WO2018051857A1

WO2018051857A1 - Adhesive sheet laminate, shaped adhesive sheet laminate, and method for producing same

Info

Publication number: WO2018051857A1
Application number: PCT/JP2017/032047
Authority: WO
Inventors: 記央佐藤; 誠稲永; 加苗鈴木; 達也村中
Original assignee: 三菱ケミカル株式会社
Priority date: 2016-09-15
Filing date: 2017-09-06
Publication date: 2018-03-22
Also published as: CN113462311A; CN109715753A; TWI798747B; TW201819185A; CN113444459A; TWI761369B; TW202138195A; CN109715753B; KR20220025253A; KR20220025254A; KR20190055822A; KR102426469B1; KR102457647B1; KR20220025251A; CN113462310A

Abstract

Provided is an adhesive sheet laminate provided with an adhesive material layer and a cover portion I peelably laminated on one surface of the adhesive material layer, as a novel adhesive sheet laminate with which it is possible to form an uneven shape matching an uneven portion of an adherend surface at high accuracy on the adhesive material layer surface, wherein the adhesive sheet laminate is characterized in that the storage modulus E'(MA) of the cover portion I at 100°C is 1.0 × 10⁶ to 2.0 × 10⁹ Pa, and the storage modulus E'(MB) of the cover portion I at 30°C is 5.0 × 10⁷ to 1.0 × 10¹⁰ Pa.

Description

Adhesive sheet laminate, shaped adhesive sheet laminate and method for producing the same

The present invention can be suitably used for forming an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, and a pen tablet. The present invention relates to a pressure-sensitive adhesive sheet laminate and a pressure-sensitive adhesive sheet laminate suitable for forming a shaped pressure-sensitive adhesive sheet laminate.

A touch panel image display device is usually configured by combining a surface protection panel, a touch panel, and an image display panel (collectively, also referred to as “component for image display device”).
In recent years, surface protection panels for touch panel image display devices such as smartphones and tablet terminals have been made of tempered glass and plastic materials such as acrylic resin plates and polycarbonate plates. The part is printed in black.
In the touch panel, a plastic film sensor is used together with the glass sensor, a touch-on lens (TOL) member in which the touch panel function is integrated with the surface protection panel, or the touch panel function is integrated in the image display panel. Members such as on-cell and in-cell are used.

In this type of image display device, in order to further improve the image visibility, the gaps between the constituent members for each image display device are made of a transparent resin such as a liquid adhesive, a thermoplastic adhesive sheet material, and an adhesive sheet material. The structure to fill is common.
By the way, in the field of image display devices centering on mobile phones and mobile terminals, in addition to thinning and high precision, design diversification has progressed, and the peripheral edge of the surface protection panel has a black frame shape. In the past, it has been common to print the concealing portion, but with the diversification of design, the frame-shaped concealing portion has begun to be formed in a color other than black. When the concealing part is formed with a color other than black, the concealing property is low, and therefore the height of the concealing part, that is, the printing part tends to be higher than that of black. Therefore, it is required that the pressure-sensitive adhesive sheet for laminating components having such a printing unit be filled to every corner following a large printing step.
Therefore, various methods for filling the printing step have been proposed.

For example, Patent Document 1 discloses a new image display device that can be bonded to a surface to be adhered in a close contact state even if the surface to be bonded to which the pressure-sensitive adhesive sheet is bonded has a step due to printing or the like. A double-sided pressure-sensitive adhesive sheet for bonding any two adherends selected from the constituent members for image display devices of a surface protection panel, a touch panel and an image display panel as a double-sided pressure-sensitive adhesive sheet, The body has a stepped portion on the adherend surface to which the double-sided pressure-sensitive adhesive sheet is adhered, and the double-sided pressure-sensitive adhesive sheet has the shape of the bonding surface to be bonded to the adherend surface along the surface shape of the adherend surface. A double-sided pressure-sensitive adhesive sheet for an image display device, which is shaped, is disclosed.

Moreover, in patent document 2, about the manufacturing method of the double-sided adhesive sheet for bonding any two adherends selected from a surface protection panel, a touch panel, and an image display panel, the double-sided adhesive sheet before bonding is A double-sided pressure-sensitive adhesive sheet for an image display device, wherein the pressure-sensitive adhesive composition having a gel fraction of less than 40% is formed into the same surface shape as the uneven shape of the bonding surface of the adherend. A manufacturing method is disclosed.

WO2014 / 073316 A1 WO2015 / 174392 A1

In recent years, in the field of image display devices centering on mobile phones and mobile terminals, there has been a further demand for thinning and high precision, and adhesive sheets for bonding image display device components also have printing steps and the like. It is required that the uneven portion on the surface of the adherend can be filled with high accuracy and that the adhesive material does not protrude outside. As a countermeasure for this, it has been studied that the surface shape of the pressure-sensitive adhesive sheet is formed in advance along the surface shape of the adherend as disclosed in the above-mentioned prior patent documents.

And in order to form the surface shape of the pressure-sensitive adhesive sheet along the surface shape of the adherend in advance, a pressure-sensitive adhesive sheet laminate in which release sheets are laminated on both sides of the pressure-sensitive adhesive sheet is press-molded. Thus, a method of forming a concavo-convex shape coinciding with the concavo-convex portion on the adherend surface is assumed.
However, as a result of actually carrying out the method using a pressure-sensitive adhesive sheet laminate formed by laminating a normal release sheet on both sides of the pressure-sensitive adhesive sheet, a concavo-convex shape coinciding with the concavo-convex portion on the adherend surface is obtained. The problem that it is difficult to form on the surface of an adhesive sheet with high accuracy has been clarified.

Therefore, the present invention relates to a pressure-sensitive adhesive sheet laminate comprising a pressure-sensitive adhesive layer and a covering portion that is detachably laminated on one side of the pressure-sensitive adhesive layer, and has an uneven shape that matches the unevenness on the adherend surface. A new pressure-sensitive adhesive sheet laminate that can be formed on the surface of the pressure-sensitive adhesive layer and a shaped pressure-sensitive adhesive sheet laminate using the pressure-sensitive adhesive sheet laminate are proposed.

The present invention relates to a pressure-sensitive adhesive sheet laminate comprising a pressure-sensitive adhesive layer and a covering portion I that is peelably laminated on one surface of the pressure-sensitive adhesive layer, and a storage elastic modulus E ′ of the covering portion I at 100 ° C. MA) is 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa, and the storage elastic modulus E ′ (MB) of the covering portion I at 30 ° C. is 5.0 × 10 ⁷ to 1.0 ×. A pressure-sensitive adhesive sheet laminate having a pressure of 10 ¹⁰ Pa is proposed.

The present invention is also a shaped pressure-sensitive adhesive sheet laminate using the pressure-sensitive adhesive sheet laminate, wherein the pressure-sensitive adhesive layer has a concave portion, a convex portion, or a concave-convex portion (referred to as “pressure-sensitive adhesive layer surface concave-convex portion”) on one surface of the front and back sides. ), And the covering portion I is in close contact with the front and back side surfaces of the pressure-sensitive adhesive layer, and is provided with a concave portion, a convex portion, or an uneven portion (referred to as a “cover portion surface uneven portion”) on the front and back side surface. In addition, a convex portion or a concave portion or a convex concave portion (referred to as a “covered portion back surface convex concave portion”) having irregularities that coincide with the concave and convex portions on the surface of the adhesive material layer on the front and back other side surfaces opposite to the one side of the front and back sides. Proposed is a shaped adhesive sheet laminate.

According to the pressure-sensitive adhesive sheet laminate proposed by the present invention, for example, after the pressure-sensitive adhesive sheet laminate is heated, a mold is pressed against the covering portion I to form a concave-convex shape that matches the concave-convex portion on the adherend surface. Can be formed on the surface of the adhesive layer with high accuracy. In addition, since the covering portion I can maintain shape retention in a normal state, it is easy to handle and is not too hard, so that it is possible to suppress unnecessary unintentional unevenness on the adhesive layer. it can.

The shaped pressure-sensitive adhesive sheet laminate proposed by the present invention comprises a pressure-sensitive adhesive sheet surface uneven portion on the front and back side surfaces of the pressure-sensitive adhesive layer, and the covering portion I is in close contact with the front and back side surfaces of the pressure-sensitive adhesive layer. The front and back one side surface is provided with a covering portion surface uneven portion, and the front and back other side surface opposite to the front and back one side is provided with a covering portion back surface convex concave portion. Thus, in the shaped pressure-sensitive adhesive sheet laminate proposed by the present invention, the covering portion I is in close contact with the front and back side surfaces of the pressure-sensitive adhesive layer, and is peeled to the front and back side surfaces of the pressure-sensitive adhesive layer. Since the covering portion I is configured to be laminated, it is possible to prevent dust and the like from adhering to the surface of the pressure-sensitive adhesive layer to reduce the adhesive force, and the pressure-sensitive adhesive layer. The shape of the uneven surface of the adhesive material layer formed on the front and back surfaces of the surface prevents moisture from absorbing moisture and collapsing, and dust adheres to the surface and reduces adhesive strength. You can also.

It is sectional drawing which showed typically an example of the adhesive sheet laminated body which is an Example of this invention. It is sectional drawing for demonstrating an example of the press process at the time of manufacturing a shaped adhesive sheet laminated body using an example of the adhesive sheet laminated body which is an Example of this invention. It is the figure which showed typically an example of the shaped adhesive sheet laminated body which is an Example of this invention, (A) is sectional drawing, (B) is a perspective view. It is the figure which showed the viscoelastic curve of the material used for the adhesive sheet laminated body produced by the Example and the comparative example. It is the perspective view which showed one side of the metal mold | die used by the Example and the comparative example.

Hereinafter, an example of the embodiment of the present invention will be described. However, the present invention is not limited to the following embodiment.

[This adhesive sheet laminate]
As shown in FIG. 1, the pressure-sensitive adhesive sheet laminate (referred to as “the present pressure-sensitive adhesive sheet laminate”) according to an example of the embodiment of the present invention can be peeled off on the front and back sides of the pressure-sensitive adhesive layer. It is the adhesive sheet laminated body provided with the coating | coated part I laminated | stacked and the coating | coated part II laminated | stacked on the front and back other side of the said adhesive material layer so that peeling is possible. Here, the covering portion II is arbitrary, and the covering portion II may not be stacked.

<Adhesive layer>
The pressure-sensitive adhesive layer of this pressure-sensitive adhesive sheet laminate can function as a double-sided pressure-sensitive adhesive sheet when the covering portion I and the covering portion II are peeled off, and has a hot melt property that softens or melts when heated. That's fine.

The pressure-sensitive adhesive layer preferably has a loss tangent tan δ (SA) at 100 ° C. of 1.0 or more. Further, the loss tangent tan δ (SB) at 30 ° C. is preferably less than 1.0.
Here, the loss tangent tan δ means the ratio (G ″ / G ′) between the loss elastic modulus G ″ and the storage elastic modulus G ′.
Since the temperature at which the pressure-sensitive adhesive sheet laminate is heat-molded is usually 70 to 120 ° C., if the loss tangent tan δ (SA) at 100 ° C. is 1.0 or more, an uneven shape is formed on the surface of the pressure-sensitive adhesive layer. It becomes easy.
Further, if the loss tangent tan δ (SB) at 30 ° C. of the pressure-sensitive adhesive layer is less than 1.0, the shape can be maintained in a normal state, so that the uneven shape matching the uneven portion on the adherend surface can be accurately obtained. The state formed on the surface of the adhesive layer can be maintained.
In general, a polymer material has both a viscous property and an elastic property, and the loss tangent tan δ is 1.0 or more, and the viscosity value becomes stronger as the value increases. On the other hand, the elastic property becomes stronger as the loss tangent tan δ is less than 1.0 and the value is further reduced. For this reason, by controlling the loss tangent tan δ at different temperatures of the adhesive layer, it becomes possible to have both formability and shape retention.

From this viewpoint, the loss tangent tan δ (SA) at 100 ° C. of the pressure-sensitive adhesive layer is preferably 1.0 or more, more preferably 1.5 or more and 30 or less, and particularly preferably 3.0 or more and 20 or less. preferable.
On the other hand, the loss tangent tan δ (SB) at 30 ° C. of the pressure-sensitive adhesive layer is preferably less than 1.0, particularly 0.01 or more and 0.9 or less, and more preferably 0.1 or more and 0.8 or less. Is preferred.

Here, the loss tangent tan δ (SA) at 100 ° C. and the loss tangent tan δ (SB) at 30 ° C. of the adhesive layer adjust the components, gel fraction, weight average molecular weight, etc. of the composition constituting the adhesive layer. Can be adjusted to the above range.

Furthermore, it is preferable that the storage elastic modulus G ′ (SA) at 100 ° C. of the pressure-sensitive adhesive layer is less than 1.0 × 10 ⁴ Pa. Moreover, it is preferable that the storage elastic modulus G '(SB) in 30 degreeC of the said adhesive material layer is 1.0 * 10 < ⁴ > Pa or more.
If the storage elastic modulus G ′ (SA) at 100 ° C. of the pressure-sensitive adhesive layer is less than 1.0 × 10 ⁴ Pa, it is preferable because sufficient moldability can be obtained. On the other hand, the storage elastic modulus at 30 ° C. of the pressure-sensitive adhesive layer. If G ′ (SB) is 1.0 × 10 ⁴ Pa or more, it is preferable from the viewpoint of shape stability after molding.

From this point of view, the storage elastic modulus G ′ (SA) at 100 ° C. of the adhesive layer is preferably less than 1.0 × 10 ⁴ Pa, among which 5.0 × 10 ¹ Pa or more or 5.0 × 10 ^3. It is more preferable that it is Pa or less, and among these, 1.0 × 10 ² Pa or more or 1.0 × 10 ³ Pa or less is more preferable.
From the above, the storage elastic modulus G ′ (SA) at 100 ° C. of the adhesive layer is 5.0 × 10 ¹ Pa or more and less than 1.0 × 10 ⁴ Pa, or 5.0 × 10 ¹ Pa or more and 5.0. X10 ³ Pa or less is more preferable, and in particular, 1.0 × 10 ² Pa or more and less than 1.0 × 10 ⁴ Pa, or 1.0 × 10 ² Pa or more and 5.0 × 10 ³ Pa or less. More preferably, it is 1.0 × 10 ² Pa or more and 1.0 × 10 ³ Pa or less.
From this viewpoint, the storage elastic modulus G ′ (SB) at 30 ° C. of the pressure-sensitive adhesive layer is preferably 1.0 × 10 ⁴ Pa or more, and more preferably 2.0 × 10 ⁴ Pa or more or 1.0 ×. 10 ⁷ Pa or less is more preferable, and among them, 5.0 × 10 ⁴ Pa or more or 1.0 × 10 ⁶ Pa or less is more preferable.
From the above, the storage elastic modulus G ′ (SB) at 30 ° C. of the adhesive layer is 1.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁷ Pa or less, or 1.0 × 10 ⁴ Pa or more and 1 0.0 × 10 ⁶ Pa or less is more preferable, among which 2.0 × 10 ⁴ Pa to 1.0 × 10 ⁷ Pa, or 2.0 × 10 ⁴ Pa to 1.0 × 10 ⁶ Pa. Or less, and most preferably 5.0 × 10 ⁴ Pa or more and 1.0 × 10 ⁶ Pa or less.

Here, the storage elastic modulus G ′ (SA) at 100 ° C. of the pressure-sensitive adhesive layer and the storage elastic modulus G ′ (SB) at 30 ° C. of the pressure-sensitive adhesive layer are components and gel fractions of the composition constituting the pressure-sensitive adhesive layer. By adjusting the weight average molecular weight or the like, the above range can be adjusted.

The temperature at which the loss tangent tan δ of the pressure-sensitive adhesive layer is 1.0 is preferably 50 to 150 ° C., more preferably 60 ° C. or more and 130 ° C. or less, and particularly preferably 70 ° C. or more or 110 ° C. or less. .
If the temperature at which the loss tangent tan δ of the pressure-sensitive adhesive layer is 1.0 is 50 to 150 ° C., the pressure-sensitive adhesive sheet laminate can be molded by heating to 50 to 150 ° C.

The glass transition temperature (Tg) of the base resin of the adhesive layer is preferably −50 to 40 ° C., more preferably −30 ° C. or higher or 25 ° C. or lower, and particularly preferably −10 ° C. or higher or 20 ° C. or lower. Further preferred. Here, the measurement of the glass transition temperature refers to the midpoint between the inflection points of the baseline shift when the temperature is increased at a rate of 3 ° C./min using a differential scanning calorimeter (DSC).
If the glass transition temperature (Tg) of the base resin of the pressure-sensitive adhesive layer is within the above range, the pressure-sensitive adhesive layer can be given adhesiveness, and the temperature at which the loss tangent tan δ of the pressure-sensitive adhesive layer becomes 1.0 is set. It is possible to adjust to 50 to 150 ° C.

As the material of the adhesive layer, a conventionally known adhesive sheet can be used as long as it can be adjusted to a predetermined viscoelastic behavior.
For example, 1) a (meth) acrylic acid ester-based polymer (including a copolymer, hereinafter referred to as “acrylic ester-based (co) polymer”) is used as a base resin, and a crosslinking monomer is necessary for this. Depending on the pressure-sensitive adhesive sheet formed by blending a crosslinking initiator or a reaction catalyst,
2) A pressure-sensitive adhesive sheet formed by using a butadiene or isoprene-based copolymer as a base resin, blending a crosslinking monomer, a crosslinking initiator or a reaction catalyst as necessary, and causing a crosslinking reaction;
3) A pressure-sensitive adhesive sheet formed by crosslinking reaction by using a silicone polymer as a base resin, blending a crosslinking monomer, a crosslinking initiator or a reaction catalyst if necessary, and the like,
4) A polyurethane-based pressure-sensitive adhesive sheet using a polyurethane-based polymer as a base resin can be used.

The physical properties of the adhesive layer itself are not an essential problem in the present invention, except for the viscoelastic properties and thermal properties described above. However, from the viewpoints of tackiness, transparency, weather resistance, and the like, those using the acrylate ester (co) polymer of 1) as a base resin are preferable.
When performance such as electrical characteristics and low refractive index is required, those based on the butadiene or isoprene-based copolymer of 2) above are preferable.
When performances such as heat resistance and rubber elasticity in a wide temperature range are required, those using the silicone copolymer of 3) as a base resin are preferable.
When performance such as removability is required, those using the polyurethane polymer of 4) as a base resin are preferable.

As an example of the pressure-sensitive adhesive layer, it was formed from a resin composition containing a (meth) acrylic copolymer (a) as a base resin, a crosslinking agent (b), and a photopolymerization initiator (c). An adhesive sheet can be illustrated.
In this case, it is necessary to satisfy the viscoelastic characteristics in an uncrosslinked state, that is, before a three-dimensionally crosslinked network structure is formed. From this viewpoint, it is preferable that the gel fraction of the adhesive layer is 40% or less.

If the gel fraction of the pressure-sensitive adhesive layer is 40% or less, the bonding between the molecular chains constituting the pressure-sensitive adhesive layer is suppressed to an appropriate range. Can be provided.
From this viewpoint, the gel fraction of the pressure-sensitive adhesive layer is preferably 40% or less, more preferably 20% or less, and particularly preferably 10% or less. In addition, the minimum of the gel fraction of an adhesive material layer is not limited, 0% may be sufficient.
In addition, the gel fraction of said adhesive material layer is a resin composition containing (meth) acrylic-type copolymer (a), a crosslinking agent (b), and a photoinitiator (c) as base resin. The same applies to the case where other resin composition is used as the adhesive layer.

((Meth) acrylic copolymer (a))
The (meth) acrylic copolymer (a) has properties such as a glass transition temperature (Tg) as appropriate depending on the type and composition ratio of the acrylic monomer and methacrylic monomer used for polymerizing the (meth) acrylic copolymer (a). It is possible to adjust.

Examples of the acrylic monomer and methacrylic monomer used for polymerizing the acrylate polymer include 2-ethylhexyl acrylate, n-octyl acrylate, n-butyl acrylate, ethyl acrylate, methyl methacrylate, and the like. Vinyl acetate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, acrylamide, acrylonitrile, methacrylonitrile, fluorine acrylate, silicone acrylate, etc., which are copolymerized with a hydrophilic group or an organic functional group, can also be used.

Among the acrylic ester polymers, (meth) acrylic acid alkyl ester copolymers are particularly preferable.
As the (meth) acrylate used for forming the (meth) acrylic acid alkyl ester copolymer, that is, the alkyl acrylate or alkyl methacrylate component, the alkyl group is n-octyl, isooctyl, 2-ethylhexyl, n-butyl, One of alkyl acrylate or alkyl methacrylate which is any one of isobutyl, methyl, ethyl and isopropyl, or a mixture of two or more selected from these is preferable.

As other components, an acrylate or methacrylate having an organic functional group such as a carboxyl group, a hydroxyl group, or a glycidyl group may be copolymerized. Specifically, a monomer component obtained by appropriately and selectively combining the alkyl (meth) acrylate component and the (meth) acrylate component having an organic functional group as a starting material is subjected to heat polymerization to form a (meth) acrylate ester copolymer. A polymer polymer can be obtained.
Among them, preferably, one of alkyl acrylates such as iso-octyl acrylate, n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture of two or more selected from these, or iso-octyl acrylate, Examples include those obtained by copolymerizing at least one or more of n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like with acrylic acid.

As the polymerization treatment using these monomers, known polymerization methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like can be employed. In this case, a thermal polymerization initiator or photopolymerization is used according to the polymerization method. An acrylic ester copolymer can be obtained by using a polymerization initiator such as an initiator.

(Acrylic copolymer (A1))
As an example of a preferable base polymer of the adhesive material layer, there can be mentioned a (meth) acrylic copolymer (A1) composed of a graft copolymer having a macromonomer as a branch component.

If the pressure-sensitive adhesive layer is composed of the acrylic copolymer (A1) as a base resin, the pressure-sensitive adhesive layer can exhibit self-adhesion while maintaining a sheet shape at room temperature, and when heated in an uncrosslinked state It has a hot melt property that melts or flows, and can be photocured, and after photocuring, it exhibits excellent cohesive force and can be bonded.
Therefore, when the acrylic copolymer (A1) is used as the base polymer of the adhesive material layer, it exhibits adhesiveness at room temperature (20 ° C.) even in an uncrosslinked state, and more preferably 50 to 100 ° C. Can be softened or fluidized when heated to a temperature of 60 ° C. or higher or 90 ° C. or lower.

The glass transition temperature of the copolymer constituting the trunk component of the acrylic copolymer (A1) is preferably −70 to 0 ° C.
At this time, the glass transition temperature of the copolymer component constituting the trunk component refers to the glass transition temperature of the polymer obtained by copolymerizing only the monomer component constituting the trunk component of the acrylic copolymer (A1). . Specifically, it means a value calculated by the Fox formula from the glass transition temperature and the composition ratio of the polymer obtained from the homopolymer of each component of the copolymer.
In addition, the calculation formula of Fox is a calculation value calculated | required by the following formula | equation, Polymer handbook [Polymer HandBook, J.M. Brandrup, Interscience, 1989].
1 / (273 + Tg) = Σ (Wi / (273 + Tgi))
[Wherein Wi represents the weight fraction of monomer i, and Tgi represents Tg (° C.) of the homopolymer of monomer i. ]

The glass transition temperature of the copolymer component constituting the backbone component of the acrylic copolymer (A1) is the flexibility of the adhesive layer at room temperature, the wettability of the adhesive layer to the adherend, The glass transition temperature is preferably −70 ° C. to 0 ° C., in particular, −65 ° C. in order for the pressure-sensitive adhesive layer to have appropriate adhesion (tackiness) at room temperature because it affects the adhesion. Above, or −5 ° C. or less, particularly preferably −60 ° C. or more or −10 ° C. or less.
However, even if the glass transition temperature of the copolymer component is the same temperature, the viscoelasticity can be adjusted by adjusting the molecular weight. For example, it can be made more flexible by reducing the molecular weight of the copolymer component.

Examples of the (meth) acrylic acid ester monomer contained in the main component of the acrylic copolymer (A1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meta Acrylate, t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl ( (Meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3,5,5-trimethylcyclohexane acrylate, p-cumylphenol EO-modified (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, etc. . These include hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate having a hydrophilic group or an organic functional group, ) Acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalate Acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxypropylsuccinic acid, crotonic acid, fumaric acid Carboxyl group-containing monomers such as maleic acid, itaconic acid, monomethyl maleate and monomethyl itaconic acid, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate , Epoxy group-containing monomers such as (meth) acrylic acid 3,4-epoxybutyl, amino group-containing (meth) acrylate monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, (meth) Acrylamide, Nt-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, maleic acid amide, maleimide, etc. Monomers containing amide group, vinyl pyrrolidone, vinyl pyridine, can also be used heterocyclic basic monomers such as vinyl carbazole.
Also, styrene, t-butylstyrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, alkyl vinyl ether, hydroxyalkyl vinyl ether, alkyl, which can be copolymerized with the acrylic monomer or methacrylic monomer. Various vinyl monomers such as vinyl monomers can also be used as appropriate.

Moreover, it is preferable that the trunk component of the acrylic copolymer (A1) contains a hydrophobic (meth) acrylate monomer and a hydrophilic (meth) acrylate monomer as constituent units.
If the trunk component of the acrylic copolymer (A1) is composed only of a hydrophobic monomer, a tendency to wet-heat whitening is recognized. Therefore, it is preferable to introduce a hydrophilic monomer into the trunk component to prevent wet-heat whitening. .

Specifically, as the main component of the acrylic copolymer (A1), a hydrophobic (meth) acrylate monomer, a hydrophilic (meth) acrylate monomer, and a polymerizable functional group at the end of the macromonomer are included. The copolymer component formed by random copolymerization can be mentioned.

Here, examples of the hydrophobic (meth) acrylate monomer include n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, and pentyl (meth) ) Acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) ) Acrylate, isononyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate , Lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyloxyethyl Examples thereof include (meth) acrylate and methyl methacrylate.
Examples of the hydrophobic vinyl monomer include vinyl acetate, styrene, t-butyl styrene, α-methyl styrene, vinyl toluene, and alkyl vinyl monomers.

Examples of the hydrophilic (meth) acrylate monomer include methyl acrylate, (meth) acrylic acid, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) ) Acrylate, hydroxyl-containing (meth) acrylate such as glycerol (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- Carboxyl group-containing monomers such as (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconic acid, maleic anhydride, anhydrous Monomers containing acid anhydride groups such as itaconic acid, monomers containing epoxy groups such as glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate And alkoxypolyalkylene glycol (meth) acrylate, N, N-dimethylacrylamide, hydroxyethylacrylamide and the like. *

The acrylic copolymer (A1) preferably contains a macromonomer-derived repeating unit by introducing a macromonomer as a branch component of the graft copolymer.
The macromonomer is a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.

The glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the acrylic copolymer (A1).
Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heating and melting temperature (hot melt temperature) of the pressure-sensitive adhesive layer 2, the glass transition temperature (Tg) of the macromonomer is 30 ° C. to 120 ° C. Among them, it is preferable to be 40 ° C or higher or 110 ° C or lower, and it is more preferable to be 50 ° C or higher or 100 ° C or lower.
With such a glass transition temperature (Tg), by adjusting the molecular weight, it is possible to maintain excellent processability and storage stability, and to adjust so as to hot-melt near 80 ° C.
The glass transition temperature of the macromonomer refers to the glass transition temperature of the macromonomer itself, and can be measured with a differential scanning calorimeter (DSC).

Further, at room temperature, the branch components are attracted to each other and can maintain a state where they are physically cross-linked as a pressure-sensitive adhesive composition, and the physical cross-linking is released by heating to an appropriate temperature. In order to obtain fluidity, it is also preferable to adjust the molecular weight and content of the macromonomer.
From this viewpoint, the macromonomer is preferably contained in the acrylic copolymer (A1) in a proportion of 5% by mass to 30% by mass, particularly 6% by mass or 25% by mass, and more preferably 8% by mass. It is preferable that the amount is 20% by mass or more.
The number average molecular weight of the macromonomer is preferably 500 or more and less than 8000, more preferably 800 or more and less than 7500, and particularly preferably 1000 or more and less than 7000.
As the macromonomer, a generally produced one (for example, a macromonomer manufactured by Toa Gosei Co., Ltd.) can be appropriately used.

The high molecular weight skeleton component of the macromonomer is preferably composed of an acrylic polymer or a vinyl polymer.
Examples of the high molecular weight skeleton component of the macromonomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) ) Acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, t-butylcyclohexyl ( (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) ) Acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3,5,5-trimethylcyclohexane acrylate, p-cumylphenol EO modified (meth) acrylate, dicyclopentanyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylic acid, (Meth) acrylate monomers such as lysidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylonitrile, alkoxyalkyl (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate, , Styrene, t-butyl styrene, α-methyl styrene, vinyl toluene, alkyl vinyl monomer, vinyl acetate, alkyl vinyl ether, hydroxyalkyl vinyl ether, and other vinyl monomers. These may be used alone or in combination of two or more. can do.

Examples of the terminal polymerizable functional group of the macromonomer include a methacryloyl group, an acryloyl group, and a vinyl group.

(Crosslinking agent (b))
As the crosslinking agent (b), a crosslinking monomer used when the acrylic ester polymer is crosslinked can be used. For example, at least one crosslinkable functional group selected from (meth) acryloyl group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, carbodiimide group, oxazoline group, aziridine group, vinyl group, amino group, imino group, and amide group The crosslinking agent which has can be mentioned, You may use 1 type or in combination of 2 or more types.
The crosslinkable functional group may be protected with a deprotectable protecting group.

Above all, a polyfunctional organic function having two or more organic functional groups such as a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups, an isocyanate group, an epoxy group, a melamine group, a glycol group, a siloxane group or an amino group. An organometallic compound having a metal complex such as a base resin, zinc, aluminum, sodium, zirconium, or calcium can be preferably used.

Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin glycidyl ether di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polyalkoxydi (meth) Acrylate, bisphenol F polyalkoxy di (meth) acrylate, polyalkylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ε-caprolactone modified tri (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Propoxylated pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) Di (meta) of ε-caprolactone adduct of acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxybivalate, neopentyl hydroxybivalate ) In addition to UV-curable polyfunctional monomers such as acrylate, trimethylolpropane tri (meth) acrylate, alkoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, polyester (meth) acrylate, Polyfunctional acrylic oligomers such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyether (meth) acrylate can be exemplified.

Among the polyfunctional (meth) acrylic acid ester monomers, among the above-mentioned polyfunctional (meth) acrylate monomers, polar functional groups such as a hydroxyl group, a carboxyl group, and an amide group can be used. Polyfunctional monomers or oligomers containing are preferred. Among these, it is preferable to use a polyfunctional (meth) acrylic acid ester having a hydroxyl group or an amide group.
From the viewpoint of preventing wet heat whitening, it is preferable to contain a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as a trunk component of the (meth) acrylate copolymer, for example, a graft copolymer, Furthermore, it is preferable to use a polyfunctional (meth) acrylic acid ester having a hydroxyl group as a crosslinking agent.
Moreover, in order to adjust effects, such as adhesiveness, heat-and-moisture resistance, and heat resistance, you may further add monofunctional or polyfunctional (meth) acrylic acid ester which reacts with a crosslinking agent.

The content of the crosslinking agent is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer, from the viewpoint of balancing the flexibility and cohesive force of the pressure-sensitive adhesive composition. In particular, the ratio is preferably 0.5 parts by mass or more and 15 parts by mass or less, and particularly preferably 1 part by mass or more or 13 parts by mass or less.

(Photopolymerization initiator (c))
When crosslinking the acrylic ester polymer, a crosslinking initiator (peroxidation initiator, photopolymerization initiator) and reaction catalyst (tertiary amine compound, quaternary ammonium compound, tin laurate compound, etc.) are appropriately used. It is effective when added.

In the case of UV irradiation crosslinking, it is preferable to blend a photopolymerization initiator (c).
The photopolymerization initiator (c) is roughly classified into two types depending on the radical generation mechanism. The photopolymerization initiator is capable of generating a radical by cleaving the single bond of the photopolymerization initiator itself, and photoexcitation. In general, the initiator and the hydrogen donor in the system form an exciplex and can be roughly classified into a hydrogen abstraction type photopolymerization initiator that can transfer hydrogen of the hydrogen donor.
Among these, the cleavage type photopolymerization initiator is decomposed when a radical is generated by light irradiation to be another compound, and once excited, it does not function as a reaction initiator. For this reason, when the intramolecular cleavage type is used as a photopolymerization initiator having an absorption wavelength in the visible light region, light-reactive light is obtained after the pressure-sensitive adhesive sheet is cross-linked by light irradiation as compared with the case of using a hydrogen abstraction type. A polymerizable initiator is preferable because it remains as an unreacted residue in the pressure-sensitive adhesive composition and is unlikely to cause an unexpected change with time or promotion of crosslinking. Further, the coloring specific to the photopolymerizable initiator is also preferable because it becomes a reaction decomposition product, so that absorption in the visible light region is eliminated and a color to be erased can be appropriately selected.
On the other hand, a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product such as a cleavage type photopolymerization initiator during radical generation reaction by irradiation of active energy rays such as ultraviolet rays, so that it is difficult to become a volatile component after completion of the reaction. Damage to the body can be reduced.

Examples of the cleavage type photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl-propane-1. -One, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- {4- (2-hydroxy- 2-methyl-propionyl) benzyl} phenyl] -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglyoxy Methyl lickate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -On, 2- (dimethylamino)- 2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide, and their derivatives Can be mentioned.

Among these, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine is a cleavage-type photopolymerization initiator, and becomes a degradation product after the reaction and discolors. Acylphosphine oxide photoinitiators such as fin oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide are preferred.
Furthermore, from the compatibility with an acrylic copolymer comprising a graft copolymer having a macromonomer as a branch component, 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator, It is preferable to use 6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide, and the like.

The content of the photopolymerization initiator is not particularly limited. For example, with respect to 100 parts by weight of the (meth) acrylic copolymer, 0.1 to 10 parts by weight, particularly 0.2 parts by weight or more and 5 parts by weight or less, and more preferably 0.5 parts by weight or more or 3 parts by weight or less. It is particularly preferable to include them in proportions. However, this range may be exceeded in balance with other elements.
A photoinitiator can be used 1 type or in combination of 2 or more types.

In addition to the above components, pigments such as pigments and dyes having near-infrared absorption characteristics, tackifiers, antioxidants, antioxidants, hygroscopic agents, ultraviolet absorbers, silane coupling agents, natural products, Various additives such as synthetic resins, glass fibers and glass beads can be appropriately blended.

(Layer structure and thickness of adhesive layer)
The adhesive material layer may be a single layer or a plurality of layers such as two layers or three layers.
The pressure-sensitive adhesive layer may have a structure in which a base layer (non-sticky layer) is provided as a core layer, and layers made of a pressure-sensitive adhesive are laminated on both sides of the base layer. . In the case of such a configuration, the base material layer as the core layer preferably has a material and characteristics such that the pressure-sensitive adhesive sheet laminate can be heat-molded. Further, the adhesive layer excluding the base material layer has the above-described characteristics with respect to loss tangent tan δ (SA), loss tangent tan δ (SB), storage elastic modulus G ′ (SA), and storage elastic modulus G ′ (SB). It is preferable.

The thickness of the adhesive layer is not particularly limited. In particular, the range of 20 μm to 500 μm is preferable. If it is this range, if it is a thin adhesive material layer like thickness 20 micrometers, the adhesive sheet excellent in the printing level | step difference followable | trackability can be provided. Moreover, in the thick adhesive material layer having a thickness of 500 μm, it is possible to suppress the overflow of the adhesive material at the time of pasting because the portion corresponding to the printing step is shaped in advance.
Accordingly, the thickness of the adhesive layer is preferably 20 μm to 500 μm, more preferably 30 μm or more and 300 μm or less, and particularly preferably 50 μm or more and 200 μm or less.

<Coating part I>
As shown in FIG. 1, the pressure-sensitive adhesive sheet laminate includes a covering portion I that is detachably laminated on one side of the pressure-sensitive adhesive layer, for example, on the side that forms irregularities on the surface.

The storage elastic modulus E ′ (MA) at 100 ° C. of the covering portion I is preferably 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa.
Since the temperature at which the pressure-sensitive adhesive sheet laminate is heat-molded is usually 70 to 120 ° C., the storage elastic modulus E ′ (MA) at 100 ° C. is 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa. For example, in the temperature range where the pressure-sensitive adhesive composition is plasticized or fluidized, the covering portion I can follow the uneven shape sufficiently and can be deformed, but also on the surface of the pressure-sensitive adhesive layer pressed by the covering portion I during molding. The desired uneven shape can be molded with high accuracy, for example, so that the corners are not rounded.

Conventionally, as a release film laminated on an adhesive sheet, a material having a high storage elastic modulus, in other words, a “hard” material has been frequently used. This is because the properties required for the release film were mainly the protection of the adhesive layer and the release property. However, according to the study by the present inventors, when a new problem of heat moldability is required in a new application of heat forming in a state where a release film is laminated on an adhesive sheet, a conventional release is required. It has been found that the above-mentioned physical properties provided in the mold film cannot be achieved. For this reason, as a result of scrutinizing the phenomena occurring during heat molding and the characteristics of the adhesive layer, it is a new problem of heat moldability that has characteristics different from those of the release films that have been generally used so far. It has been found that it is advantageous for solving the problem. In particular, it has been found that the above problem can be solved by controlling the storage elastic modulus at a specific temperature within a specific range.

From this viewpoint, the storage elastic modulus E ′ (MA) at 100 ° C. of the covering portion I is preferably 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa, and more preferably 5.0 × 10 ⁶ Pa or more. 1.0 × 10 ⁹ Pa or less, more preferably 1.0 × 10 ⁷ Pa or more or 5.0 × 10 ⁸ Pa or less.
From the above, the storage elastic modulus E ′ (MA) at 100 ° C. of the covering portion I is 1.0 × 10 ⁶ to 1.0 × 10 ⁹ Pa, or 1.0 × 10 ⁶ to 5.0 × 10 ^8. More preferably, it is Pa, more preferably 5.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa, or even more preferably 5.0 × 10 ⁶ to 1.0 × 10 ⁹ Pa. Most preferably, it is 0 × 10 ⁷ to 1.0 × 10 ⁹ Pa or less, or 1.0 × 10 ⁷ to 5.0 × 10 ⁸ Pa.

Further, the storage elastic modulus E ′ (MB) at 30 ° C. of the covering portion I is preferably 5.0 × 10 ⁷ to 1.0 × 10 ¹⁰ Pa.
If the storage elastic modulus E ′ (MB) at 30 ° C. of the covering part I is 5.0 × 10 ⁷ to 1.0 × 10 ¹⁰ Pa, shape retention can be maintained in a normal state, and handling is easy. For example, since it is easy to peel off and is not too hard, it is possible to suppress unnecessary undesired unevenness on the adhesive layer.
From this viewpoint, the storage elastic modulus E ′ (MB) at 30 ° C. of the covering portion I is preferably 5.0 × 10 ⁷ to 1.0 × 10 ¹⁰ Pa, and more preferably 1.0 × 10 ⁸ Pa or more. 8.0 × 10 ⁹ Pa or less, more preferably 1.0 × 10 ⁹ Pa or more or 5.0 × 10 ⁹ Pa or less.
From the above, the storage elastic modulus E ′ (MB) at 30 ° C. of the covering portion I is 5.0 × 10 ⁷ to 8.0 × 10 ⁹ Pa, or 5.0 × 10 ⁷ to 5.0 × 10 ^9. More preferably, it is Pa, more preferably 1.0 × 10 ⁸ Pa to 1.0 × 10 ¹⁰ Pa, or 1.0 × 10 ⁸ Pa to 8.0 × 10 ⁹ Pa, Most preferably, it is 1.0 × 10 ⁹ to 8.0 × 10 ⁹ Pa, or 1.0 × 10 ⁹ to 5.0 × 10 ⁹ Pa.

In order to adjust the storage elastic modulus at 30 ° C. and 100 ° C. of the coating part I as described above, for example, the type of the base resin, the copolymer resin component, the weight average molecular weight, the glass transition temperature, the crystallinity, etc. While adjusting the conditions of the material, it can be adjusted by adjusting the presence / absence of stretching, molding conditions, and in the case of stretching, production conditions such as stretching conditions. However, it is not limited to these methods.

Furthermore, it is preferable that the storage elastic modulus E ′ (MA) of the covering portion I at 100 ° C. and the storage elastic modulus E ′ (MB) of the covering portion I at 30 ° C. satisfy the following relational expression (1).
(1) ... E '(MB) / E' (MA) ≧ 2.0

If the storage elastic modulus E ′ (MA) of the covering portion I at 100 ° C. and the storage elastic modulus E ′ (MB) of the covering portion I at 30 ° C. satisfy the relational expression (1), sufficient formability can be obtained. More preferably.
From this viewpoint, it is preferable that E ′ (MB) / E ′ (MA) ≧ 2.0, and in particular, 30 ≧ E ′ (MB) / E ′ (MA) or E ′ (MB) / E ′ (MA ) ≧ 3.0, more preferably 10 ≧ E ′ (MB) / E ′ (MA) or E ′ (MB) / E ′ (MA) ≧ 5.0.

In order to adjust E ′ (MB) and E ′ (MA) to have the above relationship, for example, the type of base resin, copolymer resin component, weight average molecular weight, glass transition temperature, crystallinity, etc. While adjusting the conditions of the material, it can be adjusted by adjusting the presence / absence of stretching, molding conditions, and in the case of stretching, production conditions such as stretching conditions. However, it is not limited to these methods.

Furthermore, the storage elastic modulus G ′ (SA) at 100 ° C. of the pressure-sensitive adhesive layer and the storage elastic modulus E ′ (MA) of the covering portion I at 100 ° C. satisfy the following relational expression (2). preferable.
(2) .. 1.0 × 10 ³ ≦ E ′ (MA) / G ′ (SA) ≦ 1.0 × 10 ⁷

If the storage elastic modulus G ′ (SA) at 100 ° C. of the pressure-sensitive adhesive layer and the storage elastic modulus E ′ (MA) of the covering portion I at 100 ° C. satisfy the relational expression (2), sufficient formability is obtained. Is more preferable.
From this viewpoint, E ′ (MA) / G ′ (SA) is preferably 1.0 × 10 ³ to 1.0 × 10 ⁷ , and more preferably 5.0 × 10 ³ or more or 5.0 × 10 ^6. Hereinafter, it is particularly preferably 1.0 × 10 ⁴ or more or 1.0 × 10 ⁶ or less.
From the above, E ′ (MA) / G ′ (SA) is more preferably 1.0 × 10 ³ to 5.0 × 10 ⁶ , or 1.0 × 10 ³ to 1.0 × 10 ^6. Preferably, it is 5.0 × 10 ³ to 5.0 × 10 ⁶ , or more preferably 5.0 × 10 ³ to 1.0 × 10 ⁶ , and 1.0 × 10 ⁴ to 5.0 × 10 6. ⁶ or 1.0 × 10 ⁴ to 1.0 × 10 ⁶ is most preferable.

In order to adjust E ′ (MA) and G ′ (SA) to be in the above relationship, the characteristics of the adhesive layer or the covering portion I may be adjusted. The characteristics of the pressure-sensitive adhesive layer can be achieved, for example, by adjusting the components, gel fraction, weight average molecular weight, and the like of the composition constituting the pressure-sensitive adhesive layer. In addition, as the characteristics of the covering portion I, for example, the conditions of the material of the covering portion I such as the type of the base resin, the copolymer resin component, the weight average molecular weight, the glass transition temperature, and the crystallinity are adjusted, whether or not there is stretching, molding In the case of stretching, it can be adjusted by adjusting the production conditions such as stretching conditions. However, it is not limited to these methods.

Further, it is preferable that the covering portion I has a peeling force F (C) of 0.2 N / cm or less when peeling the covering portion I from the adhesive layer in an atmosphere of 30 ° C.
When the peeling force F (C) is 0.2 N / cm or less, the covering portion I can be easily peeled from the adhesive material layer.
From such a viewpoint, the peeling force F (C) is preferably 0.2 N / cm or less, more preferably 0.01 N / cm or more or 0.15 N / cm or less, and more preferably 0.02 N / cm. / Cm or more or 0.1 N / cm or less is more preferable.

The covering portion I further has a peeling force F (D) when the pressure-sensitive adhesive sheet laminate is heated to 100 ° C. for 5 minutes and then cooled to 30 ° C. Is preferably 0.2 N / cm or less.
If the peel force F (D) obtained by heating the pressure-sensitive adhesive sheet laminate at 100 ° C. for 5 minutes and then cooling to 30 ° C. and measuring in an atmosphere at 30 ° C. is approximately the same as the peel force F (C) Even if the pressure-sensitive adhesive sheet laminate is heat-molded, the peeling force F (D) does not change, so that the covering portion I can be easily peeled from the pressure-sensitive adhesive layer.
From this viewpoint, the peeling force F (D) is preferably 0.2 N / cm or less, more preferably 0.01 N / cm or more or 0.15 N / cm or less, and more preferably 0.02 N / cm. / Cm or more or 0.1 N / cm or less is more preferable.

The covering portion I preferably further has an absolute value of a difference between the peeling force F (C) and the peeling force F (D) of 0.1 N / cm or less.
The pressure-sensitive adhesive sheet laminate is heated at 100 ° C. for 5 minutes and then cooled to 30 ° C., and the difference between the peel force F (D) obtained by measurement in an atmosphere at 30 ° C. and the peel force F (C) in a normal state If the absolute value is 0.1 N / cm or less, the peeling force F (D) does not change even if the pressure-sensitive adhesive sheet laminate is heat-molded, so that the covering portion I can be easily peeled from the pressure-sensitive adhesive layer. it can.
From this viewpoint, the absolute value of the difference between the peeling force F (C) and the peeling force F (D) is preferably 0.1 N / cm or less, more preferably 0.08 N / cm or less, and particularly 0.05 N / cm. More preferably, it is as follows.

Note that the peeling force F (C) and the peeling force F (D) of the covering portion I can be prepared depending on the type of the release layer formed on one side of the covering portion I. However, it is not limited to this method.

As a structural example of the coating | coated part I, the structural example provided with the coating | coated base material layer and the release layer can be mentioned. By laminating the release layer on one surface of the covering base material layer, the covering portion I can be configured to be easily peeled from the adhesive material layer.

In this case, the covering base layer is, for example, a stretched or unstretched layer mainly composed of one type of resin or two or more types of resins selected from the group consisting of polyester, copolyester, polyolefin and copolyolefin. That is, it is preferably a single layer or a multilayer having a layer made of a stretched or non-stretched film containing these resins as a main component.

Among them, the covering base layer constituting the covering portion I is, for example, a copolymerized polyester, a polyolefin, or a stretched or non-stretched film containing a copolymerized polyolefin as a main component from the viewpoint of mechanical strength, chemical resistance, and the like. It is preferable that it is a single layer provided with the layer which consists of or multiple layers.
Specific examples of the copolymerized polyester include copolymerized polyethylene terephthalate obtained by arbitrarily copolymerizing, for example, isophthalic acid as a dicarboxylic acid, cyclohexanedimethanol, 1,4-butanediol, diethylene glycol or the like as a diol. it can.
Specific examples of the polyolefin include an α-olefin homopolymer, and examples thereof include a propylene homopolymer and a homopolymer of 4-methylpentene-1.
Specific examples of the polyolefin copolymer include copolymers such as ethylene, propylene, other α-olefins and vinyl monomers.

The release layer is preferably a layer containing a modified polyolefin in addition to a release agent such as silicone.
Here, examples of the modified olefin constituting the release layer include resins mainly composed of an unsaturated carboxylic acid or an anhydride thereof, or a polyolefin modified with a silane coupling agent.

Examples of the unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride or monoepoxy compounds of these derivatives and the acid. Ester compounds, polymers having a group capable of reacting with these acids in the molecule, and reaction products of the acids. These metal salts can also be used. Among these, maleic anhydride is more preferably used. Moreover, these copolymers can be used individually or in mixture of 2 or more types, respectively.

In order to produce a modified polyolefin-based resin, for example, these modified monomers can be copolymerized at the stage of polymerizing in advance, or these modified monomers can be graft copolymerized with the polymer once polymerized. Further, as the modified polyolefin resin, these modified monomers may be used alone or in combination, and the content thereof is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more. In the range of 5% by mass or less, preferably 4.5% by mass or less, more preferably 4.0% by mass or less is preferably used. Of these, those that have been graft-modified are preferably used.

Preferable examples of the modified polyolefin resin include maleic anhydride-modified polypropylene resin, maleic anhydride-modified polyethylene resin, maleic anhydride ethylene-vinyl acetate copolymer, and the like.

From the viewpoint of moldability, the thickness of the covering portion I is preferably 10 μm to 500 μm, more preferably 20 μm or more and 300 μm or less, and particularly preferably 30 μm or more or 150 μm or less.

<Coating II>
As described above, this pressure-sensitive adhesive sheet laminate has a covering portion I laminated on the front and back sides of the pressure-sensitive adhesive layer so as to be peelable, and can be peeled on the opposite side of the covering portion I, that is, on the other side of the pressure-sensitive adhesive layer. It can be set as the structure which laminate | stacks the coating | coated part II. Thus, handling property can be improved by laminating | stacking the coating | coated part II on the front and back other side of an adhesive material layer so that peeling is possible. However, a configuration in which the covering portion II is not stacked is also possible.

The covering portion II is not particularly limited in material and configuration as long as it is formed by being peelably laminated on the other side of the adhesive layer.

The covering portion II may be, for example, the same laminated structure and material as the covering portion I, and may be the same thickness as the covering portion I or a different thickness.
If the covering part II is the same laminate structure and material as the covering part I, it is possible to prevent warping from occurring when the present adhesive sheet laminate is heated.

The covering portion II has the same configuration as the covering portion I, but has a storage elastic modulus E ′ (MA) at 100 ° C., a storage elastic modulus E ′ (MB) at 30 ° C., and a ratio thereof (E ′ (MB) / E ′). (MA)), peel force F (C), peel force F (D), and the like may be different from those of the covering portion I.
Further, the covering portion II may have a laminated structure and material different from those of the covering portion I.
For the covering part II, for example, a generally used release film (also referred to as “release film”) can be used. Specific examples include materials having a storage elastic modulus E ′ (MC) at 100 ° C. of 2.0 × 10 ⁹ to 1.0 × 10 ¹¹ Pa, such as a biaxially stretched polyethylene terephthalate (PET) film. Etc. can be used.

[Coating I]
As a structural example of the covering portion I, a coating film in which a coating layer is provided on one side of a copolyester film, and a storage elastic modulus E ′ at 100 ° C. is 1.5 × 10 ⁹ Pa or less. The coated film (referred to as “the present coated film”) will be described.
If this coating film is used, for example, after heating the pressure-sensitive adhesive sheet laminate, the mold is pressed against a coating film provided with a coating layer having releasability so as to match the irregularities on the surface of the adherend. The uneven shape to be formed can be formed on the surface of the pressure sensitive adhesive sheet with high accuracy. In addition, since the coated film can maintain shape retention in a normal state, it is not only easy to handle, but also is not too hard, so that it is possible to suppress unnecessary unintended irregularities on the adhesive sheet. .

<Copolymerized polyester film>
The copolymerized polyester film constituting the coated film may have a single layer structure or a laminated structure. For example, in addition to the two-layer or three-layer structure, the copolymer polyester film has four layers or more unless the gist of the present invention is exceeded. The above multilayer may be used, and is not particularly limited. Also, for example, when a three-layer structure (surface layer / intermediate layer / surface layer) is used, one or more of the surface layer or intermediate layer is used as a copolymerized polyester component, and the other layers are copolymerized. It is also possible to comprise a polyester component that does not contain the component.

The copolyester film refers to a film stretched as necessary after cooling the molten polyester sheet extruded by an extrusion method.

As the dicarboxylic acid component of the copolyester, terephthalic acid is preferable. Besides, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid One or more known dicarboxylic acids such as cyclohexanedicarboxylic acid may be contained as a copolymerization component. As the diol component, ethylene glycol is preferable. In addition, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, neodymium One or more known diols such as pentyl glycol may be contained as a copolymerization component.
Of these, copolymerized polyethylene terephthalate obtained by arbitrarily copolymerizing phthalic acid or isophthalic acid as the dicarboxylic acid component and 1,4-cyclohexanedimethanol, 1,4-butanediol, diethylene glycol or the like as the diol component is more preferable.

The content of the copolymer component is preferably 1 mol% or more and 50 mol% or less, more preferably 3 mol% or more or 40 mol% or less, and further preferably 4 mol% or more or 30 mol% or less. When the content of the copolymerization component is 1 mol% or more, a concave shape, a convex shape, or an uneven shape can be formed on the pressure-sensitive adhesive sheet surface when laminated with the pressure-sensitive adhesive sheet. On the other hand, by being 50 mol% or less, not only has sufficient dimensional stability, but generation | occurrence | production of the wrinkle at the time of a process can fully be suppressed.

The melting point of the copolymerized polyester film is preferably designed to be 260 ° C. or lower, more preferably 200 to 255 ° C. When the melting point is 260 ° C. or less, sufficient strength can be obtained even in a heat treatment at a temperature lower than the melting point of the copolyester film in the heat treatment step after stretching.

It is desirable from the viewpoint of improving film workability that particles are contained in the copolymerized polyester film. As particles, inorganic particles such as calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, lithium fluoride, aluminum oxide, silicon oxide, kaolin; organic such as acrylic resin and guanamine resin Particles: Examples thereof include, but are not limited to, precipitated particles obtained by making catalyst residuals into particles. The particle size of these particles and the content in the copolyester film can be appropriately determined according to the purpose. The particles to be contained may be a single component, or two or more components may be used simultaneously. Various stabilizers, lubricants, antistatic agents and the like can also be added as appropriate.

The average particle size of the particles contained in the copolymerized polyester film is preferably 0.1 to 5.0 μm. When the average particle size of the particles is less than 0.1 μm, the slipperiness of the film becomes insufficient and workability may be lowered. On the other hand, when the average particle diameter of the particles exceeds 5.0 μm, the smoothness of the film surface may be impaired.

The content of particles contained in the copolymerized polyester film is preferably 0.01 to 0.3% by weight. When the content of the particles is less than 0.01% by weight, the slipperiness of the film becomes insufficient and workability may be lowered. On the other hand, when the content of the particles exceeds 0.3% by weight, the smoothness of the film surface may be impaired.

The method for adding particles to the copolymerized polyester film is not particularly limited, and a known method can be adopted. For example, it can be added at any stage for producing the polyester, but it is preferably added as a slurry dispersed in ethylene glycol or the like at the stage of esterification or before the start of the polycondensation reaction after completion of the transesterification reaction. The condensation reaction may proceed. Also, a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material, or a blending of dried particles and a polyester raw material using a kneading extruder. For example, a method for depositing particles in a polyester production process system.

The intrinsic viscosity of the copolyester is usually 0.40 to 1.10 dl / g, preferably 0.45 to 0.90 dl / g, more preferably 0.50 to 0.80 dl / g. When the intrinsic viscosity is less than 0.40 dl / g, the mechanical strength of the film tends to be weakened. When the intrinsic viscosity exceeds 1.10 dl / g, the melt viscosity becomes high and the extruder is overloaded. There is a case.

Next, a production example of the copolyester film will be specifically described, but it is not limited to the following production example.

First, a method of using the copolymer polyester raw material described above and cooling and solidifying a molten sheet extruded from a die with a cooling roll to obtain an unstretched sheet is preferable. In this case, in order to improve the flatness of the sheet, it is necessary to improve the adhesion between the sheet and the rotary cooling drum, and an electrostatic application adhesion method and / or a liquid application adhesion method are preferably employed.
Next, the obtained unstretched sheet is preferably stretched at least in a uniaxial direction, and more preferably biaxially stretched in a biaxial direction. For example, in the case of sequential biaxial stretching as biaxial stretching, the unstretched sheet is stretched in the machine direction in one direction by a roll or a tenter type stretching machine. The stretching temperature is usually 70 to 120 ° C., preferably 75 to 110 ° C., and the stretching ratio is usually 2.5 to 7.0 times, preferably 3.0 to 6.0 times. Next, the film is stretched in the direction perpendicular to the first-stage stretching direction (machine direction). The stretching temperature is usually 70 to 170 ° C., and the stretching ratio is usually 3.0 to 7.0 times, preferably 3.5 to 6.0 times. Subsequently, heat treatment is performed at a temperature of 150 to 270 ° C. under tension or relaxation within 30% to obtain a biaxially oriented film. In the above-described biaxial stretching, a method of performing unidirectional stretching in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.

Also, simultaneous biaxial stretching can be adopted for the production of the copolyester film. Simultaneous biaxial stretching is a method in which the unstretched sheet is stretched and oriented in the machine direction and the width direction at the same time, usually at a temperature of 70 to 120 ° C., preferably 75 to 110 ° C. The draw ratio is preferably 4 to 50 times, more preferably 7 to 35 times, and still more preferably 10 to 25 times in terms of area magnification. Subsequently, heat treatment is performed at a temperature of 150 to 250 ° C. under tension or under relaxation within 30% to obtain a biaxially stretched film. With respect to the simultaneous biaxial stretching apparatus that employs the above-described stretching method, conventionally known stretching methods such as a screw method, a pantograph method, and a linear drive method can be employed.

(Coating layer)
In this coating film, it is important to provide a coating layer on at least one side of the copolymerized polyester film. Although it does not specifically limit as a coating layer, A mold release layer, an antistatic layer, an oligomer sealing layer, an easily bonding layer, a primer layer, etc. are mentioned concretely. Especially, when manufacturing the adhesive sheet laminated body laminated | stacked with the adhesive sheet, a mold release layer is more preferable. It is also possible to combine two or more types of functional layers as described above.

As a specific example of the coating layer constituting the coating film, the release layer will be described below.

Specific examples of the resin used for the release layer include a curable silicone resin, a fluorine-based resin, and a polyolefin-based resin, among which a curable silicone resin is preferable. Either a curable silicone resin or a type having a curable silicone resin as a main component, or a modified silicone by graft polymerization with an organic resin such as a urethane resin, an epoxy resin, or an alkyd resin as long as the gist of the present invention is not impaired. A type or the like may be used.

As the type of the curable silicone resin, any of the curing reaction types such as an addition type, a condensation type, an ultraviolet curable type, an electron beam curable type, and a solventless type can be used. Specific examples include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-856, X-62-2422, X-62-2461, X, manufactured by Shin-Etsu Chemical Co., Ltd. -62-1387, X-62-5039, X-62-5040, KNS-3051, X-62-1496, KNS320A, KNS316, X-62-1574A / B, X-62-7052, X-62-7028A / B, X-62-7619, X-62-7213; YSR-3022, TPR-6700, TPR-6720, TPR-6721, TPR6500, TPR6501, UV9300, UV9425, XS56-A2775, manufactured by Momentive Performance Materials XS56-A2982, UV9430, TPR6600, TPR66 4, TPR 6605; SRX357, SRX211, SD7220, SD7292, LTC750A, LTC760A, LTC303E, SP7259, BY24-468C, SP7248S, BY24-452, DKQ3-202, DKQ3-203, manufactured by Toray Dow Corning Co., Ltd. DKQ3-205, DKQ3-210, etc. Further, a release control agent may be used in combination to adjust the release property of the release layer.

The curing conditions for forming the release layer on the copolymerized polyester film are not particularly limited. In the case of providing a release layer by off-line coating, heat treatment is usually performed at 120 to 200 ° C. for 3 to 40 seconds, preferably 100 to 180 ° C. for 3 to 40 seconds. Moreover, you may use together heat processing and active energy ray irradiation, such as ultraviolet irradiation, as needed. In addition, a conventionally well-known apparatus and energy source can be used as an energy source for hardening by active energy ray irradiation. The coating amount (after drying) of the release layer is usually 0.005 to 1 g / m ² , preferably 0.005 to 0.5 g / m ² , and more preferably 0.01 to 0.5 g from the viewpoint of coating properties. The range is 0.2 g / m ² . When the coating amount (after drying) is less than 0.005 g / m ² , the coating property may be less stable and it may be difficult to obtain a uniform coating film. On the other hand, when the coating is thicker than 1 g / m ² , the coating layer adhesion and curability of the release layer itself may be lowered.

Conventionally known coating methods such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, and curtain coating can be used as a method for providing a release layer on the copolymerized polyester film. Regarding the coating method, there is a description example in “Coating method” (Tsubaki Shoten, written by Yuji Harasaki, published in 1979).

In addition, the copolyester film may be subjected to a surface treatment in advance in order to provide a coating layer such as a corona treatment, a plasma treatment, or an ultraviolet irradiation treatment.

(Coating film)
The thickness of the coated film is usually 9 μm to 250 μm, preferably 12 μm to 125 μm, and more preferably 25 μm to 75 μm.
When the thickness is less than 9 μm, the film tension becomes insufficient, and there may be a problem that wrinkles are likely to occur when slitting. On the other hand, when it exceeds 250 μm, for example, the followability to a molded product having a curved shape may be insufficient.

The storage elastic modulus E ′ at 100 ° C. of the coated film is 1.5 × 10 ⁹ Pa or less, preferably 1.0 × 10 ⁹ Pa or less. When the storage elastic modulus E ′ is 1.5 × 10 ⁹ Pa or less, a concave shape, a convex shape, or a concave-convex shape can be formed on the pressure-sensitive adhesive sheet surface when laminated with the pressure-sensitive adhesive sheet. In order for the storage elastic modulus E ′ at 100 ° C. to satisfy the above range, it can be satisfied by adjusting the type and content of the copolymer component contained in the copolymer polyester film.
On the other hand, although it does not specifically limit as a minimum, 1.0 * 10 < ⁷ > Pa or more is preferable and 1.0 * 10 < ⁸ > Pa or more is more preferable.

The shrinkage ratio of the coated film after heating at 120 ° C. for 5 minutes is 3.0% or less, preferably 2.5% or less. When the shrinkage rate is 3.0% or less, sufficient dimensional stability is obtained, so that when the adhesive sheet is laminated, a concave shape, a convex shape, or a concave-convex shape can be formed on the pressure-sensitive adhesive sheet surface. . Furthermore, since the generation of wrinkles is suppressed during processing, wrinkles are not transferred to the pressure-sensitive adhesive sheet, and a pressure-sensitive adhesive sheet having a sufficient appearance can be produced.

Among them, the shrinkage in the machine direction (MD) after heating at 120 ° C. for 5 minutes is preferably 3.0% or less, and preferably 2.5% or less. On the other hand, although it does not specifically limit as a minimum, 0.1% or more is preferable and 0.5% or more is more preferable.

Also, the shrinkage in the machine direction and the vertical direction (TD) after heating at 120 ° C. for 5 minutes is preferably 1.0% or less, and preferably 0.8% or less. On the other hand, the lower limit is preferably −1.0% or more, more preferably −0.5% or more.

From the viewpoint of preventing contamination due to adhesion of oligomer (cyclic trimer) to the mold during molding, this coated film has an oligomer extraction amount of 1.0 from the surface of the coating layer after heat treatment (180 ° C., 10 minutes). × 10 ⁻³ mg / cm 2 or less is preferable, and 5.0 × 10 ⁻⁴ mg / cm ² or less is more preferable.
When the oligomer extraction amount exceeds the above range, contamination due to oligomer adhesion to the mold may be serious during molding. As an example, in the process of continuously heat-molding many times, mold contamination is promoted by the deposition of precipitated oligomers, so it is important to control the amount of oligomer precipitation during heating. For the above reasons, the smaller the amount of oligomer extracted, the more preferable.

[Method for producing this pressure-sensitive adhesive sheet laminate]
As an example of the manufacturing method of this adhesive sheet laminated body, the method of forming an adhesive material layer using a laminator can be mentioned, for example, by sandwiching an adhesive composition between two coating parts I or II. Moreover, as another method, the method of apply | coating an adhesive composition to the coating | coated part I or II, and forming the adhesive material layer can be mentioned. However, it is not limited to this manufacturing method.
Examples of the method for applying the pressure-sensitive adhesive composition include conventionally known coating methods such as reverse roll coating, gravure coating, bar coating, and doctor blade coating.

[This shaped adhesive sheet laminate]
Using this pressure-sensitive adhesive sheet laminate, a shaped pressure-sensitive adhesive sheet laminate 1 (referred to as “the present shaped pressure-sensitive adhesive sheet laminate 1”) having an uneven shape formed on the surface of the pressure-sensitive adhesive layer is produced as follows. Can do.

As shown in FIG. 3, the shaped adhesive sheet laminate 1 includes an adhesive material layer 2, a covering portion I that is detachably laminated on the front and back sides of the adhesive material layer 2, and the adhesive material layer 2. And the other side of the front and back of the cover part II that is laminated in a peelable manner,
The pressure-sensitive adhesive layer 2 includes a concave portion, a convex portion, or an uneven portion (referred to as “adhesive sheet surface uneven portion 2B”) on the front and back one side surface 2A, and the front and back other side surface 2C is a flat surface,
The covering portion I is in close contact with the front and back one side surface 2A of the pressure-sensitive adhesive sheet 2 and includes a concave portion, a convex portion, or an uneven portion (referred to as “covering portion surface uneven portion 3B”) on the front and back one side surface 3A. In addition, the sheet back surface 3C is provided with a convex portion, a concave portion or a convex concave portion (referred to as "protective sheet back surface convex concave portion 3D") that coincides with the adhesive sheet surface concave and convex portion 2B, in other words, is fitted.
The covering portion II may have a configuration including a flat surface along the front and back other surface 2C of the pressure-sensitive adhesive sheet 2.

The front and back other surface 2C can be a flat surface as shown in FIG. 3, and the front and back other surface 2C can also be formed to have a concave portion, a convex portion, or an uneven portion. it can.

As shown in FIG. 2, the present shaped adhesive sheet laminate 1 having such a structure is formed by subjecting the present adhesive sheet laminate to press molding, vacuum forming, pressure forming, or roll forming, thereby stacking the present adhesive sheet laminate. It can be manufactured by shaping the concavo-convex shape integrally with the body.
By manufacturing in this way, the pressure-sensitive adhesive sheet surface uneven portion 2B of the pressure-sensitive adhesive layer 2, the protective sheet surface uneven portion 3B and the protective sheet back surface concave / convex portion 3D of the covering portion I have unevenness corresponding to the same location, respectively. It can be.

The pressure-sensitive adhesive layer 2 can be used as a double-sided pressure-sensitive adhesive sheet for bonding together two image display device constituent members (each also referred to as “adhered body”) constituting the image display device, for example.
That is, the pressure-sensitive adhesive sheet surface uneven portion 2B in the pressure-sensitive adhesive layer 2 is a concave portion, a convex portion, or a concave-convex portion (“adhered surface uneven portion”) on the bonding surface (also referred to as “bonding surface”) of the adherend. So that they can be formed in the same contour shape. Therefore, the adhesive sheet surface uneven part 2B in the shaped adhesive sheet laminate 1 can be fitted to the adherend surface uneven part in the image display device constituting member as the adherend.

Here, as the image display device, for example, a smartphone or a tablet including a liquid crystal display device (LCD), an organic EL display device (OLED), electronic paper, a micro electro mechanical system (MEMS) display, a plasma display (PDP), and the like A terminal, a mobile phone, a television, a game machine, a personal computer, a car navigation system, an ATM, a fish finder, and the like can be given. However, it is not limited to these.
The image display device constituent member as the adherend is a member constituting these image display devices, and examples thereof include a surface protection panel, a touch panel, and an image display panel. 1 can be used for bonding any two adherends selected from, for example, a surface protection panel, a touch panel, and an image display panel. For example, it can be used to bond a surface protection panel and a touch panel, or a touch panel and an image display panel. However, the adherend is not limited to these.

<Manufacturing method>
Here, the detail of the manufacturing method of this shaped adhesive sheet laminated body 1 is demonstrated.

As described above, as shown in FIG. 2, by manufacturing the pressure-sensitive adhesive sheet laminate by heating and forming it, the concave-convex shape is integrally formed on the pressure-sensitive adhesive sheet laminate 1. Can do.
In this case, examples of the forming method include press forming, vacuum forming, pressure forming, forming by a roll, forming by lamination, and the like. Among these, press molding is particularly preferable from the viewpoints of moldability and workability.

A more specific example will be described.
The pressure-sensitive adhesive sheet laminate is preheated with a heater, and the pressure-sensitive adhesive sheet laminate is transported to a press molding machine when it is heated to a predetermined temperature, and has a shape corresponding to the printed step shape of the adherend in advance. By performing press working with a mold and cooling, the shape of the pressure-sensitive adhesive sheet laminate 1 can be produced by transferring the shape of the mold to one side of the pressure-sensitive adhesive sheet laminate and forming the unevenness on one side. .

At this time, the preheating of the pressure-sensitive adhesive sheet laminate is preferably performed at a temperature at which the pressure-sensitive adhesive layer is softened, specifically 70 to 120 ° C.

The material of the type | mold used for uneven | corrugated shaping is not specifically limited. For example, resin-based materials such as silicone resin and fluororesin, and metal-based materials such as stainless steel and aluminum can be used. Among these, metal molds that can be controlled in temperature during molding are particularly preferred because high-precision moldability is required for forming irregularities on the adherend.
Further, the cooling after the press working may be performed after the mold is opened, or the mold may be cooled and cooled at the same time as pressing.

In the present invention, molding conditions such as pressing pressure and pressing time are not particularly specified, and may be appropriately adjusted depending on the dimension and shape to be molded, the material to be used, and the like.
Moreover, you may cut using a Thomson blade, a rotary blade, etc. after a shaping | molding process.

[Manufacturing method of the present shaped adhesive sheet laminate]
Next, an adhesive material layer and a covering portion I that is detachably laminated on one surface of the adhesive material layer are provided. A particularly preferable embodiment of a method for producing a shaped pressure-sensitive adhesive sheet laminate having a structure formed by shaping a part ”will be described.

In the invention relating to the present production method 1 and the present production method 2 described later, an adhesive material layer surface irregularity coinciding with the irregularities on the surface of the adherend can be formed on the adhesive material layer surface with high accuracy, and preferably continuous. The present invention proposes a new method for producing a shaped pressure-sensitive adhesive sheet laminate that can be produced.

As an example of an embodiment of the present invention, an adhesive material layer and a covering portion I that is detachably laminated on one surface of the adhesive material layer are provided, and one surface of the adhesive material has a concave portion, a convex portion, or an uneven portion ( In the method for producing a shaped pressure-sensitive adhesive sheet laminate having a configuration in which the “adhesive material layer surface irregularity portion” is shaped, the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer are peelably laminated on one surface. And a heating method for forming a heated pressure-sensitive adhesive sheet laminate and cooling to produce a shaped pressure-sensitive adhesive sheet laminate, and heating the pressure-sensitive adhesive sheet laminate Then, molding was started in a state where the storage elastic modulus E ′ (MS) of the covering portion I was 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa, and the storage elastic modulus E ′ (MF) of the covering portion I was ) Features that exits the molding while it is ^{^{5.0 × 10 7 ~ 1.0 × 10}} 10 Pa We propose a method for manufacturing a new shaping adhesive sheet laminate (referred to as "production method 1") to.
The present manufacturing method 1 further proposes that the heated pressure-sensitive adhesive sheet laminate is molded using a cooled mold in the new method for producing a shaped pressure-sensitive adhesive sheet laminate.

According to this manufacturing method 1, for example, after the pressure-sensitive adhesive sheet laminate is heated, the covering portion I starts forming in a predetermined state, and the covering portion I finishes forming in the predetermined state. An uneven shape matching the uneven portion on the surface of the adherend can be formed with high accuracy on the surface of the adhesive layer.
Furthermore, when the heated pressure-sensitive adhesive sheet laminate is molded, if it is molded using a cooled mold, it can be cooled at the same time as the molding, and the process can be completed simultaneously. Can do.

<This manufacturing method 1>
This manufacturing method 1 is a method for manufacturing a shaped pressure-sensitive adhesive sheet laminate (referred to as “the present manufacturing method”) according to an example of the present embodiment. It is a manufacturing method provided with the process of shape | molding and cooling an adhesive sheet laminated body (molding | cooling process).

The present manufacturing method 1 may include other steps as long as it includes the heating step and the forming / cooling step. For example, you may provide processes, such as a heat treatment process, a conveyance process, a slit process, and a cutting process, as needed. However, it is not limited to these processes.

(Adhesive sheet laminate)
The pressure-sensitive adhesive sheet laminate as a starting member in the production method 1 only needs to include a pressure-sensitive adhesive layer and a covering portion I that is detachably laminated on one surface of the pressure-sensitive adhesive layer, and includes other members. It may be. For example, as shown in FIG. 1, an adhesive material layer, a covering portion I that is detachably laminated on one side of the adhesive material layer, and a peelable laminate on the other side of the adhesive material layer. A pressure-sensitive adhesive sheet laminate provided with the covering portion II can be exemplified. However, whether or not the covering portion II is provided is arbitrary, and the covering portion II may not be stacked.
In addition, it is as above-mentioned about the detail of an adhesive sheet laminated body.

(Heating process)
In the present production method 1, the pressure-sensitive adhesive sheet laminate is heated so that the storage elastic modulus E ′ (M) of the covering portion I is in the range of 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa. preferable.
If the storage elastic modulus E ′ (M) of the covering portion I is in the above range, the covering portion I can be deformed to an extent suitable for molding, and a desired uneven shape is accurately formed on the surface of the adhesive layer. It can be shaped.
From this viewpoint, it is preferable to heat the pressure-sensitive adhesive sheet laminate so that the storage elastic modulus E ′ (M) of the covering portion I is 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa. 5.0 × 10 ⁶ Pa or more or 1.0 × 10 ⁹ Pa or less, more preferably 1.0 × 10 ⁷ Pa or more or 5.0 × 10 ⁸ Pa or less.
From the above, the adhesive sheet laminate is heated, and the storage elastic modulus E ′ (M) of the covering portion I is 1.0 × 10 ⁶ to 1.0 × 10 ⁹ Pa, or 1.0 × 10 ⁶ to 5 More preferably, it is in a state of 0.0 × 10 ⁸ , among which 5.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa, or 5.0 × 10 ⁶ to 1.0 × 10 ⁹ Pa. More preferably, the state is 1.0 × 10 ⁷ to 1.0 × 10 ⁹ Pa, or most preferably 1.0 × 10 ^{7 to} 5.0 × 10 ⁸ .

Here, in order to adjust the storage elastic modulus E ′ (M) of the covering portion I within the above range by heating the pressure-sensitive adhesive sheet laminate, the components and gel components of the composition constituting the covering portion I can be adjusted. It can adjust by adjusting heating temperature according to a rate, a weight average molecular weight, etc. However, it is not limited to this method.

Further, the pressure-sensitive adhesive sheet laminate is heated so that the storage elastic modulus E ′ (M) of the covering portion I is 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa, and the storage elasticity of the pressure-sensitive adhesive layer is It is even more preferable that the rate G ′ (S) is less than 1.0 × 10 ⁴ Pa.
If the storage elastic modulus E ′ (M) of the covering portion I is adjusted to the above range, the above-described effects can be obtained, and in addition, the storage elastic modulus G ′ (S) of the adhesive layer is 1. If it is less than 0 * 10 < ⁴ > Pa, sufficient moldability can be provided to an adhesive material layer.
From this viewpoint, the pressure-sensitive adhesive sheet laminate is heated so that the storage elastic modulus E ′ (M) of the covering portion I is in the above range, and the storage elastic modulus G ′ (S) of the pressure-sensitive adhesive layer is 1. In a state of less than 0.0 × 10 ⁴ Pa, particularly in a state of 5.0 × 10 ¹ Pa or more or 5.0 × 10 ³ Pa or less, in particular, 1.0 × 10 ² Pa or more or 1.0 × 10 ³ It is preferable to be in a state of Pa or less.
From the above, the pressure-sensitive adhesive sheet laminate is heated, the storage elastic modulus E ′ (M) of the covering portion I is in the above range, and the storage elastic modulus G ′ (S) of the pressure-sensitive adhesive layer is 5 .0 × ¹⁰ 1 Pa or more 1.0 × less than ¹⁰ 4 Pa, or more preferably to the state is not more than 5.0 × ¹⁰ 1 Pa or more 5.0 × ¹⁰ 3 Pa, among others, 1.0 × 10 ² Pa or more 1.0 × less than ¹⁰ 4 Pa, or more preferably be a state is 1.0 × ¹⁰ 2 Pa or more 5.0 × ¹⁰ 3 Pa or less, 1.0 × ¹⁰ 2 Pa or more 1 Most preferably, it is in a state of 0.0 × 10 ³ Pa or less.

Here, the storage elastic modulus G ′ (S) of the pressure-sensitive adhesive layer is adjusted by adjusting the heating temperature according to the components, gel fraction, weight average molecular weight, etc. of the composition constituting the pressure-sensitive adhesive layer. Can do. However, it is not limited to this method.

Furthermore, it is particularly preferable to heat the pressure-sensitive adhesive sheet laminate so that the value of the loss tangent tan δ of the pressure-sensitive adhesive layer becomes 1.0 or more. The loss tangent tan δ will be described later.
If the value of the loss tangent tan δ of the pressure-sensitive adhesive layer is 1.0 or more, it is preferable that the adhesive material layer is flexible enough to be molded.
From this point of view, it is particularly preferable to heat the pressure-sensitive adhesive sheet laminate so that the value of the loss tangent tan δ of the pressure-sensitive adhesive layer is 1.0 or more. More preferably, it is 3.0 or more or 10 or less. However, the upper limit is not limited to this.

In this production method 1, it is preferable to heat the pressure-sensitive adhesive sheet laminate so that the surface temperature of the covering portion I becomes 70 to 180 ° C.
If the surface temperature of the covering portion I is 70 ° C. or higher, the adhesive layer can be sufficiently softened and the covering portion I can be sufficiently deformed. It is preferable because adverse effects such as generation of heat and decomposition of the adhesive layer due to heat can be suppressed.
From this point of view, it is preferable that the pressure-sensitive adhesive sheet laminate is heated so that the surface temperature of the covering portion I becomes 70 to 180 ° C., particularly 75 ° C. or higher or 150 ° C. or lower, especially 80 ° C. or higher or 120 ° C. It is even more preferable that the temperature is not higher than ° C.

As a method for heating the pressure-sensitive adhesive sheet laminate, for example, a method of heating the pressure-sensitive adhesive sheet laminate from above and below between upper and lower heating plates provided with a heating body such as an electric heater, a method of directly sandwiching with a heating plate, The method using a heating roll, the method of immersing in hot water, etc. can be mentioned. However, it is not limited to these methods.

(Molding / cooling process)
In this step, the pressure-sensitive adhesive sheet laminate heated as described above is formed, and the pressure-sensitive adhesive sheet laminate is formed and cooled. That is, the pressure-sensitive adhesive sheet laminated body in a state where the pressure-sensitive adhesive layer and the covering portion I are laminated and integrated is formed as it is. Therefore, the covering portion I is formed by the mold, and the adhesive material layer is also simultaneously formed through the covering portion I.

In this step, the heated pressure-sensitive adhesive sheet laminate may be molded and then cooled, or may be cooled simultaneously with the molding. For example, by pressing with a cooled mold, molding and cooling can be performed simultaneously and completed simultaneously. Thereby, this manufacturing method 1 can be implemented continuously so that it may mention later.

The molding method is not particularly limited as long as the uneven shape can be integrally formed with the pressure-sensitive adhesive sheet laminate. For example, press molding, vacuum forming, pressure forming, shaping by a roll, compression molding, shaping by lamination and the like can be mentioned. Among these, press molding is particularly preferable from the viewpoints of moldability and workability.

The material of the mold is not particularly limited. For example, resin-based materials such as silicone resin and fluororesin, and metal-based materials such as stainless steel and aluminum can be used. Among these, metal molds that can be controlled in temperature during molding are particularly preferred because high-precision moldability is required for forming irregularities on the adherend.
As the mold cooling means, a usual cooling means can be adopted. For example, cooling means by water cooling or compressed air can be mentioned.

For example, as shown in FIG. 2, the mold is a bonding surface of an adherend that adheres a predetermined uneven shape, for example, an adhesive material layer, to the inner wall surface of at least one of the pair of molds to be opened and closed. By providing a concave / convex shape coincident with the concave or convex portion or the concave / convex portion (also referred to as “bonding surface”), the pressure-sensitive adhesive sheet laminate is press-molded, vacuum-molded, compressed-air molded or rolled using the mold. By forming, the uneven shape can be transferred to the pressure-sensitive adhesive sheet laminate and shaped.

In this step, as described above, molding is started in a state where the storage elastic modulus E ′ (MS) of the covering portion I in the pressure-sensitive adhesive sheet laminate is 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa. Is preferred.
Here, “start molding” means, for example, in the case of molding using a mold, closes the mold, that is, starts pressing the pressure-sensitive adhesive sheet laminate with the mold.

If the storage elastic modulus E ′ (MS) of the covering portion I is in the range of 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa, the covering portion I can be deformed to an extent suitable for molding, In addition, a desired uneven shape can be accurately formed on the surface of the adhesive layer.
From this point of view, it is preferable to start forming the pressure-sensitive adhesive sheet laminate in a state where the storage elastic modulus E ′ (MS) of the covering portion I is 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa. It is even more preferable to start molding in a state of 0.0 × 10 ⁶ Pa or more or 1.0 × 10 ⁹ Pa or less, in particular, a state of 1.0 × 10 ⁷ Pa or more or 5.0 × 10 ⁸ Pa or less. preferable.
From the above, the storage elastic modulus E ′ (MS) of the covering portion I is 1.0 × 10 ⁶ to 1.0 × 10 ⁹ Pa, or 1.0 × 10 ⁶ to 5.0 × 10 ⁸ Pa. It is more preferable to start forming the pressure-sensitive adhesive sheet laminate in a state, among which 5.0 × 10 ⁶ to 1.0 × 10 ⁹ Pa or 5.0 × 10 ⁶ to 5.0 × 10 ⁸ Pa More preferably, the molding is started in a state of 1.0 × 10 ⁷ to 1.0 × 10 ⁹ Pa, or 1.0 × 10 ⁷ to 5.0 × 10 ⁸ Pa. Is most preferred.

Further, the storage elastic modulus E ′ (MS) of the covering portion I is 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa, and the storage elastic modulus G ′ (SS) of the adhesive layer is 1.0. It is even more preferable to start forming the pressure-sensitive adhesive sheet laminate in a state of less than × 10 ⁴ Pa.
In addition to being able to obtain the effects described above if molding is started in a state where the storage elastic modulus E ′ (MS) of the covering portion I is within the above range, the storage elastic modulus G ′ (SS) of the adhesive layer ) Starts in a state of less than 1.0 × 10 ⁴ Pa, the pressure-sensitive adhesive layer can be formed in a state having more sufficient formability.
From this point of view, the storage elastic modulus E ′ (MS) of the covering portion I is in the above range, and the storage elastic modulus G ′ (SS) of the adhesive layer is less than 1.0 × 10 ⁴ Pa. More preferably, the G ′ (SS) is 5.0 × 10 ¹ Pa or more or 5.0 × 10 ³ Pa or less, more preferably 1.0 × 10 ² Pa or more or 1.0 × 10. ^It is even more preferable to start molding in a state of ³ Pa or less.
From the above, the storage elastic modulus E ′ (MS) of the covering portion I is in the above range, and the storage elastic modulus G ′ (SS) of the adhesive layer is 5.0 × 10 ¹ Pa or more. It is more preferable to start molding in a state of less than 0 × 10 ⁴ Pa or 5.0 × 10 ¹ Pa to 5.0 × 10 ³ Pa, and above all, 1.0 × 10 ² Pa to 1. It is more preferable to start molding in a state of less than 0 × 10 ⁴ Pa or 1.0 × 10 ² Pa to 5.0 × 10 ³ Pa, and more preferably 1.0 × 10 ² Pa to 1.0 ×. Most preferably, molding is started in a state of 10 ³ Pa or less.

Further, it is preferable to start molding in a state where the surface temperature of the covering portion I is 70 to 180 ° C.
If the surface temperature of the covering portion I is 70 ° C. or higher, the adhesive layer is sufficiently softened and the covering portion I can be sufficiently deformed. This is preferable because generation of wrinkles and decomposition of the adhesive layer due to heat can be suppressed.
Therefore, it is preferable to start molding in a state where the surface temperature of the covering portion I is 70 to 180 ° C., and above all, 75 ° C. or more and 150 ° C. or less, and more preferably 80 ° C. or more and 120 ° C. or less. Even more preferred.

On the other hand, in this step, it is preferable to finish the molding in a state where the storage elastic modulus E ′ (MF) of the covering portion I is 5.0 × 10 ⁷ to 1.0 × 10 ¹⁰ Pa.
Here, “finishing the molding” means ending the molding pressure on the pressure-sensitive adhesive sheet laminate, and means that the mold is opened if molding is performed.

If the storage elastic modulus E ′ (MF) of the covering portion I is in the range of 5.0 × 10 ⁷ Pa to 1.0 × 10 ¹⁰ Pa, it is preferable because the shape stability after molding is excellent.
From this point of view, it is preferable that the molding is finished in a state where the storage elastic modulus E ′ (MF) of the covering portion I is 5.0 × 10 ⁷ to 1.0 × 10 ¹⁰ Pa. It is even more preferable to finish the molding in a state of ⁸ Pa or more or 8.0 × 10 ⁹ Pa or less, in particular, a state of 1.0 × 10 ⁹ Pa or more or 5.0 × 10 ⁹ Pa or less.
From the above, in this step, the storage elastic modulus E ′ (MF) of the covering portion I is 5.0 × 10 ⁷ to 8.0 × 10 ⁹ Pa, or 5.0 × 10 ⁷ to 5.0 ×. More preferably, the molding is finished in a state of 10 ⁹ Pa, and in particular, 1.0 × 10 ⁸ to 8.0 × 10 ⁹ Pa, or 1.0 × 10 ⁸ to 5.0 × 10 ⁹ Pa. The molding is preferably finished in a certain state, and the molding is finished in a state of 1.0 × 10 ⁹ to 8.0 × 10 ⁹ Pa or 1.0 × 10 ⁹ to 5.0 × 10 ⁹ Pa. Most preferred.

Furthermore, it is molded in a state where the storage elastic modulus E ′ (MF) of the covering portion I is in the above range and the storage elastic modulus G ′ (SF) of the adhesive layer is 1.0 × 10 ⁴ Pa or more. It is even more preferable to end the process.
In addition to obtaining the above-described effects if the molding is completed in a state where the storage elastic modulus E ′ (MF) of the covering portion I is within the above range, the storage elastic modulus G ′ ( If molding is finished in a state where SS) is 1.0 × 10 ⁴ Pa or more, the molded pressure-sensitive adhesive layer can maintain its shape.
From this viewpoint, the storage elastic modulus E ′ (MF) of the covering portion I is in the above range, and the storage elastic modulus G ′ (SF) of the adhesive layer is 1.0 × 10 ⁴ Pa or more. It is preferable to finish the molding, and among them, the storage elastic modulus G ′ (SF) of the pressure-sensitive adhesive layer is 5.0 × 10 ⁴ Pa or more or 5.0 × 10 ⁷ Pa or less. More preferably, the molding is finished in a state of x10 ⁴ Pa or more or 1.0 x 10 ⁷ Pa or less.

Further, it is preferable to finish the molding in a state where the surface temperature of the covering portion I is less than 50 ° C. For example, in the case of press molding, it is preferable to open the mold while the surface temperature is less than 50 ° C.
If the surface temperature of the covering portion I is less than 50 ° C. and the storage elastic modulus E ′ (MS) of the covering portion I is in the range of 5.0 × 10 ⁷ to 1.0 × 10 ¹⁰ Pa, the molded body after molding is finished. This is preferable because it can be prevented from being deformed when the material is taken out and warping due to thermal contraction of the covering portion I can be suppressed.
From this point of view, the molding is finished in a state where the surface temperature of the covering portion I is less than 50 ° C., particularly in a state where the surface temperature is 0 ° C. or more or 45 ° C. or less, and in particular, in a state where it is 10 ° C. or more or 40 ° C. Is preferred.

Furthermore, the storage elastic modulus E ′ (MS) of the covering portion I at the start of molding and the storage elastic modulus E ′ (MF) of the covering portion I at the end of forming satisfy the following relational expression (1). preferable.
(1) E '(MF) / E' (MS) ≧ 1.3
Here, if the storage elastic modulus E ′ (MS) of the covering portion I and the storage elastic modulus E ′ (MF) of the covering portion I at the end of molding satisfy the relational expression (1), the molding is started at the start of molding. It is preferable because it is as soft as possible and has hardness to the extent that the molded shape can be maintained after completion of molding.
From this point of view, it is preferable that E ′ (MF) / E ′ (MS) ≧ 1.3. Above all, 100 ≧ E ′ (MF) / E ′ (MS) or E ′ (MF) / E ′ (MS ) ≧ 3.0, more preferably 50 ≧ E ′ (MF) / E ′ (MS) or E ′ (MF) / E ′ (MS) ≧ 5.0. However, the upper limit of E ′ (MF) / E ′ (MS) is not limited to this.

Moreover, the storage elastic modulus E ′ (MF) of the covering portion I at the end of the molding and the storage elastic modulus G ′ (SF) of the adhesive layer at the end of the molding satisfy the following relational expression (2). Is preferred.
(2) .. E ′ (MF) / G ′ (SF) ≦ 1.0 × 10 ⁷
Here, if the storage elastic modulus E ′ (MF) of the covering portion I at the end of the molding and the storage elastic modulus G ′ (SF) of the adhesive layer at the end of the molding satisfy the relational expression (2). The formed pressure-sensitive adhesive layer can maintain its shape.
From this viewpoint, it is preferable that E ′ (MF) / G ′ (SF) ≦ 1.0 × 10 ⁷ , and 1.0 ≦ E ′ (MF) / G ′ (SF) or E ′ (MF) among them. /G′(SF)≦5.0×10 ⁶ , of which 1.0 × 10 ¹ ≦ E ′ (MF) / G ′ (SF) or E ′ (MF) / G ′ (SF) ≦ 1.0 More preferably, it is × 10 ⁶ .

Again, in this production method 1, the mold may be press-molded and cooled after the mold is opened, or the mold may be cooled and cooled at the same time as the press molding. If the mold is cooled in this way and cooled at the same time as the press molding, the cooling can be completed at the same time as the molding. Therefore, since the shaped pressure-sensitive adhesive sheet laminate can be conveyed to the next step immediately after the molding and cooling are completed, the shaped pressure-sensitive adhesive sheet laminate can be continuously produced.

When cooling at the same time as the mold forming, the surface temperature of the mold is preferably 0 to 50 ° C.
If the surface temperature of the mold is 50 ° C. or less, the shape of the pressure-sensitive adhesive sheet laminate can be fixed in a short time, the resulting molded body is accurate, and warps due to thermal shrinkage in the cooling process after molding. It is preferable from the viewpoint of suppression.
Accordingly, the surface temperature of the mold is preferably 0 to 50 ° C., more preferably 10 ° C. or more and 40 ° C. or less, and more preferably 15 ° C. or more and 30 ° C. or less.

In addition, conditions concerning press molding such as a press pressure and a press time are not particularly limited, and may be appropriately adjusted depending on a dimension and shape to be molded, a material to be used, and the like.

(Other)
The shaped pressure-sensitive adhesive sheet laminate obtained in the molding / cooling step may be wound as it is, may be heat-treated, or may be cut into a predetermined size and shape.
When cutting, for example, a cutting method using a Thomson blade or a rotary blade can be used.

In this manufacturing method 1, it is preferable to manufacture a shaped adhesive sheet laminated body continuously.
For example, the pressure-sensitive adhesive sheet laminate is transported to a heating unit such as a heater, and the heating unit stops the transport for a predetermined time and heats it while heating or while transporting, and then heats the pressure-sensitive adhesive sheet laminate to a molding unit. For example, it is transferred to a molding die, and in the molding unit, for example, a cooled die is pressed and cooled at the same time as molding, and further transported to the next unit as necessary. A shaped pressure-sensitive adhesive sheet laminate can be produced.

<Production Method 2>
As an example of an embodiment of the present invention, an adhesive material layer and a covering portion I that is detachably laminated on one surface of the adhesive material layer are provided, and one surface of the adhesive material has a concave portion, a convex portion, or an uneven portion ( In the method for producing a shaped pressure-sensitive adhesive sheet laminate having a configuration in which the “adhesive material layer surface irregularity portion” is shaped, the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer are peelably laminated on one surface. A manufacturing method for manufacturing a shaped pressure-sensitive adhesive sheet laminate by heating a pressure-sensitive adhesive sheet laminate comprising a covering portion I and forming the heated pressure-sensitive adhesive sheet laminate with a mold, the pressure-sensitive adhesive sheet laminate Heating to start molding in a state where the surface temperature of the covering portion I is 70 to 180 ° C., and taking out the shaped adhesive sheet laminate from the mold after the surface temperature of the covering portion I becomes less than 60 ° C. Method for producing a shaped pressure-sensitive adhesive sheet laminate (“Production Method 2”) It referred to) propose.

According to this production method 2, the pressure-sensitive adhesive sheet laminate is heated and molding is started in a state where the surface temperature of the covering portion I is 70 to 180 ° C. After the surface temperature of the covering portion I becomes less than 60 ° C. By taking out the shaped pressure-sensitive adhesive sheet laminate from the mold, for example, a concavo-convex shape coinciding with the concavo-convex portion on the adherend surface can be formed with high accuracy on the surface of the pressure-sensitive adhesive layer.

The present production method 2 is a production method including a step of heating (adhesion sheet laminate) described later (heating step), and forming and cooling the heated adhesive sheet laminate (molding / cooling step).

The present manufacturing method 2 may include other steps as long as it includes the heating step and the molding / cooling step. For example, you may provide processes, such as a heat treatment process, a conveyance process, a slit process, and a cutting process, as needed. However, it is not limited to these processes.

(Adhesive sheet laminate)
The pressure-sensitive adhesive sheet laminate as a starting member in the present production method 2 only needs to include the pressure-sensitive adhesive layer and the covering portion I that is detachably laminated on one surface of the pressure-sensitive adhesive layer, and includes other members. It may be. For example, as shown in FIG. 1, an adhesive material layer, a covering portion I that is detachably laminated on one side of the adhesive material layer, and a peelable laminate on the other side of the adhesive material layer. A pressure-sensitive adhesive sheet laminate provided with the covering portion II can be exemplified. However, whether or not the covering portion II is provided is arbitrary, and the covering portion II may not be stacked.
In addition, it is as above-mentioned about the detail of an adhesive sheet laminated body.

(Heating process)
In this step, the pressure-sensitive adhesive sheet laminate is heated so that the surface temperature of the covering portion I becomes 70 to 180 ° C.
If the surface temperature of the covering portion I is 70 ° C. or higher, the adhesive layer can be sufficiently softened and the covering portion I can be sufficiently deformed. It is preferable because adverse effects such as generation of heat and decomposition of the adhesive layer due to heat can be suppressed.
From this point of view, it is preferable that the pressure-sensitive adhesive sheet laminate is heated so that the surface temperature of the covering portion I becomes 70 to 180 ° C., particularly 75 ° C. or higher or 150 ° C. or lower, especially 80 ° C. or higher or 120 ° C. It is even more preferable that the temperature is not higher than ° C.
From the above, it is more preferable that the pressure-sensitive adhesive sheet laminate is heated so that the surface temperature of the covering portion I is 70 to 150 ° C. or 70 to 120 ° C. Among them, 75 to 150 ° C. or 75 to 120 ° C. is more preferable, and 80 to 150 ° C. or 80 to 120 ° C. is most preferable.

(Molding / cooling process)
In this step, it is preferable to start forming the pressure-sensitive adhesive sheet laminate with the surface temperature of the covering portion I being heated to 70 to 180 ° C. as described above. That is, it is preferable to form the pressure-sensitive adhesive sheet laminate in a state where the pressure-sensitive adhesive layer and the covering portion I are laminated and integrated. If it does in this way, the adhesive material layer can also be shape | molded through the said coating | coated part I simultaneously with the shaping | molding part I being shape | molded.

In this step, the heated pressure-sensitive adhesive sheet laminate may be molded and then cooled, or may be cooled simultaneously with the molding. For example, by pressing with a cooled mold, molding and cooling can be performed simultaneously and completed simultaneously. Thereby, this manufacturing method 2 can be implemented continuously so that it may mention later.

The molding method is not particularly limited as long as the uneven shape can be integrally formed with the pressure-sensitive adhesive sheet laminate. For example, press molding, vacuum forming, pressure forming, shaping by roll (roll forming molding), compression molding, shaping by lamination and the like can be mentioned. Among these, press molding is particularly preferable from the viewpoints of moldability and workability.

When molding using a mold, the material of the mold is not particularly limited. For example, resin-based materials such as silicone resin and fluororesin, and metal-based materials such as stainless steel and aluminum can be used. Among these, metal molds that can be controlled in temperature during molding are particularly preferred because high-precision moldability is required for forming irregularities on the adherend.
As the mold cooling means, a usual cooling means can be adopted. For example, cooling means by water cooling or compressed air can be mentioned.

As described above, the molding is preferably started in a state where the surface temperature of the covering portion I is 70 to 180 ° C. If the surface temperature of the covering portion I is 70 ° C. or higher, the adhesive layer is sufficiently softened and the covering portion I can be sufficiently deformed. This is preferable because generation of wrinkles and decomposition of the adhesive layer due to heat can be suppressed.
Therefore, it is preferable to start molding in a state where the surface temperature of the covering portion I is 70 to 180 ° C., and above all, 75 ° C. or more and 150 ° C. or less, and more preferably 80 ° C. or more and 120 ° C. or less. Even more preferred.

On the other hand, in this step, it is preferable to finish the molding in a state where the surface temperature of the covering portion I is less than 60 ° C. For example, in the case of press molding, it is preferable to open the mold in a state where the surface temperature is less than 60 ° C.
Here, “finishing the molding” means ending the molding pressure on the pressure-sensitive adhesive sheet laminate, and means that the mold is opened if molding is performed.

If the surface temperature of the covering portion I is less than 60 ° C., it is preferable that the covering portion I can be prevented from being deformed when the molded body is taken out after completion of molding, or warping due to thermal shrinkage of the covering portion I can be suppressed. .
From this point of view, the molding is finished in a state where the surface temperature of the covering portion I is less than 60 ° C., particularly in a state where the surface temperature is 0 ° C. or more or 50 ° C. or less, and in particular, in a state where the surface temperature is 10 ° C. or more or 40 ° C. or less. Is preferred.

Again, in this production method 2, the mold may be press-molded and cooled after the mold is opened, or the mold may be cooled and cooled at the same time as the press molding. If the mold is cooled in this way and cooled at the same time as the press molding, the cooling can be completed at the same time as the molding. Therefore, since the shaped pressure-sensitive adhesive sheet laminate can be conveyed to the next step immediately after the molding and cooling are completed, the shaped pressure-sensitive adhesive sheet laminate can be continuously produced.

When cooling at the same time as the mold forming, the surface temperature of the mold is preferably less than 60 ° C.
If the surface temperature of the mold is less than 60 ° C., the shape of the pressure-sensitive adhesive sheet laminate can be fixed in a short time, the resulting molded body is accurate, and warps due to thermal shrinkage in the cooling process after molding. It is preferable from the viewpoint of suppression.
Therefore, the surface temperature of the mold is preferably less than 60 ° C, more preferably 0 ° C or more or 50 ° C or less, and more preferably 10 ° C or more or 40 ° C or less.

Further, the difference in surface temperature of the covering portion I at the start of molding and at the end of molding is preferably 10 to 100 ° C., more preferably 20 ° C. or more and 90 ° C. or less. When the surface temperature difference of the covering portion I is 10 to 100 ° C., for example, when the uneven shape is transferred to the pressure-sensitive adhesive sheet laminate and shaped, the shaped pressure-sensitive adhesive sheet is immediately after finishing the molding and cooling. Since the laminate can be conveyed to the next step, the shaped pressure-sensitive adhesive sheet laminate can be continuously produced.

In this manufacturing method 2, it is preferable to manufacture a shaped adhesive sheet laminated body continuously.
For example, the pressure-sensitive adhesive sheet laminate is transported to a heating unit such as a heater, and the heating unit stops the transport for a predetermined time and heats it while heating or while transporting, and then heats the pressure-sensitive adhesive sheet laminate to a molding unit. For example, it is transferred to a molding die, and in the molding unit, for example, a cooled die is pressed and cooled at the same time as molding, and further transported to the next unit as necessary. A shaped pressure-sensitive adhesive sheet laminate can be produced.

<Application>
Here, an example of the usage of the shaped adhesive sheet laminate 1 will be described.
In recent years, as mobile phones, smartphones, tablet terminals, and the like are generalized, there are many cases in which an image display unit is damaged by a user accidentally dropping it. In particular, when the image display device is a touch panel system, not only the display becomes difficult to see due to breakage, but also the touch panel operation itself becomes impossible or causes a failure due to a physical failure or water intrusion. Therefore, there is a case where repair, that is, repair, in which only the image display unit is replaced is performed.
In the repair of the image display device, the adhesive sheet is also used when a new image display unit is loaded. Usually, repair is often performed as a manual work by a repair worker, and skill of the repair worker is required. That is, if it is not an expert, when an image display part is loaded via an adhesive sheet, air will enter inside or an adhesive material will protrude.
On the other hand, if this shaped adhesive sheet laminate 1 is used, a highly accurate step shape or the like can be given in advance. For example, a step shape corresponding to the model of the image display device is given in advance to the adhesive material layer. By doing so, the repair work is greatly simplified and can be carried out without requiring the skill of a repair worker. Thus, the pressure-sensitive adhesive sheet laminate of the present invention can be usefully used for repairing image display devices.

<Explanation of words>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), “X is preferably greater than X” or “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.

In the present invention, the boundary between the sheet and the film is not clear, and it is not necessary to distinguish the two in terms of the wording in the present invention. Therefore, in the present invention, even when the term “film” is used, the term “sheet” is included. "Film" is also included.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.

[Group 1 of Examples and Comparative Examples]
<Coating part 1-I>
The cover portion 1-I of the pressure-sensitive adhesive sheet laminate in Examples 1-1 to 1-3 and Comparative Example 1-1 (hereinafter collectively referred to as “Example / Comparative Group 1”) includes the following: The coating parts 1-A to 1-D were used. The value of each storage modulus is shown in Table 1.

Covering portion 1-A: a film obtained by laminating a release layer (thickness: 2 μm) made of a silicone compound on one side of a biaxially stretched isophthalic acid copolymerized PET film (thickness: 75 μm).
Covering part 1-B: a film obtained by laminating a release layer (thickness: 38 μm) made of modified polyolefin on one side of an unstretched polyolefin film (thickness: 50 μm) made of 4-methylpentene-1.
Covering portion 1-C: a film made of a polyolefin film (thickness: 70 μm) made of unstretched polypropylene.
Covering part 1-D: a film obtained by laminating a release layer (thickness: 2 μm) made of a silicone compound on one side of a biaxially stretched homo-PET film (thickness: 75 μm).

<Example 1-1>
(Production of double-sided PSA sheet)
As the (meth) acrylic copolymer (1-a), 15 parts by mass (18 mol%) of a polymethyl methacrylate macromonomer having a number average molecular weight of 2400 (Tg: 105 ° C.) and butyl acrylate (Tg: −55 ° C.) 81 1 kg of acrylic copolymer (1-a-1) (weight average molecular weight 230,000) obtained by random copolymerization of 4 parts by mass (7 mol%) with 75 parts by mass (75 mol%) and acrylic acid (Tg: 106 ° C.) As a cross-linking agent (1-b), 90 g of glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (1-b-1), and 2, 4, as photopolymerization initiator (1-c) 6-trimethylbenzophenone and 4-methylbenzophenone mixture (manufactured by Lanberti, product name: Ezacure TZT) (1-c-1) 15 g of resin mixture is uniformly mixed and used for the adhesive layer -1 were produced. The resulting resin composition had a glass transition temperature of −5 ° C.

The obtained resin composition 1-1 was sandwiched between two sheets of PET film (Mitsubishi Resin Co., Ltd., product name: Diafoil MRV-V06, thickness: 100 μm) and covering portion 1-A, Using a laminator, the resin composition 1-1 was shaped into a sheet so that the thickness of the resin composition 1-1 was 100 μm, and the pressure-sensitive adhesive sheet laminate 1-1 was produced. The release layer side of the covering portion 1-A was disposed so as to be in contact with the resin composition 1-1.

The obtained pressure-sensitive adhesive sheet laminate 1-1 was thermoformed by the following process using a vacuum / pressure forming machine (Daiichi Jitsugyo Co., Ltd., model FKS-0632-20). 1 was produced.
That is, with the IR heater preheated to 400 ° C., the surface of the pressure-sensitive adhesive sheet laminate 1-1 was heated to 100 ° C. and then cooled to 25 ° C., and the mold clamping pressure was 8 MPa. Was subjected to press molding for 5 seconds to produce a shaped pressure-sensitive adhesive sheet laminate 1-1 having irregularities formed on the surface.

<Example 1-2>
A pressure-sensitive adhesive sheet laminated body 1-2 and a shaped pressure-sensitive adhesive sheet laminated body 1-2 were produced in the same manner as in Example 1-1 except that the coating part 1-B was used instead of the coating part 1-A. .

<Example 1-3>
A pressure-sensitive adhesive sheet laminate 1-3 and a shaped pressure-sensitive adhesive sheet laminate 1-3 were produced in the same manner as in Example 1-1 except that the coating portion 1-C was used instead of the coating portion 1-A. .

<Comparative Example 1-1>
A pressure-sensitive adhesive sheet laminate 1-4 and a shaped pressure-sensitive adhesive sheet laminate 1-4 were produced in the same manner as in Example 1-1 except that the coating portion 1-D was used instead of the coating portion 1-A. .

<Measurement and evaluation method>
Examples 1-1 to 1-3 / Methods for measuring and evaluating various physical properties of the samples obtained in Comparative Example 1-1 will be described.

(Elastic modulus of the coating)
Covering parts 1-A to 1-D used in Example 1 and Comparative Example 1 were cut into a length of 50 mm and a width of 4 mm, respectively, and a dynamic viscoelastic device (ITA Measurement Control Co., Ltd. DVA-200) was used. The distance between chucks was measured with a strain of 25 mm and 1%. The measurement temperature range was −50 ° C. to 150 ° C., the frequency was 1 Hz, and the heating rate was 3 ° C./min. The value of the storage elastic modulus at 100 ° C. of the obtained data was E ′ (MA), and the value of the storage elastic modulus at 30 ° C. was E ′ (MB).

(Elastic modulus of adhesive layer)
The pressure-sensitive adhesive layers obtained in Group 1 of Examples and Comparative Examples were overlapped and laminated to a thickness of 1 mm, and measured using a rheometer (MARSII manufactured by Thermo Fisher Scientific). The measurement temperature range was −50 ° C. to 150 ° C., the frequency was 1 Hz, and the heating rate was 3 ° C./min.
In the obtained data, the storage elastic modulus value at 100 ° C. is G ′ (SA), the loss elastic modulus value is G ″ (SA), the storage elastic modulus value at 30 ° C. is G ′ (SB), and the loss elastic modulus. The rate value was G ″ (SB), and the value of G ″ / G ′ under each temperature condition was the loss tangent tan δ (SA, SB) of each adhesive material layer.

(Gel fraction)
The gel fraction of the pressure-sensitive adhesive layer was obtained by collecting about 0.05 g of each pressure-sensitive adhesive layer obtained in Group 1 of Examples and Comparative Examples, and measuring the mass (X) in advance with a SUS mesh (# 200). After wrapping the bag and closing the bag mouth, measuring the mass (Y) of the wrap, immersing it in 100 ml of ethyl acetate and storing it in the dark at 23 ° C. for 24 hours, then removing the wrap at 70 ° C. It was heated for 4.5 hours to evaporate the adhering ethyl acetate, the mass (Z) of the dried packet was measured, and the calculated mass was substituted into the following formula.
Gel fraction [%] = [(ZX) / (YX)] × 100

(Formability)
In order to confirm the moldability, a molding test of Group 1 of Examples and Comparative Examples was performed using a mold described below. That is, as shown in FIG. 5, the upper and lower molds of the molding mold are convex molds having a length of 270 mm, a width of 170 mm, and a thickness of 40 mm, and the upper and lower molds have a length of 270 mm, The aluminum plate was 170 mm wide and 40 mm thick.
As shown in FIG. 5, a convex portion having a length of 187 mm, a width of 125 mm, and a height of 1 mm is provided in the center on the molding surface of the convex mold. , 75 μm and 100 μm, four rectangular concave portions (89 mm long and 58 mm wide) in plan view are provided.

The covering portions 1-A to 1-D of the shaped pressure-sensitive adhesive sheet laminate formed with unevenness obtained by the method described in the group 1 of Examples / Comparative Examples are peeled off, and the concave portions corresponding to the printing steps and the display The height from the convex portion corresponding to the surface was measured in a non-contact manner using a scanning white interference microscope.
Measure the height h of the convex part (edge part with the concave part) of the molded body with respect to the depth of the mold of 100 μm, and the transfer rate derived from the following calculation formula is 50% or more: ○, less than 50% Each was evaluated as x.
Transfer rate (%) = h (molded body height) / 100 (mold depth) × 100

(Peeling force)
The pressure-sensitive adhesive sheet laminate produced in Group 1 of Examples and Comparative Examples was cut into a length of 150 mm and a width of 50 mm, and the interface between the coating portions 1-A to 1-D and the pressure-sensitive adhesive layer was 180 at a test speed of 300 mm / min. ° A peel test was performed.
The peeled force in an environment of 30 ° C. was F (C), and after heating at 100 ° C. for 5 minutes and then naturally cooling to 30 ° C., the peel strength was F (D). A peel force of 1 to D was used.

The evaluation results of the pressure-sensitive adhesive sheet laminates 1-1 to 1-4 and the shaped pressure-sensitive adhesive sheet laminates 1-1 to 1-4 obtained in Examples and Comparative Examples are shown in Table 1.

From the results of Table 1 and FIG. 4 and the test results conducted so far, as shown in Examples 1-1 to 1-3, the storage elastic modulus E ′ (MB) at 30 ° C. is 5.0 × 10. ^A coating portion having a storage elastic modulus E ′ (MA) at 100 ° C. of ⁷ × 1.0 × 10 ¹⁰ Pa and a storage modulus E ′ (MA) of 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa is laminated on the adhesive layer. As a result, it was confirmed that the concavo-convex shape can be shaped with high accuracy in the adhesive material layer.
On the other hand, as shown in Comparative Example 1-1, when a biaxially stretched homo-PET film generally used widely as a release film is used, the storage elastic modulus of the covering portion is 2.0 × 10 ⁹ Pa even in a high temperature range. For this reason, sufficient unevenness could not be formed on the adhesive layer even when thermoforming.
From the above, the storage elastic modulus E ′ (MB) at 30 ° C. is 5.0 × 10 ⁷ to 1.0 × 10 ¹⁰ Pa and the storage elastic modulus E ′ (MA) at 100 ° C. is 1. It was found that a shaped pressure-sensitive adhesive sheet with good irregularities can be obtained by laminating a covering portion of 0 × 10 ⁶ to 2.0 × 10 ⁹ Pa on the pressure-sensitive adhesive layer and performing molding.

More preferably, the loss tangent tan δ (A) at 100 ° C. of the adhesive layer satisfies the condition of 1.0 or more, and the loss tangent tan δ (B) at 30 ° C. of the adhesive layer satisfies the condition of less than 1.0. It was also found that more accurate shaping can be achieved by using such a pressure-sensitive adhesive sheet laminate.

Therefore, by using the pressure-sensitive adhesive sheet laminate as described above, the irregularities corresponding to the printing steps of the image display device as the adherend are accurately shaped, so that there is no gap between the adherend and the printing. It is possible to confirm that a shaped pressure-sensitive adhesive sheet laminate for an image display device that can be satisfactorily bonded without causing the adhesive material to overflow even on an adherend having a narrow frame design can be manufactured. did it.

Moreover, when it sees about peeling force, the heating-cooling conditions at the time of measuring peeling force F (D), ie, the conditions which carry out natural cooling to 30 degreeC after heating for 5 minutes at 100 degreeC manufacture a shaped adhesive sheet laminated body. This is a typical heating / cooling condition. In any of the above examples, the absolute value of the difference between the peeling force F (C) and the peeling force F (D) was 0.1 N / cm or less. It was confirmed that the peel force of -D was not different from the peel force of the covering portions 1-A to 1-D in the pressure-sensitive adhesive sheet laminate.

[Group 2 of Examples and Comparative Examples]
<Coating part 2-I>
A biaxially stretched isophthalate is used as the covering portion I of the pressure-sensitive adhesive sheet laminate in Examples 2-1 to 2-4 and Comparative Example 2-1 (hereinafter collectively referred to as “Group 2 of Examples and Comparative Examples”). A film obtained by laminating a release layer (thickness: 2 μm) made of a silicone compound on one side of an acid copolymerized PET film (thickness: 75 μm) was used. Each storage modulus value is shown in Table 2.

<Example 2-1>
(Production of double-sided PSA sheet)
As the (meth) acrylic copolymer (2-a), 15 parts by mass (18 mol%) of a polymethyl methacrylate macromonomer (Tg: 105 ° C.) having a number average molecular weight of 2400 and 81 of butyl acrylate (Tg: −55 ° C.) 1 kg of acrylic copolymer (2-a-1) (weight average molecular weight 230,000) obtained by random copolymerization of 4 parts by mass (7 mol%) with 75 parts by mass (75 mol%) and acrylic acid (Tg: 106 ° C.) As a crosslinking agent (2-b), 90 g of glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (2-b-1), and 2, 4, as photopolymerization initiator (2-c) 6-trimethylbenzophenone and 4-methylbenzophenone mixture (manufactured by Lanberti, product name: Ezacure TZT) (2-c-1) 15 g of resin is uniformly mixed and used for the adhesive layer -1 were produced. The resulting resin composition had a glass transition temperature of −5 ° C.

The obtained resin composition 2-1 was sandwiched between two sheets of a PET film (manufactured by Mitsubishi Plastics, product name: Diafoil MRV-V06, thickness: 100 μm) and a covering part 2-I. Using a laminator, the resin composition 2-1 was shaped into a sheet so that the thickness was 100 μm, and an adhesive sheet laminate 2-1 was produced. The release layer side of the covering portion 2-I was disposed so as to be in contact with the resin composition 2-1.

The obtained pressure-sensitive adhesive sheet laminate 2-1 was subjected to thermoforming by the following process using a vacuum / pressure forming machine (Daiichi Jitsugyo Co., Ltd., FKS-0632-20 type) and a molding die, and shaped adhesive. A sheet laminate 2-1 was produced.
As shown in FIG. 5, the mold for molding is a convex mold having a length of 270 mm, a width of 170 mm, and a thickness of 40 mm, and the upper and lower molds have a length of 270 mm and a width. The aluminum plate was 170 mm and 40 mm thick. As shown in FIG. 5, a convex portion having a length of 187 mm, a width of 125 mm, and a height of 1 mm is provided in the center on the molding surface of the convex mold, and the depth is 25 μm and 50 μm in the molding surface of the convex portion. , 75 μm and 100 μm, four rectangular recesses (89 mm long and 58 mm wide) in plan view were provided.

It was molded by heating with an IR heater preheated to 400 ° C. until the surface of the covering portion 2-I of the pressure-sensitive adhesive sheet laminate 2-1 reached 100 ° C. That is, the storage elastic modulus E ′ (MS) of the covering portion 2-I is 2.1 × 10 ⁸ Pa, and the storage elastic modulus G ′ (SS) of the adhesive layer is 2.9 × 10 ² Pa. Then, press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa using a molding die whose mold surface temperature was cooled to 30 ° C., and the storage elastic modulus E ′ (MF) of the covering portion 2-I was 2 .8 × a ¹⁰ 9 Pa, the storage modulus G of the adhesive material layer '(SF) is open the mold while it is 6.1 × ¹⁰ 4 Pa, the shaped adhesive sheet formed by irregularities shaped into the surface A layered product 2-1 was produced.

The ratio E ′ (MF) / E of the storage elastic modulus E ′ (MS) of the covering portion 2-I at the start of molding to the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of the forming. '(MS) was 13.3.
Further, the ratio E ′ (MF) / G ′ of the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of molding to the storage elastic modulus G ′ (SF) of the adhesive layer at the end of molding. SF) was 4.6 × 10 ⁴ .
Further, the loss tangent tan δ (SS) of the adhesive layer at the start of molding was 4.8, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding was 0.6.

<Example 2-2>
The pressure-sensitive adhesive sheet laminate 2-1 used in Example 2-1 was heated using an IR heater preheated to 400 ° C. until the surface of the covering portion 2-I of the pressure-sensitive adhesive sheet laminate 2-2 reached 110 ° C. And then molded. That is, the storage elastic modulus E ′ (MS) of the covering portion 2-I is 1.3 × 10 ⁸ Pa, and the storage elastic modulus G ′ (SS) of the adhesive layer is 9.6 × 10 ¹ Pa. Then, press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa using a molding die whose mold surface temperature was cooled to 30 ° C., and the storage elastic modulus E ′ (MF) of the covering portion 2-I was 2 .8 × a ¹⁰ 9 Pa, the storage modulus G of the adhesive material layer '(SF) is open the mold while it is 6.1 × ¹⁰ 4 Pa, the shaped adhesive sheet formed by irregularities shaped into the surface A layered product 2-2 was produced.

<Example 2-3>
The pressure-sensitive adhesive sheet laminate 2-1 used in Example 2-1 was heated using an IR heater preheated to 400 ° C. until the surface of the covering portion 2-I of the pressure-sensitive adhesive sheet laminate 2-3 became 90 ° C. And then molded. That is, the storage elastic modulus E ′ (MS) of the covering portion 2-I is 3.5 × 10 ⁸ Pa, and the storage elastic modulus G ′ (SS) of the adhesive layer is 8.9 × 10 ² Pa. Then, press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa using a molding die whose mold surface temperature was cooled to 30 ° C., and the storage elastic modulus E ′ (MF) of the covering portion 2-I was 2 .8 × a ¹⁰ 9 Pa, the storage modulus G of the adhesive material layer '(SF) is open the mold while it is 6.1 × ¹⁰ 4 Pa, the shaped adhesive sheet formed by irregularities shaped into the surface A layered product 2-3 was produced.

The ratio E ′ (MF) / E of the storage elastic modulus E ′ (MS) of the covering portion 2-I at the start of molding to the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of the forming. '(MS) was 8.0.
Further, the ratio E ′ (MF) / G ′ of the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of molding to the storage elastic modulus G ′ (SF) of the adhesive layer at the end of molding. SF) was 4.6 × 10 ⁴ .
Further, the loss tangent tan δ (SS) of the adhesive layer at the start of molding was 2.7, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding was 0.6.

<Example 2-4>
The pressure-sensitive adhesive sheet laminate 2-1 used in Example 2-1 was heated using an IR heater preheated to 400 ° C. until the surface of the covering portion 2-I of the pressure-sensitive adhesive sheet laminate 2-4 reached 70 ° C. And then molded. That is, the storage elastic modulus E ′ (MS) of the covering portion 2-I is 1.9 × 10 ⁹ Pa, and the storage elastic modulus G ′ (SS) of the adhesive layer is 6.4 × 10 ³ Pa. Then, press molding was performed for 5 seconds under a clamping pressure of 8 MPa using a molding die whose mold surface temperature was cooled to 25 ° C., and the storage elastic modulus E ′ (MF) of the covering portion 2-I was 2 .8 × a ¹⁰ 9 Pa, the storage modulus G of the adhesive material layer '(SF) is open the mold while it is 6.1 × ¹⁰ 4 Pa, the shaped adhesive sheet formed by irregularities shaped into the surface A layered product 2-4 was produced.

The ratio E ′ (MF) / E of the storage elastic modulus E ′ (MS) of the covering portion 2-I at the start of molding to the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of the forming. '(MS) was 1.4.
Further, the ratio E ′ (MF) / G ′ of the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of molding to the storage elastic modulus G ′ (SF) of the adhesive layer at the end of molding. SF) was 4.6 × 10 ⁴ .
Further, the loss tangent tan δ (SS) of the adhesive layer at the start of molding was 1.4, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding was 0.6.

<Comparative Example 2-1>
The pressure-sensitive adhesive sheet laminate 2-1 used in Example 2-1 was heated using an IR heater preheated to 400 ° C. until the surface of the covering portion 2-I of the pressure-sensitive adhesive sheet laminate 2-5 reached 60 ° C. And then molded. That is, the storage elastic modulus E ′ (MS) of the covering portion 2-I is 2.4 × 10 ⁹ Pa, and the storage elastic modulus G ′ (SS) of the adhesive layer is 1.3 × 10 ⁴ Pa. Then, press molding was performed for 5 seconds under a clamping pressure of 8 MPa using a molding die whose mold surface temperature was cooled to 25 ° C., and the storage elastic modulus E ′ (MF) of the covering portion 2-I was 2 .8 × a ¹⁰ 9 Pa, the storage modulus G of the adhesive material layer '(SF) is open the mold while it is 6.1 × ¹⁰ 4 Pa, the shaped adhesive sheet formed by irregularities shaped into the surface A layered product 2-5 was produced.

The ratio E ′ (MF) / E of the storage elastic modulus E ′ (MS) of the covering portion 2-I at the start of molding to the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of the forming. '(MS) was 1.2.
Further, the ratio E ′ (MF) / G ′ of the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of molding to the storage elastic modulus G ′ (SF) of the adhesive layer at the end of molding. SF) was 4.6 × 10 ⁴ .
Further, the loss tangent tan δ (SS) of the adhesive layer at the start of molding was 1.1, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding was 0.6.

The ratio E ′ (MF) / E of the storage elastic modulus E ′ (MS) of the covering portion 2-I at the start of molding to the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of the forming. '(MS) was 8.0.
Further, the ratio E ′ (MF) / G ′ of the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of molding to the storage elastic modulus G ′ (SF) of the adhesive layer at the end of molding. SF) was 9.7 × 10 ³ .
Further, the loss tangent tan δ (SS) of the adhesive layer at the start of molding was 0.6, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding was 0.6.

<Measurement and evaluation method>
The measurement methods and evaluation methods for various physical properties of the samples obtained in Examples 2-1 to 2-4 and Comparative Example 2-1 will be described.

(Elastic modulus of the coating)
The storage elastic modulus E ′ (MS) and E ′ (MF) of the covering portion 2-I was cut into a length of 50 mm and a width of 4 mm, and a dynamic viscoelastic device (ITA Measurement Control Co., Ltd. DVA-200) was used. The distance between chucks was measured with a strain of 25 mm and 1%. The measurement temperature range was −50 ° C. to 150 ° C., the frequency was 1 Hz, and the heating rate was 3 ° C./min.
The value of the storage elastic modulus at each molding start temperature in Examples and Comparative Examples was E ′ (MS), and the value of the storage elastic modulus at each molding end temperature was E ′ (MF).

In Example 2-1, since the temperature at the start of molding is 100 ° C., the storage elastic modulus E ′ (MS) of Example 2-1 is the storage elastic modulus E ′ (MA) at 100 ° C. .
Moreover, since the temperature at the time of completion of molding was 30 ° C. for any of the group 2 of the example / comparative example, the E ′ (MF) was stored at 30 ° C. for the group 2 of any example / comparative example. It is the same as the elastic modulus E ′ (MB).

(Elastic modulus of adhesive layer)
The pressure-sensitive adhesive layers obtained in Group 2 of Examples / Comparative Examples were stacked to a thickness of 1 mm and measured using a rheometer (MARSII manufactured by Thermo Fisher Scientific Co.). The measurement temperature range was −50 ° C. to 150 ° C., the frequency was 1 Hz, and the heating rate was 3 ° C./min.
In the obtained data, the value of storage elastic modulus at 100 ° C. is G ′ (SA), the value of loss elastic modulus is G ″ (SA), the value of storage elastic modulus at 30 ° C. is G ′ (SB), the loss The value of elastic modulus was G ″ (SB), and the value of G ″ / G ′ under each temperature condition was the loss tangent tan δ (SA, SB) of each adhesive material layer.

On the other hand, for the storage elastic modulus G ′ (SA) and G ′ (SB) of the adhesive material layer, the adhesive material layers obtained in the group 2 of Examples and Comparative Examples were stacked and laminated to a thickness of 1 mm. It was measured using (Thermo Fisher Scientific MARSII). The measurement temperature range was −50 ° C. to 150 ° C., the frequency was 1 Hz, and the heating rate was 3 ° C./min.
In the obtained data, the storage elastic modulus value at each molding start temperature of Group 2 of Examples and Comparative Examples is G ′ (SS), the loss elastic modulus value is G ″ (SS), and each molding is completed. The storage elastic modulus value at hourly temperature is G ′ (SF), the loss elastic modulus value is G ″ (SF), and the G ″ / G ′ value under each temperature condition is The loss tangent tan δ (SS, SF) was used.

(Gel fraction)
About the gel fraction of the adhesive material layer, about 0.05 g of each of the adhesive material layers obtained in Group 2 of Examples and Comparative Examples was sampled, and the mass (X) was measured in advance with a SUS mesh (# 200). Wrap it in a bag, close the bag by closing the mouth, measure the mass (Y) of the bag, immerse it in 100 ml of ethyl acetate and store it in the dark at 23 ° C. for 24 hours. Was heated for 4.5 hours to evaporate the adhering ethyl acetate, the mass (Z) of the dried packet was measured, and the obtained mass was substituted into the following formula.
Gel fraction [%] = [(ZX) / (YX)] × 100

(Formability)
The height of the concave portion corresponding to the printing step and the convex portion corresponding to the display surface is peeled off from the covering portion I of the shaped pressure-sensitive adhesive sheet laminate obtained by the group 2 of Examples and Comparative Examples. Were measured in a non-contact manner using a scanning white interference microscope.
Measure the height h of the convex part (edge part with the concave part) of the molded body with respect to the depth of the mold of 100 μm, and the transfer rate derived from the following calculation formula is 50% or more: ○, less than 50% Each was evaluated as x.
Transfer rate (%) = h (molded body height) / 100 (mold depth) × 100

(Peeling force)
The pressure-sensitive adhesive sheet laminate produced in Example 2 and Comparative Example 2 was cut into a length of 150 mm and a width of 50 mm, and the 180 ° peel test was performed at a test speed of 300 mm / min on the interface between the covering part 2-I and the pressure-sensitive adhesive layer. went.
The peeled force in an environment of 30 ° C. was F (C), and after heating at 100 ° C. for 5 minutes and then naturally cooling to 30 ° C., the peel strength was F (D). It was set as the peeling force.

The evaluation results of the shaped adhesive sheet laminates 2-1 to 2-5 obtained in Examples 2-1 to 2-4 and Comparative Example 2-1 are shown in Table 2.

From the results of Table 2 and FIG. 4 and the test results conducted so far, as shown in Examples 2-1 to 2-4, the storage elastic modulus E ′ (MS) of the covering portion 2-I at the start of molding is shown. ) Is 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa, and the storage elastic modulus E ′ (MF) of the covering portion 2-I at the end of molding is 5.0 × 10 ⁷ to 1.0. It was confirmed that the uneven shape can be shaped with high accuracy in the adhesive layer by performing the molding while adjusting to be × 10 ¹⁰ Pa.
On the other hand, as shown in Comparative Example 2-1, when the storage elastic modulus E ′ (MS) of the covering portion 2-I at the start of molding is larger than 2.0 × 10 ⁹ Pa, the adhesive material even if thermoforming is performed. Sufficient irregularities could not be formed on the layer.
From the above, the storage elastic modulus E ′ (MS) of the covering part 2-I at the start of molding is 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa, and the covering part 2 at the end of molding -I shaped storage pressure-sensitive adhesive sheet that is formed with good irregularities by adjusting the storage elastic modulus E '(MF) of I to 5.0 × 10 ⁷ to 1.0 × 10 ¹⁰ Pa. It turns out that can be obtained.

More preferably, the loss tangent tan δ (SS) of the adhesive layer at the start of molding satisfies the condition of 1.0 or more, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding is less than 1.0. It was also found that more accurate shaping can be achieved by performing molding while adjusting so as to satisfy the above.

Therefore, by using the pressure-sensitive adhesive sheet laminate as described above, the unevenness corresponding to the printing steps of the image display device as the adherend is accurately shaped, so that there is no gap between the adherend and the printing. It is possible to confirm that a shaped pressure-sensitive adhesive sheet laminate for an image display device that can be satisfactorily bonded without causing the adhesive material to overflow even on an adherend having a narrow frame design can be manufactured. did it.

Moreover, when it sees about peeling force, the heating-cooling conditions at the time of measuring peeling force F (D), ie, the conditions which carry out natural cooling to 30 degreeC after heating for 5 minutes at 100 degreeC manufacture a shaped adhesive sheet laminated body. This is a typical heating / cooling condition. In all of the above examples, the absolute value of the difference between the peeling force F (C) and the peeling force F (D) was 0.1 N / cm or less, so it was confirmed that the peeling force hardly changed before and after heating. It was done.

Further, the pressure-sensitive adhesive sheet laminate was heated to start molding in a state where the storage elastic modulus E ′ (MS) of the covering portion 2-I was 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa. When the molding is finished in a state where the storage elastic modulus E ′ (MF) of the part 2-I is 5.0 × 10 ⁷ to 1.0 × 10 ¹⁰ Pa, the unevenness coincident with the uneven portion on the adherend surface. It was found that the shape can be formed with high accuracy on the surface of the adhesive layer.

[Group 3 of Examples and Comparative Examples]
<Coating 3-I>
Covering portion 3-I of the pressure-sensitive adhesive sheet laminate in Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-2 (hereinafter collectively referred to as “Example / Comparative Group 3”) A film obtained by laminating a release layer (thickness: 2 μm) made of a silicone compound on one side of a biaxially stretched isophthalic acid copolymerized PET film (thickness: 75 μm) was used. Each storage modulus value is shown in Table 3.

<Example 3-1>
(Production of double-sided PSA sheet)
As the (meth) acrylic copolymer (3-a), 15 parts by mass (18 mol%) of a polymethyl methacrylate macromonomer (Tg: 105 ° C.) having a number average molecular weight of 2400 and 81 of butyl acrylate (Tg: −55 ° C.) 1 kg of acrylic copolymer (3-a-1) (weight average molecular weight 230,000) obtained by random copolymerization of 4 parts by mass (7 mol%) with 75 parts by mass (75 mol%) and acrylic acid (Tg: 106 ° C.) And 90 g of glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (3-b-1) as the crosslinking agent (3-b), and 2, 4, as the photopolymerization initiator (3-c). 6-trimethylbenzophenone and 4-methylbenzophenone mixture (manufactured by Lanberti, product name: Ezacure TZT) (3-c-1) 15 g of resin is uniformly mixed and used for the adhesive layer -1 were produced. The resulting resin composition had a glass transition temperature of −5 ° C.

The obtained resin composition 3-1 was sandwiched between two pieces of a PET film (Mitsubishi Resin, product name: Diafoil MRV-V06, thickness: 100 μm) and a covering portion 3-I, Using a laminator, the resin composition 3-1 was shaped into a sheet so that the thickness of the resin composition 3-1 was 100 μm, and an adhesive sheet laminate 3-1 was produced. The release layer side of the covering portion 3-I was disposed so as to be in contact with the resin composition 3-1.

The obtained pressure-sensitive adhesive sheet laminate 3-1 was thermoformed by the following process using a vacuum / pressure forming machine (Daiichi Jitsugyo Co., Ltd., model FKS-0632-20) and a molding die, and shaped adhesive. A sheet laminate 3-1 was produced.
As shown in FIG. 5, the mold for molding is a convex mold having a length of 270 mm, a width of 170 mm, and a thickness of 40 mm, and the upper and lower molds have a length of 270 mm and a width. The aluminum plate was 170 mm and 40 mm thick. As shown in FIG. 5, a convex portion having a length of 187 mm, a width of 125 mm, and a height of 1 mm is provided in the center on the molding surface of the convex mold, and the depth is 25 μm and 50 μm in the molding surface of the convex portion. , 75 μm and 100 μm, four rectangular recesses (89 mm long and 58 mm wide) in plan view were provided.

With an IR heater preheated to 400 ° C., the surface of the covering portion 3-I of the pressure-sensitive adhesive sheet laminate 3-1 is heated to 100 ° C., and the heated pressure-sensitive adhesive sheet laminate 3-1 is heated to the mold surface temperature. Using a molding die cooled to 30 ° C., press-molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, then the die was opened, and a shaped pressure-sensitive adhesive sheet laminate 3- 1 was produced.

<Example 3-2>
The adhesive sheet laminate 3-1 used in Example 3-1 was heated using an IR heater preheated to 400 ° C. until the surface of the covering portion 3-I of the adhesive sheet laminate 3-2 reached 70 ° C. Then, the pressure-sensitive adhesive sheet laminate 3-1 in the heated state was subjected to press molding for 5 seconds under the condition of a clamping pressure of 8 MPa using a molding die whose mold surface temperature was cooled to 30 ° C. And a shaped pressure-sensitive adhesive sheet laminate 3-2 having a surface with irregularities was produced.

<Example 3-3>
The pressure-sensitive adhesive sheet laminate 3-1 used in Example 3-1 is heated using an IR heater preheated to 400 ° C. until the surface of the covering portion 3-I of the pressure-sensitive adhesive sheet laminate 3-3 reaches 100 ° C. Then, the pressure-sensitive adhesive sheet laminate 3-1 in the heated state was subjected to press molding for 5 seconds under the condition of a clamping pressure of 8 MPa using a molding die whose mold surface temperature was adjusted to 50 ° C. And a shaped pressure-sensitive adhesive sheet laminate 3-3 having a surface with irregularities was produced.

<Comparative Example 3-1>
The adhesive sheet laminate 3-1 used in Example 3-1 was heated using an IR heater preheated to 400 ° C. until the surface of the coating portion 3-I of the adhesive sheet laminate 3-5 reached 60 ° C. Then, the pressure-sensitive adhesive sheet laminate 3-1 in the heated state was subjected to press molding for 5 seconds under the condition of a clamping pressure of 8 MPa using a molding die whose mold surface temperature was cooled to 30 ° C. And a shaped pressure-sensitive adhesive sheet laminate 3-4 formed by forming irregularities on the surface was produced.

<Comparative Example 3-2>
The adhesive sheet laminate 3-1 used in Example 3-1 was heated using an IR heater preheated to 400 ° C. until the surface of the covering portion 3-I of the adhesive sheet laminate 3-5 reached 100 ° C. Then, the pressure-sensitive adhesive sheet laminate 3-1 in the heated state was subjected to press molding for 5 seconds under the condition of a clamping pressure of 8 MPa using a molding die whose mold surface temperature was adjusted to 80 ° C. And a shaped pressure-sensitive adhesive sheet laminate 3-5 having a surface with irregularities was produced.

<Measurement and evaluation method>
A method for measuring and evaluating various physical properties of the samples obtained in Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-2 will be described.

(Elastic modulus of the coating)
The storage elastic modulus of the covering part 3-I was cut into a length of 50 mm and a width of 4 mm, and the distance between chucks was 25 mm and a strain of 1% using a dynamic viscoelastic device (ITA Measurement Control Co., Ltd. DVA-200). Measured over time. The measurement temperature range was −50 ° C. to 150 ° C., the frequency was 1 Hz, and the heating rate was 3 ° C./min.
In the obtained data, the storage elastic modulus value of the covering portion 3-I at 30 ° C. was E ′ (MB), and the storage elastic modulus value of the covering portion 3-I at 100 ° C. was E ′ (MA).

(Elastic modulus of adhesive layer)
The pressure-sensitive adhesive layers obtained in Group 3 of Examples / Comparative Examples were stacked to a thickness of 1 mm and measured using a rheometer (MARSII manufactured by Thermo Fisher Scientific). The measurement temperature range was −50 ° C. to 150 ° C., the frequency was 1 Hz, and the heating rate was 3 ° C./min.
In the obtained data, the value of storage elastic modulus at 100 ° C. is G ′ (SA), the value of loss elastic modulus is G ″ (SA), the value of storage elastic modulus at 30 ° C. is G ′ (SB), the loss The value of elastic modulus was G ″ (SB), and the value of G ″ / G ′ under each temperature condition was the loss tangent tan δ (SA, SB) of each adhesive material layer.

(Formability)
The covering portion I of the shaped pressure-sensitive adhesive sheet laminate formed with unevenness obtained in the group 3 of Examples / Comparative Examples is peeled off, and the height between the concave portion corresponding to the printing step and the convex portion corresponding to the display surface Were measured in a non-contact manner using a scanning white interference microscope.
The height h of the convex part (edge part with the concave part) of the molded body with respect to the mold depth of 100 μm is measured, and the transfer rate derived from the following formula is 50% or more. Each thing was evaluated as “x”.
Transfer rate (%) = h (molded body height) / 100 (mold depth) × 100

(Warp / swell)
The pressure-sensitive adhesive sheet laminate produced under each molding condition of Example 3 and Comparative Example 3 was cut into a square having a length of 100 mm, and the height of each vertex was measured. The height of the obtained four points was averaged and the value was taken as a warp. Those having a warp height of less than 10 mm were judged as “◯”, and those having a warp height of 10 mm or more were judged as “x”.

(Peeling force)
The pressure-sensitive adhesive sheet laminate produced in Example 3 / Comparative Example 3 was cut into a length of 150 mm and a width of 50 mm, and the 180 ° peel test was performed at a test speed of 300 mm / min on the interface between the coating part 3-I and the pressure-sensitive adhesive layer. went.
The peeled force in an environment of 30 ° C. was F (C), and after heating at 100 ° C. for 5 minutes and then naturally cooling to 30 ° C., the peel strength was F (D). It was set as the peeling force.

Table 3 shows the evaluation results of the shaped adhesive sheet laminates 3-1 to 3-5 obtained in Examples 3-1 to 3-3 and Comparative examples 3-1 to 3-2.

From the results shown in Table 3 and the test results conducted so far, as shown in Examples 3-1 to 3-3, molding was started with the surface temperature of the covering portion 3-I being 70 to 180 ° C. Then, after the surface temperature of the covering portion 3-I becomes less than 60 ° C., the molding is finished and the molded product is taken out from the mold, so that the concavo-convex shape is accurately formed on the adhesive layer. Confirmed that it can.
On the other hand, as shown in Comparative Example 3-1, when the temperature of the covering portion 3-I at the start of molding is less than 70 ° C., sufficient unevenness can be formed in the adhesive layer even if thermoforming is performed. could not.
Further, as shown in Comparative Example 3-2, when the surface temperature of the covering portion 3-I is 70 ° C. or more when the molding is finished and the molded product is taken out from the mold, the molded product is caused by the thermal contraction of the sheet. It was found that warp and undulation occurred in the case.
In view of the above, in order to perform uneven shape shaping with higher accuracy, molding is started with the surface temperature of the covering portion 3-I being 70 to 180 ° C., and the surface temperature of the covering portion 3-I is less than 60 ° C. After that, it was found preferable to perform the molding so that the molding is finished and the molded product is taken out from the mold.

[Example Group 4]
The polyester raw materials used in the following Examples 4-1 to 4-5 (hereinafter collectively referred to as “Example Group 4”) are as follows.

(Method for producing polyester 4-A)
Take 100 parts of dimethyl terephthalate, 70 parts of ethylene glycol, and 0.07 part of calcium acetate monohydrate in a reactor, heat up and evaporate methanol to conduct transesterification, and take about 4 and a half hours after starting the reaction. The temperature was raised to 230 ° C. to substantially complete the transesterification reaction.
Next, 0.04 part of phosphoric acid and 0.035 part of antimony trioxide were added and polymerized in accordance with a conventional method. That is, the reaction temperature was gradually raised to finally 280 ° C., while the pressure was gradually reduced to finally 0.05 mmHg. After 4 hours, the reaction was completed, and chipped into polyester 4-A according to a conventional method. The intrinsic viscosity IV of the obtained polyester chip was 0.70 dl / g.

(Method for producing polyester 4-B)
Polyester 4-B was produced in the same manner as for polyester A except that in the production method of polyester 4-A, 78 mol% of terephthalic acid and 22 mol% of isophthalic acid were used as dicarboxylic acid units. The intrinsic viscosity IV of the obtained polyester chip was 0.70 dl / g.

(Method for producing polyester 4-C)
When the polyester 4-A was produced, 6000 ppm of amorphous silica having an average particle size of 3 μm was added to prepare polyester 4-C.

(Method for producing polyester 4-D)
When the polyester 4-A was produced, 6000 ppm of amorphous silica having an average particle diameter of 4 μm was added to prepare polyester 4-D.

[Example 4-1]
The raw materials in which the polyesters 4-B, 4-A, and 4-D are mixed at a ratio of 65% by weight, 30% by weight, and 5% by weight are melt-extruded by a melt extruder to obtain a single layer amorphous sheet. It was.
Next, the sheet was coextruded on a cooled casting drum and solidified by cooling to obtain a non-oriented sheet. Next, the film was stretched 3.4 times at 80 ° C. in the machine direction (longitudinal direction), and further stretched 3.9 times at 80 ° C. in the direction perpendicular to the machine direction (lateral direction) through a preheating process in a tenter. After biaxial stretching, a heat treatment was performed at 185 ° C. for 3 seconds, and then a 6.4% relaxation treatment was performed in the width direction to obtain a polyester film having a thickness of 50 μm. The evaluation results are shown in Table 4 below.

[Example 4-2], [Example 4-3]
A polyester film was obtained in the same manner as in Example 4-1, except that the conditions were changed to those shown in Table 4 below. The evaluation results are shown in Table 4 below.

[Example 4-4]
The raw materials obtained by mixing the polyesters 4-A and 4-C in proportions of 86% by weight and 14% by weight are used as raw materials for the surface layer, and the polyesters 4-B and 4-A are 45% by weight and 55% by weight, respectively. The raw materials mixed in proportion were used as intermediate layer raw materials. Two types and three layers (surface layer / intermediate layer / surface layer) of amorphous sheets were obtained by melt extrusion using different melt extruders.
Next, the sheet was coextruded on a cooled casting drum, and cooled and solidified to obtain a non-oriented sheet. Next, the film was stretched 3.4 times in the machine direction (MD) at 82 ° C., and further subjected to a preheating process in the tenter and stretched 3.9 times in the direction perpendicular to the machine direction (width direction, TD) at 110 ° C. After biaxial stretching, a heat treatment was performed at 210 ° C. for 3 seconds, and then a 2.4% relaxation treatment was performed in the width direction to obtain a polyester film having a thickness of 50 μm. The evaluation results are shown in Table 4 below.

[Example 4-5]
A polyester film was obtained in the same manner as in Example 4-4 except that the conditions shown in Table 4 were changed. The evaluation results are shown in Table 4 below.

<Measurement and evaluation method>
The measurement method and evaluation method of various physical property values of the samples obtained in Group 4 of the examples will be described.

(1) Storage elastic modulus (E ')
About the film obtained by the group 4 of the Example, the sample of 30 mm of longitudinal directions x 5 mm of width directions was extract | collected so that a longitudinal direction might turn into a machine direction. Next, using a dynamic viscoelastic device (“DVA-220” manufactured by IT Measurement & Control Co., Ltd.), the sample was sandwiched and fixed on a chuck set at an interval of 20 mm, and then the temperature was increased from room temperature to 10 ° C./min. The storage elastic modulus was measured up to 200 ° C. at a frequency of 10 Hz. The storage elastic modulus at 100 ° C. was read from the obtained data.

(2) Heat shrinkage rate A sample was cut out in a strip shape (15 mm width × 150 mm length) from the center position in the width direction of the film obtained in the group 4 of the example so that the longitudinal direction of the sample was the measurement direction, and in a no-tension state The film was heat-treated in an atmosphere at 120 ° C. for 5 minutes, the length of the sample before and after the heat treatment was measured, and the thermal contraction rate (%) of the film was calculated by the following formula. In the following formula, a is the sample length before the heat treatment, and b is the sample length after the heat treatment.
Heat shrinkage rate (%) = [(ab) / a] × 100

(3) Film Surface Oligomer Amount after Heat Treatment The polyester film was treated for 10 minutes in a hot air circulation oven at 180 ° C. in a nitrogen atmosphere with the film obtained in Group 4 of the example. The surface of the polyester film after the heat treatment was brought into contact with DMF (dimethylformamide) for 3 minutes to dissolve the oligomer deposited on the surface. For this operation, for example, the method described in the elution apparatus used for the single-side elution method in the elution test can be adopted in the voluntary standard for food containers and packaging made of synthetic resin such as polyolefin.
Next, the concentration of the obtained DMF was adjusted by a method such as dilution if necessary, and supplied to liquid chromatography (Shimadzu LC-2010) to determine the amount of oligomer in DMF. This value was brought into contact with DMF. Dividing by the film area, the amount of oligomer on the film surface (mg / cm2) was obtained.
The amount of oligomer in DMF was determined from the peak area ratio between the standard sample peak area and the measured sample peak area (absolute calibration curve method).
The standard sample was prepared by accurately weighing an oligomer (cyclic trimer) collected in advance and dissolving it in accurately measured DMF. The concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg / ml.

(4) Molding suitability As a (meth) acrylic copolymer, 15 parts by mass (18 g%) of polymethyl methacrylate macromonomer (Tg: 105 ° C.) having a number average molecular weight of 2400 and butyl acrylate (Tg: −55 ° C.) As a crosslinking agent, 1 kg of an acrylic copolymer (weight average molecular weight 230,000) obtained by random copolymerization of 81 parts by mass (75 mol%) and 4 parts by mass (7 mol%) of acrylic acid (Tg: 106 ° C.) 90 g of glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (b-1) and a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone as a photopolymerization initiator (manufactured by Lanberti, product name) : Ezacure TZT) 15 g was uniformly mixed to prepare a resin composition used for the pressure-sensitive adhesive sheet.
The obtained resin composition is sandwiched from above and below with two release films obtained from the polyester fill shown in Group 4 of the Examples (the upper and lower combinations are sandwiched between the same release films), and a laminator is used. The resin composition was shaped into a sheet shape so that the thickness was 100 μm, and an adhesive sheet laminate was produced. In addition, it arrange | positioned so that the mold release layer side of a polyester film may contact | connect a resin composition.
The obtained pressure-sensitive adhesive sheet laminate was thermoformed by the following process using a vacuum / pressure forming machine (Daiichi Jigyo Co., Ltd., model FKS-0632-20) to produce a shaped pressure-sensitive adhesive sheet laminate. That is, with an IR heater preheated to 400 ° C., the surface of the pressure-sensitive adhesive sheet laminate was heated to 100 ° C., and then cooled to 25 ° C. for 5 seconds under a clamping pressure of 8 MPa. Press-molding was performed to produce a shaped pressure-sensitive adhesive sheet laminate having irregularities formed on the surface.
The polyester film of the shaped pressure-sensitive adhesive sheet laminate with irregularities is peeled off, and the heights of the concave and convex parts of the shaped pressure-sensitive adhesive sheet are measured by a non-contact method using a scanning white interference microscope, respectively, and molded The height of the body was h.
The height h of the convex part of the molded body with respect to the depth of the mold of 100 μm is measured. The transfer rate derived from the following formula is 70% or more, ○, 50% or more and less than 70%, Δ, 50% Those less than were evaluated as x.
Transfer rate (%) = h (molded body height) / 100 (mold depth) × 100

(5) Adhesive layer appearance (wrinkles)
The appearances of the pressure-sensitive adhesive layer laminates obtained by the method described in (4) before press molding were evaluated by the evaluation methods shown below.
<Evaluation method>
○: Laminated without wrinkles, maintaining good appearance.
X: Wrinkles are generated on the film, and the wrinkles are transferred to the adhesive layer, so that the product cannot be used.

The shaped adhesive sheet laminate of the present invention is suitable for forming an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, and a pen tablet. Can be used.
The pressure-sensitive adhesive sheet laminate and the coated film of the present invention can be suitably used when forming such a shaped pressure-sensitive adhesive sheet laminate.

Claims

In the pressure-sensitive adhesive sheet laminate comprising the pressure-sensitive adhesive layer and the covering portion I laminated in a peelable manner on one side of the pressure-sensitive adhesive layer,
The storage elastic modulus E ′ (MA) of the covering portion I at 100 ° C. is 1.0 × 10 6 to 2.0 × 10 9 Pa, and the storage elastic modulus E ′ of the covering portion I at 30 ° C. ( MB) is 5.0 × 10 7 to 1.0 × 10 10 Pa, A pressure-sensitive adhesive sheet laminate.
The pressure-sensitive adhesive sheet laminate according to claim 1, wherein the storage elastic modulus E '(MA) and the storage elastic modulus E' (MB) satisfy the following relational expression (1).
(1) E ′ (MB) / E ′ (MA) ≧ 2.0
The loss tangent tan δ (SA) at 100 ° C. of the pressure-sensitive adhesive layer is 1.0 or more, and the loss tangent tan δ (SB) at 30 ° C. of the pressure-sensitive adhesive layer is less than 1.0. The pressure-sensitive adhesive sheet laminate according to claim 1 or 2.
The adhesive modulus G ′ (SA) at 100 ° C. of the adhesive layer is less than 1.0 × 10 4 Pa, and the storage modulus G ′ (SB) at 30 ° C. of the adhesive layer is 1.0. The pressure-sensitive adhesive sheet laminate according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive sheet laminate is 10 4 Pa or more.
The storage elastic modulus E ′ (MA) at 100 ° C. of the covering portion I and the storage elastic modulus G ′ (SA) at 100 ° C. of the pressure-sensitive adhesive layer satisfy the following relational expression (2). The pressure-sensitive adhesive sheet laminate according to any one of claims 1 to 4.
(2) 1.0 × 10 3 ≦ E ′ (MA) / G ′ (SA) ≦ 1.0 × 10 7
The covering portion I includes a covering base material layer and a release layer,
The covering base material layer has a stretched or non-stretched layer mainly composed of one kind of resin or two or more kinds of resins selected from the group consisting of polyester, copolymerized polyester, polyolefin and copolymerized polyolefin. The pressure-sensitive adhesive sheet laminate according to any one of claims 1 to 5, wherein
The pressure-sensitive adhesive sheet laminate according to any one of claims 1 to 6, wherein the pressure-sensitive adhesive layer and the covering portion I satisfy the following conditions (I) to (III).
(I) The peeling force F (C) at the time of peeling the said coating | coated part I from the said adhesive material layer in 30 degreeC atmosphere is 0.2 N / cm or less.
(II) The pressure-sensitive adhesive sheet laminate is heated to 100 ° C. for 5 minutes and then cooled to 30 ° C., and the peeling force F (D) when peeling the covering portion I from the pressure-sensitive adhesive layer in a 30 ° C. atmosphere is 0.2N. / Cm or less.
(III) The absolute value of the difference between the peeling force F (C) and the peeling force F (D) is 0.1 N / cm or less.
The pressure-sensitive adhesive layer is formed from a resin composition containing a (meth) acrylic copolymer (a), a crosslinking agent (b), and a photopolymerization initiator (c). Item 8. The pressure-sensitive adhesive sheet laminate according to any one of Items 1 to 7.
A shaped pressure-sensitive adhesive sheet laminate using the pressure-sensitive adhesive sheet laminate according to any one of claims 1 to 8,
The pressure-sensitive adhesive layer includes a concave portion, a convex portion, or an uneven portion (referred to as an “adhesive material layer surface uneven portion”) on the front and back side surfaces, and
The covering portion I is in close contact with the front and back side surfaces of the pressure-sensitive adhesive layer, and has a concave portion, a convex portion, or an uneven portion (referred to as a “cover portion surface uneven portion”) on the front and back side surface, A shaped pressure-sensitive adhesive sheet comprising a convex part or a concave part or a convex concave part (referred to as a "covered part rear surface convex concave part") that has irregularities that coincide with the concave and convex parts on the surface of the adhesive material layer on the front and back other side surfaces opposite to the side Laminated body.
The pressure-sensitive adhesive layer is a double-sided pressure-sensitive adhesive sheet for bonding two adherends,
The pressure-sensitive adhesive layer surface unevenness portion corresponds to a concave portion, a convex portion, or an uneven portion (referred to as an “adherent surface unevenness portion”) on the adherend surface of any one of the adherends. The shaped pressure-sensitive adhesive sheet laminate according to claim 9.
11. The shaped adhesive sheet laminate according to claim 10, wherein any one of the adherends is selected from the group consisting of a surface protection panel, a touch panel and an image display panel.
9. The pressure-sensitive adhesive sheet laminate according to claim 1, wherein the pressure-sensitive adhesive sheet laminate is heated, and an uneven shape is formed on at least one side of the pressure-sensitive adhesive sheet by press molding, vacuum forming, pressure forming or roll forming. A method for producing a shaped adhesive sheet laminate.
A coating film constituting the covering portion I of the pressure-sensitive adhesive sheet laminate according to any one of claims 1 to 8,
A coated film having a coated layer on at least one side of a copolymerized polyester film, having a storage elastic modulus E ′ at 100 ° C. of 1.5 × 10 9 Pa or less, and after heating at 120 ° C. for 5 minutes A coated film having a shrinkage rate of 3.0% or less.
The coated film according to claim 13, wherein the storage elastic modulus E ′ at 100 ° C. is 1.0 × 10 8 Pa or more.
The coated film according to claim 13 or 14, wherein the surface oligomer amount after heating at 180 ° C for 10 minutes is 1.0 x 10 -3 mg / cm 2 or less.
The coated film according to any one of claims 13 to 15, wherein the coated layer is a release layer containing a curable silicone resin.
An adhesive material layer and a covering portion I that is detachably laminated on one surface of the adhesive material layer, and one surface of the adhesive material has a concave portion, a convex portion, or an uneven portion ("adhesive material layer surface uneven portion"). In the manufacturing method of a shaped pressure-sensitive adhesive sheet laminate having a configuration formed by
The pressure-sensitive adhesive layer is provided with an adhesive material layer and a covering portion I that is detachably laminated on one surface of the pressure-sensitive adhesive material layer, and the heated pressure-sensitive adhesive sheet laminate is formed and cooled to form pressure-sensitive adhesive. A manufacturing method for manufacturing a sheet laminate,
The pressure-sensitive adhesive sheet laminate is heated and molding is started in a state where the storage elastic modulus E ′ (MS) of the covering portion I is 1.0 × 10 6 to 2.0 × 10 9 Pa, and the covering portion I is stored. A method for producing a shaped pressure-sensitive adhesive sheet laminate, characterized in that the molding is terminated in a state where the elastic modulus E ′ (MF) is 5.0 × 10 7 to 1.0 × 10 10 Pa.
Heating the pressure-sensitive adhesive sheet laminate including the pressure-sensitive adhesive layer and the covering portion I laminated to be peelable on one surface of the pressure-sensitive adhesive layer, and using the cooled mold, the heated pressure-sensitive adhesive sheet laminate The method for producing a shaped pressure-sensitive adhesive sheet laminate according to claim 17, wherein the molding is performed.
The storage elastic modulus E ′ (MS) of the covering portion I at the start of molding and the storage elastic modulus E ′ (MF) of the covering portion I at the end of forming satisfy the following relational expression (1): The manufacturing method of the shaped adhesive sheet laminated body of Claim 17 or 18.
(1) E '(MF) / E' (MS) ≧ 1.3
By heating the pressure-sensitive adhesive sheet laminate, the storage elastic modulus E ′ (MS) of the covering portion I is 1.0 × 10 6 to 2.0 × 10 9 Pa, and the storage elastic modulus G ′ of the pressure-sensitive adhesive layer is Molding is started in a state where (SS) is less than 1.0 × 10 4 Pa,
The storage elastic modulus E ′ (MF) of the covering portion I is 5.0 × 10 7 to 1.0 × 10 10 Pa, and the storage elastic modulus G ′ (SF) of the adhesive layer is 1.0 × 10 4. The method for producing a shaped pressure-sensitive adhesive sheet laminate according to any one of claims 17 to 19, wherein the molding is completed in a state of Pa or higher.
The storage elastic modulus E ′ (MF) of the covering portion I at the end of the molding and the storage elastic modulus G ′ (SF) of the pressure-sensitive adhesive layer at the end of the molding satisfy the following relational expression (2). The method for producing a shaped pressure-sensitive adhesive sheet laminate according to any one of claims 17 to 20.
(2) E ′ (MF) / G ′ (SF) ≦ 1.0 × 10 7
An adhesive material layer and a covering portion I that is detachably laminated on one surface of the adhesive material layer, and one surface of the adhesive material has a concave portion, a convex portion, or an uneven portion ("adhesive material layer surface uneven portion"). In the manufacturing method of a shaped pressure-sensitive adhesive sheet laminate having a configuration formed by
Heating the pressure-sensitive adhesive sheet laminate including the pressure-sensitive adhesive layer and the covering portion I laminated on one surface of the pressure-sensitive adhesive layer, and shaping the heated pressure-sensitive adhesive sheet laminate with a mold A manufacturing method for manufacturing an adhesive sheet laminate,
The pressure-sensitive adhesive sheet laminate is heated to start molding in a state where the surface temperature of the covering part I is 70 to 180 ° C., and after the surface temperature of the covering part I becomes less than 60 ° C., the shaped pressure-sensitive adhesive sheet is laminated from the mold. A method for producing a shaped pressure-sensitive adhesive sheet laminate, wherein the body is taken out.
23. The method for producing a shaped pressure-sensitive adhesive sheet laminate according to claim 22, wherein the forming is performed by any one of press forming, vacuum forming, pressure forming, roll forming, and compression forming.
24. The method for producing a shaped pressure-sensitive adhesive sheet laminate according to claim 22 or 23, which is continuously produced using the molding method.
The covering portion I includes a covering base material layer and a release layer,
The coating substrate layer is mainly composed of one type of resin or two or more types of resins selected from the group consisting of non-stretched polyester, stretched polyester, copolymerized polyester, unstretched polyolefin, stretched polyolefin and copolymerized polyolefin. The method for producing a shaped pressure-sensitive adhesive sheet laminate according to any one of claims 17 to 24, comprising a layer.
The pressure-sensitive adhesive layer is formed from a resin composition containing a (meth) acrylic copolymer (a), a crosslinking agent (b), and a photopolymerization initiator (c). Item 26. A method for producing a shaped pressure-sensitive adhesive sheet laminate according to any one of Items 17 to 25.
In the shaped pressure-sensitive adhesive sheet laminate, the pressure-sensitive adhesive layer includes a concave portion, a convex portion, or a concave-convex portion (referred to as “pressure-sensitive adhesive layer surface concave-convex portion”) on the front and back side surfaces, and
The covering portion I is in close contact with the front and back side surfaces of the pressure-sensitive adhesive layer, and has a concave portion, a convex portion, or an uneven portion (referred to as a “cover portion surface uneven portion”) on the front and back side surface, It is provided with a convex portion or a concave portion or a convex concave portion (referred to as a “covered portion back surface convex concave portion”) corresponding to the surface irregularity portion of the covering portion on the front and back other surface opposite to the side. The method for producing a shaped pressure-sensitive adhesive sheet laminate according to any one of claims 17 to 26.
The pressure-sensitive adhesive layer is a double-sided pressure-sensitive adhesive sheet for bonding two adherends,
The pressure-sensitive adhesive layer surface unevenness portion corresponds to a concave portion, a convex portion, or an uneven portion (referred to as an “adherent surface unevenness portion”) on the adherend surface of any one of the adherends. The manufacturing method of the shaped adhesive sheet laminated body of Claim 27 to do.
The method for producing a shaped pressure-sensitive adhesive sheet laminate according to claim 28, wherein any one of the adherends is selected from the group consisting of a surface protection panel, a touch panel, and an image display panel.
The pressure-sensitive adhesive laminate is heated, and an uneven shape is formed on at least one surface of the pressure-sensitive adhesive sheet by press forming, vacuum forming, pressure forming or roll forming. A method for producing a shaped adhesive sheet laminate.