslinked polyoxyalkylene compound is preferably a polyoxyalkylene alkane skeleton-containing polyoxyalkylene compound as long as it is less than 10% by mass, but it is preferably as small as possible. It is preferred to use a polyoxyalkylene compound having no polyalkylenyloxyalkylene skeleton and only a polyoxymethane compound having a polydimethyloxane skeleton.

The polyoxyalkylene rubber adhesive layer (B) in the present invention may contain a reinforcing agent such as cerium oxide as long as it does not impair the effects of the present invention, but is particularly preferably completely free of a reinforcing agent.

The polyoxyalkylene rubber adhesive layer (B) may contain an adhesion improver for improving the polyoxyalkylene rubber adhesive layer (B) and the polyester base film (A). Or the adhesive strength of the hot water-resistant water-improving layer (E) to be described later so that the polyoxyalkylene rubber adhesive layer (B) is hardly peeled off. In terms of the adhesion improver, it is preferred to use a compound having an active reactive group with respect to a radical reaction. In the case of the compound, a (meth)acrylic acid derivative, an allyl derivative or the like can be exemplified, and it is preferred to have two or more unsaturated bonds, particularly three or more derivatives. These compounds can be widely used as a co-crosslinking agent of rubber, and examples thereof include esters of polyhydric alcohols and (meth)acrylic acid, allyl esters of polycarboxylic acids, triallyl isocyanurate, and three. Allyl cyanurate or the like.

The ester of the above-mentioned polyol and (meth)acrylic acid is an ester compound in which two or more alcoholic hydroxyl groups of a polyol having two or more alcoholic hydroxyl groups are esterified with (meth)acrylic acid. Specifically, for example, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol (meth)acrylate, 1, 6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,2'-bis[4-(methyl)propenyloxydiethoxyphenyl]propane , glycerol di(meth) acrylate, glycerol tri(meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl alcohol di (meth) acrylate, neopentyl alcohol three ( Methyl) acrylate, neopentyl alcohol tetra (meth) acrylate, tetramethylol methane di(meth) acrylate, tetramethylol methane tri(meth) acrylate, tetramethylol tetra ( A methyl acrylate, a dimer diol di(meth) acrylate or the like is preferable, and a compound containing three or more (meth) acryl fluorenyl groups is particularly preferable. Further, the above compounds are exemplified by the respective individual ester compounds of acrylic acid and methacrylic acid, but may also be in the form of a mixed ester of acrylic acid and methacrylic acid.

Further, examples of the allyl ester of a polyvalent carboxylic acid include diallyl phthalate, diallyl 1,2,4,-benzenetricarboxylate, and tetraallyl pyromellitate.

The above-mentioned adhesiveness improver may be used alone or in combination of two or more. Further, the adhesion improving agent used in the invention is not limited to the above-exemplified compounds.

The amount of the above-mentioned adhesiveness improving agent is preferably 0.2 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polyoxyalkylene compound component. The blending amount of the tackifier is set to 0.2 parts by mass or more, whereby the effect of improving the heat-resistant water adhesion of the adhesive layer is made larger. On the other hand, when the amount of the adhesion improving agent is more than 20 parts by mass, not only the effect of improving the heat-resistant water adhesion is saturated, but conversely, the effect is further deteriorated.

The lower limit of the thickness of the polyoxyalkylene rubber adhesive layer (B) is preferably 3 μm from the point of adhesion, preferably 5 μm, more preferably 8 μm. On the other hand, the upper limit of the thickness of the polyoxyalkylene rubber adhesive layer (B) is determined from the viewpoint of economy, and the range in which the undercut elastic modulus or the adhesive force can be stably maintained is determined. For example, the upper limit of the thickness is preferably 200 μm, more preferably 180 μm.

In the present invention, the method for forming the polyoxyalkylene rubber adhesive layer (B) is not limited, and the uncrosslinked polyoxyalkylene compound is dissolved or dispersed in a solvent, and if necessary, an adhesion improving agent is added to prepare a coating. The liquid is applied by a coating method and then subjected to a crosslinking treatment to form an appropriate embodiment.

For example, the uncrosslinked polyoxygenated oil is preferably dissolved in an aromatic hydrocarbon such as toluene, so that it is preferably dissolved in the solvent by a coating method. When the uncrosslinked polyoxyxene oil is used, the plasticizing step of the compound caused by the necessary kneading or the like is not required when the conventional meltable type of the polyoxyalkylene rubber compound is dissolved in a solvent. Further, the storage stability of the obtained coating liquid is good, and the viscosity-increasing phenomenon such as gelation which is common in the preparation of the solution of the polyoxyalkylene rubber compound does not occur. Further, in the solution of the polyoxyalkylene rubber compound, there is a possibility that the formation of foreign matter due to the undissolved polysiloxane rubber compound can be suppressed, so that the coating liquid having high clarity can be obtained. .

The polyoxyalkylene rubber adhesive layer (B) is, for example, a coating liquid containing the above polyoxyxylene oil or the like, on the surface of the polyester base material film (A), or the polyester base material film (A). Coating the surface of the hot-water-resistant adhesion improving layer (E) formed on the surface or the surface of the release layer (C) formed on the surface of the polyester film (D), and then laminating or not laminating other layers for crosslinking treatment It can be formed.

The crosslinking method of the polyoxyalkylene compound may be, for example, thermal crosslinking such as peroxide crosslinking or addition reaction crosslinking, or may be cross-linking due to high energy active rays such as electron beam or γ-ray. . It is believed that when the active line is irradiated with a polyoxyalkylene compound, hydrogen is extracted from the methyl group of the polydimethyloxane, similarly between the polyoxyalkylene compound adjacent to the hydrogen extracted from the methyl group. A cross-linking reaction is produced. Therefore, in the crosslinking method by the active line, it is necessary to prevent the radical from occurring in the peroxide of the polyoxyalkylene compound or the like, or an additive such as a catalyst for crosslinking. Therefore, the contamination of the adherend due to the residue of the additives can be suppressed, and the adhesive which can be re-peeled is an appropriate crosslinking method. In the thermal crosslinking, the crosslinking agent is necessary. Due to the blending of the crosslinking agent, it is necessary to gradually harden after heating, so that the processability is remarkably lowered, or the gelation may be impossible depending on the case. The problem of pot life, and the method of cross-linking due to active lines does not consider such a problem. Further, in the crosslinking of the peroxide or the cross-linking of the addition reaction, it is not easy to cause the usual crosslinking reaction to become non-uniform. Further, since cross-linking is completed in a short time and efficiently, there is an advantage of productivity improvement and the like.

Among the active rays, the electron beam crosslinking method is suitable from the viewpoint of easily obtaining an irradiation device (EB irradiation device) or easily controlling the degree of crosslinking. The electron beam irradiation amount in the EB irradiation device is preferably in the range of 5 to 50 Mrad. When the amount of electron beam irradiation is 5 Mrad or more, the crosslinking reaction of the polyoxyalkylene compound can be promoted, and the residual gel with respect to the binder can be reduced at the time of re-peeling, and the re-peelability can be improved. On the other hand, when the amount of electron beam irradiation is set to 50 Mrad or less, the decrease in the adhesiveness due to excessive crosslinking reaction or the increase in the elastic modulus of the undercut can be suppressed.

In the case of sticking to the adhesive, the lower limit of the adhesive force of the adhesive layer of the polyoxyalkylene rubber (B) is 0.01 N/20 mm in terms of the reliability at the time of use. The stretching speed is preferably 300 mm/min, more preferably 0.05 N/20 mm. On the other hand, in terms of improving the removability and ensuring good removability, the upper limit of the adhesive strength of the polyoxyalkylene rubber adhesive layer (B) is preferably 1.0 N/20 mm, more preferably 0.5 N/ 20mm. Further, in the case of evaluation by the above evaluation method, the adhesive layer does not remain on the glass surface, that is, it is preferable that the residue is not repellent.

In the present invention, it is important that the polyoxyalkylene rubber adhesive layer (B) is firmly adhered to the polyester base film (A). In other words, it is necessary to prevent the polyoxyalkylene rubber adhesive layer (B) from being peeled off from the polyester base film side. For example, a cutter knife is inserted between the polyester base film (A) and the polyoxyalkylene rubber adhesive layer (B), and the tearing (dividing interface) is performed by applying a force to the finger. It is better to connect the strength firmly and not to separate the interface. In the proper aspect of the present invention, there is a heat-resistant water adhesion improving layer (E) between the polyester-based base film (A) and the polyoxyalkylene rubber adhesive layer (B), and the heat-resistant water adhesion property The thickness of the modified layer (E) is thin, so the true interface in the above-mentioned separation interface is not likely to be analyzed, and is not clear. In short, the polyoxyalkylene rubber adhesive layer (B) and the polyester base material film (A) are firmly bonded, and it is preferable to separate the interface. Hereinafter, in the present invention, the above characteristics are simply referred to as adhesion.

Further, it is preferable to maintain the above-mentioned adhesiveness even when the adhesive sheet of the present invention is stored in hot water for a long period of time. Specifically, it is preferable that the polyoxyalkylene rubber adhesive layer (B) is not peeled off when evaluated by the hot water adhesion evaluation method shown below. Hereinafter, the adhesive hot water durability is also referred to as hot water adhesion.

[heat resistant water adhesion]

Next, a method for evaluating the heat-resistant water adhesion property which is an important effect of the adhesive sheet of the present invention will be described.

In the case of measuring the heat-resistant water adhesion of the polyoxyalkylene rubber adhesive layer (B), the adhesive sheet was cut into 50 mm × 50 mm to peel off the separator film of the polyoxyalkylene rubber adhesive layer (B). In a 500 cc capped cylindrical glass container to which 400 cc of distilled water was placed, the sample was submerged in water so that the polyoxyalkylene rubber adhesive layer (B) became the lower side, and the sample was immersed in water. The container is covered with a lid. In the case where only the weight of the sample itself is not immersed in water, for example, a polyester film of 60 mm × 60 mm and a thickness of 188 μm is placed on the sample to obtain a weight. The size or material of the weight is not particularly limited as long as the entire sample is immersed in water. The container filled with the sample was placed in a gear oven set at 80 ° C and allowed to stand for 24 hours. After the heat treatment, the container was taken out from the oven, and the sample was taken out immediately, and the end portion was applied from the side of the adhesive layer (B) of the polyoxyalkylene rubber rubber to the end portion and wiped 10 times to evaluate whether or not the adhesive layer (B) of the polyoxyalkylene rubber rubber was evaluated. When the polyester base material film (A) side was peeled off, the polyoxyalkylene rubber adhesive layer (B) was not peeled off, and the polyoxyalkylene rubber adhesive layer (B) peeled off was ×.

The evaluation method of the heat-resistant water adhesion is that the adhesive sheet is a single-sided adhesive sheet, or the adhesive sheets on both sides are the same. If the sample is a double-sided adhesive sheet, it is preferable to evaluate the heat-resistant water adhesion of the polyoxyalkylene rubber adhesive layer (B).

In the heat-resistant water-adhesive property, if the adhesive layer of the polyoxyalkylene rubber adhesive layer (B) is not peeled off, for example, a member such as a touch panel for a car navigation system is used, and even if it is exposed to high temperature and humidity In the following, since the interfacial surface of the interface between the polyoxyalkylene rubber adhesive layer (B) and the polyester base film (A) can be suppressed, the reliability of the device can be improved, and at the same time, after being used for a long period of time in an excessively harsh environment It is excellent in workability such as decomposition into various components.

[heat-resistant water adhesion improving layer (E)]

In the evaluation of the above-mentioned heat-resistant water adhesion of the adhesive sheet of the present invention, in order to prevent the polyoxyalkylene rubber adhesive layer (B) from being peeled off, the polyester-based base film (A) and the polyoxyalkylene rubber adhesive layer ( It is preferable to provide a heat-resistant water adhesion improving layer (E) between B). The thickness of the hot water-resistant water-improving layer (E) is preferably 0.01 to 0.5 μm. When the thickness of the hot water-resistant water-improving layer (E) is 0.01 to 0.5 μm, good heat-resistant water adhesion can be exhibited. However, in the above range, the heat-resistant water adhesion is lowered (the measurement method described later cannot be ○) It is not good. The thickness is preferably in the range of 0.03 to 0.4 μm, more preferably 0.05 to 0.3 μm.

As a heat resistant water adhesion improving layer (E), a crosslinked polymer layer (crosslinked polymer layer) is suitable, and in the case of a layer in which a polymer is crosslinked by a crosslinking agent, self-crossing is useful. The case of a layer of a linked polymer.

The polymer which can be used in the method of crosslinking by a crosslinking agent is not particularly limited, and is preferably at least one selected from the group consisting of polyester, polyurethane, and acrylic polymer. The above polymers may be used singly or in combination of two or three different types.

[Polyester for heat-resistant water adhesion improving layer (E)]

Since the above polyester has an ester bond in the main chain or the side chain, it is obtained by polycondensing a polyvalent carboxylic acid and ethylene glycol.

As the polyvalent carboxylic acid component constituting the polyester, an aromatic, aliphatic, alicyclic dicarboxylic acid or a trivalent or higher polyvalent carboxylic acid or such an ester derivative can be used.

For the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, ortho citric acid, 2,5-dimethyl terephthalic acid, 1,4-naphthalene dicarboxylic acid, biphenyl group can be used. Carboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,2-bisphenoxyethane-p,p'-dicarboxylic acid, phenylindane dicarboxylic acid, and the like. In terms of the strength or heat resistance of the hot water-resistant water-improving layer (E), the aromatic dicarboxylic acid is preferably used in an amount of 30 mol% or more based on 100 mol% of the polyvalent carboxylic acid component. It is preferably 35 mol% or more, more preferably 40 mol% or more of polyester.

Further, as the aliphatic and alicyclic dicarboxylic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentane can be used. Dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like, and such ester-forming derivatives.

As the ethylene glycol component of the polyester, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butane can be used. Alcohol, 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, neopentyl glycol, 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'-thiodi Phenol, bisphenol A, 4,4'-methylene diphenol, 4,4'-(2-sub-lower Diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidene phenol, 4,4'-isopropylidene diol, cyclopentane -1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, and the like.

Further, in the case where the polyester is used as a coating liquid, it is easy to make the polyester water-soluble or water-dispersible, and the carboxylic acid (salt)-containing compound contains a sulfonic acid (salt) group. The compound, the phosphonic acid group-containing compound or the like is preferably copolymerized.

The compound containing a carboxylic acid (salt) group may, for example, be 1,2,4,-benzenetricarboxylic acid, 1,2,4,-benzenetricarboxylic anhydride, pyromellitic acid, pyromellitic anhydride, or 4 -Methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentane Tetracarboxylic acid, 3,3',4,4'-diphenyl ketone tetracarboxylic acid, 5-(2,5-dicarbonyltetrahydroindenyl)-3-methyl-3-cyclohexene-1, 2-dicarboxylic acid, 5-(2,5-dicarbonyltetrahydroindenyl)-3-cyclohexene-1,2-dicarboxylic acid, cyclopentanetetracarboxylic acid, 2,3,6,7- Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol trimellitate, 2,2',3,3'-diphenyltetracarboxylic acid, thiophene-2,3 , 4,5-tetracarboxylic acid, ethylene tetracarboxylic acid, etc., or such alkali metal salts, alkaline earth metal salts, ammonium salts and the like.

As the compound containing a sulfonic acid (salt) group, for example, sulfo terephthalic acid, 5-sulfoisodecanoic acid, 4-sulfoisodecanoic acid, 4-sulfonaphthalene-2,7-dicarboxylate can be used. An acid, a sulfo-p-xylene glycol, a 2-sulfo-1,4-bis(hydroxyethoxy)benzene or the like, or an alkali metal salt, an alkaline earth metal salt or an ammonium salt.

As the compound containing a phosphonic acid group, for example, phosphoric acid terephthalic acid, 5-phosphoisophthalic acid, 4-phosphoric acid, 4-phosphonate-2,7-dicarboxylic acid, phosphoric acid can be used. A base-p-xylene glycol, a 2-phospho-1,4-bis(hydroxyethoxy)benzene or the like, or an alkali metal salt, an alkaline earth metal salt or an ammonium salt.

Further, in the present invention, for the polyester, for example, a modified polyester copolymer such as a block copolymer modified with acrylic acid, a urethane or an epoxy group, or a graft copolymer may be used.

In the case of an appropriate polyester, as the acid component, terephthalic acid, isophthalic acid, sebacic acid, or 5-sodium sulfoisophthalic acid may be exemplified, and as the diol component, it may be exemplified. A copolymer selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, and neopentyl glycol. In the case where water resistance is necessary, a copolymer obtained by substituting 1,2,4,-benzenetricarboxylic acid for sodium 5-sulfoisophthalic acid as a copolymerization component can be suitably used.

The above polyester can be produced by the following production method. For example, the dicarboxylic acid component is made of terephthalic acid, isophthalic acid, or 5-sodium sulfoisophthalic acid, and the diol component is ethylene glycol or neopentyl glycol. These monomers are directly subjected to an esterification reaction, or a method in which the first stage of the transesterification reaction is carried out, and the second stage of the polycondensation reaction of the first stage reaction product is produced.

In this case, for example, an alkali metal, an alkaline earth metal, manganese, cobalt, zinc, ruthenium, osmium, a titanium compound or the like can be used as the reaction catalyst.

In addition, the method of the polyester having a carboxyl group at the terminal and/or the side chain is disclosed in JP-A-54-46294, JP-A-60-209073, JP-A-62-240318 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is described in the publication of the publication No. 62-240318, etc., that a trivalent or higher polyvalent carboxylic acid is copolymerized and produced, and of course, it may be a method other than these.

Further, for the water-dispersible polyester resin, for example, a commercially available "Vylonal (registered trademark)" series (manufactured by Toyobo Co., Ltd.) can be used.

The intrinsic viscosity of the polyester is not particularly limited, and the point of adhesion is preferably 0.3 dl/g or more, more preferably 0.35 dl/g or more, and most preferably 0.4 dl/g or more. The glass transition temperature (hereinafter, abbreviated as Tg) of the polyester is preferably 0 to 130 ° C, more preferably 10 to 85 ° C.

By using a polyester having a Tg of 0 ° C or higher, the heat-resistant water adhesion can be improved, and the hot water-resistant water-improving layer (E) can be suppressed by laminating the surface of the polyester-based base film (A). A blocking phenomenon such as when winding at one end. Further, by using a polyester having a Tg of 130 ° C or less, the stability or water dispersibility can be maintained satisfactorily.

[Polyurethane for heat-resistant water adhesion improving layer (E)]

Next, the polyurethane is described. The polyurethane having a urethane bond is not particularly limited, and the main component is a polymer obtained by polymerizing a polyhydric alcohol compound with a polyisocyanate compound.

As the polyol compound, for example, polyethylene glycol, polypropylene glycol, polyethylene/propylene glycol, polybutanediol, hexanediol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, Triethylene glycol, polycaprolactone, polyhexyl adipate, polybutylene adipate, trimethylolpropane, trimethylolethane, glycerin, acrylic polyol, and the like.

Further, as the polyisocyanate compound, for example, toluene diisocyanate, exohexyl diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate, an adduct of toluene diisocyanate and trimethylolpropane, and exohexyl diisocyanate can be used. An adduct with trimethylolethane or the like.

In the synthesis of the polyurethane, a well-known chain extender or a crosslinking agent may be contained in addition to the above-mentioned polyol compound and polyisocyanate compound. As the chain extender or crosslinking agent, ethylene glycol, propylene glycol, butane didiol, diethylene glycol, ethylene diamine, diethylene ethyltriamine or the like can be used.

In order to obtain a stable aqueous dispersion of polyurethane, it is preferred to synthesize a polyurethane having a high water affinity, and specifically, an anionic group may be introduced into the polyurethane. For example, in a method of using a compound having an anionic group, a method of reacting an unreacted isocyanate group of a produced polyurethane with a compound having an anionic group, or using a method using a compound having an anionic group, for example, in a polyalcohol, a polyisocyanate, a chain extender, or the like A method in which a base of an active hydrogen of a polyurethane is reacted with a specific compound or the like is produced.

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

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

Further, for example, in the case of a polyurethane aqueous dispersion, a "Hydran (registered trademark)" series (manufactured by Dainippon Ink and Chemicals, Inc.) can also be used.

[Acrylic polymer for heat-resistant water adhesion improving layer (E)]

In order to constitute a monomer component of the above acrylic polymer, for example, an alkyl acrylate or an alkyl methacrylate (alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, or the like) may be used. Isobutyl, tert-butyl, 2-ethylhexyl, lauryl, stearyl, cyclohexyl, phenyl, benzyl, phenylethyl, etc.; 2-hydroxyethyl (meth)acrylate, a hydroxyl group-containing monomer such as 2-hydroxypropyl (meth)acrylate; (meth) acrylamide N-methyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N a guanamine-containing monomer such as N-dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-phenyl (meth) acrylamide; An amine group-containing monomer such as N,N-diethylaminoethyl (meth)acrylate; an epoxy group-containing monomer such as glycidyl (meth)acrylate; (meth)acrylic acid and the like The monomer containing a carboxyl group or a salt thereof, etc., such as a salt (a lithium salt, a sodium salt, a potassium salt, etc.), may be used for (co)polymerization using one type or two or more types. Further, these other types of monomers can be used in combination.

In the case of other kinds of monomers, an epoxy group-containing monomer such as allyl epoxidized propyl ether; styrene sulfonic acid, ethylene sulfonic acid and the like (lithium salt, sodium salt, potassium) can be used. a salt containing a sulfonic acid group and the like, such as a salt, an ammonium salt, or the like; crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like (lithium salt, sodium salt, Monomers containing carboxyl groups or salts thereof such as potassium salts, ammonium salts, etc.; anhydride-containing monomers such as maleic anhydride and itaconic anhydride; ethylene isocyanate, allyl isocyanate, styrene, and vinyl methyl ether , vinyl ethyl ether, ethylene three alkoxy decane, alkyl maleic acid monoester, alkyl fumarate monoester, acrylonitrile, methacrylonitrile, alkyl itaconic acid monoester, Vinylene chloride, vinyl acetate, vinyl chloride, and the like.

Further, as the acrylic polymer, a modified acrylic polymer such as a block copolymer or a graft copolymer modified with a polyester, a polyurethane, an epoxy resin or the like can be used.

The lower limit of the Tg of the acrylic polymer in terms of heat-resistant water adhesion or sticking resistance is preferably -10 ° C, the lower limit is 0 ° C, and the lower limit is 10 ° C. On the other hand, the upper limit of the Tg of the acrylic polymer in terms of heat-resistant water adhesion or film-forming property is preferably 90 ° C, more preferably 50 ° C, and most preferably 40 ° C. Further, the weight average molecular weight (Mw) of the acrylic polymer is preferably 50,000 or more, more preferably 300,000 or more, and the point of heat-resistant water adhesion is desirable.

The acrylic polymer is preferably selected from the group consisting of methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, acrylamide, N-methylol acrylamide, A copolymer of a group of monomers of acrylic acid or the like.

The acrylic polymer is dissolved in water and emulsified or suspended. As a user of the aqueous liquid, it is preferable in terms of environmental pollution or explosion-proof property at the time of coating. Such a water-based acrylic polymer may be copolymerized with a monomer having a hydrophilic group (acrylic acid, methacrylic acid, acrylamide, ethylenesulfonic acid, a salt thereof, or the like) or emulsified by a reactive emulsifier or an surfactant. It is produced by a method such as polymerization, suspension polymerization, or non-soap polymerization.

Further, a commercially available acrylic emulsion may be used, and for example, "Joncryl (registered trademark)" series (manufactured by BASF Corporation, Japan) may be used.

[Reagent used in hot water adhesion improving layer (E)]

In the present invention, the polyester, the polyurethane, and the acrylic polymer are preferably crosslinked. In the case where the above-mentioned polymer is crosslinked by using a crosslinking agent, a cross-linking reaction can be carried out using a functional group such as a carboxyl group, a hydroxyl group, a hydroxymethyl group, a decylamino group or the like which is present in the above-mentioned polymer. Things. For example, a melamine-based crosslinking agent, an oxazoline-based crosslinking agent, an isocyanate-based crosslinking agent, an aziridine-based crosslinking agent, an epoxy-based crosslinking agent, a methylolated or an alkanolated urea can be used. A acrylamide-based, polyamine-based resin, a guanamine epoxy compound, various decane coupling agents, various titanate coupling agents, and the like. In particular, the melamine-based crosslinking agent and the oxazoline-based crosslinking agent can be suitably used in terms of compatibility with the above polymer or heat-resistant water adhesion.

The melamine-based crosslinking agent is not particularly limited, and a methylolated melamine derivative obtained by condensing melamine, melamine, and formaldehyde can be used to partially or completely etherify a lower alcohol by reacting a lower alcohol with methylolated melamine. Or such mixtures and the like. Further, as the melamine-based crosslinking agent, a condensate of a monomer or a polymer of two or more polymers or a mixture thereof may be used. As the etherified lower alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol or the like can be used. Further, a methylolated melamine resin such as methylated trimethylol melamine or butylated hexamethylol melamine is preferred. Further, since the thermal curing of the melamine-based crosslinking agent can be promoted, an acidic catalyst such as p-toluenesulfonic acid can be used.

Further, the oxazoline-based crosslinking agent is not particularly limited as long as the functional group is an oxazoline group, and at least one or more oxazoline group-containing monomers are contained, and at least one or more It is preferred that one of the other monomers is copolymerized to obtain an oxazoline group-containing copolymer.

In the case of a monomer containing an oxazoline group, 2-vinyl-2-oxazoline, 2-ethylene-4-methyl-2-oxazoline, 2-ethylene-5-methyl-2-oxo can be used. Oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc. These one or a mixture of two or more kinds may be used. Among them, 2-isopropenyl-2-oxazoline is industrially easy to purchase.

In the copolymer containing an oxazoline group, if at least one other monomer used together with the oxazoline group-containing monomer is a monomer copolymerizable with the oxazoline group-containing monomer, It is not particularly limited, and for example, (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate may be used. Or methacrylates; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid; unsaturated nitriles such as (meth)acrylonitrile; (meth) acrylamide, N - unsaturated decylamines such as hydroxymethyl (meth) acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; and olefins such as ethylene and propylene Classes; halogen-containing α,β-unsaturated monomers such as ethylene chloride, vinyl chloride, and fluorinated ethylene; α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene Alternatively, one or a mixture of two or more kinds may be used.

Further, in the case of a polymer containing an oxazoline group, for example, "Epocros (registered trademark)" series (manufactured by Nippon Shokubai Co., Ltd.) is commercially available.

The isocyanate-based crosslinking agent is not particularly limited as long as it has an isocyanate group as a functional group in the compound, and it is preferably used as a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule.

The polyfunctional isocyanate compound can be obtained by using a low molecular or high molecular aromatic, aliphatic diisocyanate or a trivalent or higher polyisocyanate. As the polyisocyanate, butyl diisocyanate, hexyl diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate can be used. Isophorone diisocyanate and a terpolymer of the isocyanate compounds. Further, an excess amount of the isocyanate compound may be exemplified by low molecular weight active hydrogen such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine or triethanolamine. A compound or a polymer active hydrogen compound such as a polyester polyol, a polyether polyol, or a polydecylamine is reacted to obtain a terminal isocyanate group-containing compound.

Further, in the case where an isocyanate compound is used as the crosslinking agent, a blocked isocyanate compound can also be used. The blocked isocyanate is prepared by subjecting the above isocyanate compound and a blocking agent to an addition reaction by a conventionally known method.

Examples of the isocyanate blocking agent include phenols such as phenol, cresol, xylenol, resorcin, nitrophenol, and chlorophenol; thiophenols such as thiophenol and methylthiophenol. ; anthraquinones such as acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime; alcohols such as methanol, ethanol, propanol, butanol; halogen substitutions such as chlorohydrin and 1,3-dichloro-2-propanol; Alcohols; tertiary alcohols such as tertiary butanol and tertiary pentanol; decylamine such as ε-caprolactam, δ-valeroguanamine, γ-butylide, β-propionamide Classes; aromatic amines; quinone imines; active methylene compounds such as acetoacetone, acetamidine acetate, ethyl malonate; mercaptans; imines; ureas; Base compounds; hydrogen sulfite soda and the like.

The epoxy group-based crosslinking agent is not particularly limited as long as it has an epoxy group as a functional group in the compound, and it is preferred to use a polyfunctional epoxy compound having two or more epoxy groups in one molecule. .

In terms of polyfunctional epoxy compounds, there are, for example, diglycidyl ether of bisphenol A and oligomers thereof, diepoxypropyl ether of hydrogenated bisphenol A and oligomers thereof, o-nonanoic acid epoxide Propyl ester, diepoxypropyl isophthalate, diepoxypropyl terephthalate, diepoxypropyl p-hydroxybenzoate, diepoxypropyl tetrahydrophthalate, hexahydroquinone Diethylene oxide propyl ester, diepoxypropyl succinate, diepoxypropyl adipate, diepoxypropyl sebacate, ethylene glycol diepoxypropyl ether, propylene glycol bicyclo Oxypropyl propyl ether, 1,4-butanediol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether and polyalkylene glycol diepoxypropyl ether, 1,2, Tris-propyl benzoate, trisepoxypropyl iso-cyanate, 1,4-diepoxypropyl hydroxybenzene, diglycidyl propylene urea, glycerol triglycol Alkyl ether, trimethylolpropane triepoxypropyl ether, neopentyl alcohol triepoxypropyl ether, triglycidyl ether of a glycerol epoxide adduct, and the like.

As the crosslinking agent, a phenol formaldehyde resin which is an alkylated phenol or phenol or the like, and a formaldehyde condensate such as urea, melamine, benzoguanamine, and the like may be used. An amine-based resin such as an alkyl ether compound formed from an alcohol having 1 to 6 carbon atoms.

In terms of phenol formaldehyde resin, there are, for example, alkylated (methyl, ethyl, propyl, isopropyl or butyl) phenol, p-tert-amyl phenol, 4,4'-second-butylene phenol, three-stage Butylphenol, o-, m-, p-cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl- a condensate of phenols such as o-cresol, p-phenylphenol or xylenol with formaldehyde.

As the amino resin, there are, for example, methoxylated methylol urea, methoxylated methylol N, N-ethylene urea, methoxylated methylol dicyanamide, methoxylated methylol Melamine, methoxylated hydroxymethylbenzoguanamine, butoxylated methylol melamine, butoxylated hydroxymethylbenzoguanamine, etc., preferably methoxylated methylol melamine, Butoxylated methylol melamine and methylolated benzoguanamine.

The above polymer (polyester, polyurethane, acrylic polymer) and a crosslinking agent may be used in combination at any ratio, and in order to make the heat-resistant water adhesion effect of the present invention more prominent, it is relative to polymerization. The amount of the crosslinking agent is preferably 2 parts by mass or more and 50 parts by mass or less, more preferably 3 to 25 parts by mass, based on 100 parts by mass of the crosslinking agent. When the amount of the crosslinking agent added is less than 2 parts by mass, the effect of addition is small, and when it exceeds 50 parts by mass, the heat-resistant water adhesion tends to be lowered.

[self-crosslinking polymer of heat-resistant water adhesion improving layer (E)]

In the present invention, in addition to the above-described method, it is preferred to form the hot water-resistant water-improving layer (E) by using, for example, a self-crosslinking polymer obtained by introducing a crosslinkable functional group into the polymer. The crosslinking method in the case of using a self-crosslinking type polymer may be, for example, thermal crosslinking, or may be cross-linking due to a high-energy active line such as ultraviolet rays, electron beams, and γ-rays.

Hereinafter, as a self-crosslinking type polymer, a specific method will be exemplified in the case of a polyester.

The self-crosslinking type polyester which can be suitably used in the present invention is a polyester-based graft copolymer obtained by grafting a compound having at least one radical polymerizable double bond to a hydrophobic copolymerized polyester. The "grafting" of the polyester-based graft copolymer in the present invention means a branched polymer formed by a polymer which is different from the main chain in a dry polymer which is a main chain. The graft polymerization is usually carried out by dissolving a hydrophobic copolymerized polyester in an organic solvent, and reacting at least one radical polymerizable monomer using a radical initiator. Hydrophobic copolyester is a polyester which is not dissolved in water and is inherently water-insoluble, so it is used as a dry polymer when it is used as a graft polymerization. It is excellent in heat-resistant water adhesion.

The hydrophobic copolyester is in the range of 100 mol% of the dicarboxylic acid component, the aromatic dicarboxylic acid is 60-99.5 mol%, the aliphatic dicarboxylic acid and/or the alicyclic dicarboxylic acid is 0-39.5 m. %, the dicarboxylic acid containing a radical polymerizable double bond is preferably 0.5 to 10 mol%. More preferably, the aromatic dicarboxylic acid is 68 to 98 mol%, the aliphatic dicarboxylic acid and/or the alicyclic dicarboxylic acid is 0 to 30 mol%, and the dicarboxylic acid having a polymerizable unsaturated double bond is 2 to 2 7 moles %.

The aromatic dicarboxylic acid is 60 mol% or more, and when the aliphatic dicarboxylic acid and/or the alicyclic dicarboxylic acid is 39.5 mol% or less, the hot water resistance is good. Further, by using 0.5 mol% or more of the dicarboxylic acid containing a radical polymerizable double bond, the grafting efficiency with respect to the radical polymerizable monomer of the polyester resin can be improved. On the other hand, it is set at 10 mol% or less to suppress a significant increase in the viscosity of the reaction solution after the grafting reaction, since the reaction can be uniformly performed.

As the aromatic dicarboxylic acid, the aliphatic and/or alicyclic dicarboxylic acid, any of the compounds exemplified herein can be used. Examples of the dicarboxylic acid containing a radically polymerizable double bond include α, β-unsaturation of fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and the like. Dicarboxylic acid; 2,5-lower An alicyclic dicarboxylic acid or the like containing an unsaturated double bond such as an alkenyldicarboxylic anhydride or a tetrahydrofurfuric anhydride. In the dicarboxylic acid containing the polymerizable unsaturated double bonds, in terms of polymerizability, fumaric acid, maleic acid, 2,5-lower Alkenyldicarboxylic acid is preferred.

Any of the exemplified compounds can also be used as the diol component. It is also possible to use two or more kinds of diol components. Among them, an aliphatic diol having 2 to 10 carbon atoms and an alicyclic diol having 6 to 12 carbon atoms are preferred.

In the hydrophobic copolymerized polyester, 0 to 5 mol% of a trifunctional or higher polycarboxylic acid and/or a polyalcohol may be copolymerized. In terms of a trifunctional or higher polycarboxylic acid, there are 1,2,4,-benzenetricarboxylic acid (anhydride), pyromellitic acid (anhydride), diphenylketonetetracarboxylic acid (anhydride), trimesic acid, and ethylene. Alcohol bis (dehydrated trimellitate), glycerol (dehydrated trimellitate) and the like. Further, as the trifunctional or higher polyalcohol, glycerin, trimethylolethane, trimethylolpropane, neopentylol or the like can be used.

The tricarboxylic acid or higher polycarboxylic acid and/or polyalcohol is copolymerized in an amount of from 0 to 5 mol%, preferably from 0 to 3 mol%, based on the total acid component or the total diol component, and if it is in this range It can inhibit gelation during polymerization.

Further, the weight average molecular weight of the hydrophobic copolymerized polyester is preferably 5,000 in terms of the hot water adhesion. Further, in terms of gelation at the time of polymerization, etc., the upper limit is preferably 50,000.

After the hydrophobic copolyester is synthesized, graft polymerization is carried out. The graft polymerization is carried out by dissolving at least one radical polymerizable monomer using a radical initiator in a state in which the hydrophobic copolymerized polyester is dissolved in an organic solvent. Further, the reaction product after completion of the graft reaction may contain, in addition to the graft copolymer of the hydrophobic copolymerized polyester and the radical polymerizable monomer, a hydrophobic copolymerized polyester which does not undergo grafting, and A (co)polymer obtained by grafting a radically polymerizable monomer of a hydrophobic copolymerized polyester. The polyester-based graft copolymer in the present invention is not only the above-mentioned polyester-based graft copolymer, but also includes a reaction mixture containing: a hydrophobic copolymerized polyester which does not undergo grafting, and is not grafted. A (co)polymer and a monomer (residual monomer) are obtained from a radical polymerizable monomer.

In the present invention, the acid value of the reactant obtained by graft-polymerizing a radical polymerizable monomer to a hydrophobic copolymerized polyester is 600 eq/10 ⁶ g or more in terms of heat-resistant water adhesion. good. More preferably, the acid value of the reactant is 1200 eq/10 ⁶ g or more. When the acid value of the reactant is less than 600 eq/10 ⁶ g, there is a case where the heat-resistant water adhesion is lowered.

Further, it is suitable for the purpose of the present invention that the mass ratio of the desired hydrophobic copolymerized polyester to the radically polymerizable monomer is in the range of polyester/radical polymerizable monomer = 40/60 to 95/5. It is expected that it is 55/45 to 93/7, and most desirably is in the range of 60/40 to 90/10.

When the mass ratio of the hydrophobic copolymerized polyester is 40% by mass or more, the excellent adhesion of the polyester can be exhibited. On the other hand, when the mass ratio of the hydrophobic copolymerized polyester is 95% by mass or less, the sticking resistance is improved, and the acid value of the reactant can be adjusted to the above range.

The graft polymerization reaction product is in the form of a solution or dispersion of an organic solvent or a solution or dispersion of an aqueous solvent. In particular, the dispersion of the aqueous solvent, that is, the form of the aqueous dispersion is preferably in the working environment and coating properties. Therefore, in terms of the radically polymerizable monomer to be grafted, it is preferred to use a radically polymerizable monomer which must contain a hydrophilic radical polymerizable monomer. Next, after graft polymerization is carried out in an organic solvent, the organic solvent is distilled off, and when water is added, an aqueous dispersion can be obtained.

The hydrophilic radically polymerizable single system means a radical polymerizable monomer having a hydrophilic group or having a group which can become a hydrophilic group later. The radical polymerizable monomer having a hydrophilic group may, for example, be a radical polymerizable monomer containing a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphite group, a sulfonic acid group, a guanamine group, or a fourth-order ammonium salt group. . On the other hand, the radical polymerizable monomer having a group which can be changed to a hydrophilic group may, for example, be a radical polymerizable monomer containing an anhydride group, a glycidyl group or a chloro group. Among these, in terms of water dispersibility, a carboxyl group is preferred, and a radical polymerizable monomer having a carboxyl group or a group having a carboxyl group is preferred.

In order to make the acid value of the graft reactant within the above-mentioned appropriate range, it is preferred to contain a carboxyl group or a radical polymerizable monomer having a group having a carboxyl group. The monomer may, for example, be fumaric acid or monoethyl fumarate; maleic acid and its anhydride, monoethyl maleate; itaconic acid and its anhydride, itaconic acid Monoester; acrylic acid, methacrylic acid; and such salts (sodium, potassium, ammonium) and the like. Preferred is maleic anhydride. The above monomers may be copolymerized by using one type or two or more types.

The radically polymerizable monomer to be grafted may contain other kinds of monomers while setting the acid value as much as possible in the above range. For other types of monomers, the monomers available for the synthesis of the acrylic polymer can be used as they are.

As the graft polymerization initiator to be used in the present invention, there are, for example, organic peroxides or organic azo compounds which are well known to those skilled in the art. The organic peroxide may, for example, be a phenylhydrazine peroxide, a tertiary butyl peroxytrimethylacetate or an organic azo compound, and may have, for example, 2,2'-azobisisobutyronitrile. 2,2'-azobis(2,4-dimethylvaleronitrile). The amount of the polymerization initiator to be used in the graft polymerization is at least 0.2% by mass or more, preferably 0.5% by mass or more based on the radical polymerizable monomer.

In addition to the polymerization initiator, a chain transfer agent for adjusting the chain length of the branched polymer, such as octyl mercaptan, mercaptoethanol, 3-tributyl-4-hydroxyanisole, can be used as needed. . In this case, it is desirable to add a range of 0 to 5% by mass based on the polymerizable monomer.

The graft reaction product is preferably neutralized with a basic compound, and water dispersion can be easily performed by neutralization. In the case of a basic compound, a compound which is vaporized at the time of coating formation is expected, and ammonia, an organic amine or the like is suitably used. Suitable compounds are, for example, triethylamine, N,N-diethylethanolamine, N,N-dimethylethanolamine, aminoethanolamine, N-methyl-N,N-diethanolamine, isopropylamine. , imino bispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, secondary butylamine, propylamine, methyl Aminopropylamine, dimethylaminopropylamine, methylimidopropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, and the like.

The basic compound is expected to be in the range of 5.0 to 9.0 of the pH of the aqueous dispersion by at least partially neutralizing or completely neutralizing the carboxyl group content contained in the graft reaction product. When a basic compound having a boiling point of 100 ° C or less is used, the amount of residual basic compound in the coating after drying is small, and the hot water adhesion can be improved under a severe environment such as high temperature or high humidity.

The weight average molecular weight of the radically polymerizable monomer polymer is preferably from 500 to 50,000 in the graft reaction product. It is generally difficult to control the weight average molecular weight of the radical polymerizable monomer polymer to less than 500, and the grafting efficiency is lowered, and the hydrophilicity of the copolymerized polyester tends to be insufficient. Further, the graft polymer of the radical polymerizable monomer forms water and a layer of the dispersed particles, and in order to obtain a water and a layer having a sufficient thickness and a stable aqueous dispersion, the radical polymerizable monomer is graft-polymerized. The weight average molecular weight of the substance is expected to be 500 or more.

The weight average molecular weight of the radical polymerizable monomer graft polymer is preferably 50,000 in terms of polymerizability in solution polymerization. In order to set the weight average molecular weight of the graft polymer of the radical polymerizable monomer to be in the range of 500 to 50,000, the dose may be appropriately combined, the monomer dropping time, the polymerization time, the reaction solvent, the monomer composition or, if necessary, It is preferred to carry out a chain transfer agent or a polymerization inhibitor.

The glass transition temperature of the graft copolymer is not particularly limited, and is preferably 20 ° C or higher, and more preferably 40 ° C or higher in consideration of heat resistant water adhesion.

In the present invention, a reactant obtained by graft-polymerizing a radical polymerizable monomer to a hydrophobic copolymerized polyester has self-crosslinkability because a hydroxyl group in the polyester reacts with a carboxyl group present in the graft portion. In addition, it is not crosslinked at normal temperature, but is an intermolecular reaction such as a hydrogen radical extraction reaction by a thermal radical, and is crosslinked without a crosslinking agent, by heat during drying at the time of coating formation. Thereby, a high degree of heat-resistant water adhesion can be exhibited. The degree of crosslinking of the coating can be evaluated by various methods, and examples thereof include a method of measuring the ratio of insoluble matter such as a chloroform solvent in which both the hydrophobic copolymerized polyester and the grafted polymer are dissolved.

The ratio of the insoluble matter to be applied by heat treatment at about 80 ° C for 5 minutes at 120 ° C is preferably 50% by mass or more, more preferably 70% by mass, in terms of heat-resistant water adhesion and adhesion resistance. the above.

For example, a commercially available product such as "Vylonal (registered trademark) AGN702) (manufactured by Toyobo Co., Ltd.) can be used as the self-crosslinking type polyester resin aqueous dispersion.

Further, the grafted polyurethane can be prepared in a manner similar to the above.

[Additive for heat-resistant water adhesion improving layer (E)]

In the hot water-resistant water-improving layer (E), various additives such as an antioxidant, a heat-resistant stabilizer, a weathering stabilizer, an ultraviolet absorber, an organic slip agent, and a pigment may be blended in such a range as not to impair the effects of the present invention. , dyes, organic or inorganic particles, fillers, antistatic agents, nucleating agents, and the like.

In particular, when the inorganic particles are added to the hot water-resistant water-improving layer (E), for example, the polyester-based base film (A) surface layer heat-resistant water-adhesive improving layer (E) is wound at one end. It is good because it can improve the slipperiness or sticking resistance. In this case, as the inorganic particles to be added, cerium oxide, colloidal cerium oxide, aluminum oxide, alumina sol, kaolin, talc, mica, calcium carbonate or the like can be used. The inorganic particles to be used preferably have an average particle diameter of 0.005 to 5 μm, more preferably 0.01 to 3 μm, most preferably 0.05 to 2 μm. The amount of the inorganic particles to be used is not particularly limited, and is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the polymer in the hot water-resistant water-improving layer (E).

[Formation method of heat-resistant water adhesion improving layer (E)]

The hot water-resistant water-improving layer (E) is selected from the group consisting of a mixture of one or more polymers and a crosslinking agent composed of the above-mentioned polyester, polyurethane, and acrylic polymer. Since the body or the aqueous dispersion of the self-crosslinking type polymer is formed, it is the easiest to form by the coating method. On the surface of the predetermined laminated polyoxyalkylene rubber adhesive layer (B) of the polyester base film (A), the coating liquid for the hot water resistant adhesion improving layer (E) can be applied. The unstretched film applied to the polyester base film (A), followed by stretching in at least one direction, coating after longitudinal stretching, and coating on the surface of the film subjected to alignment treatment Wait, any method can do. In the case of producing the polyester base film (A), the coating is applied before the crystal alignment of the film is completed, and thereafter, after stretching in at least one direction, the crystal alignment of the polyester film is completed, that is, the so-called in-line coating. The method is easy to form a film, so that the effect of the present invention can be remarkably exhibited. Further, in the present invention, in addition to the case where the transparent conductive layer is formed on the other surface, it is preferable to form the heat-resistant water-adhesive improving layer (E) on both surfaces of the polyester-based base film (A). In particular, in the case where the polyoxyalkylene rubber adhesive layers (B) and (B') are formed on both sides of the polyester base film (A), the adhesive layer of the polyoxyalkylene rubber can be improved by this corresponding method (B) And (B') are important for the heat-resistant water adhesion to the polyester base film (A).

In the case of applying a coating liquid for a hot water-resistant water adhesion improving layer (E) to an unstretched film of the polyester base film (A), various coating methods such as a reverse roll coating method and a gravure brush coating method can be used. A rod coating method, a bar coating method, a Meyer horizontal bar coating method, a die coating method, a spray coating method, and the like.

[release layer (C)]

The adhesive sheet of the present invention protects the adhesive layer (B) of the polyoxyalkylene rubber, and the separator film is adhered to the adhesive layer (B) of the polyoxyalkylene rubber, wherein the separator film is composed of the polyester film (D). And the release layer (C) formed on the surface thereof. The peel strength of the polyoxyalkylene rubber adhesive layer (B) and the release layer (C) was controlled to be 0.03 to 1.0 N/20 mm. When the peeling strength is 0.03 N/20 mm or more, good peeling property can be exhibited, and at the same time, in the case of winding the adhesive sheet, floating of the separator film formed by the release layer (C) and the polyester film (D) can be suppressed. , and can maintain the taste of the adhesive sheet. On the other hand, when it is 1.0 N/20 mm or less, the peeling property of the above-mentioned separator film can be improved. In order to control the peeling strength in the above range, it is preferred to provide the release layer (C) having the following structure on the surface of the polyester film (D). Further, the peel strength can be measured in the following manner.

First, the surface 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 laminated body containing one side and a laminated body containing the other side, and each is placed on a chuck of a tensile testing machine. . That is, for example, in the case of measuring the peel strength of the adhesive layer of the polysiloxane rubber (B) and the release layer (C), the interface between the adhesive layer (B) of the polyoxyalkylene rubber and the release layer (C) The adhesive sheet was slightly peeled off, and each of the polyoxyalkylene rubber adhesive layer (B) and the release layer (C) was exposed. In this case, the separator film (C) and the polyester film (D) are separated by a chuck on one side, and the polyoxyxane rubber adhesive layer (B) is held on the other side of the chuck. The layered body. Next, the T-type peel strength was measured by the method described in JIS K 6854-3. The tensile tester can perform a T-peel test using a product name "autograph" (manufactured by Shimadzu Corporation) or the like under the conditions of a chuck distance of 50 mm, a temperature of 23 ° C, and a tensile speed of 200 mm / min. At the time of peeling off, the end of the film was lifted by a rod in such a manner as to maintain the T shape. The maximum strength at the time of T-stripping was defined as the peel strength. Hereinafter, in the present invention, the above characteristics are simply referred to as peelability.

The release layer (C) is preferably a non-polyoxyalkylene compound when considering the releasability with the polyoxyalkylene rubber adhesive layer (B). In the case where the release layer is formed of a cured product of a hardened polyoxyalkylene compound which is widely used as a release layer, since it has a high affinity with the polyoxyalkylene rubber adhesive layer (B), it is agglomerated. When the polyoxyalkylene compound of the oxyalkylene rubber adhesive layer (B) is crosslinked, the polyoxyalkylene rubber adhesive layer (B) and the release layer (C) are cross-linked, and the peeling property is lowered. situation. In order to obtain stable peelability, the release layer is preferably formed by using a release agent substantially free of a polyoxyalkylene compound. In addition, the "release layer is made of a non-polyoxyalkylene compound" means that the release layer is formed of a compound (or a composition) containing 10% by mass or less of the polyoxyalkylene compound. The amount of the polyoxyalkylene compound is 5% by mass or less, and the polyoxyalkylene compound is preferably 0% by mass.

Further, the release layer (C) may be a metal or inorganic film, and may have a peeling stability or a cost, and may be obtained from a composition containing a binder resin, a polymer wax component, and an antistatic agent. It is better.

In terms of the binder resin, one or more polymers selected from the group consisting of polyester, polyurethane, and acrylic polymer are preferred, and the polymers may be used alone or in combination. Or 3 to use.

As the polyester, the polyurethane, and the acrylic polymer, the same ones as those exemplified as the constituent polymer of the hot water-resistant water-improving layer (E) can be used. The necessity of crosslinking the binder resin is low, and the crosslinking agent may be used in combination with the heat resistant water adhesion improving layer (E), and a self-crosslinking type polymer may also be used.

A well-known material can be used for the polymer wax component used in the present invention. For example, a wax emulsion such as a polyethylene-based, polypropylene-based, acrylic-based, or fatty acid-based one, and the like, in particular, a polymer wax having excellent thermal decomposition stability in a hard form having no adhesiveness, has an effect on the improvement of the peeling property. And, when the film is wound, it is preferable to suppress the wax transfer to the opposite side surface. Further, the wax has an appropriate number average molecular weight of from 1,000 to 10,000, more preferably from 1,500 to 6,000.

When the total amount of the polymer wax component and the binder resin is 100% by mass, the solid content is preferably 2 to 10% by mass. It is more preferably from 3 to 8 mass%. When the amount of the polymer wax component added is 2% by mass or more, the peeling property with the polyoxyalkylene rubber adhesive layer (B) can be improved after the crosslinking treatment, and the lubricity of the separator film can be improved. On the other hand, the addition amount of the polymer wax component is 10% by mass or less, and the peeling force can be maintained, and the occurrence of the channeling phenomenon can be suppressed in the production step of the adhesive sheet. Further, since the fluctuation of the polymer wax component from the release layer (C) can be suppressed, the surface of the polyoxyalkylene rubber adhesive layer (B) after the crosslinking treatment is contaminated.

The antistatic agent used in the release layer (C) is not particularly limited as long as it is miscible with the binder resin or is compatible, and a commercially available material can be used. For example, an anionic, cationic, nonionic, amphoteric surfactant or a polymeric surfactant can be used. It is preferred that the polymer type antistatic agent having a small amount of bleed out is preferable. As the polymer type antistatic agent, any of an anionic type, a cationic type, and a nonionic type can be used, and an anionic type and a nonionic polymer type antistatic agent are suitable.

The anionic polymer type antistatic agent is preferably a polar polymer having at least one polar group selected from a sulfonic acid group, a carboxyl group, and a sulfate group, or a salt thereof. It is necessary for the polar group to set the polymer to 5 mol% or more per molecule. In the polar polymer having such conductivity, the polar group may contain a hydroxyl group, an amine group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, or a vinyl group. Among these, an antistatic agent containing styrenesulfonic acid or a salt thereof as a repeating unit is suitable.

As such an antistatic agent, polystyrenesulfonic acid or a salt thereof can be exemplified. The salt may, for example, be an ammonium salt, a lithium salt or a sodium salt. The polystyrene sulfonic acid or a salt thereof is, for example, not neutralized or various salts which are sold by the NSC Corporation of Japan under the trade name of VERSA-TL (registered trademark). Further, in the case of an antistatic agent containing styrenesulfonic acid or a salt thereof as a repeating unit, a styrenesulfonic acid-maleic acid copolymer may be used and sold by NSC Corporation of Japan.

On the other hand, the nonionic polymer type surfactant contains aniline or a derivative thereof, pyrrole or a derivative thereof, isothianaphthene or a derivative thereof, acetylene or a derivative thereof, thiophene or a derivative thereof. A π-electron conjugated conductive polymer as a constituent unit is preferable. Among these, in order to reduce the amount of coloration, a π-electron conjugated conductive polymer containing thiophene or a derivative thereof as a constituent unit is preferred. The π-electron conjugated conductive polymer may contain a single polymer in which only one type of constituent unit is used as a repeating unit, and may contain a copolymer in which two or more constituent units are used as a repeating unit.

For the conductive polymer containing thiophene or a derivative thereof as a constituent unit, for example, "Baytron (registered trademark) P" series manufactured by Stark Wittck Co., Ltd., and "Denatron (registered trademark) P manufactured by Nagase ChemteX Co., Ltd. -502RG", "Denatron (registered trademark) P-502S", Konisol F202, F205, F210, P810 (trade name) manufactured by Inscontec Co., Ltd., CPS-AS-XO3 (trade name) manufactured by Shin-Etsu Polymer Co., Ltd., etc. Sold.

The amount of the antistatic agent in the release layer (C) is not uniform because of the type of the binder resin and the type of the antistatic agent, so that the polyoxane rubber of the release layer (C) cannot be used. The peeling strength of the adhesive layer (B) can be adjusted to the respective ranges described above.

For example, in the case where an anionic surfactant is used as an antistatic agent, the amount of the antistatic agent blended in the range of the peel strength of the polyoxyalkylene rubber adhesive layer (B) from the release layer (C) becomes the range. When the total amount of the binder resin is 100% by mass, the solid content is preferably 2 to 10% by mass, more preferably 3 to 8% by mass. By setting the amount of the anionic surfactant to 2% by mass or more, the peeling property from the polyoxyalkylene rubber adhesive layer (B) after the crosslinking treatment can be made good, and the separation film can be prevented. The electrostatic properties are good. On the other hand, by setting the amount of the antistatic agent to 10% by mass or less, the peeling force can be maintained, and the occurrence of the channeling phenomenon can be suppressed in the production step of the transparent conductive polyester film composite. Further, since the fluctuation of the polymer wax component from the release layer (C) can be suppressed, the surface of the polyoxyalkylene rubber adhesive layer (B) after the crosslinking treatment is contaminated.

When the release layer (C) having the above-described configuration is formed on the polyester film (D), other additives such as a binder resin, a polymer wax component, an antistatic agent, and optionally a surface roughening material are mixed and set in advance. It is preferred to adjust the amount of the resin composition and apply it. The resin composition may contain an surfactant, an anti-UV agent, an antioxidant, or the like for improving coatability. The coating method is preferably carried out by using a usual coating device such as a gravure coater, a reverse roll coater, a reverse roll coater, an air knife coater, or a bar coater, and the method is not limited thereto. In the same manner as in the case of the hot water-resistant water-improving layer (E), it is exemplified that the film (D) which is stretched in one axial direction is coated with the resin composition in one axial direction, and further in the same direction as the previous one. The so-called in-line coating method of stretching in the right-angle direction of stretching, or the so-called off-line coating method after coating after biaxial stretching.

The thickness of the release layer (C) is such that the peeling force is set to an appropriate range, and is preferably 0.03 to 1 μm in the dry state, more preferably 0.05 to 0.5 μm.

[Composition of the adhesive sheet of the present invention]

The simplest configuration of the adhesive sheet of the present invention is a single layer in the order of the polyester base film (A), the polyoxyalkylene rubber adhesive layer (B), the release layer (C), and the polyester film (D). Adhesive sheet. Each layer may be laminated via another layer. As described above, it is preferable to provide a hot water resistant adhesion improving layer (E) between the polyester base film (A) and the polyoxyalkylene rubber adhesive layer (B).

In the adhesive sheet of the single-sided tape type, a functional layer can be formed on the opposite side of the surface on which the polyoxyalkylene rubber adhesive layer (B) of the polyester-based base film (A) is formed. The functional layer may, for example, be one layer selected from the group consisting of a damage prevention layer, an antireflection layer, and an antifouling layer. By forming one of the functional layers on the surface of the adhesive sheet, it is possible to impart a damage prevention function or an antireflection function, or to impart an antifouling function to the adhesive sheet. Further, in order to prevent the functional layer from being blocked, the functional layer may be laminated in two or more layers. In the case of laminating, the order of the damage preventing layer, the antireflection layer, and the antifouling layer is preferably started from the polyester base film (A).

The anti-damage layer is not particularly limited, and a polyester resin, a polyurethane resin, an acrylic resin, a melamine resin, an epoxy resin, a polyoxyalkylene resin, or a polyimide is used. It is preferred that the resin or the like is thermally crosslinked by a crosslinking agent or a layer in which active light such as an electron beam or an ultraviolet ray is hardened. The thickness of the damage preventing layer is preferably in the range of 1 to 50 μm, more preferably in the range of 2 to 30 μm. In the case where it is thinner than 1 μm, the damage prevention function cannot be sufficiently exhibited, and at a thickness exceeding 50 μm, the speed of the resin coating layer is remarkably slowed, and it is difficult to obtain good results in productivity. In the method of laminating the damage preventing layer, it is preferable to coat the resin by a gravure brushing method, a reverse roll method, a mold method, or the like, and then externally heat, ultraviolet rays, electron beams, or the like.

The antireflection layer is not particularly limited, and it is preferable to laminate a single layer or two or more layers with a material having a refractive index different from that of the polyester base film (A). In the case of a single layer, it is preferred to use a material having a refractive index smaller than that of the polyester base film (A). In the case of a multilayer structure of two or more layers, the layer adjacent to the polyester-based base film (A) is made of a material having a refractive index larger than that of the film (A), and the layer thereon is selected to have a refractive index ratio of Small materials are better. In terms of such an antireflection layer, the organic material may be 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. In the case of In ₂ O ₃ or the like, a film is formed by a dry coating process such as a vacuum deposition method, a sputtering method, a CVD method, or an ion plating method, or a resin composition having such particles is applied.

The thickness of the antireflection layer is not particularly limited, and the single layer is preferably 50 nm to 150 nm, and the multilayer layer is preferably 100 nm to 500 nm.

As for the material for forming the anti-fouling layer, as long as it has transparency as much as possible and can satisfy the required performance, no matter what kind of material can be used without limitation. For example, a compound having a hydrophobic group, more specifically, fluorocarbon or perfluorodecane, or the like, or such a polymer compound is suitable. Further, in order to improve the fingerprint erasing property, a polymer compound having an oil-repellent group such as a methyl group is suitable.

As a method of forming the anti-fouling layer, a vacuum film forming process such as a vacuum deposition method, a sputtering method, a plasma CVD method, or a plasma polymerization method, or a micro-gravure brush, a screen, a dip, or the like can be used. Various coating methods such as wet process. The thickness of the anti-contamination layer is preferably set to a function of not damaging the anti-reflection layer, for example, in the case of laminating the anti-reflection layer, and is usually 50 nm or less.

Further, in the adhesive sheet of the single-sided tape type, a transparent conductive layer can be formed on the side opposite to the surface on which the adhesive layer (B) of the polyester base film (A) is formed.

Typical examples of the transparent conductive material include metals such as Au, Ag, and Cu; metal oxides such as In ₂ O ₃ , SnO ₂ , and ZnO ₂ or such composite oxides; polyaniline, polyacetylene, and polythiophene; A conductive polymer such as polyparaphenylene, polyparaphenylene vinyl or polypyrrole. Among them, a metal oxide such as In ₂ O ₃ , SnO ₂ or ZnO ₂ or a composite oxide thereof is preferred. In the above-mentioned SnO ₂ , ZnO ₂ , Sb ₂ O ₃ , WO ₃ , ZrO ₂ , SiO ₂ or the like, one or more kinds of dopants can be used. The content of the dopant is preferably in the range of 0.1 to 50% by mass based on the metal oxide or the composite oxide. When the content is less than 0.1% by mass, the function as a dopant is not sufficiently exhibited, and when it exceeds 50% by mass, the original properties of the metal oxide or the composite oxide are hindered.

When a transparent conductive layer is produced from the above conductive polymer, it is preferably dissolved in a suitable solvent and a known coating method is used.

When the above-mentioned metal, metal oxide, or composite oxide is used to form a transparent conductive layer, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, or the like can be used. For example, in the case of a sputtering method, a usual sputtering method using an oxide target, a reactive sputtering method using a metal target, or the like can be used. At this time, oxygen, nitrogen, water vapor, or the like may be introduced into the reactive gas system, and a method such as ozone addition, plasma irradiation, or ion assisted may be used in combination. Further, a bias voltage such as direct current, alternating current, or high frequency may be applied to the substrate without impairing the object of the present invention.

Further, the temperature at which the transparent conductive layer is formed on the polyester base film (A) is preferably 150 ° C or lower. When the temperature at which the film formation is desired exceeds 150 ° C, the feed speed of the film has to be extremely slow, which is not preferable in terms of productivity.

Further, it is preferable that the degree of vacuum at the time of sputtering is in the range of 0.01 to 10 Pa. In a vacuum having a vacuum higher than 0.01 Pa, since stable discharge cannot be performed, sputtering is unstable. Further, even if the vacuum is lower than 10 Pa, stable discharge cannot be performed, and sputtering is not stable. Further, the same applies to other methods such as a vapor deposition method and a CVD method.

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 is difficult to form a continuous film, and it is difficult to exhibit good conductivity. Moreover, in the case where the thickness is thicker than 800 nm, transparency is difficult to be lowered, which is not preferable.

The adhesive sheet of the present invention may be a double-sided adhesive sheet. The constitution of the double-sided adhesive sheet may be any composition if it contains the polyester base material (A) and the polyoxyalkylene rubber adhesive layer (B). Preferred composition is polyester film (D) / release layer (C) / polyoxyalkylene rubber adhesive layer (B) / hot water adhesion improving layer (E) / polyester base film (A) / Heat resistant water adhesion improving layer (E) / polyoxyalkylene rubber adhesive layer (B') / release layer (C') / polyester film (D'), or polyester film (D) / release layer (C)/polyoxyalkylene rubber adhesive layer (B)/heat-resistant water adhesion improving layer (E)/polyester base film (A)/heat-resistant water adhesion improving layer (E)/acrylic adhesive Layer (F) / release layer (C") / polyester film (D").

The release layer (C') may have the same composition as the release layer (C) or may be a different composition. A suitable example of the release layer (C') is the same as the appropriate example of the release layer (C). The release layer (C") is in contact with the acrylic adhesive layer (F), so that between the polyoxyalkylene rubber adhesive layer (B) and the release layer (C), such as polyoxyalkylene compounds In the case where the cross-linking reaction is low, it is possible to use any of the compositions for the release layer. Further, the polyester films (D') and (D") may be the same as the polyester film (D). The composition may also be a film of different composition. Suitable examples of the polyester films (D') and (D") are the same as those of the polyester film (D).

Polyester film (D) / release layer (C) / polyoxyalkylene rubber adhesive layer (B) / hot water adhesion improving layer (E) / polyester base film (A) / heat resistant water bonding The modified layer (E) / polyoxyalkylene rubber adhesive layer (B') / release layer (C') / polyester film (D') formed on both sides of the adhesive sheet of the polyoxyalkylene rubber adhesive layer ( B'), release layer (C') and polyester film (D'), which are the same as each of the polyoxyalkylene rubber adhesive layer (B), the release layer (C) and the polyester film (D) or The situation is better.

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

Examples of the (meth) acrylate having an alkyl group having 1 to 18 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate. Ester, butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (methyl) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, Isodecyl acrylate (meth)acrylate, decyl methacrylate, dodecyl (meth)acrylate, and the like. These (meth) acrylates can be used alone or in combination of two or more.

Further, a monomer component (copolymerizable monomer) having the above (meth) acrylate and copolymerizability may also be used. In particular, when the acrylic polymer is crosslinked, the copolymerizable monomer is preferably a monomer for modifying the acrylic adhesive, and any of the monomers for the known modification can be used. The copolymerizable monomers may be used singly or in combination of two or more.

Specifically, the copolymerizable monomer can be used as a monomer component constituting the acrylic polymer for the hot water-resistant water-improving layer (E) or a monomer exemplified as another monomer, and further, for example, An α-olefin monomer such as ethylene or propylene is used.

In terms of the monomer for reforming, it is preferable to contain the functional group-containing monomer, and among these, a hydroxyl group-containing monomer or a carboxyl group-containing monomer is preferable, and acrylic acid is particularly preferable. Further, crosslinking of the acrylic polymer can be carried out by using a functional group (particularly a polar group) derived from a monomer for reforming.

In order to obtain a polymerization method of the acrylic polymer, a solution polymerization method using an polymerization initiator such as an azo compound or a peroxide, an emulsion polymerization method or a bulk polymerization method, and a photoinitiator may be used to irradiate light or A polymerization method in which radiation is carried out. In the present invention, a method (radical polymerization method) which is decomposed and polymerized using a polymerization initiator which generates a radical can be suitably employed. In the radical polymerization, a peroxide such as phenylhydrazine peroxide, a tertiary butyl maleate or the like, 2,2'-azobisisobutyronitrile, azobisisoprene is usually used. A polymerization initiator such as an azo compound such as a nitrile is used. The amount of the polymerization initiator used may be usually used in the case of polymerizing the acrylic monomer, and is, for example, about 0.005 to 10 parts by mass, preferably 0.1 to 5 parts by mass per 100 parts by mass of the total of the monomer components. About.

The ratio of the (meth) acrylate having a carbon number of 1 to 18 alkyl groups as the main monomer component of the acrylic polymer is 50% by mass based on 100% by mass of the monomer component. More than % is better. It is preferably 80% by mass or more, more preferably 90% by mass or more. Therefore, the ratio of the copolymerizable monomer other than the above (meth) acrylate is 50% by mass or less based on 100% by mass of the monomer component.

The acrylic polymer obtained by polymerizing the monomer component can be used as it is. Further, it is also possible to perform curing by crosslinking the acrylic polymer. When the polymer is crosslinked, the cohesive force of the adhesive can be further increased. A crosslinking agent can be used for crosslinking. That is, in the acrylic adhesive, a crosslinking agent may be blended together with the acrylic polymer. Further, the cross-linking of the polymer, the heat crosslinking method can be suitably used.

As the crosslinking agent, any of the crosslinking agents exemplified as the crosslinking agent which can be used in the hot water-resistant water-improving layer (E) can be used. The crosslinking agent is preferably a melamine crosslinking agent, an epoxy crosslinking agent or an isocyanate crosslinking agent. The crosslinking agent may be used singly or in combination of two or more. The amount of the melamine-based crosslinking agent and/or the epoxy-based crosslinking agent to be used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the acrylic polymer. The amount of the isocyanate-based crosslinking agent to be used is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, per 100 parts by mass of the acrylic polymer.

In the acrylic adhesive, various additives can be added as needed. For example, in order to adjust the adhesive property, an adhesive resin (for example, a rosin-based resin, a terpene-based resin, a petroleum resin, a coumarone/indene resin, a styrene-based resin, or the like) may be blended. From the viewpoint of improving the colorless transparency of the double-sided adhesive sheet or suppressing the change in color tone, it is preferable to impart an adhesive resin to the hydrogenated type, and the blending ratio is preferably such a range that the haze of the both-side adhesive sheet does not rise. Further, as an additive other than the adhesive resin, various additives such as a filler such as a plasticizer or fine powder of cerium oxide, a coloring agent, an ultraviolet absorber, and an surfactant may be blended. The amount of these additives to be used may be any of the usual amounts suitable for the acrylic adhesive.

The adhesion of the acrylic adhesive layer (F) can be controlled by a method of adjusting the ratio of the monomer for reforming (including the functional group-containing copolymerizable monomer) and the crosslinking agent, or by using a surfactant method.

The thickness of the acrylic adhesive layer (F) is not particularly limited, and is preferably, for example, 3 to 200 μm. It is preferably 5 to 150 μm, more preferably 10 to 100 μm.

Moreover, as the acrylic pressure-sensitive adhesive, for example, "SK Dyne" series manufactured by Soken Chemical Co., Ltd. can be used. Among them, it is preferred to use an optical adhesive such as an optical adhesive.

The method for forming the acrylic pressure-sensitive adhesive layer (F) is not limited. For example, a coating liquid in the form of a solution of an organic solvent or a coating liquid in the form of an aqueous dispersion can be simply coated by a coating method.

Further, a hot water-resistant water-improving layer (D) is provided between the acrylic pressure-sensitive adhesive layer (F) and the polyester base material film (A), and the acrylic pressure-sensitive adhesive layer (F) and the base material film can be improved ( E) can also be bonded.

The adhesion of the acrylic adhesive layer (F) can be the same as that of the adhesive layer of the polyoxyalkylene rubber (B), and can be as small as possible. The method of using the double-sided adhesive tape of the present invention can be suitably selected and set. For example, the application method for re-peelability on both sides is the same as the adhesion of the polyoxyalkylene rubber adhesive layer (B), that is, 0.01 to 1.0 N/20 mm (180-degree peel test on glass, pull) The range of the stretching speed of 300 mm/min is preferred. On the other hand, in the case where the single surface is firmly fixed, it is preferable to set it higher than the above range. For example, in the case where the touch panel portion of the touch panel is bonded to the display device portion, the adhesion is preferably 5.0 N/20 mm or more, and for example, 5.0 to 30 N/20 mm is an appropriate range. A more preferable range is 8.0 to 25 N/20 mm.

[Indentation elastic modulus of the adhesive layer (B) and (B') of the polyoxyalkylene rubber of the present invention]

The inventors of the present invention have disclosed a patent for limiting the dynamic hardness of the surface of the self-adhesive layer formed of a flexible polymer to a specific range (see, for example, Japanese Laid-Open Patent Publication No. 2003-119434, No. 2001-139903, and Japanese Patent Publication No. 2002-149341).

However, the dynamic hardness disclosed in the above-mentioned literature is a load when the indenter is squeezed from the outermost surface of the adhesive layer to a depth of 3 μm, and only the surface hardness necessary for exhibiting adhesion is exhibited. Therefore, the adhesive layer disclosed in the hardness range of the above-mentioned document can exhibit adhesiveness with the softness of the surface, and adhesion to the adhesive is feasible.

However, due to the expansion of the market, for example, the venting of air in the case of sticking or the adhesion to the surface of a non-planar adhesive body has begun to occur due to insufficient shape compliance with the surface shape. The inventors of the present invention first found out that the results of the exhausting and the shape compliance of the biting-in air are opposite characteristics, and the polyoxane is required to coexist. The optimization of the indentation modulus of the rubber adhesive layers (B) and (B') is important.

The polyoxyalkylene rubber adhesive layer (B) and/or (B') preferably has a embossing modulus of 0.5 to 20 N/mm ² as measured by the following method. If it is less than 0.5N/mm ^{2, it} will reduce the discharge of the ingested air, which is not good. Further, there is a case where the cutting workability is lowered during the slit processing or the stamping processing of the double-sided adhesive sheet. On the other hand, when it exceeds 20 N/mm ² , it is unsatisfactory due to a decrease in shape compliance. The embossing modulus is preferably 0.6 to 15 N/mm ^{2 , more} preferably 0.7 to 10 N/mm ² .

However, the image display panel described later and the protective panel of the protective image display panel are bonded together by the double-sided adhesive sheet of the present invention, and in order to improve the visibility of the image display device, the indentation modulus is 0.5 to 0.5 in the case of use. 5N/mm ^{2 is} preferred. In general, in order to protect the impact panel, a tempered glass, a polycarbonate resin (PC) plate, or an acrylic resin plate is used. The back surface can be provided with a light shielding film in such a manner as to fit the screen frame as needed to surround the peripheral portion of the panel. This light-shielding film is formed by printing of a paint, and usually has a thickness of 5 to 15 μm, so that the back surface of the protective panel is not flat. Therefore, the adhesive sheets on both sides of the adhesive layer are provided on both surfaces of the base film, and bubbles are generated because the height difference of the brushed portion cannot be absorbed. In this case, the indentation modulus of the polyoxyalkylene rubber adhesive layers (B) and (B') is controlled to the above range so that the balance between moderate elasticity and restorability with respect to deformation becomes good, for example, on the paste. In the case where the above-mentioned light shielding film forms a protective panel, the occurrence of bubbles can be suppressed.

The embossing elastic modulus indicates that the elasticity and deformation of the adhesive layer are restored, and the thickness, hardness, molecular weight, and crosslinking degree of the polyoxyalkylene rubber adhesive layers (B) and (B') can be controlled. That is, when the thickness of the adhesive layer is increased, since the elasticity of the adhesive layer is small, the elastic modulus of the undercut can be reduced. Further, since the hardness of the adhesive layer is increased as the hardness of the adhesive layer is increased, the elastic modulus of the undercut becomes large. On the other hand, as the molecular weight increases, the molecules are entangled with each other, so that the restorability with respect to deformation is improved, so that the embossing modulus is small. Further, when the degree of crosslinking is lowered, the restorability with respect to deformation is lowered, and the embossing modulus is increased.

[Method for measuring the modulus of indentation]

The sample was cut out about 2 cm square, and the opposite side of the measurement surface was fixed with a non-carrier acrylic adhesive (thickness 25 μm) or a cyanoacrylate adhesive on a glass plate having a thickness of 1 mm or more. . Further, in the case where there is an adhesive layer on the opposite side of the measurement surface, it is fixed to the glass plate by the adhesive layer.

After the sample was placed on the glass plate and the sample was placed for 30 minutes or more, the separator film on the measurement surface was peeled off, and the dynamic ultra-fine hardness meter DUH-211 (manufactured by Shimadzu Corporation) was used, and the measurement was performed under the next measurement conditions.

"Measurement conditions" 1) Setting Test mode: load - load test Indenter: inter-ridge angle 115 degrees, triangular cone indenter: indenter elastic modulus: 1.140×10 ⁶ N/mm ² : Poisson's ratio: 0.07 Soft sample measurement: Yes Cf-Ap, As correction: Yes 2) Conditions Test force: 0.50mN Load speed: 0.0150mN / sec Load hold time: 5 seconds In addition to load hold time: 5 seconds [Optical Characteristics of Adhesive Sheet of the Present Invention]

The adhesive sheet of the present invention preferably has a total light transmittance of 80% or more and a haze of 2.0% or less in applications requiring high transmittance. The total light transmittance is 85% or more, and the haze is preferably 1.5% or less. Further, after storage at 85 ° C for 200 hours at 65 ° C, the total light transmittance and haze are preferably in the above-mentioned appropriate ranges.

[Method of Manufacturing Adhesive Sheet of the Present Invention]

The method for forming the polyoxyalkylene rubber adhesive layer (B) is as described above. The other layer may be formed at the same time as or after formation of the polyoxyalkylene rubber adhesive layer (B). Further, the separator film is separately formed to be laminated on the polyoxyalkylene rubber adhesive layer (B) and the acrylic pressure-sensitive adhesive layer (F). The adhesive sheet of the present invention controls the peeling force of the separation film and the polyoxyalkylene rubber adhesive layer (B) to a proper range, and the step of winding the adhesive sheet, etc., can suppress the occurrence of the above-mentioned channeling phenomenon, thereby being stable The production of high quality adhesive sheets.

[Use of Adhesive Sheet of the Present Invention]

In the case where the adhesive sheet of the present invention is missed, the adhesive sheet can be easily removed and can be reattached again. It has excellent adhesion durability between the adhesive layer and the base polyester film, and can be suitably used even in the case of use under severe conditions. Further, it is excellent in workability when it is bonded to various members or to various members, and when the upper electrode for an touch panel or an image display device is manufactured.

The one-sided adhesive sheet of the present invention is useful as a protective film for protecting a display screen of an image display device. Examples of the image display device include a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence panel (ELP), a touch panel, a CRT (cathode tube) display, and the like. The single-sided adhesive sheet of the present invention can be suitably used for the protection of the display screen in the manufacturing steps of the device, in addition to the protection of the display screen.

A single-sided adhesive sheet having a functional layer is also useful as a protective film for a display screen and as a surface member of a touch panel. Further, a single-sided adhesive sheet in which a transparent conductive layer is laminated is useful as a touch panel member such as a lower electrode for a touch panel. When a single-sided adhesive sheet having a transparent conductive layer is used as the lower electrode, the touch panel portion and the display device can be attached with a polyoxyalkylene rubber adhesive layer (B), and the touch panel portion can be attached. The space with the display device is buried with an adhesive layer. As a result, since the light reflection of the interface can be suppressed in the above space, the effect of improving the visibility of the display image can be exhibited. Further, since the polyoxyalkylene rubber adhesive layer (B) is formed of a polyoxyalkylene rubber having both adhesiveness and re-peelability, for example, even when there is a missed contact, the above-mentioned adhesion is caused. It is also easy to remove the two members, and the effect of re-sticking can be exhibited.

Further, when the upper electrode for a touch panel is manufactured, the single-sided adhesive sheet is also useful. For example, in a transparent substrate having a conductive laminated body in which a transparent conductive layer is laminated on a transparent substrate, an upper electrode for a touch panel can be manufactured by adhering a single-sided adhesive sheet having a functional layer. In addition, a transparent substrate in which a functional laminate of one or more functional layers selected from the group consisting of a damage prevention layer, an antireflection layer, and an antifouling layer is laminated on a transparent substrate is transparent even if it is laminated. The single-sided adhesive sheet of the conductive layer can also be used to manufacture the upper electrode for the touch panel. The transparent substrate in the conductive laminated body or the functional laminated body is not limited to the polyester film, and can be exemplified Cyclic polyolefin such as alkenyl polymer; polyamide resin such as nylon 6, nylon 4, nylon 66, nylon 12; acrylic resin; polycarbonate; triethylenesulfonyl cellulose (TAC) Wait for the film. The resin used in the films may be a small amount of a copolymer having a copolymer component. Further, these resins may be used alone or in combination of one or more kinds of other resins. In the case of film formation, it can be carried out in the same manner as the method exemplified in the case of producing the polyester base film (A). However, TAC is preferably thinned by a casting method. The appropriate thickness of the transparent substrate is not particularly limited, and is preferably 5 to 30 μm.

The two-sided adhesive sheet is suitable for fitting the components of the touch panel or the image display device. For example, the overlay sheet of the electrostatic capacitive touch panel and the coordinate detecting sheet are attached, the touch panel portion of the resistive touch panel is attached to the display device, or the image display device is displayed. It is appropriate that the panel is attached to the protective panel that protects the image display panel. Further, for example, the conductive laminate and the functional laminate are bonded to each of the adhesive layers of the double-sided adhesive sheet, whereby the upper electrode for a touch panel can be manufactured.

The present invention relates to an upper electrode for a touch panel and an image display device which are manufactured using the adhesive sheet of the present invention. The upper electrode for a touch panel of the present invention can have the excellent characteristics of the adhesive sheet of the present invention, and has good cushioning property by having the elasticity of the adhesive layer of the polyoxyalkylene rubber (B). The pen of the panel has excellent sliding resistance.

Moreover, the two-sided adhesive sheet is suitable for fitting the image display panel and the protective panel for protecting the image display panel. When there is an air layer between the image display panel and the protective panel, the difference in refractive index between the air layer and the protective panel is caused by the reflection of light, and the light of the sunlight or the backlight is scattered, so that the brightness or contrast is lowered, so that The visibility is deteriorated, and the adhesive sheet is adhered to both sides, and since the space between the image display panel and the protective panel is buried, the deterioration of visibility can be suppressed. Moreover, even when it is used for the manufacture of an image display device, it is possible to effectively utilize the characteristics excellent in adhesion or removability.

Further, the bonding method of the image display panel and the protective panel is not particularly limited. For example, after the separation film on one side of the adhesive sheet is peeled off from the surface of the adhesive layer, one of the image display panel or the protective panel is adhered to the both surfaces in advance, and then the residual panel is suitably bonded. Further, when heat and pressure are applied by a heat press or the like as needed, it is possible to bond more reliably. It is preferable to arrange the two-sided adhesive sheet to make the adhesive layer of the polyoxyalkylene rubber relatively in the direction of the re-applied operation, or on the panel side which can be predicted to be the desired one. The polyoxyalkylene rubber adhesive layer is excellent in removability. Further, in the range where there is no problem in the configuration, the adhesive sheets on both sides of the protective panel and the image display panel may be adhered to each other.

Example

The present invention is not limited by the following examples, and the present invention is of course not limited by the following examples, and the scope of the present invention can be appropriately modified and implemented, and these are all included in the present invention. The technical scope of the invention. Further, the measurement/evaluation method employed in the examples is as follows. Further, in the examples, "parts" means "mass parts", and "%" means "% by mass" unless otherwise notified.

1. Peel strength (peelability) of the separator film

First, a sample having a length of about 200 mm and a width of 20 mm was exposed, and the surface on which the peel strength was to be measured was exposed, and the laminate was divided into a separator and a laminate other than the separator, and each was set on a chuck of a tensile tester. That is, for example, in the case of a double-sided adhesive sheet, in the case of measuring the peeling strength of the interface between the release layer (C) and the polyoxyalkylene rubber adhesive layer (B), in the release layer (C) and the polyoxyalkylene rubber The interface of the adhesive layer (B) slightly peels off the adhesive sheets on both sides, and exposes the release layer (C) and the polyoxyalkylene rubber adhesive layer (B). In this case, the film (DC) separated by the polyester film (D) and the release layer (C) is held by the chuck on one side, and the remaining portion is held by the chuck on the other side. Next, the T-type peel strength was measured by the method described in JIS K6854-3. The tensile tester used was a product name "Autograph" (manufactured by Shimadzu Corporation), and a T-peel test was carried out under the conditions of a chuck distance of 50 m, a temperature of 23 ° C, and a tensile speed of 200 mm/min. At the time of peeling, the end portion of the film was raised by a rod in such a manner as to maintain the T shape. The maximum strength at the time of T-peeling was taken as the peel strength. In the case where the release layer (C) and the polyoxyalkylene rubber adhesive layer (B) were not peeled off, no measurement was made due to difficulty in peeling. In this case, the release layer (C) indicates that it cannot function as a release layer. The measurement of the peel strength of the other interface was measured in the same manner as above.

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

The polyoxyalkylene rubber adhesive layer (B) or (B') and the polyester base film (A) are firmly adhered via the heat-resistant water adhesion improving layer (E), so that the polysiloxane is evaluated. When the peel strength of the alkane rubber adhesive layer (B) or (B') is applied, a cutting blade is inserted between the polyester base film (A) and the peeling force is applied by means of an applied force (the separation interface). The peeling strength was not able to clearly separate the interface to ○, and the interface that could be separated was ×, and was evaluated.

3. The heat-resistant water adhesion of the adhesive layer of polyoxyalkylene rubber

The sample was cut into 50 mm × 50 mm, and the separator film in which the polyoxyalkylene rubber adhesive layer (B) and/or (B') were laminated was peeled off. The sample was placed in a 500 cc closed cylindrical glass vessel filled with distilled water, and the sample was submerged in water so that the adhesive layer (B) was placed on the lower side, so that the entire sample was immersed in water and the container was covered. In the case where only the weight of the sample is not immersed in water, for example, a polyester film of 60 mm × 60 mm and a thickness of 188 μm is placed on the sample and weighed by weight. The size or material of the weight is not particularly limited, and it is preferred to immerse the entire sample in water. The sample container was placed, placed in a gear oven set at 80 ° C, and allowed to stand for 24 hours. After the heat treatment, the container was taken out from the oven, and the sample was taken out immediately. The adhesive layer (B) or (B') side was applied to the end portion to wipe the end portion 10 times with the fingertip to evaluate the polyoxyalkylene rubber. Whether the adhesive layer (B) or (B') is peeled off from the polyester base film (A), the adhesive layer of the polyoxyalkylene rubber is not peeled off, and the adhesive layer of the polyoxyalkylene rubber is peeled off.

4. Adhesion of the adhesive layer of polyoxyalkylene rubber

The adhesion to the glass of the polyoxyalkylene rubber adhesive layer (B) or (B') was measured by a 180-degree peeling method in accordance with JIS ZO237. As the glass, heat-resistant glass having a thickness of 3 mm and a width of 30 mm was used. The sample was made to have a width of 20 mm, and the glass was attached to the glass twice using a 2 kg roller at a speed of about 29 mm/sec. The tensile speed was 300 mm/min, and the tensile test was carried out in an atmosphere of 23 ° C to make the maximum tensile strength an adhesive force (N/20 mm).

5. Full light transmittance and haze

The total light transmittance is measured in accordance with JIS K7361-1, and the haze system is JIS K7136, and the haze meter "NDH-2000" manufactured by Nippon Denshoku Industries Co., Ltd. is used. This measurement was carried out by peeling off the separator film.

6. The concave modulus of the adhesive layer of polyoxyalkylene rubber

The sample was cut at an angle of about 2 cm, and the opposite side of the measurement surface was fixed to a non-carrier-form acrylic adhesive (thickness 25 μm) or a cyanoacrylate-based adhesive on a glass plate having a thickness of 1 mm or more. Further, in the case where there is an adhesive layer on the opposite side of the measurement surface, it is fixed to the glass plate by the adhesive layer. Further, in the case where the both sides of the polyoxyalkylene rubber adhesive layers (B) and (B') were adhered to each other, the adhesive layers (B) and (B') of the both sides of the polyoxyalkylene rubber were measured.

After the sample was placed on the glass plate and the sample was placed for 30 minutes or more, the separator film on the measurement surface was peeled off, and the measurement was carried out under the second measurement conditions using a dynamic ultra-fine hardness meter DUH-211 (manufactured by Shimadzu Corporation).

"Measurement conditions"

1) Set test mode: Load - In addition to the load test using the indenter: the angle between the edges is 115 degrees, the triangular cone indenter: the indenter elastic modulus: 1.140 × 10 ⁶ N / mm ² : the indenter Poisson's ratio: 0.07 soft sample determination : There is Cf-Ap, As correction: Yes

2) Conditional test force: 0.50mN load speed: 0.0150mN/sec load hold time: 5 seconds except load hold time: 5 seconds

7. The clarity of the coating solution

100 cc of the coating liquid for forming a polyoxyalkylene rubber adhesive layer (B) or (B') was filtered through a metal mesh of 200 mm (200 mm diameter) of 40 mm Φ to visually confirm the presence or absence of insoluble matter, and no insoluble matter. The case is ○, and the case of insoluble matter is ×.

8. Solution stability of the coating solution

The coating liquid for forming a polyoxyalkylene rubber adhesive layer (B) or (B') was sealed in a sealed state, and the change in viscosity of the solution at room temperature (23 ° C) for 90 days was evaluated, and the stability of the solution was judged. The viscosity change of the solution is within ±20%, and the viscosity of the solution is more than ±20%.

In addition, the viscosity was measured by a B-type viscometer.

9. Determination of the number average molecular weight of polyoxyalkylene compounds

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

"Measurement conditions" device: Waters 410 column: Shodex K806M+K802 Flow rate: 1.0 ml/min Injection amount: 200 μl Solvent: Toluene-converted polystyrene detector: differential refractometer

Example 1

(1) Preparation of coating liquid for forming a heat-resistant water adhesion improving layer (E)

[Preparation of water-dispersible copolyester resin]

The water-dispersible copolyester was synthesized by using a pressurized esterification reaction tank of the auxiliary distillation column and two polycondensation reaction tanks of the auxiliary vacuum generator to form the polycondensation catalyst as a polycondensation catalyst in a batch manner.

The copolymerization composition of water-dispersible copolyester is terephthalic acid / isononanoic acid / 5 - sulfoisophthalic acid / / neopentyl glycol / ethylene glycol = 50 / 43 / 7 / / 70 / 30 (Mo Ear ratio), the reducing viscosity was 0.68 dl/g.

[Modulation of coating liquid)

100 parts of the above-mentioned water-dispersible copolyester crushed product was subjected to water dispersion in a predetermined manner. With respect to 100 parts of the solid content of the aqueous dispersion, the methylolated melamine resin "Saimel (registered trademark) 303" (manufactured by Mitsui Cytec Co., Ltd.) was added in five portions to the solid content, and "Catalyst 600" was added to the catalyst system. 0.025 parts of Mitsui Cytec Co., Ltd., which was well stirred and used as a coating liquid (E-1).

(2) Production of polyester base film (A) and lamination of hot water adhesion improving layer (E)

The particles of polyethylene terephthalate (intrinsic viscosity: 0.65 dl/g) containing 0.04% of amorphous cerium oxide microparticles having an average particle diameter (SEM method) of 1.5 μm were sufficiently vacuum dried, and then supplied to the mixture. The 280 ° C extruder was extruded into a sheet shape by a T-shaped die, and was wound on a mirror casting drum having a surface temperature of 30 ° C by using an electrostatic external casting method and cooled and solidified. This unstretched film was passed through a heating roll group of 95 ° C while being stretched 3.5 times in the longitudinal direction to form a one-axis stretched film. Corona discharge treatment was applied to both surfaces of the film, and the coating liquid (E-1) was applied to both of the treated surfaces. The one-axis stretched film was held by a jig while being guided to a preheating zone, dried at 110 ° C, and then continuously stretched 3.5 times in the width direction in a heating zone of 125 ° C. Further, at 225 ° C, 6% relaxation was carried out in the width direction while heat treatment was performed for 6 seconds. A laminated body having a thickness of 100 μm laminated on both sides of a two-axis stretched polyethylene terephthalate base film (A), a crosslinked heat-resistant water adhesion improving layer (E) having a thickness of 0.08 μm can be obtained. (a).

(3) The layer of the damage prevention layer

On the one surface of the layered product (a), a solution of 5 parts of methyl ethyl ketone was added to the ultraviolet curable hard coat coating (manufactured by Dairi Seiki Co., Ltd.: "Seikabeam (registered trademark) EXF-). 01B": a solid solution of 100%) of 5 parts, which was dried at 70 ° C for 1 minute to remove the solvent. Next, this layered product at feed speed 5m / branch intake, while high pressure mercury lamp at an irradiation distance 15 _c m ultraviolet irradiation 200mJ / cm ^2. An anti-damage layer laminate (b) having an anti-damage layer having a thickness of 3 μm can be obtained.

(4) Layer of anti-reflection layer

On the surface of the damage preventing layer of the damage preventing layer laminate (b), the obtained high refractive index coating agent was applied by the following method, and dried at 150 ° C for 2 minutes to form a high refractive index layer having a thickness of 0.1 μm.

On the high refractive index layer, a low refractive index coating agent obtained by the following method was applied, and dried at 150 ° C for 2 minutes to form a low refractive index layer having a film thickness of 0.1 μm. The obtained laminated film was irradiated with ultraviolet rays of 1000 mJ/cm ² to completely cure the antireflection layer and the damage prevention layer, thereby obtaining a laminate (c) having an antireflection layer.

(4-1) Modulation 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 placed in a reaction vessel, and reacted at 80 ° C for 7 hours under a nitrogen atmosphere to obtain a weight average molecular weight. A solution of 30,000 polymer in isopropyl alcohol. The obtained polymer solution was further diluted with isopropyl alcohol to a solid content of 5% to obtain an acrylic resin solution.

The obtained acrylic resin solution was mixed according to the following composition to obtain a high refractive index coating agent.

Acrylic resin solution: 5 parts of bisphenol A diglycidyl ether: 0.25 part of titanium oxide particles having an average particle diameter of 20 nm: 0.5 part of triphenylphosphine: 0.05 part of isopropyl alcohol: 14.25 parts

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

45 parts of 2,2,2-trifluoroethyl acrylate, 45 parts of perfluorooctyl ethyl acrylate, 10 parts of acrylic acid, 1.5 parts of azoisobutyronitrile, and 200 parts of methyl ethyl ketone were placed in a reaction vessel. The reaction was carried out at 80 ° C for 7 hours under a nitrogen atmosphere to obtain a methyl ethyl ketone solution of a polymer having a weight average molecular weight of 20,000. The obtained polymer solution was diluted with methyl ethyl ketone to a solid content of 5% to obtain a fluoropolymer solution.

The obtained fluoropolymer solution was mixed according to the following compounding composition to obtain a low refractive index coating agent.

Fluoropolymer solution: 44 parts of 1,10-bis(2,3-epoxypropoxy)-2,2,3,3,4,4,5,5,6,6,7,7,8 , 8,9,9-hexadecafluorononane ("Fluorite FE-16": manufactured by Kyoei Chemical Co., Ltd.): 1 part of triphenylphosphine: 0.1 part of methyl ethyl ketone: 19 parts

(5) Modulation of coating liquid for forming layer (C)

"Vylonal (registered trademark) MD-1200" (manufactured by Toyobo Co., Ltd.) which is a water-dispersible copolymerized polyester resin, a polyethylene-based emulsion wax for the polymer wax component, and an anion for the antistatic agent. An antistatic agent (sodium dodecyldiphenyloxydisulfonate), and a surface-roughening material using styrene-benzoguanamine-based organic spherical microparticles having an average particle diameter of 2 μm "Epostar (registered trademark) MS" (manufactured by Nippon Shokubai Co., Ltd.) and colloidal cerium oxide having an average particle diameter of 0.05 μm.

Using a homogenizer, the organic spherical fine particles of the surface roughening material are sufficiently dispersed in a mixed liquid of water and isopropyl alcohol (mass ratio: 80/20), and then become a binder with respect to the total mass of the coating liquid. 2.5% of the resin, 0.13% of the polymer wax component, 0.13% of the antistatic agent, 0.025% of the organic spherical fine particles, and 0.3% of the colloidal cerium oxide were sufficiently mixed to prepare a coating liquid for forming a release layer (C-1).

(6) Production of separator film (DC) (manufacture of polyester film (D) and laminate of release layer (C))

The particles of polyethylene terephthalate (inherent viscosity 0.65 dl/g) were sufficiently vacuum dried, and then supplied to an extruder heated at 280 ° C, and extruded into a sheet shape by a T-shaped die, using static electricity. The cast casting method was wound around a mirror casting drum having a surface temperature of 30 ° C and cooled and solidified. This unstretched film was passed through a heating roll group of 95 ° C while being stretched 3.5 times in the longitudinal direction to form a one-axis stretched film. The coating liquid for forming a release layer (C-1) was applied to both surfaces of the one-axis alignment film. The coated one-axis stretched film was held by a jig while being guided to a preheating zone, dried at 110 ° C, and then continuously stretched 3.5 times in the width direction in a heating zone of 125 ° C. Further, at 225 ° C, 6% relaxation was carried out in the width direction, and heat treatment was performed for 6 seconds. A laminate (d) (separation film (DC-1)) having a thickness of 50 μm of a release layer (C) having a thickness of 0.15 μm in a two-layer layer of the polyester film (D) was obtained.

(7) Multilayer of polyoxyalkylene rubber adhesive layer (B)

A non-reactive polyoxane which is substantially free of a reinforcing agent such as cerium oxide and has a number average molecular weight of 150,000 (measured by GPC method, converted to polystyrene) by an uncrosslinked polydimethyl siloxane skeleton An alkane compound ("KF-96H-500,000 cs"; manufactured by Shin-Etsu Chemical Co., Ltd.) was weighed to a mass ratio of 23% to toluene, and was placed in a mixer equipped with a vacuum defoaming device together with toluene at atmospheric pressure. Stir at room temperature for 15 hours and dissolve in toluene. In the obtained solution, trimethylolpropane trimethacrylate was added in two portions with respect to 100 parts of the above polyoxyalkylene compound, and after uniformly stirring, a vacuum defoaming device was driven to make a gauge pressure. The mixture was degassed by stirring under a vacuum of -750 mmHg for further 20 minutes. Next, the defoamed polyoxyalkylene compound solution is supplied to a roll coater to apply the polyoxymethane compound solution to the dried thickness on the surface of the heat-resistant water-adhesive improving layer (E) of the layered product (c). It was 25 μm, then introduced into an oven and dried at 80 °C. A laminated body (e) in which the uncrosslinked polyoxyalkylene rubber adhesive layer (B-1) is formed on one side of the laminated body (c) can be obtained.

On the surface of the uncrosslinked polyoxyalkylene rubber adhesive layer (B-1) of the above laminated body (e), the laminated body (d) (separating film (DC-1)) is superposed on one surface, and the pressing roller (pressure) 30 N/cm ² ) Pressing to carry out continuous lamination. The obtained laminated body (f) is continuously introduced into an electron beam irradiation apparatus, and an electron beam is irradiated with energy of 200 KV and 18 Mrad from the side of the separator film (DC-1) to carry out crosslinking of the adhesive layer, and the crosslinked polysiloxane is provided. The laminate (f') (protective film for display screen) of the alkane rubber adhesive layer (B) is wound into a roll shape. In the manufacturing steps up to this point, the occurrence of the channeling phenomenon of the separator film (DC-1) was not observed.

The characteristics of the protective film for displaying a screen image obtained in the first embodiment and the characteristics of the coating liquid for forming the adhesive layer (B) of the polyoxyalkylene oxide are shown in Table 1.

The protective film for a display screen obtained in the present embodiment is excellent in transparency, and the polyoxyalkylene rubber adhesive layer (B) and the polyester base film (A) are firmly adhered via the hot water resistant adhesion improving layer (E). The adhesion to the ground is excellent in adhesion and heat-resistant water adhesion. Moreover, the peeling force of the mold release layer (C) and the adhesive layer (B) is also moderate, and is excellent in peelability, and is a high-quality protective film for display screens. Further, the clarity of the coating liquid for forming the adhesive layer (B) in the production of the protective film for a display screen is excellent in stability, and it is confirmed that the handleability and handling stability are excellent.

Comparative example 1

In the method of the first embodiment, a protective film for a display screen was obtained in the same manner as in Example 1 except that the coating liquid (E-1) for forming the hot water-resistant water adhesion improving layer (E) was stopped. The evaluation results are shown in Table 1.

The protective film for a display screen obtained in Comparative Example 1 was bonded to the polyester base film (A) and heat-resistant water by the adhesive film of the polyoxyalkylene rubber adhesive layer (B) as compared with the film of Example 1. Poor sex and low quality.

Comparative example 2

In the method of the first embodiment, the coating liquid (E-1) for forming a hot water-resistant water adhesion improving layer (E) is added, and the methylolated melamine resin is added as a crosslinking agent. 1 A protective film for a display screen is obtained in the same manner. The evaluation results are shown in Table 1.

The protective film for display screen obtained in Comparative Example 2 has good peeling strength between the adhesive layer of the polyoxyalkylene rubber (B) and the release layer (C), whereas the adhesive layer of the polyoxyalkylene rubber (B) and The heat-resistant water adhesion between the polyester base film (A) is poor.

Comparative example 3

In the method of the first embodiment, the coating liquid (C-1) for forming the release layer (C) was mixed, and the polymer wax component and the antistatic agent were blended, and the display method was obtained in the same manner as in Example 1. Protective film. The evaluation results are shown in Table 1.

The protective film for a display screen obtained in Comparative Example 3 was obtained by peeling off the separator film from the polyoxyalkylene rubber adhesive layer (B), but peeling property was poor. Therefore, since it cannot be used as a protective film for a display screen, evaluation other than peeling property cannot be performed.

Comparative Examples 4 and 5

In the method of the first embodiment, in addition to the coating liquid (C-1) for forming the release layer (C), the blending of the polymer wax component in Comparative Example 4 and the combination of the antistatic agent in Comparative Example 5 were suspended. Further, in the same manner as in Example 1, a protective film for a display screen was obtained. The evaluation results are shown in Table 1.

The protective film for a display screen obtained in Comparative Example 4 was not able to peel off the separator film from the polyoxyalkylene rubber adhesive layer (B). Therefore, in the film for display screen protection of Comparative Example 4, evaluation other than the peeling property could not be performed. Moreover, the peeling strength of the separator film of Comparative Example 5 was large, and the peeling property of the separator film was poor.

Comparative Example 6

In the method of the first embodiment, the same method as in the first embodiment was carried out except that the release film was a polyester film for mold release ("E7002"; manufactured by Toyobo Co., Ltd.) having a thickness of 38 μm which was treated with polysiloxane. A protective film for a display screen is obtained. Further, the polyoxyalkylene rubber adhesive layer (B) is a layer in contact with the polyoxyalkylene treated surface. The evaluation results are shown in Table 1.

The protective film for a display screen obtained in Comparative Example 6 was the same as Comparative Example 3, and the release film was not peeled off from the polyoxyalkylene rubber adhesive layer (B), and the peeling property was poor. It is assumed that cross-linking and bonding occurs between the adhesive layer of the polyoxyalkylene rubber (B) and the release layer of the separator film by EB cross-linking. Therefore, it cannot be used as a protective film for a display screen. On the other hand, in the protective film for a display screen of Comparative Example 6, evaluation other than the peeling property could not be performed.

Comparative Example 7

In the method of the first embodiment, a protective film for a display screen was obtained in the same manner as in Example 1 except that the thickness of the hot water-resistant water-improving layer (E) was changed to 0.7 μm. The evaluation results are shown in Table 1.

The protective film for a display screen obtained in Comparative Example 7 has good adhesion between the polyester base film (A)/polyoxyalkylene rubber adhesive layer (B), but is displayed in the same manner as in the first embodiment. In comparison with the protective film for the screen, the heat-resistant water adhesion of the polyoxyalkylene rubber adhesive layer (B) was poor.

Comparative Example 8

In the method of Comparative Example 2, a protective film for a display screen was obtained in the same manner as in Comparative Example 2 except that the preparation of the coating liquid for forming a polyoxyalkylene rubber adhesive layer (B) was changed to the following. The thickness of the polyoxyalkylene rubber adhesive layer was the same as in Comparative Example 2, and was adjusted to 25 μm after drying. The evaluation results are shown in Table 1.

[Preparation of coating liquid (B-2) for forming a polyoxyalkylene rubber adhesive layer (B)]

60 parts of a polyoxymethane compound of a polydimethyloxane skeleton, 25 parts of a polyoxyalkylene compound of a polydimethylene oxyalkylene skeleton, and 15 parts of cerium oxide to form a highly transparent polyoxyl An alkane rubber compound ("TSE260-3U"; rubber hardness: 30 °; manufactured by Momentive Performance Materials Co., Ltd., Japan) was weighed so that the mass ratio to toluene was 23%, and it was put together with toluene in a mixer equipped with a vacuum defoaming device. It was stirred at room temperature for 15 hours at atmospheric pressure and dissolved in toluene. To 100 parts of the rubber compound, 2 parts of trimethylolpropane trimethacrylate was added to the obtained solution, and after uniformly stirring, the vacuum defoaming device was driven, and under a vacuum of -750 mmHg, and then 20 The mixture was stirred and defoamed in a minute to obtain a coating liquid (B-2) for forming a polyoxyalkylene rubber adhesive layer (B). Further, the above polyoxyalkylene rubber compound is used after 6 months from the purchase.

In the protective film for a display screen obtained in Comparative Example 8, the problem of the protective film for a display screen obtained in Comparative Example 2 was added, and the clarity and storage stability of the coating liquid were poor.

Reference example 1

In the method of the first embodiment, the coating liquid for forming the hot water-resistant water-improving layer (E) was changed to 8 parts of organic polyoxane ("KS-744"; manufactured by Shin-Etsu Chemical Co., Ltd.) and a catalyst. In the same manner as in Example 1, 0.06 parts of "PL-3" (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in a solution of 100 parts by mass of toluene, and a protective film for a display screen was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

In the protective film for a display screen obtained in Reference Example 1, the polyoxyalkylene rubber adhesive layer (B) and the polyester base film (A) have poor heat-resistant water adhesion properties and are low in quality.

Example 2

When the polyester base film (A) of Example 1 was produced, a polyester base film (A-) was obtained in the same manner as in Example 1 except that the application of the coating liquid (E-1) was stopped. 2). Corona treatment was performed on both sides of the polyester base film (A-2). In addition, a copolymerized polyester resin solution ("vylon (registered trademark) 30SS"; manufactured by Toyobo Co., Ltd.) and a polyisocyanate-based crosslinking agent ("Coronet (registered trademark) HX"; manufactured by Japan Polyurethane Co., Ltd.) The coating liquid (E-2) for the hot water-resistant water adhesion improving layer (E) was prepared by blending the solid content ratio with 100:3 (parts). This coating liquid (E-2) was applied to both sides of the polyester-based base film (A-2) after corona treatment, and dried by application using a coater. A heat-resistant water-adhesive improving layer (E-2) cross-linked on both sides of the polyester-based base film (A-2) was obtained as a laminated body. Using this laminate, a protective film for a display screen was obtained in the same manner as in Example 1. Further, the thickness of the hot water-resistant water-improving layer (E-2) after the biaxial stretching was 0.31 μm each. The evaluation results are shown in Table 2.

The protective film for a display screen obtained in the present embodiment has the same characteristics as the protective film for a display screen obtained in Example 1, and has high quality.

Comparative Example 9

In the case of the preparation of the coating liquid (E-2) of the second embodiment, a display screen was obtained in the same manner as in the first embodiment except that the "Coronet HX" of the crosslinking agent was stopped and only "vylon 30SS" was used. Use a protective film. The evaluation results are shown in Table 2.

In the protective film for a display screen obtained in Comparative Example 9, the polyoxyalkylene rubber adhesive layer (B) and the polyester base film (A) had poor heat-resistant water adhesion.

Examples 3 to 5

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

The protective film for a display screen obtained in the above examples has the same characteristics as the protective film for a display screen obtained in Example 1, and has high quality.

[Example 3: Coating liquid for heat-resistant water adhesion improving layer]

100 parts of the solid content of the acrylic emulsion ("Joncryl (registered trademark) PDX-7630A"; manufactured by BASF Japan Co., Ltd.), and 10 parts of the "Saimel 303" and 0.04 parts of the above "Catalyst 600" were mixed to improve the heat-resistant water adhesion. Coating liquid for layer (E-3).

[Coating liquid for adhesive adhesion improving layer of Example 4]

The solid content of the polyurethane dispersion ("Hydran (registered trademark) AP40"; manufactured by Dainippon Ink Co., Ltd.) is 100 parts, and the oxazoline crosslinking agent makes "Epocros (registered trademark) WS -700" (manufactured by Nippon Shokubai Co., Ltd.) was added in three portions to form a coating liquid (E-4) for a hot water-resistant water adhesion improving layer.

[Coating liquid for heat-resistant water adhesion improving layer of Example 5]

40 parts of a self-crosslinking type polyester resin aqueous dispersion "Vylonal (registered trademark) AGN702" (manufactured by Toyobo Co., Ltd.), 24 parts of water and 36 parts of isopropyl alcohol, and further 10% of an anionic surfactant was added. 0.6 parts of aqueous solution, 1 part of propionic acid, 1.8 parts of 20% aqueous dispersion of colloidal cerium oxide particles (average particle diameter of 40 nm), and dry cerium oxide particles (average particle diameter: 200 nm; average-minor particle size: 40 nm) 1.1 parts of a 4% aqueous dispersion was used as a coating liquid (E-5) for a heat-resistant water adhesion improving layer.

Example 6

In the method of the first embodiment, a protective film for a display screen was obtained in the same manner as in Example 1 except that the separator film (DC-2) produced by the following method was used. The evaluation results are shown in Table 2.

[Modulation of Separated Film (DC-2)]

The coating liquid (C-1) used for the production of the separator film (DC-1) of Example 1 was applied onto a polyester film (D: 100 μm) using a wire bar (N0.5). The coating amount of the coating liquid (C-1) is about 8 to 10 g per 1 m ² of the base film (wet state). It was dried at 160 ° C for about 60 seconds to obtain a separator film (DC-2).

The protective film for a display screen obtained in the sixth embodiment has the same characteristics as the protective film for a display screen obtained in the first embodiment and is of high quality. Further, in the same manner as in the first embodiment, the occurrence of floating of the separator film (DC-2) was not observed at the time of manufacture of the protective film for display screen.

Example 7

In the method of the first embodiment, the polymer wax component of the coating liquid (C-1) used for the separation film (DC-1) was changed to an acrylic wax emulsion ("ST-200"; Japan Other than the catalyst company, a protective film for a display screen was obtained in the same manner as in the first embodiment. The evaluation results are shown in Table 2.

The protective film for a display screen obtained in the seventh embodiment has the same characteristics as the protective film for a display screen obtained in the first embodiment, and is high in quality. Further, in the same manner as in the first embodiment, when the protective film for a display screen was produced, the floating of the separator film could not be seen.

Example 8

In the method of the first embodiment, the antistatic agent for the coating liquid (C-1) for producing the separator film (DC-1) was changed to an anionic antistatic agent ("TB214"; the first industrial pharmaceutical company). Other than the system, a protective film for a display screen was obtained in the same manner as in the first embodiment. The evaluation results are shown in Table 3.

The protective film for a display screen obtained in the eighth embodiment has the same characteristics as the protective film for a display screen obtained in the first embodiment, and is high in quality. Further, in the same manner as in the first embodiment, the occurrence of floating of the separator film was not observed at the time of production of the protective film for display screen.

Example 9

In the method of the first embodiment, the polymer wax component of the coating liquid (C-1) used for the production of the separator film (DC-1) was changed to 0.2%, and the antistatic agent was changed to 0.3%. A protective film for a display screen was obtained in the same manner as in Example 1. The evaluation results are shown in Table 3.

The protective film for a display screen obtained in the ninth embodiment has the same characteristics as those of the protective film for a display screen obtained in the first embodiment. Further, in the same manner as in the first embodiment, the occurrence of floating of the separator film was not observed at the time of production of the protective film for display screen.

Comparative Example 10

In the method of the first embodiment, the polymer wax component of the coating liquid (C-1) used for the production of the separator film (DC-1) was changed to 1.3%, and the antistatic agent was changed to 1.5%. A protective film for a display screen was obtained in the same manner as in Example 1. The evaluation results are shown in Table 3.

The peeling strength of the separator film (DC) of the protective film for a display screen obtained in Comparative Example 10 was approximately ON/20 mm, and the peeling was extremely good. When the protective film for a display screen was produced, there was a floating of the separator film (float). )occur.

Example 10

In the method of Example 1, the surface of the layered body (d) of the separator film (DC-1) to be produced, the coating liquid (B-3) for the polyoxyalkylene rubber adhesive layer (B) prepared by the following method was used. In the same manner as in Example 1, a polyoxyalkylene rubber adhesive layer (B-3) was laminated to obtain a layered product (g). On the surface of the polyoxyalkylene rubber adhesive layer (B-3) of the obtained laminate (g), the surface of the heat-resistant water-adhesive improving layer (E) of the layered product (c) produced in Example 1 was overlapped while The pressure roller (pressure: 30 N/cm ² ) was pressed to carry out continuous lamination. The obtained laminated body (h) was further continuously introduced into an electron beam irradiation apparatus, and an electron beam was irradiated from the side of the laminated film (DC-1) laminated body (d) at an energy of 200 KV and 18 Mrad to carry out a polyoxyalkylene rubber adhesive layer (B). -3) crosslinking, so that the laminated body (h') after crosslinking is wound into a roll shape. In the manufacturing steps up to this point, the occurrence of the channeling phenomenon of the separator film was not observed.

The protective film for a display screen obtained in the present embodiment has the same characteristics as the protective film for a display screen obtained in Example 1, and is of high quality. The evaluation results are shown in Table 3.

[Preparation of Coating Liquid for Polyoxyalkylene Rubber Adhesive Layer (B-3)]

It does not substantially contain a reinforcing agent such as cerium oxide, and weighs a non-reactive polyoxymethane which is an uncrosslinked polydimethyl siloxane skeleton having a number average molecular weight of 170,000 (measured by GPC method and converted to polystyrene). The compound ("KF-96H-100,000 cs"; manufactured by Shin-Etsu Chemical Co., Ltd.) was made into a mass ratio of 23% with respect to toluene, and was put into a stirrer equipped with a vacuum defoaming device together with toluene at room temperature under atmospheric pressure. Stir for 15 hours and dissolve in toluene. In the obtained solution, trimethylolpropane trimethacrylate was added in two portions with respect to 100 parts of the above polyoxyalkylene compound, and after uniformly stirring, a vacuum defoaming device was driven to measure a vacuum of -750 mmHg. The mixture was further stirred for 20 minutes and defoamed.

Example 11

Using the polyoxyalkylene compound solution prepared in Example 1, the polysiloxane compound solution was applied to one side of the layered product (a) obtained in Example 1, and dried to a thickness of 25 μm, and then introduced into an oven at 80°. Dry at °C. The laminated body (i) in which the uncrosslinked adhesive layer (B-1) is formed on one side of the laminated body (a) can be obtained.

On the surface of the uncrosslinked adhesive layer (B-1) of the laminated body (i), the laminated body (d) was placed, and pressed by a pressure roller (pressure: 30 N/cm ² ) to carry out continuous lamination. The obtained laminated body (j) is continuously introduced into the electron beam irradiation apparatus, and the electron beam is irradiated with energy of 200 KV and 18 Mrad from the side of the laminated body (d) to carry out crosslinking of the adhesive layer, and the polyfluorene oxide is provided after crosslinking. The laminated body (j') of the rubber adhesive layer (B) is wound into a roll shape. In the manufacturing steps up to this point, the occurrence of the channeling phenomenon of the separator film was not observed.

(6) Lamination of acrylic adhesive layer (F)

"SKDyne 2094" (manufactured by Nippon Chemical Co., Ltd.), an optical acrylic adhesive, was applied to the surface of the layered body (a) of the layered product (j') so that the thickness after drying was 25 μm, and was carried out at 130 °C. It dried in minutes to form an acrylic adhesive layer (F). Laminating the surface of the adhesive layer (F) to form a 38 μm-thick separation film (D"C") of polyethylene terephthalate treated (release layer C") with polyethylene terephthalate (" E7002"; manufactured by Toyobo Co., Ltd.) The side of the polyoxane treatment side contact was obtained to obtain a double-sided adhesive sheet. In this step, the occurrence of the channeling phenomenon of the separation film cannot be seen.

The characteristics of the double-sided adhesive sheet obtained in the above Example 11 and the characteristics of the coating liquid for forming the adhesive layer of the polyoxyalkylene rubber (B) are shown in Table 4.

The double-sided adhesive sheet obtained in the present embodiment is excellent in transparency, and the polyoxyalkylene rubber adhesive layer (B) and the polyester base material film (E) are firmly adhered via the heat-resistant water adhesion improving layer (E). Bonding. Further, the release force of the release layer (C) and the polyoxyalkylene rubber adhesive layer (B) is also moderate, and it is a high-quality double-sided adhesive sheet. Further, in the production of the double-sided adhesive sheet, the coating liquid for forming the polyoxyalkylene rubber adhesive layer (B) is excellent in clarity and stability, and it is confirmed that the workability and the handling stability are excellent.

Comparative Example 11

In the method of Example 11, except that the blending of the polymer wax component of the coating liquid (C-1) for forming the release layer (C) and the antistatic agent was stopped, the double-sided adhesion was obtained in the same manner as in Example 11. Sheet. The evaluation results are shown in Table 4.

In the double-sided adhesive sheet obtained in Comparative Example 11, although the separator film was peeled off from the polyoxyalkylene rubber adhesive layer (B), it could not be peeled off. Therefore, it cannot be used as a double-sided adhesive sheet.

Example 12

On the single side of the layered product (d) produced in Example 1, a polyoxyalkylene rubber adhesive layer (B-1) was formed in the same manner as in Example 1. On the surface of the polyoxyalkylene rubber adhesive layer (B-1), the laminate (a) produced in Example 1 was laminated to obtain a laminate (k). The obtained layered product (k) was further introduced into the electron beam irradiation apparatus, and the layered body (k') was obtained by crosslinking the polyoxyalkylene rubber adhesive layer (B-1) in the same manner as in the first embodiment. Using this laminate (k'), a double-sided adhesive sheet was obtained in the same manner as in Example 11 and wound into a roll shape. The channeling phenomenon of the separation film was not observed in the manufacturing step. The evaluation results are shown in Table 4.

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

Example 13

Using the two-sided adhesive sheet obtained in Example 11 or 12, the face sheet of the face sheet of the electrostatic capacitance type touch panel was bonded to the coordinate detecting sheet. First, a cover sheet was attached to the side of the acrylic adhesive layer (F), and then a polypyrylene rubber adhesive layer (B) was used, and the sheet was attached to the coordinates. The workability of these sticking steps is good.

Since the polyoxyalkylene rubber adhesive layer (B) is excellent in removability, it can be easily peeled off even if it is accidentally lost. Therefore, the occurrence of defective products due to misplacement can be eliminated. Further, for example, when the adhesive sheet is bonded to the side of the adhesive layer (B) of the polyoxyalkylene rubber, the loss of the facing sheet due to the mistake can be eliminated.

Example 14

The two-sided adhesive sheet obtained in the embodiment 11 or 12 is used to bond the touch panel portion of the resistive touch panel to the display device. In the same manner as in the thirteenth embodiment, the workability in the sticking step can be improved. Further, for example, when the bonding is performed so that the polyoxyalkylene rubber adhesive layer (B) side becomes a display device, as in the thirteenth embodiment, the loss of the display device due to the missed loss can be eliminated.

Example 15

Using the polyoxyalkylene compound solution prepared in the same manner as in Example 1, the polysiloxane compound solution was applied to both sides of the layered product (a) obtained in Example 1, and dried to a thickness of 25 μm, and then introduced into an oven. Dry at 80 °C. The laminated body (1) in which the uncrosslinked polyoxyalkylene rubber adhesive layers (B-1) and (B'-1) are formed on both sides of the laminated body (a) can be obtained.

The layered body (d) obtained in Example 1 is superposed on the surfaces of the uncrosslinked polyoxyalkylene rubber adhesive layers (B-1) and (B'-1) on both sides of the above laminated body (1) (separating film DC) At the same time as D'C'), the pressure was applied by a pressure roller (pressure: 30 N/cm ² ) to carry out continuous lamination. The obtained layered product (m) is continuously introduced into the electron beam irradiation apparatus, and the electron beam is irradiated with energy of 200 KV and 16 Mrad from the side of the layered body (d) on the surface of (B-1) to carry out crosslinking of the adhesive layer. The laminated body (m') of the adhesive layer (B1) is wound into a roll shape. The layered body (m') is again introduced into the electron beam irradiation apparatus, and the electron beam is irradiated from the side of the layered body (d) on the surface of (B'-1) at an energy of 200 KV and 18 Mrad to crosslink the adhesive layer. The laminated body (m'') having the adhesive layer (B'1) is wound into a roll shape. In the manufacturing steps up to this point, the occurrence of the channeling phenomenon of each of the separator films was not observed.

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

The double-sided adhesive sheet obtained in this example is excellent in transparency. Further, the polyoxyalkylene rubber adhesive layer (B) is strongly adhered to the polyester base film (A) via the hot water adhesion improving layer (E), and the heat resistant water adhesion improving layer is interposed therebetween. (E) The polyoxyalkylene rubber adhesive layer (B') is firmly bonded to the polyester base film (A) to provide excellent adhesion and heat-resistant water adhesion. Moreover, the release force of the release layer (C) and the polyoxyalkylene rubber adhesive layer (B) and the release layer (C') and the polyoxyalkylene rubber adhesive layer (B') are also moderate, and are exfoliating. Excellent high quality double-sided adhesive sheet. Further, in the production of the double-sided adhesive sheet, the coating liquid for forming the polyoxyalkylene rubber adhesive layers (B) and (B') is excellent in clarity and stability, and it is confirmed that the handleability and handling stability are excellent.

Comparative Example 12

In the method of the first embodiment, the double-sided adhesive sheet was obtained in the same manner as in Example 15 except that the blending of the polymer wax component of the coating liquid (C-1) for forming the release layer (C) and the antistatic agent was stopped. . The evaluation results are shown in Table 5.

In the double-sided adhesive sheet obtained in Comparative Example 12, the respective separator films were peeled off from the polyoxyalkylene rubber adhesive layers (B) and (B'), but they were not peeled off, and the peeling property was poor. Therefore, it cannot be used as a double-sided adhesive sheet.

Example 16

Using the double-sided adhesive sheet obtained in Example 15, the overlay sheet of the face sheet of the capacitive touch panel was bonded to the coordinate detecting sheet. The workability of these sticking steps is good. Further, since the polyoxyalkylene rubber adhesive layer (B) is excellent in removability, it can be easily peeled off even if it is accidentally lost. Therefore, it is possible to eliminate the occurrence of defective products caused by mistakes. In particular, in the double-sided adhesive sheet of the present invention, both of the adhesive layers are excellent in re-peelability, and the loss due to the misregistration of both the overlay sheet and the coordinate detecting sheet can be eliminated.

Example 17

The two-sided adhesive sheet obtained in Example 15 was used to bond the touch panel portion of the resistive touch panel to the display device. As in the case of Example 16, the workability in the bonding step was good. Further, in the same manner as in the sixteenth embodiment, it is possible to eliminate the loss of the display device and the panel caused by the misplacement.

Example 18

(1) Manufacture of a single-sided adhesive sheet having an anti-damage layer and a polyoxyalkylene rubber adhesive layer

In the same manner as in Example 1, a coating liquid (E-1) for a hot water-resistant water adhesion improving layer was prepared. Further, in the same manner as in Example 1, a laminate of the polyester base film (A) and the coating liquid (E-1) was produced, and the laminate was produced on both sides of the biaxially oriented polyethylene terephthalate base film. 0.08 μm of the crosslinked heat-resistant water adhesion improving layer (E) having a thickness of 12 μm of the layered body (n).

The polyoxoxane compound solution prepared in the same manner as in Example 1 was applied to one side of the above laminated body (n) so that the thickness of the polyoxyalkylene compound solution after drying was 25 μm, and then it was introduced into an oven and dried at 80 ° C. . An uncrosslinked polyoxyalkylene rubber adhesive layer (B-1) can be obtained as a laminate (o) formed on one side of the laminate (n).

The layered body (d) (separating film) produced in Example 1 was superposed on the surface of the uncrosslinked polyoxyalkylene rubber adhesive layer of the above laminated body (o), followed by a pressing roll (pressure 30 N/cm ^{2 )} Pressing to perform continuous lamination. The obtained layered product (p) is continuously introduced into an electron beam irradiation apparatus, and an electron beam is irradiated from the side of the separator film at an energy of 200 KV and 18 Mrad to carry out crosslinking of the adhesive layer, and the crosslinked layer is provided with a polyoxyalkylene rubber adhesive layer ( The layered body (p') of B) is wound into a roll shape. In the manufacturing steps up to this point, the occurrence of the channeling phenomenon of the separator film was not observed.

An ultraviolet curable hard coat coating ("Seikabeam (registered trademark) EXF-OIB) on the opposite side of the polysiloxane rubber adhesive layer (B) of the laminate (p'); manufactured by Daisei Seiki Co., Ltd.) After coating, the film thickness after drying was 5 μm, and the solvent was dried, and the ultraviolet ray was irradiated with a high-pressure mercury lamp at 800 mJ/cm ² to deposit a damage-preventing layer. A single-sided adhesive sheet having a damage-preventing layer was obtained. As shown in Table 6.

(2) Manufacture of a transparent conductive laminate (2-1) having a transparent conductive layer laminated on a transparent substrate

The non-adhesive treatment surface of a polyester film ("Cosmoshine (registered trademark) A4100; manufactured by Toyobo Co., Ltd.; 75 μm) is 0.533 Pa (4 × 10 ^-3 ) in an amount of 80% by volume of argon and 20% by volume of oxygen. In the atmosphere of the drag ear, a thickness of 400 is formed by reactive sputtering using an indium-tin alloy. A transparent conductive layer is formed of a composite oxide of indium oxide and tin oxide to obtain a transparent conductive laminate (2-1).

(3) Manufacture of upper electrode for touch panel

The separator film of the polyoxyalkylene rubber adhesive layer (B) having the single-sided adhesive sheet having the damage prevention layer obtained in the above is peeled off and adhered to the transparent conductive layer of the transparent conductive laminate (2-1). On the opposite side, the upper electrode for the touch panel is obtained. The workability of the pasting steps is good. On the other hand, since the polyoxyalkylene rubber adhesive layer (B) is excellent in removability, it can be easily peeled off even if it is accidentally lost. Therefore, it is possible to eliminate the occurrence of defective products caused by mistakes.

The above-mentioned touch panel panel upper electrode was used and the pen slip resistance test was performed in the following manner. That is, the two upper electrodes are opposed to each other with a spacer having a thickness of 100 μm so that the transparent conductive layers are opposed to each other, and the load of 5. ON is applied to the pen of the polyacetal (the shape of the front end: 0.8 mmR), at a linear sliding test of 100,000 times (50,000 times back and forth) at 23 ° C and 44% RH. At this time, the sliding distance was 30 mm and the sliding speed was 60 mm/sec.

After the sliding resistance test, first, whether or not the sliding portion was whitened was visually observed, and no whitening was observed on the electrode. In addition, when the sliding resistance was measured by the pen load of 0.5 N, the ON resistance (the resistance value when the upper and lower electrodes were in contact) was measured, and the value was maintained within 3 times of the initial value, and it was confirmed that the pen sliding resistance was excellent.

Comparative Example 13

In the method of the first embodiment, the same as in Example 18 except that the blending of the polymer wax component and the antistatic agent for the release coating layer (C-1) for forming the release film was suspended. Single-sided adhesive sheet with a damage-proof layer. The evaluation results of the one-sided adhesive sheets obtained in Comparative Example 13 are shown in Table 6. The adhesive layer of the polyoxyalkylene rubber from which the single-sided adhesive sheet is to be peeled off allows the separation film to be peeled off but cannot be peeled off. Therefore, the manufacture of the upper electrode for the touch panel is suspended.

Comparative Example 14

In the method of Example 18, except for the application of the coating liquid (E-1) for forming the hot water-resistant water-improving layer, the single-sided adhesive sheet was obtained in the same manner as in Example 18, and the upper portion for the touch panel was obtained. electrode. The evaluation results of the one-sided adhesive sheet having the damage prevention layer obtained in Comparative Example 14 are shown in Table 6. The single-sided adhesive sheet, the adhesive layer of the polyoxyalkylene rubber (B) and the polyester-based base film (A) have poor adhesion to the heat-resistant water and have low quality.

In the pen slip resistance test of the upper electrode for a touch panel, the whitening of the sliding portion was not confirmed at 23 ° C and 44% RH. However, at 50 ° C and 65% RH, it was confirmed that the sliding portion was whitened. Further, the ON resistance can be maintained within 3 times of the initial value at 23 ° C and 44% RH. However, at 50 ° C and 65% RH, it is 6 times the initial value. In the single-sided adhesive sheet, it is the result of poor adhesion of hot water.

Comparative Example 15

In the method of the example 18, except that the thickness of the hot water-resistant water-improving layer (E) was changed to 0.7 μm, the single-sided adhesive sheet having the damage-preventing layer was obtained in the same manner as in Example 18, and the touch type was obtained. The upper electrode for the panel. The evaluation results of the one-sided adhesive sheets obtained in Comparative Example 15 are shown in Table 6. This single-sided adhesive sheet is low in quality due to poor adhesion of hot water. The same results as in Comparative Example 14 were obtained by evaluation of the upper electrode for the touch panel.

Example 19

In an atmosphere of 0.533 Pa (4 x 10 ^-3 Torr) formed by 80% by volume of argon gas and 20% by volume of oxygen, in Example 18, by reactive sputtering using an indium-tin alloy. On the other side of the laminated body (n), a transparent conductive layer formed of a composite oxide of indium oxide and tin oxide having a thickness of 400 A is formed to obtain a transparent conductive laminated body (2-2).

The polyoxonane compound solution prepared in the same manner as in Example 1 was coated on the single side of the transparent conductive laminate (2-2), and the polypyroxylate compound solution was applied so as to have a thickness of 25 μm after drying, and then introduced into the baking. The furnace was dried at 80 °C. A laminate (q) having an uncrosslinked polyoxyalkylene rubber adhesive layer (B-1) formed on one surface of the transparent conductive laminate (2-2) can be obtained.

The layered body (d) (separating film) produced in Example 1 was superposed on the surface of the uncrosslinked polyoxyalkylene rubber adhesive layer of the above laminated body (q) while being pressed by a roll (pressure 30 N/cm ^{2 )} Pressing to perform continuous lamination. The obtained laminate is continuously introduced into an electron beam irradiation apparatus, and an electron beam is irradiated from the side of the separator film at an energy of 200 KV and 18 Mrad to crosslink the adhesive layer of the polyoxyalkylene rubber, and the polyoxyalkylene rubber is adhered after crosslinking. The one-sided adhesive sheet having the transparent conductive layer of the layer (B) is wound into a roll shape. In the manufacturing steps up to this point, the occurrence of the channeling phenomenon of the separator film was not observed. The evaluation results of the characteristics of the one-side adhesive sheet and the coating liquid for forming the adhesive layer of the polyoxyalkylene rubber (B) are shown in Table 7.

The single-sided adhesive sheet having the transparent conductive layer obtained in the present embodiment is excellent in transparency. Further, the polyoxyalkylene rubber adhesive layer (B) and the polyester base film (A) are firmly adhered to each other via the hot water-resistant adhesion improving layer (E), and the adhesiveness and heat-resistant water adhesion are adhered. Excellent in sex. Further, the releasing force of the release layer (C) and the polyoxyalkylene rubber adhesive layer (B) is also moderate, and it is a high-quality single-sided adhesive sheet excellent in peelability. Further, the coating liquid for forming the polyoxyalkylene rubber adhesive layer (B) in the production of the single-sided adhesive sheet is also excellent in clarity and stability, and is also excellent in workability and handling stability.

Comparative Example 16

In the method of the first embodiment, the same as in the embodiment 19 except that the coating liquid (C-1) for forming the release layer is used to terminate the blending of the polymer wax component and the antistatic agent. A single-sided adhesive sheet having a transparent conductive layer is obtained. The evaluation results of the one-sided adhesive sheets obtained in Comparative Example 16 are shown in Table 7. The polyoxyalkylene rubber adhesive layer (B) from which the single-sided adhesive sheet is to be peeled off, but cannot be peeled off. Therefore, the manufacture of the upper electrode for the touch panel is suspended.

Example 20

(1) Manufacture of a laminate (1) having a structure in which a transparent substrate is laminated with a damage prevention layer

One side coating of a polyester film ("cosmoshine (registered trademark) A4300"; manufactured by Toyobo Co., Ltd.; 75 μm) to make an ultraviolet curing type hard coating ("Seikabeam (registered trademark) EXF-01B"; The film thickness after drying was 5 μm, and after drying the solvent, ultraviolet rays were irradiated at 800 mJ/cm ² with a high pressure mercury lamp to obtain a laminate (1) in which the damage prevention layer was laminated.

(2) Manufacture of upper electrode for touch panel

The separator film having the single-sided adhesive sheet having the transparent conductive layer obtained by the method of Example 19 is peeled off, and bonded to the opposite surface of the damage preventing layer of the laminated body (1) in which the damage preventing layer is laminated. Create the upper electrode for the touch panel. The workability of these sticking steps is good. Further, since the polyoxyalkylene rubber adhesive layer (B) is excellent in removability, it can be easily peeled off even if it is accidentally lost. Therefore, it is possible to eliminate the occurrence of defective products caused by mistakes.

The pen slip resistance test was carried out at 23 ° C and 44% RH in the same manner as in Example 18 using the above-described upper electrode for a touch panel. After the sliding resistance test, it was visually observed whether the sliding portion was whitened, and whitening could not be seen. In addition, when the ON resistance (the resistance value when the upper and lower electrodes are in contact) is measured when the sliding load is 0.5 N, the initial value is kept within 3 times, and it is confirmed that the pen sliding resistance is excellent.

Comparative Example 17

In the method of Example 20, except that the one-sided adhesive sheet having the transparent conductive layer was not used, and the transparent conductive laminated body (2-2) obtained in Example 19 was laminated (the polyoxyalkylene rubber adhesive layer was laminated) In the same manner as in Example 20, the pen slip resistance test was carried out in the same manner as in Example 20 except that the two sheets were laminated. In the sliding part, whitening is visible, and the value of the ON resistance is 15 times of the initial value, and the pen sliding resistance is also poor.

Example 21

(1) Manufacture of two-sided adhesive sheets

The polyoxyxane rubber adhesive layer (B) having the laminated body (p') of the crosslinked polyoxyalkylene rubber adhesive layer (B) produced in Example 18 on one side was coated on the opposite side and coated on the opposite side. The acrylic adhesive ("SKDyne 2094" (manufactured by Soken Chemical Co., Ltd.) was used to make the thickness after drying to 25 μm, and dried at 130 ° C for 3 minutes to form an acrylic adhesive layer (F). On the surface of the acrylic adhesive layer (F), a separator film ("E7002"; Toyo) having a thickness of 12 μm made of polyethylene terephthalate (D''C'') treated with polyoxymethane was laminated. The side of the polyoxyalkylene treated side of the spinning company was in contact with each other to obtain a double-sided adhesive sheet. The characteristics of the obtained two-sided adhesive sheet are shown in Table 8. No channeling phenomenon of the separation film was observed in this step.

(2) Manufacture 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 adhered to the opposite surface of the transparent conductive layer of the transparent conductive laminate (2-1) produced in Example 18. Then, the separator film on the side of the polyoxyalkylene rubber adhesive layer (B) was peeled off, and adhered to the opposite side of the damage preventing layer of the layered body (1) laminated with the damage preventing layer produced in Example 20, and the contact was obtained. The upper electrode of the control panel. The workability in these pasting steps is good. Further, since the polyoxyalkylene rubber adhesive layer (B) is excellent in removability, it can be easily peeled off even if it is accidentally lost. Therefore, it is possible to eliminate the occurrence of defective products caused by mistakes.

Using the above-described upper electrode for a touch panel, the pen slip resistance test was carried out at 23 ° C and 44% RH in the same manner as in Example 18. After the sliding resistance test, it was visually observed whether the sliding portion was whitened, and whitening could not be seen. In addition, when the sliding resistance was measured by the pen load of 0.5 N, the ON resistance (resistance value at the time of contact between the upper and lower electrodes) was confirmed to be within 3 times of the initial value, and the pen sliding resistance was excellent.

Comparative Example 18

The laminate (3) produced in Example 21 and the transparent conductive laminate (2-1) produced in Example 18 were not bonded together by a double-sided adhesive sheet, but a laminate (3) and a transparent conductive laminate. In the same manner as in Example 21 except that the body (2-1) was superposed, the pen slip resistance test was carried out to confirm the whitening of the sliding portion. Moreover, it is known that the ON resistance is 15 times of the initial value, and the pen sliding durability is also poor.

Comparative Example 19

In the method of Example 18, a double-sided adhesive sheet was obtained in the same manner as in Example 21 except that the application of the coating liquid (E-1) for forming a hot water-resistant water-improving layer was stopped, and an upper electrode for a touch panel was obtained. The evaluation results of the double-sided adhesive sheets obtained in Comparative Example 19 are shown in Table 8. The two-sided adhesive sheet has low quality due to poor adhesion between the adhesive layer of the polyoxyalkylene rubber (B) and the polyester base film (A) and heat-resistant adhesion.

In the pen slip resistance test of the upper electrode for the touch panel, it was not possible to confirm whitening at the sliding portion at 23 ° C and 44% RH. However, at 50 ° C and 65% RH, it was confirmed that the sliding portion was whitened. . Further, the ON resistance was maintained within 3 times of the initial value at 23 ° C and 44% RH, but was 6 times the initial value at 50 ° C and 65% RH. In the two-sided adhesive sheet obtained in the comparative example, the result of poor adhesion of hot water resistance was reflected.

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-resistant water-improving layer (E) was changed to 0.7 μm, and an upper electrode for a touch panel was obtained. The evaluation results of the double-sided adhesive sheets obtained in this comparative example are shown in Table 8. The adhesive sheet on both sides is low in quality due to poor adhesion of hot water. When the upper electrode for the touch panel was evaluated, the same results as in the above Comparative Example 19 were obtained.

Comparative Example 21

The method of the first embodiment is the same as that of the embodiment 21 except that the polymer wax component and the antistatic agent which are stopped by the coating liquid (C-1) for forming the release layer are used in the production of the separator film. Get two adhesive sheets. The evaluation results of the double-sided adhesive sheets obtained in this comparative example are shown in Table 8. Although the adhesive layer of the polyoxyalkylene rubber from which the two sides are attached is peeled off the separation film, it cannot be peeled off. Therefore, the manufacture of the upper electrode for the touch panel is suspended.

Example 22

In the same manner as in Example 1, a coating liquid (E-1) for preparing a hot water-resistant water-improving layer was prepared. Further, in the same manner as in Example 1, a laminate of the polyester base film (A) and the coating liquid (E-1) was produced, and the thickness of the two-layer layer of the biaxially-stretched polyethylene terephthalate base film was produced. A laminated body (r) having a thickness of 38 μm of 0.08 μm crosslinked heat resistant water adhesion improving layer (E).

In the preparation method of the polyoxyalkylene compound solution of Example 1, except that the amount of trimethylolpropane trimethacrylate was changed to 1.0 part, the same procedure as in Example 1 was carried out, and the prepared polyoxane was prepared. The compound solution was applied to one surface of the above laminated body (r) so as to have a thickness of 175 μm after drying, and then dried in an oven at 80 ° C. A laminate (s) in which the uncrosslinked polyoxyalkylene rubber adhesive layer (B-4) is formed on one side of the laminate (r) can be obtained.

The layered body (d) (separating film) produced in Example 1 was superposed on the surface of the uncrosslinked polyoxyalkylene rubber adhesive layer of the above laminated body (s) while being pressed by a pressing roll (pressure: 30 N/cm ² ). , continuous layering. The obtained laminated body is continuously introduced into the electron beam irradiation apparatus, and the electron beam is irradiated with energy of 700 KV and 18 Mrad from the side of the separation film to carry out crosslinking of the adhesive layer, and the polyoxyalkylene rubber adhesive layer (B) is provided after crosslinking. The laminate (t) is wound into a roll shape. In the manufacturing steps up to this point, the occurrence of the channeling phenomenon of the separator film was not observed.

On the opposite side of the layer of the polyoxyalkylene rubber adhesive layer (B) of the laminate (t), it was applied as an optical acrylic adhesive SKDyne 2094 (manufactured by Soken Chemical Co., Ltd.) so that the thickness after drying became 75 μm. It was dried at 130 ° C for 3 minutes to form an acrylic adhesive layer (F). The surface of the acrylic pressure-sensitive adhesive layer (F) was laminated so that the polyethylene terephthalate-treated polyethylene terephthalate (D"C") was formed into a film having a thickness of 38 μm (E7002; manufactured by Toyobo Co., Ltd.). The side of the polyoxyalkylene treated side becomes a contact, and a double-sided adhesive sheet can be obtained. The characteristics of the obtained double-sided adhesive sheet and the characteristics of the coating liquid for forming the adhesive layer of the polyoxyalkylene compound-based adhesive layer are shown in Table 9. In this step, the occurrence of the channeling phenomenon of the separation film cannot be seen.

The double-sided adhesive sheet obtained in this example is excellent in transparency (total light transmittance and haze value). Further, the polyoxyalkylene rubber adhesive layer (B) and the polyester base film (A) are firmly adhered to each other via the hot water-resistant adhesion improving layer (E), and the adhesiveness and heat-resistant water adhesion are adhered. Excellent in sex. Further, the releasing force of the release layer (C) and the polyoxyalkylene rubber adhesive layer (B) is also moderate, and it is a high-quality double-sided adhesive sheet excellent in peelability. Further, the coating liquid for forming the polyoxyalkylene rubber adhesive layer (B) in the production of the double-sided adhesive sheet is also excellent in clarity and stability, and it is confirmed that the handleability and handling stability are excellent.

Comparative Example 22

In the method of Example 22, a double-sided adhesive sheet was obtained in the same manner as in Example 22 except that the application of the coating liquid (E-1) for forming a hot water-resistant water-adhesive layer was stopped. The evaluation results of the two-sided adhesive sheets are shown in Table 9. The adhesive sheet on both sides has a low quality in the adhesion between the polyoxyalkylene rubber adhesive layer (B) and the polyester base film (A) and the heat-resistant water adhesion.

Comparative Example 23

In the method of the first embodiment, the coating liquid (C-1) used for forming the release layer is used to terminate the blending of the polymer wax component and the antistatic agent, and the other embodiment 22 The same two sides of the adhesive sheet were obtained. The evaluation results of the two-sided adhesive sheets are shown in Table 9. Although the adhesive layer of the polyoxyalkylene rubber from which the two sides are attached is peeled off, the separation film cannot be peeled off. Therefore, it cannot be used as a double-sided adhesive sheet.

Example 23

[Polyoxirane rubber compound is a laminate of adhesive layers)

A non-reactive aggregate which is substantially free of a reinforcing agent such as cerium oxide and an uncrosslinked polydimethyl siloxane skeleton having a number average molecular weight of 170,000 (measured by GPC method and converted to polystyrene) The oxirane compound (KF-96H-100,000 cs; manufactured by Shin-Etsu Chemical Co., Ltd.) was weighed to a mass ratio of 23% to toluene, and was placed in a vacuum degassing device mixer together with toluene at atmospheric pressure. Stir at room temperature for 15 hours and dissolve in toluene. In the obtained solution, trimethylolpropane trimethacrylate was added in two portions with respect to 100 parts of the above polyoxyalkylene compound, and after uniformly stirring, the vacuum defoaming device was driven to make the gauge pressure at -750 mmHg. Under vacuum, it was further stirred for 20 minutes to defoam. Next, the defoamed polyoxyalkylene compound solution was supplied to a roll coater, and the polysiloxane compound solution was applied to one surface of the layered product (d) (separating film) produced in Example 1, and dried. The thickness was 150 μm, and then it was introduced into an oven and dried at 80 °C. A laminate (u) in which an uncrosslinked polyoxyalkylene rubber adhesive layer is formed on the surface of the separator film can be obtained.

On both surfaces of the layered product (r) produced in Example 22, the surface of the uncrosslinked polyoxyalkylene rubber adhesive layer of the layered product (u) was superposed and pressed by a pressure roller (pressure: 30 N/cm ² ). Continuous layering. The obtained laminate was continuously introduced into an electron beam irradiation apparatus, and an electron beam was irradiated from the separator film side at an energy of 700 KV and 18 Mrad to crosslink the polyoxyalkylene compound-based adhesive layer, and the two-sided adhesive sheet was wound after crosslinking. In the form of a roll. The irradiation of the electron beam is performed by dividing the irradiation of the electron beam twice. The evaluation results of the obtained double-sided adhesive sheet characteristics are shown in Table 9. In the manufacturing steps up to this point, the occurrence of the channeling phenomenon of each of the separator films was not observed.

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

Example 24

In the method of the embodiment 22, the thickness of the polyoxyalkylene rubber adhesive layer (B) was changed to 45 μm, and the electron beam irradiation conditions were changed to 200 kV and 18 Mrad, except that the total thickness of the laminate (r) was changed to 125 μm. Otherwise, a double-sided adhesive sheet was obtained in the same manner as in Example 22. The evaluation results of the obtained double-sided adhesive sheets are shown in Table 9.

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

Example 25

In the method of Example 24, a double-sided adhesive sheet was obtained in the same manner as in Example 24 except that the thickness of the acrylic pressure-sensitive adhesive layer (F) was changed to 25 μm and the electron beam irradiation conditions were performed twice at 200 kV and 18 Mrad. The evaluation results of the obtained double-sided adhesive sheets are shown in Table 9.

Example 26

In the method of Example 22, except that the thickness of the acrylic adhesive layer (F) was changed to 25 μm, and the thickness of the polyoxyalkylene rubber adhesive layer (B) was changed to 20 μm, the other methods were obtained in the same manner as in Example 22. Adhesive on both sides. The evaluation results of the obtained double-sided adhesive sheets are shown in Table 9.

Example 27

In the method of the example 22, except that the thickness of the polyoxyalkylene rubber adhesive layer (B) was changed to 75 μm, and the electron beam irradiation conditions were changed to 200 kV and 12 Mrad, the two-sided adhesive sheet was obtained in the same manner as in Example 22. . The evaluation results of the obtained double-sided adhesive sheets are shown in Table 9.

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

In Example 28, the separator film was peeled off from each of the two-sided adhesive sheets of Examples 22 to 27 to bond the surface protective panel and the image display panel. For the double-sided adhesive sheets obtained in Examples 22 and 24 to 27, first, the surface protective panel was attached to the acrylic adhesive layer (F) side, and then the image display panel was attached to the polyoxyalkylene rubber adhesive layer (B). side. The adhesive sheet on both sides obtained in Example 23 is a polyoxyalkylene rubber adhesive layer on both sides, and the surface protection panel may be attached to one surface. In this case, the surface protection panel is first attached, and then, the sticker is attached. The image display panel. After the respective pasting, the autoclave was placed, and the treatment was carried out for 30 minutes at 50 ° C and 5 atm.

The workability when it is attached is good. In addition, since the polyoxyalkylene rubber adhesive layer (B) is excellent in removability, the image display panel can be easily removed even if a mislabeling occurs or after the work is attached. Therefore, the loss of the image display panel of the expensive member due to the mislabeling can be eliminated. On the other hand, in the two-sided adhesive sheet obtained in Example 23, the two sides are the adhesive layer of the polyoxyalkylene rubber, and both sides have excellent removability, so that the offset between the surface protection panel and the image display panel can be eliminated. loss.

Further, in the case where the double-sided adhesive sheets obtained in Examples 22, 23 and 27 were used, the adhesive strength of the polyoxyalkylene rubber adhesive layer (B) was moderate, and the shape compliance was excellent, and the air was eaten. The squeezing property can be appropriately adjusted, for example, by using a light-shielding film formed by brushing or the like due to a coating to rotate the inner peripheral portion of the protective panel in a manner corresponding to the frame to have a μm order. In the case of the high and low difference protection panel, since the difference in height can be absorbed and the bubble which is eaten can be extruded, no bubble occurs in the height difference portion.

On the other hand, in the case where the double-sided adhesive sheets obtained in Examples 24 to 26 were used, since the polyaraphthenic rubber adhesive layer (B) had a large indentation modulus, it was compared with the adhesive sheets of Examples 23 and 27. Since the shape compliance is somewhat degraded, when a protective panel having a large difference is used, bubbles may occur around the step.

Further, in the case of using a flat protective panel having no height difference, even if the double-sided adhesive sheet of any of Examples 22 to 27 is used, the occurrence of bubbles or the ingestion of bubbles can be suppressed. Further, even if bubbles occur, the air discharge property changes with time, and the bubbles disappear.

Example 29 and Comparative Example 24

The surface protection panel of the commercially available mobile phone is removed, and the removed image display panel and the surface protection panel are bonded to each of the two-sided adhesive sheets of Examples 22 to 27 (Example 29), and only The distance between the thickness portions of the two-sided adhesive sheets was set between the image display panel and the surface protective panel (Comparative Example 24), and the visibility of the images in the two cases was evaluated. Observe the same image by visually observing each other and compare the visibility of the two images. As a result, the visibility of the image of the person who adhered to the two-sided adhesive sheet (Example 29) was good.

Industrial availability

The adhesive sheet of the present invention forms a polyoxyalkylene rubber adhesive layer (B) or an adhesive layer of a crosslinked polyoxyalkylene compound containing a polydimethylsiloxane skeleton having both adhesion and releasability. Since (B') is formed, even if there is, for example, a mistake, it can be easily peeled off and can be reattached again.

Moreover, the adhesive sheet of the present invention has excellent adhesion durability between the adhesive layer of the polyoxyalkylene rubber (B) or the adhesive layer (B') and the polyester-based base film (A), even under severe conditions. For the components used, it can also be used properly. Further, the peeling force of the separator film laminated on the surface of the polyoxyalkylene rubber adhesive layer (B) or the adhesive layer (B') is controlled to an appropriate range, and the step of winding the adhesive sheet or the like is suppressed because the channel flow can be suppressed. The phenomenon occurs, so it is possible to stably produce high-quality adhesive sheets. Moreover, the workability at the time of using an adhesive sheet bonding member is also excellent.

Further, since the adhesive sheet of the present invention is rich in variations in its constitution, it can be applied to various uses. For example, if it is a single-sided adhesive sheet, it is useful as a surface protection film or a touch panel of a display screen. If it is a double-sided adhesive sheet, the components in the touch panel or the image display device are mutually It is useful to stick it.

The upper electrode for a touch panel of the present invention is useful for manufacturing 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 electroluminescence (organic EL), or the like.

Claims (19)

An adhesive sheet which is at least a polyester-based base film (A), a hot water-resistant adhesion improving layer (E), and a crosslinked polyoxyalkylene rubber adhesive layer having a polydimethylsiloxane skeleton (B), the release layer (C) and the polyester film (D) are laminated, with or without other layers interposed, and the hot water adhesion improving layer (E) A reaction product comprising a polymer and a crosslinking agent, the polymer being selected from the group consisting of polyester, polyurethane, and acrylic polymer; or containing self-crosslinking The self-crosslinking type polymer is selected from the group consisting of a self-crosslinking type polyester, a polyurethane, and an acrylic polymer. When the hot water adhesion is evaluated by the following method, the polyoxyalkylene rubber adhesive layer (B) is not peeled off from the polyester base film (A) side, and the polyoxyalkylene rubber adhesive layer (B) The peeling strength with the release layer (C) is 0.03 to 1.0 N/20 mm, and the evaluation method of the heat-resistant water adhesion property is: when measuring the heat-resistant water adhesion property of the polyoxyalkylene rubber adhesive layer (B) will The adhesive sheet as a sample was cut into 50 mm × 50 mm, and the separator film of the polyoxyalkylene rubber adhesive layer (B) was peeled off; in a 500 cc capped cylindrical glass container filled with distilled water of 400 cc, to gather The sample of the oxane rubber adhesive layer (B) is placed on the lower side so that the sample is submerged in water, and the container is covered with the sample immersed in the water; the sample is loaded The container is placed in a gear oven set at 80 ° C and allowed to stand for 24 hours; after heat treatment, the container is taken out from the oven and the sample is quickly taken out, from the side of the adhesive layer of the polyoxyalkylene rubber (B) The abdominal force was applied to the end portion for 10 times to evaluate whether the polyoxyalkylene rubber adhesive layer (B) was peeled off from the polyester base film (A), and the polyoxyalkylene rubber adhesive layer (B) was not peeled off. The peeling layer of the polyoxyalkylene rubber adhesive layer (B) is ×. The adhesive sheet of claim 1, wherein the release layer (C) comprises a layer of a binder resin, a polymer wax component, and an antistatic agent. The adhesive sheet of claim 1, wherein the polyoxyalkylene rubber adhesive layer (B) comprises a polyoxyalkylene rubber, the polyoxyalkylene rubber having a number average molecular weight of 50,000 to 500,000 The uncrosslinked body of the polyoxyalkylene compound of the methyloxane skeleton is crosslinked. The adhesive sheet according to claim 1, wherein the polyoxyalkylene rubber adhesive layer (B) has an indentation elastic modulus of 0.5 to 20 N/mm ² as measured by the following method, and the indentation elastic modulus is The measuring method is: cutting the sample at an angle of about 2 cm, and fixing the opposite side of the measuring surface with an acrylic adhesive (thickness 25 μm) or a cyanoacrylate-based adhesive on a glass plate having a thickness of 1 mm or more; In addition, when there is an adhesive layer on the opposite side of the measurement surface, it is fixed to the glass plate by the adhesive layer; after the sample is attached to the glass plate, the separation film of the measurement surface is peeled off after being placed for 30 minutes or more, and the dynamics are used. The ultra-micro hardness tester DUH-211 (manufactured by Shimadzu Corporation) was measured under the next measurement conditions; "Measurement conditions" 1) Setting: Test mode: Load-except load test, using indenter: edge angle 115 degrees, triangular cone Indenter (indenter elastic modulus: 1.140×10 ⁶ N/mm ² , indenter Poisson's ratio: 0.07), soft sample measurement: Yes, Cf-Ap, As correction: Yes; 2) Condition: Test force: 0.50 mN , load speed: 0.0150mN / sec, load hold time: 5 seconds, except Carrier holding time: 5 seconds. The adhesive sheet according to claim 1, wherein the side of the polyester-based base film (A) on which the polyoxyalkylene rubber adhesive layer (B) is formed on the opposite side of the surface is formed to be selected from the group consisting of One or more functional layers of the group, the antireflection layer, and the antifouling layer. The adhesive sheet according to claim 1, wherein a transparent conductive layer is formed on the opposite side of the surface on which the polyoxyalkylene rubber adhesive layer (B) of the polyester base film (A) is formed. The adhesive sheet of claim 1, wherein the side of the adhesive layer (B) of the polyester base film (A) is formed on the opposite side of the surface According to the order of the crosslinked polyoxyalkylene rubber adhesive layer (B'), the release layer (C') and the polyester film (D') having a polydimethylsiloxane skeleton, with or without Lamination is carried out through the other layers. The adhesive sheet according to claim 1, wherein the adhesive layer (B) of the polyester base film (A) is formed on the opposite side of the surface, according to the acrylic adhesive layer (F) The order of the release layer (C") and the polyester film (D") is laminated with or without other layers. An adhesive sheet according to claim 1 or 5, wherein the polyoxyalkylene rubber adhesive layer (B) is attached to a display screen of the image display device and protects the display screen. An adhesive sheet according to any one of claims 5 to 8, which is used as a member of a touch panel. For example, the adhesive sheet of claim 7 or 8 is used for the overlay of the overlay sheet of the electrostatic capacitive touch panel and the coordinate detecting sheet. The adhesive sheet of claim 7 or 8 is used for the touch panel portion of the resistive touch panel and the display device. An upper electrode for a touch panel, which is characterized in that a transparent substrate of a conductive laminate formed by laminating a transparent conductive layer on a transparent substrate and a polyoxyalkylene rubber as an adhesive sheet of claim 5 Adhesive layer (B) fits. An upper electrode for a touch panel, which is one or more functions selected from the group consisting of a damage prevention layer, an antireflection layer, and an antifouling layer A transparent substrate in which a functional laminate of a transparent substrate is laminated and a polyoxyalkylene rubber adhesive layer (B) as an adhesive sheet of claim 6 is attached. An upper electrode for a touch panel, characterized by a polyoxyalkylene rubber adhesive layer (B) and a polyoxyalkylene rubber adhesive layer (B') as an adhesive sheet of claim 7 of the patent application, or Applying the adhesive layer of the adhesive layer of the polyoxyalkylene rubber adhesive layer (B) and the acrylic adhesive layer (F) to adhere to the transparent substrate and having a transparent conductive layer to form a transparent transparent conductive layer A base material and a transparent base material having a functional laminated body formed by laminating one or more functional layers selected from the group consisting of a damage preventing layer, an antireflection layer, and an antifouling layer. An image display device which is bonded to an image display panel by a polyoxyalkylene rubber adhesive layer (B) and a polyoxyalkylene rubber adhesive layer (B') as an adhesive sheet of claim 7 Protect the protective panel of the image display panel. The image display device of claim 16, wherein the adhesive layer of the polyoxyalkylene rubber adhesive layer (B) and/or the polyoxyalkylene rubber adhesive layer (B') is as claimed in the patent application. The indentation modulus of the measurement of the indentation modulus of the four items was 0.5 to 5 N/mm ² . An image display device characterized in that an image display panel is bonded to a polyoxyalkylene rubber adhesive layer (B) and an acrylic adhesive layer (F) as an adhesive sheet of claim 8 of the patent application, and the image is protected A protective panel like a display panel. The image display device of claim 18, wherein the polyoxyalkylene rubber adhesive layer (B) of the adhesive sheet is pressure measured by a method for measuring a concave modulus of elasticity according to item 4 of the patent application. The concave modulus is 0.5 to 5 N/mm ² .