KR20220025254A - Adhesive sheet laminate, shaped adhesive sheet laminate, and method for producing same - Google Patents

Abstract

A new pressure-sensitive adhesive sheet laminate capable of forming on the surface of the pressure-sensitive adhesive layer an uneven shape matching the uneven portions on the surface of an adherend with high precision, comprising: a pressure-sensitive adhesive layer; The provided adhesive sheet laminate WHEREIN: The storage elastic modulus E' (MA) in 100 degreeC of the said coating part I is 1.0 x 10 ⁶ -2.0 x 10 ⁹ Pa, and in 30 degreeC of the said coating part I, A storage modulus of elasticity E' (MB) of 5.0×10 ⁷ to 1.0×10 ¹⁰ Pa is proposed.

Description

Adhesive sheet laminate, shaped adhesive sheet laminate, and manufacturing method thereof

INDUSTRIAL APPLICATION This invention can be used suitably when forming image display apparatuses, such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet, for example. ) It is related with the adhesive sheet laminated body preferable for forming an adhesive sheet laminated body, and a shaping|shaped adhesive sheet laminated body.

The touch panel system image display apparatus is normally comprised by combining a surface protection panel, a touch panel, and an image display panel (collectively, it is also called "a structural member for image display apparatuses").

In recent years, plastic materials such as an acrylic resin plate and polycarbonate plate are used together with tempered glass for a surface protection panel of a touch panel type image display device such as a smart phone or a tablet terminal, and the surface protection panel other than the viewing aperture The periphery of is printed in black.

In addition, in the touch panel, a plastic film sensor is used together with a glass sensor, a touch-on-lens (TOL) member in which the touch panel function is integrated with the surface protection panel is used, or an on-cell in which the touch panel function is integrated into the image display panel. (On Cell) or the member made in Cell (In Cell) is used.

In this type of image display device, in order to further improve image visibility, a structure in which a gap between the constituent members for an image display device is filled with a transparent resin such as a liquid adhesive, a thermoplastic adhesive sheet material, and an adhesive sheet material is common.

By the way, in the field of image display devices centered on mobile phones and mobile terminals, in addition to thickness reduction and high precision, design diversification is progressing, and black concealment in the periphery of the surface protection panel is frame-shaped. Although printing a copy was conventionally common, with the diversification of designs, forming this frame-shaped hidden part in a color other than black is starting to be performed. In the case of forming the concealed portion in a color other than black, since the hiding property is low, the height of the concealed portion, that is, the printed portion, tends to be higher than that of black. Therefore, it is calculated|required that the adhesive sheet for pasting up the structural member provided with such a printing part follows a large printing level|step difference and fills every corner.

So, conventionally, various methods for filling the printing step have been proposed.

For example, in Patent Document 1, a new double-sided pressure-sensitive adhesive sheet for an image display device that can be adhered to the adherend surface without a gap even if there is a level difference due to printing or the like on the adherend surface to which the adhesive sheet is bonded. , A surface protection panel, a touch panel, and a double-sided pressure-sensitive adhesive sheet for bonding any two adherends selected from constituent members for image display devices of an image display panel, wherein at least one adherend is an adherend to which the double-sided pressure-sensitive adhesive sheet is adhered. A double-sided pressure-sensitive adhesive sheet for an image display device is disclosed which has a step portion on its surface, and the double-sided pressure-sensitive adhesive sheet is formed by shaping the shape of the bonding surface to be bonded to the adherend to conform to the surface shape of the adherend.

Moreover, in patent document 2, about the manufacturing method of the double-sided adhesive sheet for bonding any two to-be-adhered bodies selected from a surface protection panel, a touch panel, and an image display panel, the double-sided adhesive sheet before bonding has a gel fraction of 40% A method for manufacturing a double-sided pressure-sensitive adhesive sheet for an image display device is disclosed, wherein the pressure-sensitive adhesive composition is used to form the same surface shape as the concave-convex shape of the bonding surface of the adherend.

WO 2014/073316 A1 WO 2015/174392 A1

In recent years, in the field of image display devices centered on cellular phones and mobile terminals, thickness reduction and high precision have been further demanded. It is calculated|required that it can fill accurately and that an adhesive material does not protrude outward at the same time. As a countermeasure for that, as disclosed by the above-mentioned prior patent document, forming the surface shape of an adhesive sheet to conform to the surface shape of a to-be-adhered body beforehand, and forming it is examined.

Then, in order to form the surface shape of the pressure-sensitive adhesive sheet in advance to conform to the surface shape of the adherend in this way, a pressure-sensitive adhesive sheet laminate in which release sheets are laminated on both sides of the pressure-sensitive adhesive sheet is press-molded, A method of forming a concave-convex shape conforming to the concavo-convex portion on the surface of the complex is contemplated.

However, as a result of actually carrying out the above method using a pressure-sensitive adhesive sheet laminate in which a normal release sheet is laminated on both sides of the pressure-sensitive adhesive sheet, the concave-convex shape corresponding to the concavo-convex portion on the surface of the adherend is formed on the surface of the pressure-sensitive adhesive sheet with high precision. The task of being difficult to do has become clear.

Therefore, the present invention relates to a pressure-sensitive adhesive sheet laminate comprising a pressure-sensitive adhesive layer and a covering portion formed to be peelably laminated on one side of the pressure-sensitive adhesive layer, in which the concavo-convex shape corresponding to the concavo-convex portion on the surface of the adherend is accurately formed on the surface of the pressure-sensitive adhesive material layer. It is intended to propose a new adhesive sheet laminate that can be formed, and a shaped adhesive sheet laminate using the adhesive sheet laminate.

The present invention relates to a pressure-sensitive adhesive sheet laminate comprising a pressure-sensitive adhesive layer and a covering portion I that is laminated on one side of the pressure-sensitive adhesive layer so as to be peelable. is 1.0×10 ⁶ to 2.0×10 ⁹ Pa, and the storage elastic modulus E′ (MB) of the coating part I at 30° C. is 5.0×10 ⁷ to 1.0×10 ¹⁰ Pa. We propose a laminate.

The present invention also provides a shaped pressure-sensitive adhesive sheet laminate using the pressure-sensitive adhesive sheet laminate, wherein the pressure-sensitive adhesive layer has concave portions, convex portions, or uneven portions (referred to as “adhesive material layer surface concavo-convex portions”) on one surface of the front and back sides, Further, the coating part I is closely attached to the front and back one surface of the adhesive material layer, and has concave parts, convex parts, or uneven parts (referred to as "coated part surface irregularities") on the front and back one side surfaces, and further, A shaped pressure-sensitive adhesive sheet laminate having convex portions, concave portions, or concavo-convex portions (referred to as “coated back surface concavo-convex portions”) having concavities and convexities conforming to the surface concavo-convex portions of the pressure-sensitive adhesive layer on the front and back surfaces opposite to one front and back sides; suggest

According to the pressure-sensitive adhesive sheet laminate proposed by the present invention, for example, after heating the pressure-sensitive adhesive sheet laminate, the coating portion I is molded by pressing a mold to form an uneven shape matching the uneven portion on the surface of the adherend. can be formed with high precision on the surface of the adhesive material layer. In addition, since the coating part I can maintain shape-retaining property in its state, it is not only easy to handle, but it is not too hard, so it suppresses unnecessary unintentional unevenness in the pressure-sensitive adhesive layer. can do.

The shaped pressure-sensitive adhesive sheet laminate proposed by the present invention is provided with pressure-sensitive adhesive sheet surface irregularities on one surface of the front and back sides of the pressure-sensitive adhesive layer, and the covering portion I is in close contact with the front and back one side surfaces of the pressure-sensitive adhesive layer, on the front and back surfaces on one side It is provided with the surface uneven|corrugated part of the coating part, and is provided with the uneven|corrugated part on the back surface of a coating part on the other front and back surfaces opposite to the said front and back one side. In this way, 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 one side surfaces of the pressure-sensitive adhesive layer, and the covering portion I is peelable on the front and back one side surfaces of the pressure-sensitive adhesive layer. Since this laminated structure is provided, it is possible to prevent the adhesion of dust or the like to the surface of the pressure-sensitive adhesive layer, thereby reducing the adhesive strength, and furthermore, the shape of the surface irregularities on the surface of the pressure-sensitive adhesive layer formed on the front and back one side of the pressure-sensitive adhesive layer It can also be prevented that it collapses by absorbing moisture in the air, or that the adhesive force decreases due to dust or the like adhering to the surface.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows 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 shaping adhesive sheet laminated body using an example of the adhesive sheet laminated body which is an Example of this invention.
It is a figure which shows typically an example of the shaping|molding adhesive sheet laminated body which is an Example of this invention, (A) is sectional drawing, (B) is a perspective view.
4 is a view showing the viscoelasticity curve of the material used for the pressure-sensitive adhesive sheet laminate prepared in Examples and Comparative Examples.
It is a perspective view which showed one side of the metal mold|die used by the Example and the comparative example.

An example of embodiment of this invention is described below. However, the present invention is not limited to the following embodiments.

[This adhesive sheet laminate]

An adhesive sheet laminate (referred to as "this adhesive sheet laminate") according to an example of the embodiment of the present invention is, as shown in FIG. It is an adhesive sheet laminated body provided with the coating|covering part I which consists of, and the coating|covering part II formed by laminating|stacking so that peeling is possible on the front and back other side of the said adhesive material layer. Here, the coating part II is arbitrary, and it is good also as a structure in which the coating part II is not laminated|stacked.

<Adhesive layer>

The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet laminate can function as a double-sided pressure-sensitive adhesive sheet when the coating portion I and the coating portion II are peeled off, and may have hot-melt properties that soften or melt when heated.

The pressure-sensitive adhesive layer preferably has a loss tangent tan δ (SA) of 1.0 or more at 100°C. Moreover, it is preferable that the loss tangent tanδ (SB) in 30 degreeC is less than 1.0.

Here, the loss tangent tanδ means the ratio (G''/G') of the loss modulus G'' and the storage modulus G'.

Since the temperature at the time of heat-molding this pressure-sensitive adhesive sheet laminate is usually 70 to 120° C., when the loss tangent tan δ (SA) at 100° C. is 1.0 or more, it is easy to shape the concavo-convex shape on the surface of the pressure-sensitive adhesive material layer. .

In addition, 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 the state, so that the concavo-convex shape corresponding to the concavo-convex portion on the surface of the adherend is accurately formed on the surface of the adhesive material layer. The formed state can be maintained.

In general, polymer materials have both viscous properties and elastic properties, and the higher the loss tangent tanδ is 1.0 or higher, the stronger the viscous properties. On the other hand, when the loss tangent tan δ is less than 1.0, the smaller the value, the stronger the elastic properties. For this reason, by controlling the loss tangent tan δ at different temperatures of the pressure-sensitive adhesive layer, it is possible to have both moldability and shape retention properties.

From this point of view, the loss tangent tan ? (SA) at 100°C of the pressure-sensitive adhesive layer is preferably 1.0 or more, particularly preferably 1.5 or more or 30 or less, and particularly preferably 3.0 or more or 20 or less.

On the other hand, the loss tangent tan ? (SB) at 30°C of the pressure-sensitive adhesive layer is preferably less than 1.0, particularly preferably 0.01 or more or 0.9 or less, and particularly preferably 0.1 or more or 0.8 or less.

Here, the loss tangent tanδ (SA) at 100°C and the loss tangent tanδ (SB) at 30°C of the pressure-sensitive adhesive layer are determined by adjusting the components, gel fraction, weight average molecular weight, etc. of the composition constituting the pressure-sensitive adhesive layer. It can be adjusted within the above range.

Moreover, it is preferable that the storage elastic modulus G'(SA) in 100 degreeC of an adhesive material layer is less than 1.0x10 ⁴ Pa. Moreover, it is preferable that the storage elastic modulus G'(SB) in 30 degreeC of the said adhesive material layer is 1.0x10 ⁴ Pa or more.

It is preferable that the storage elastic modulus G'(SA) in 100 degreeC of an adhesive material layer is less than 1.0x10 ⁴ Pa, since sufficient moldability is obtained, on the other hand, the storage elastic modulus G'(SB) in 30 degreeC of an adhesive material layer. It is preferable from a viewpoint of shape stability after shaping|molding that is 1.0x10 ⁴ Pa or more.

From this point of view, the storage elastic modulus G' (SA) at 100° C. of the pressure-sensitive adhesive layer is preferably less than 1.0 × 10 ⁴ Pa, and more preferably 5.0 × 10 ¹ Pa or more or 5.0 × 10 ³ Pa or less, Among them, 1.0×10 ² Pa or more or 1.0×10 ³ Pa or less is more preferable.

From the above, it is more preferable that the storage elastic modulus G' (SA) of the pressure-sensitive adhesive layer at 100°C 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 5.0×10 ³ Pa or less. and, among them, 1.0×10 ² Pa or more and less than 1.0×10 ⁴ Pa, or more preferably 1.0×10 ² Pa or more and 5.0×10 ³ Pa or less, and 1.0×10 ² Pa or more and 1.0×10 ³ Pa or less Most preferred.

In addition, from this point of view, 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. and more preferably 5.0×10 ⁴ Pa or more or 1.0×10 ⁶ Pa or less.

Further, from the above, the storage elastic modulus G' (SB) at 30°C of the pressure-sensitive 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 1.0×10 ⁶ Pa or less More preferably, they are 2.0×10 ⁴ Pa or more and 1.0×10 ⁷ Pa or less, or 2.0×10 ⁴ Pa or more and 1.0×10 ⁶ Pa or less, more preferably 5.0×10 ⁴ Pa or more and 1.0×10 ⁶ Pa It is most preferable that it is below.

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 the components, gel fraction, and weight average of the composition constituting the pressure-sensitive adhesive layer. It can adjust to the said range by adjusting molecular weight etc.

The temperature at which the loss tangent tan δ of the pressure-sensitive adhesive layer becomes 1.0 is preferably 50 to 150°C, more preferably 60°C or more or 130°C or less, and more 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 becomes 1.0 is 50 to 150°C, the pressure-sensitive adhesive sheet laminate can be heated to 50 to 150°C, whereby die molding can be performed.

The glass transition temperature (Tg) of the base resin of the pressure-sensitive adhesive layer is preferably -50 to 40°C, more preferably -30°C or more or 25°C or less, and more preferably -10°C or more or 20°C or less. Here, the glass transition temperature is measured using a differential scanning calorimeter (DSC) to determine the midpoint between the inflection points of the baseline shift when the temperature is raised at a rate of 3°C/min. means

If the glass transition temperature (Tg) of the base resin of the adhesive layer is within the above range, tackiness can be imparted to the adhesive layer, and the temperature at which the loss tangent tanδ of the adhesive layer becomes 1.0 can be adjusted to 50 to 150° C. Do.

As the material of the pressure-sensitive adhesive layer, a conventionally known pressure-sensitive adhesive sheet can be used as long as it is a material that can be prepared with a predetermined viscoelastic behavior.

For example, 1) (meth)acrylic acid ester-based polymer (meaning including copolymer, hereinafter referred to as “acrylic acid ester-based (co)polymer”) is used as a base resin, and a crosslinking monomer, if necessary A pressure-sensitive adhesive sheet formed by blending a crosslinking initiator, a reaction catalyst, etc., and crosslinking reaction;

2) A pressure-sensitive adhesive sheet formed by using butadiene or an isoprene-based copolymer as a base resin, mixing it with a crosslinking monomer, and optionally a crosslinking initiator or a reaction catalyst, and crosslinking reaction;

3) A pressure-sensitive adhesive sheet formed by using a silicone-based polymer as a base resin, mixing it with a crosslinking monomer, and optionally a crosslinking initiator or a reaction catalyst, and performing a crosslinking reaction;

4) Polyurethane-type adhesive sheet etc. which used the polyurethane-type polymer as base resin are mentioned.

The physical properties of the pressure-sensitive adhesive layer itself are not essential in the present invention, except for the above-described viscoelastic properties and thermal properties. However, it is preferable to use the acrylic acid ester-based (co)polymer of 1) as the base resin from the viewpoints of adhesiveness, transparency, and weather resistance.

When performance such as electrical characteristics and low refractive index are required, it is preferable to use the butadiene or isoprene-based copolymer of 2) as the base resin.

When performance, such as heat resistance and rubber elasticity in a wide temperature range, is requested|required, it is preferable to use the silicone type polymer of said 3) as a base resin.

When performance such as releasability is required, it is preferable to use the polyurethane-based polymer of 4) as the base resin.

As an example of the adhesive layer, an adhesive sheet formed of a resin composition containing a (meth)acrylic copolymer (a) as a base resin, a crosslinking agent (b), and a photoinitiator (c) can be exemplified.

In this case, it is necessary to satisfy the above-mentioned viscoelastic properties in an uncrosslinked state, that is, in a state before a three-dimensionally crosslinked network structure is formed. From this point of view, the gel fraction of the pressure-sensitive adhesive layer is preferably 40% or less.

When the gel fraction of the pressure-sensitive adhesive layer is 40% or less, the bonding between molecular chains constituting the pressure-sensitive adhesive layer is suppressed within an appropriate range, so that it is possible to provide adequate fluidity when molding into a shaped pressure-sensitive adhesive sheet laminate.

From this point of view, the gel fraction of the pressure-sensitive adhesive layer is preferably 40% or less, and particularly preferably 20% or less, particularly preferably 10% or less. In addition, the lower limit of the gel fraction of an adhesive material layer is not limited, 0 % may be sufficient.

In addition, the gel fraction of the adhesive layer is not limited to the case of using a resin composition containing a (meth)acrylic copolymer (a), a crosslinking agent (b), and a photopolymerization initiator (c) as a base resin. The same applies to the case of using another resin composition as the material layer.

((meth)acrylic copolymer (a))

For the (meth)acrylic copolymer (a), properties such as the glass transition temperature (Tg) are appropriately adjusted depending on the type, composition ratio, and polymerization conditions of the acrylic monomer or methacrylic monomer used for polymerization. possible.

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

Among the acrylic acid ester polymers, (meth)acrylic acid alkylester copolymers are particularly preferred.

As the (meth)acrylate, that is, the alkyl acrylate or alkyl methacrylate component used to form the (meth)acrylic acid alkylester-based copolymer, the alkyl group is n-octyl, isooctyl, 2-ethylhexyl, n-butyl , isobutyl, methyl, ethyl, isopropyl any one of alkyl acrylate or alkyl methacrylate, or a mixture of two or more selected from them.

As another component, you may copolymerize the acrylate or methacrylate which has organic functional groups, such as a carboxyl group, a hydroxyl group, and a glycidyl group. Specifically, a (meth)acrylic acid ester copolymer is obtained by heat-polymerizing a monomer component in which the alkyl (meth)acrylate component and the (meth)acrylate component having an organic functional group are appropriately and selectively combined as a starting material. can

Among them, preferably, one or a mixture of two or more selected from alkyl acrylates such as iso-octyl acrylate, n-octyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, or What copolymerized acrylic acid with at least 1 type or more, such as iso-octyl acrylate, n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, etc. is mentioned.

As the polymerization treatment using these monomers, known polymerization methods such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization can be employed. An acrylic acid ester copolymer can be obtained by using an initiator.

(Acrylic copolymer (A1))

As an example of a preferable base polymer of an adhesive material layer, the acrylic copolymer (A1) which consists of a graft copolymer provided with a macromonomer as a branch component is mentioned.

When the adhesive layer is composed of the acrylic copolymer (A1) as the base resin, the adhesive layer can exhibit self-adhesiveness while maintaining the sheet shape at room temperature, and melts when heated in an uncrosslinked state. It has a hot-melt property to flow, and can further be photocured, and can be adhered by exhibiting excellent cohesive force after photocuring.

Therefore, when the acrylic copolymer (A1) is used as the base polymer for the pressure-sensitive adhesive layer, it exhibits tackiness at room temperature (20°C) even in an uncrosslinked state, and is 50 to 100°C, more preferably 60°C or higher or 90°C. When heated to a temperature of ℃ or less, it may have a property of softening or fluidizing.

The glass transition temperature of the copolymer constituting the stem 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 stem component refers to the glass transition temperature of the polymer obtained by copolymerizing only the monomer component constituting the stem component of the acrylic copolymer (A1). Specifically, it means a value calculated by Fox's formula from the glass transition temperature and composition ratio of the polymer obtained from the homopolymer of each component of the copolymer.

In addition, Fox's calculation formula is a calculated value calculated|required by the following formula, and can be calculated|required using the value described in Polymer Handbook [Polymer HandBook, J. Brandrup, Interscience, 1989].

1/(273+Tg)=Σ(Wi/(273+Tgi))

[Wherein, Wi is the weight fraction of the monomer i, and Tgi is the Tg (°C) of the homopolymer of the monomer i.]

Since the glass transition temperature of the copolymer component constituting the stem component of the acrylic copolymer (A1) affects the flexibility of the pressure-sensitive adhesive layer at room temperature, the wettability of the pressure-sensitive adhesive layer to the adherend, that is, the adhesiveness, adhesion In order for the material layer to obtain adequate adhesion (tackiness) at room temperature, the glass transition temperature is preferably -70°C to 0°C, and among them -65°C or higher or -5°C or lower, especially It is especially preferable that it is -60 degreeC or more or -10 degrees C or less.

However, even if the glass transition temperature of the said copolymer component was the same temperature, viscoelasticity can be adjusted by adjusting molecular weight. For example, by making the molecular weight of a copolymer component small, it can make it more flexible.

As the (meth)acrylic acid ester monomer contained in the stem component of the acrylic copolymer (A1), for example, 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 (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, dicyclopentenyl (meth) Acrylate, dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, etc. are mentioned. In these, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate having a hydrophilic group or an organic functional group containing hydroxyl groups (meth) Acrylate, (meth)acrylic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethylphthalic acid, 2 -(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropylmaleic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2 -Contains carboxyl group-containing monomers such as (meth)acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconic acid, and acid anhydride groups such as maleic anhydride and itaconic anhydride Monomer, (meth)acrylic acid glycidyl, α-ethyl acrylate glycidyl, (meth)acrylic acid 3,4-epoxybutyl, etc. epoxy group-containing monomer, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth) Amino group-containing (meth)acrylic acid ester monomers such as acrylate, (meth)acrylamide, Nt-butyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, maleic acid amide, a monomer containing an amide group such as maleimide, a heterocyclic basic monomer such as vinyl pyrrolidone, vinyl pyridine, vinyl carbazole, etc. You can also use

In addition, styrene, t-butylstyrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, alkyl vinyl ether, hydroxyalkyl, copolymerizable with the acrylic monomer or methacrylic monomer. Various vinyl monomers, such as vinyl ether and an alkylvinyl monomer, can also be used suitably.

Moreover, it is preferable that the stem component of an acrylic copolymer (A1) contains a hydrophobic (meth)acrylate monomer and a hydrophilic (meth)acrylate monomer as a structural unit.

When the stem component of the acrylic copolymer (A1) is composed of only a hydrophobic monomer, the tendency to whiten by moist heat is recognized. Therefore, it is preferable to also introduce a hydrophilic monomer to the stem component to prevent wet heat whitening.

Specifically, as the stem 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 randomly copolymerized. and synthetic components.

Here, as the said hydrophobic (meth)acrylate monomer, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acryl Rate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethyl Hexyl 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 (meth)acrylate, and methyl methacrylate.

Examples of the hydrophobic vinyl monomer include vinyl acetate, styrene, t-butylstyrene, α-methylstyrene, vinyltoluene, and an alkylvinyl monomer.

Examples of the hydrophilic (meth)acrylate monomer include methyl acrylate, (meth)acrylic acid, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acryl. Hydroxyl group-containing (meth)acrylates, such as rate, hydroxybutyl (meth)acrylate, and glycerol (meth)acrylate, (meth)acrylic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-( Meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2- (meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleic acid , carboxyl group-containing monomers such as monomethyl itaconic acid, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, glycidyl (meth)acrylate, α-ethyl acrylate glycidyl, 3,4- (meth)acrylic acid Epoxy group-containing monomers, such as epoxybutyl, Alkoxy polyalkylene glycol (meth)acrylates, such as methoxy polyethylene glycol (meth)acrylate, N,N- dimethyl acrylamide, hydroxyethyl acrylamide, etc. are mentioned.

It is preferable that the acrylic copolymer (A1) introduce|transduces a macromonomer as a branch component of a graft copolymer, and contains the repeating unit derived from a macromonomer.

A macromonomer is a polymeric monomer which has a polymerizable functional group at the terminal and a high molecular weight skeleton component.

It is preferable that the glass transition temperature (Tg) of the macromonomer is 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 heat melting temperature (hot melt temperature) of the adhesive layer 2, the glass transition temperature (Tg) of the macromonomer is 30°C to 120°C. It is preferable that it is 40 degreeC or more or 110 degrees C or less especially, and it is more preferable that it is 50 degrees C or more or 100 degrees C or less especially.

If it is such a glass transition temperature (Tg), while being able to maintain outstanding processability and storage stability by adjusting molecular weight, it can adjust so that it may be hot-melted at 80 degreeC vicinity.

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).

In addition, at room temperature, the branch components attract each other to maintain a state as if physically crosslinked as a pressure-sensitive adhesive composition, and furthermore, by heating to an appropriate temperature, the physical crosslinking is released so that fluidity can be obtained. It is also preferable to adjust the molecular weight and content of

From this point of view, the macromonomer is preferably contained in a proportion of 5% by mass to 30% by mass in the acrylic copolymer (A1), among them 6% by mass or more or 25% by mass or less, and particularly 8% by mass or more or It is preferable that it is 20 mass % or less.

Moreover, it is preferable that the number average molecular weights of a macromonomer are 500 or more and less than 8000, Especially, it is preferable that they are 800 or more or less than 7500, Especially, it is 1000 or more or less than 7000.

As a macromonomer, what is generally manufactured (For example, the macromonomer made by Dong-A Synthesis, etc.) can be used suitably.

It is preferable that the high molecular weight skeleton component of a macromonomer is comprised from an acryl-type polymer or a vinyl-type polymer.

As the high molecular weight skeleton component of the macromonomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylic Rate, 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-trimethylcyclohexaneacrylate, p-cumylphenol EO-modified (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl ( Meth) acrylate, benzyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, (meth) acrylamide, N,N-dimethyl (meth) acryl (meth)acrylate monomers such as amide, (meth)acrylonitrile, alkoxyalkyl (meth)acrylate, alkoxypolyalkylene glycol (meth)acrylate, styrene, t-butylstyrene, α-methylstyrene, vinyl Various vinyl monomers, such as toluene, an alkylvinyl monomer, vinyl acetate, an alkylvinyl ether, and hydroxyalkyl vinyl ether, are mentioned, These can be used individually or in combination of 2 or more types.

As a terminal polymerizable functional group of the said macromonomer, a methacryloyl group, an acryloyl group, a vinyl group, etc. are mentioned, for example.

(crosslinking agent (b))

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

Further, the crosslinkable functional group may be protected by a protecting group capable of being deprotected.

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

As said polyfunctional (meth)acrylate, 1, 4- butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol glycidyl ether di ( Meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, bisphenol A polyethoxydi( meth)acrylate, bisphenol A polyalkoxydi(meth)acrylate, bisphenol F polyalkoxydi(meth)acrylate, polyalkylene glycol di(meth)acrylate, trimethylolpropane trioxyethyl(meth)acrylate, ε-caprolactone-modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate (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, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxyl Neopentylglycol di(meth)acrylate cypivalate, di(meth)acrylate of ε-caprolactone adduct of neopentylglycol hydroxypivalate, trimethylolpropane tri(meth)acrylate, alkoxylated trimethylolpropane tri( UV-curable polyfunctional monomers such as meth)acrylate and ditrimethylolpropanetetra(meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyether Polyfunctional acrylic oligomers, such as (meth)acrylate, are mentioned.

Among the above, from the viewpoint of improving the effect of suppressing wet heat and adhesion to an adherend, polyfunctional monomers containing a polar functional group such as a hydroxyl group, a carboxyl group, or an amide group among the polyfunctional (meth)acrylic acid ester monomers Or an oligomer is preferable. Especially, it is preferable to use polyfunctional (meth)acrylic acid ester which has a hydroxyl group or an amide group.

From the viewpoint of preventing moist heat whitening, it is preferable to contain a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as a stem component of the (meth)acrylic acid ester copolymer, for example, a graft copolymer, and further, As a crosslinking agent, it is preferable to use polyfunctional (meth)acrylic acid ester which has a hydroxyl group.

Moreover, in order to adjust effects, such as adhesiveness, heat-and-moisture resistance, heat resistance, you may add monofunctional or polyfunctional (meth)acrylic acid ester which reacts with a crosslinking agent further.

Content of the crosslinking agent, from a viewpoint of balancing the softness|flexibility and cohesive force of an adhesive composition, it is preferable to contain in the ratio of 0.1-20 mass parts with respect to 100 mass parts of said (meth)acrylic-type copolymers, Especially, 0.5 mass part or more Or 15 mass parts or less, Especially, it is especially preferable that it is a ratio of 1 mass part or more or 13 mass parts or less.

(Photoinitiator (c))

When crosslinking the acrylic acid ester polymer, it is effective to appropriately add a crosslinking initiator (peroxidation initiator, photopolymerization initiator) or reaction catalyst (tertiary amine compound, quaternary ammonium compound, tin laurate compound, etc.).

In the case of UV irradiation crosslinking, it is preferable to mix|blend a photoinitiator (c).

The photopolymerization initiator (C) is largely classified into two types by the radical generation mechanism, a cleavage type photoinitiator capable of generating radicals by cleavage decomposition of a single bond of the photopolymerization initiator itself, and a photoexcited initiator; A hydrogen donor in the system forms an exciplex and is roughly classified as a hydrogen abstraction type photopolymerization initiator capable of transferring hydrogen of a hydrogen donor.

The cleavage-type photoinitiator in these decomposes|disassembles when generating a radical by light irradiation to become another compound, and once excited, it ceases to have a function as a reaction initiator. For this reason, when the cleavage type is used as a photopolymerization initiator having an absorption wavelength in the visible ray region, compared to the case of using a hydrogen extraction type, after crosslinking the pressure-sensitive adhesive sheet by irradiation with light, the photopolymerization initiator having a photoreactivity is the present pressure-sensitive adhesive. It remains as an unreacted residue in the composition, and since it is low possibility of causing the unexpected change with time of an adhesive sheet, or acceleration|stimulation of crosslinking, it is preferable. Moreover, also regarding the coloring peculiar to a photoinitiator, since absorption of a visible ray range disappears by becoming a reaction decomposition product, and it can select suitably the thing which loses color, it is preferable.

On the other hand, the hydrogen extraction type photopolymerization initiator does not generate decomposition products like the cleavage type photopolymerization initiator during the radical generation reaction by irradiation with active energy rays such as ultraviolet rays. Damage can be reduced.

Examples of the cleavage type photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1-phenyl. -Propan-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), methyl phenylglyoxylate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinopropan-1-one, 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 fin oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, derivatives thereof, etc. are mentioned.

Among these, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide from the point of becoming a decomposition product after reaction in a cleavage-type photoinitiator and decolorizing An acylphosphine oxide-based photoinitiator such as (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide is preferable. Do.

In addition, from the compatibility with the acrylic copolymer consisting of a graft copolymer having a macromonomer as a branch component, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl) as a photoinitiator ) ethoxyphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc. are preferably used.

Content in particular of a photoinitiator is not restrict|limited. For example, 0.1 to 10 parts by mass, especially 0.2 parts by mass or more or 5 parts by mass or less, especially 0.5 parts by mass or more or 3 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic copolymer ) is particularly preferred. However, in balance with other factors, you may exceed this range.

A photoinitiator can be used 1 type or in combination of 2 or more type.

In addition to the above components, if necessary, pigments such as pigments or dyes having near-infrared absorption properties, tackifiers, antioxidants, antioxidants, moisture absorbers, ultraviolet absorbers, silane coupling agents, natural or synthetic resins, glass fibers or glass Various additives, such as beads, can also be mix|blended suitably.

(Layer structure and thickness of adhesive layer)

In addition to a single layer, multiple layers, such as two layers and three layers, may be sufficient as an adhesive material layer.

In addition, the adhesive material layer may have a base material layer (a layer which does not have adhesiveness) as a core layer, and the structure in which the layer which consists of an adhesive material is laminated|stacked on both sides of the said base material layer may be sufficient. In the case of such a structure, it is preferable that the base material layer as a core has a material and characteristic by which an adhesive sheet laminated body can be heat-molded. In addition, the pressure-sensitive adhesive layer excluding the base layer preferably has the above characteristics with respect to loss tangent tanδ (SA), loss tangent tanδ (SB), storage elastic modulus G′ (SA) and storage elastic modulus G′ (SB). .

The thickness of the pressure-sensitive adhesive layer is not particularly limited. Especially, the range of 20 micrometers - 500 micrometers is preferable. If it is within this range, for example, if it is a thin adhesive material layer, such as 20 micrometers in thickness, the adhesive sheet excellent in print level difference tracking property can be provided. Moreover, in the thick adhesive material layer like 500 micrometers in thickness, the overflow of the adhesive material at the time of bonding can also be suppressed because the printing level difference equivalent part is shape|molding beforehand.

Accordingly, the thickness of the pressure-sensitive adhesive layer is preferably 20 µm to 500 µm, and more preferably 30 µm or more or 300 µm or less, and more preferably 50 µm or more or 200 µm or less.

<Cloth Ⅰ>

As shown in FIG. 1, this adhesive sheet laminated body is provided with the coating|covering part I formed by laminating|stacking so that peeling is possible on the front and back one side of an adhesive material layer, for example, the side which shapes the unevenness|corrugation on the surface.

It is preferable that the storage elastic modulus E' (MA) in 100 degreeC of the coating|coated part I is 1.0x10 ⁶ -2.0x10 ⁹ Pa.

Since the temperature at the time of heat-molding this adhesive sheet laminated body is 70-120 degreeC normally, if the storage elastic modulus E' (MA) in 100 degreeC is 1.0x10 ⁶ -2.0x10 ⁹ Pa, the said adhesive composition is In the plasticizing or flowing temperature range, the coating part I is also deformable by sufficiently following the uneven shape, and the desired uneven shape on the surface of the pressure-sensitive adhesive layer pressed by the coating part I during molding can be obtained with high precision, for example. For example, it can be molded so that the corners are not rounded.

Conventionally, as a release film laminated|stacked on a pressure-sensitive adhesive sheet, a material having a high storage elastic modulus, in other words, a “hard” material has been widely used. This is because the properties required for the release film were mainly protection of the pressure-sensitive adhesive layer and releasability. However, according to the examination of the present inventors, in a new application of heat forming in a state in which a release film is laminated on an adhesive sheet, when a new subject such as heat formability is requested, the conventional release film has the It has been discovered that such physical properties cannot be achieved. For this reason, as a result of precisely examining the phenomena occurring during heat molding and the characteristics of the pressure-sensitive adhesive layer, one of the characteristics different from the release films that have been generally used so far is the new problem of heat formability. To solve it, I found an advantage. In particular, it was discovered that the said subject could be solved by controlling the storage elastic modulus in a specific temperature to a specific range.

From this viewpoint, it is preferable that the storage modulus E' (MA) of the coating part I at 100°C is 1.0×10 ⁶ to 2.0×10 ⁹ Pa, and among them, 5.0×10 ⁶ Pa or more or 1.0×10 ⁹ Pa Hereinafter, it is more preferable that it is 1.0×10 ⁷ Pa or more or 5.0×10 ⁸ Pa or less among them.

From the above, it is more preferable that the storage elastic modulus E' (MA) of the coating part I at 100°C is 1.0×10 ⁶ to 1.0×10 ⁹ Pa, or 1.0×10 ⁶ to 5.0×10 ⁸ Pa, Among them, 5.0×10 ⁶ to 2.0×10 ⁹ Pa, or 5.0×10 ⁶ to 1.0×10 ⁹ Pa, more preferably 1.0×10 ⁷ to 1.0×10 ⁹ Pa, or 1.0×10 ⁷ to It is most preferably 5.0×10 ⁸ Pa.

Moreover, it is preferable that the storage elastic modulus E' (MB) in 30 degreeC of the coating|coated part I is 5.0x10< ⁷ >-1.0x10< ¹⁰ >Pa.

If the storage elastic modulus E' (MB) of the coating part I at 30°C is 5.0×10 ⁷ to 1.0×10 ¹⁰ Pa, since shape retaining properties can be maintained in the state, handling is easy, for example, peeling Not only is it easy to do it, but since it is not too hard, it can suppress giving unnecessary unintentional unevenness|corrugation to an adhesive material layer.

From this viewpoint, it is preferable that the storage modulus E' (MB) of the coating part I at 30°C is 5.0×10 ⁷ to 1.0×10 ¹⁰ Pa, especially 1.0×10 ⁸ Pa or more or 8.0×10 ⁹ Pa Hereinafter, it is more preferable that it is 1.0×10 ⁹ Pa or more or 5.0×10 ⁹ Pa or less among them.

From the above, it is more preferable that the storage modulus E' (MB) of the coating part I at 30°C is 5.0×10 ⁷ to 8.0×10 ⁹ Pa or 5.0×10 ⁷ to 5.0×10 ⁹ Pa, Among them, 1.0×10 ⁸ Pa to 1.0×10 ¹⁰ Pa, or 1.0×10 ⁸ Pa to 8.0×10 ⁹ Pa, more preferably 1.0×10 ⁹ to 8.0×10 ⁹ Pa, or 1.0×10 Most preferably, it is 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, copolymer resin component, weight average molecular weight, glass transition temperature, crystallinity, etc. of the coating part I In addition to adjusting the conditions of the material of However, it is not limited to these methods.

Moreover, it is preferable that the storage elastic modulus E'(MA) in 100 degreeC of the coating|coated part I and the storage elastic modulus E'(MB) in 30 degreeC of the coating|coated part I satisfy|fill the following relational expression (1).

(One)… E'(MB)/E'(MA)≥2.0

When the storage elastic modulus E' (MA) at 100 ° C. of the coated part I and the storage elastic modulus E' (MB) at 30 ° C. of the coated part I satisfy the above relational expression (1), sufficient moldability is obtained. more preferable from

From this point of view, it is preferable that E'(MB)/E'(MA)≥2.0, and among them, 30≥E'(MB)/E'(MA) or E'(MB)/E'(MA)≥2.0 It is more preferable that it is 3.0, and among these, it is especially preferable that 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. of the material of the coating part I While adjusting conditions, it can adjust by adjusting manufacturing conditions, such as the presence or absence of extending|stretching, shaping|molding conditions, and extending|stretching conditions, when extending|stretching. However, it is not limited to these methods.

Furthermore, it is that the storage elastic modulus G'(SA) in 100 degreeC of the said adhesive material layer and the storage elastic modulus E'(MA) in 100 degreeC of the said coating part I satisfy the following relational expression (2) desirable.

(2)… 1.0×10 ³ ≤E'(MA)/G'(SA)≤1.0×10 ⁷

When the storage elastic modulus G' (SA) at 100° C. of the pressure-sensitive adhesive layer and the storage elastic modulus E′ (MA) at 100° C. of the coating part I satisfy the above relational expression (2), sufficient moldability is obtained more preferably from

From this point of view, E'(MA)/G'(SA) is preferably 1.0×10 ³ to 1.0×10 ⁷ , especially 5.0×10 ³ or more or 5.0×10 ⁶ or less, especially 1.0×10 ⁴ It is especially preferable that it is more than or 1.0x10< 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 , and 5.0×10 ³ to 5.0× 10 ⁶ , or 5.0×10 ³ to 1.0×10 ⁶ , more preferably 1.0×10 ⁴ to 5.0×10 ⁶ , or 1.0×10 ⁴ to 1.0×10 ⁶ most preferably.

In order to adjust E'(MA) and G'(SA) so that it may become the said relationship, what is necessary is just to adjust the characteristic of the adhesive material layer or the coating part I. 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 coating part I, for example, the presence or absence of stretching while adjusting the conditions of the material of the coating part I, such as the type of base resin, copolymer resin component, weight average molecular weight, glass transition temperature, crystallinity, etc. In the case of forming conditions and extending|stretching, it can adjust by adjusting manufacturing conditions, such as extending|stretching conditions. However, it is not limited to these methods.

Further, the coating portion I preferably has a peeling force F(C) of 0.2 N/cm or less when peeling the coating portion I from the pressure-sensitive adhesive layer in an atmosphere of 30°C.

When the peeling force F(C) is 0.2 N/cm or less, the coating portion I can be easily peeled from the pressure-sensitive adhesive layer.

From this point of view, the peeling force F(C) is preferably 0.2 N/cm or less, and more preferably 0.01 N/cm or more or 0.15 N/cm or less, and among them, 0.02 N/cm or more or 0.1 N/cm or less. It is more preferable that it is less than or equal to cm.

In the coating part I, the peeling force F (D) when the adhesive sheet laminate is heated at 100° C. for 5 minutes and then cooled to 30° C. to peel the coating part I from the pressure-sensitive adhesive layer in an atmosphere of 30° C. is 0.2 It is preferable that it is N/cm or less.

The adhesive sheet laminated body is cooled to 30 degreeC after heating at 100 degreeC for 5 minutes, and if the peeling force F(D) obtained by measuring in 30 degreeC atmosphere is the same grade as the said peeling force F(C), an adhesive sheet laminated body Since the peeling force F(D) does not change even if it is heat-molded, the said coating part I can be peeled easily from the adhesive material layer.

From this point of view, the peeling force F(D) is preferably 0.2 N/cm or less, and more preferably 0.01 N/cm or more or 0.15 N/cm or less, and particularly 0.02 N/cm or more or 0.1 N/cm or less. It is more preferable that it is less than or equal to cm.

In the coating part I, it is preferable that 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 absolute value of the difference between the peel force F (D) obtained by heating the pressure-sensitive adhesive sheet laminate at 100° C. for 5 minutes and then cooling it to 30° C. and measuring in a 30° C. atmosphere, and the peel force F (C) in the normal state If it is 0.1 N/cm or less, even if the adhesive sheet laminated body is heat-molded, since peeling force F(D) does not change, the said coating part I can be peeled easily from the adhesive material layer.

From this point of view, the absolute value of the difference between the peel force F(C) and the peel force F(D) is preferably 0.1 N/cm or less, and more preferably 0.08 N/cm or less, and more preferably 0.05 N/cm or less. Do.

In addition, the peeling force F(C) and peeling force F(D) of the coating part I can be prepared by the kind etc. of the mold release layer formed on one side of the coating part I. However, it is not limited to this method.

As a structural example of the coating part I, the structural example provided with the coating base material layer and a mold release layer is mentioned. By laminating a release layer on the single side|surface of a covering base material layer, it can comprise so that the covering part I may peel easily from an adhesive material layer.

At this time, the coating base layer is, for example, a stretched or unstretched layer mainly composed of one resin or two or more resins selected from the group consisting of polyester, copolyester, polyolefin and copolyolefin, that is, It is preferable that it is a single-layer or multi-layer provided with the layer which consists of a stretched or unstretched film which has these resin as a main component.

Among them, the coating base layer constituting the coating portion I is, from the viewpoint of mechanical strength and chemical resistance, for example, a layer made of a stretched or unstretched film containing, for example, copolyester, polyolefin, or copolyolefin as a main component. It is preferable that it is a single-layer or multi-layer having a.

Specific examples of the copolymerized polyester include copolymerized polyethylene terephthalate obtained by arbitrarily copolymerizing isophthalic acid as dicarboxylic acid, cyclohexanedimethanol, 1,4-butanediol, diethylene glycol, etc. as diols.

Specific examples of the polyolefin include α-olefin homopolymers, and examples thereof include propylene homopolymers and 4-methylpentene-1 homopolymers.

Specific examples of the polyolefin copolymer include copolymers of ethylene, propylene, and other α-olefins and vinyl monomers.

It is preferable that the said release layer sets it as a layer containing modified polyolefin other than mold release agents, such as silicone.

Here, as a modified olefin which comprises the said mold release layer, resin which has as a main component the polyolefin modified with unsaturated carboxylic acid or its anhydride, or a silane-type coupling agent is mentioned.

As said unsaturated carboxylic acid or its anhydride, the monoepoxy compound of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic acid anhydride, itaconic acid, itaconic anhydride, or a derivative thereof, and an ester of the acid compounds, and reaction products of polymers and acids having groups capable of reacting with these acids in the molecule. Moreover, these metal salts can also be used. Among these, maleic anhydride is used more preferably. In addition, these copolymers can be used individually or in mixture of 2 or more types, respectively.

In order to prepare the modified polyolefin-based resin, for example, in the step of polymerizing the polymer in advance, these modified monomers may be copolymerized, or the modified monomer may be graft copolymerized with the polymer once polymerized. In addition, as a modified polyolefin resin, these modified monomers are used individually or a plurality of them, and the content is 0.1 mass % or more, Preferably it is 0.3 mass % or more, More preferably, it is 0.5 mass % or more, 5 mass % or less , Preferably 4.5 mass % or less, More preferably, the thing in the range of 4.0 mass % or less is used suitably. Among these, what was graft-modified is used suitably.

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

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

<Cathing part Ⅱ>

As described above, in this pressure-sensitive adhesive sheet laminate, the coating part I is laminated so as to be peelable on one side of the front and back sides of the pressure-sensitive adhesive layer, and the coating part II is formed on the opposite side to the cover I, that is, on the other side of the pressure-sensitive adhesive layer, on the front and back sides so that the coating part II is peelable. It can be set as the structure formed by laminating|stacking. Thus, handling property can be improved by laminating|stacking the coating part II so that peeling is possible on the front and back other side of an adhesive material layer. However, it is also possible to set it as the structure which does not laminate|stack the covering part II.

The coating part II will not specifically limit the material and structure, as long as it is laminated|stacked so that peeling is possible on the front and back other side of an adhesive material layer.

The coating part II may have the same laminated structure and material as the coating part I, for example, and in that case, the same thickness as the coating part I or a different thickness may be sufficient as it.

If the coating part II is the same laminated structure and material as the coating part I, it can prevent that curvature arises when this adhesive sheet laminated body is heated etc.

Coating part II has the same structure as coating part I, and storage elastic modulus E'(MA) in 100 degreeC, storage elastic modulus E'(MB) in 30 degreeC, and their ratio (E'(MB)/E) '(MA)), peeling force F(C), peeling force F(D), etc. different from the coating part I may be employed.

In addition, the coating part II may have a different lamination structure and material from the said coating part I.

For coating part II, the normally used release film (it is also called a "release film") can also be used, for example. Specific examples thereof include materials having a storage elastic modulus E' (MA) of 2.0×10 ⁹ to 1.0×10 ¹¹ Pa at 100° C., for example, a biaxially stretched polyethylene terephthalate (PET) film, etc. is available.

[Cloth Ⅰ]

As a structural example of the coating part I, it is a coated film in which an application layer is provided on one side of a co-polyester film, and a storage elastic modulus E' at 100° C. is 1.5×10 ⁹ Pa or less. ') will be described.

When this coating film is used, for example, after heating the pressure-sensitive adhesive sheet laminate, by pressing a mold on the coating film provided with an application layer having releasability, the uneven shape corresponding to the uneven portion on the surface of the adherend is adhered. It can be formed with high precision on the sheet surface. Moreover, since an application film can maintain shape retention property in a state, not only handling is easy, but since it is not too hard, it can suppress giving out unnecessary unintentional unevenness to an adhesive sheet.

<Copolymerized polyester film>

The co-polyester film constituting the present application film may have a single-layer structure or a laminated structure, for example, in addition to the two-layer or three-layer structure, as long as it does not exceed the gist of the present invention, four or more multilayers may be used, and in particular It is not limited. In addition, for example, when it is set as a three-layer structure (surface layer / intermediate layer / surface layer), any one or two or more layers of the surface layer or intermediate layer are used as a copolymer polyester component, and the other layers are copolymerized components. It is also possible to comprise with the polyester component which does not contain.

In addition, after cooling the molten polyester sheet extruded by the extrusion method, a co-polyester film points out the extended|stretched film as needed.

As the dicarboxylic acid component of the co-polyester, terephthalic acid is preferable. Other than that, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and diphenyl ether dicarboxylic acid You may contain 1 or more types of well-known dicarboxylic acids, such as main acid and cyclohexanedicarboxylic acid, as a copolymerization component. Moreover, as a diol component, ethylene glycol is preferable, In addition, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, 1, 4- cyclohexane dimethanol, diethylene glycol, triethylene glycol, polyalkylene. You may contain 1 or more types of well-known diols, such as glycol and neopentyl glycol, as a copolymerization component.

Among these, copolymerized polyethylene terephthalate obtained by copolymerizing phthalic acid, isophthalic acid as a dicarboxylic acid component, and 1,4-cyclohexanedimethanol, 1,4-butanediol, diethylene glycol, etc. as a diol component is more preferable.

1 mol% or more and 50 mol% or less are preferable, as for content of a copolymerization component, 3 mol% or more or 40 mol% or less are more preferable, 4 mol% or more or 30 mol% or less are still more preferable. When content of a copolymerization component is 1 mol% or more and it laminates|stacks with an adhesive sheet, concave shape, convex shape, or uneven|corrugated shape can be formed in the adhesive sheet surface. On the other hand, when it is 50 mol% or less, it not only has sufficient dimensional stability, but can fully suppress generation|occurrence|production of the wrinkle at the time of a process.

Melting|fusing point of a co-polyester film becomes like this. Preferably it is 260 degrees C or less, It is preferable to design so that it may become the range more preferably 200-255 degreeC. When the said melting|fusing point is 260 degrees C or less, in the heat processing process after extending|stretching, it becomes possible to obtain sufficient intensity|strength also in the heat processing of the temperature lower than melting|fusing point of a co-polyester film.

It is preferable from the point of film workability improvement to contain particle|grains in a co-polyester film. Examples of the particles include inorganic particles such as calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, lithium fluoride, aluminum oxide, silicon oxide, and kaolin; organic particles such as acrylic resin and guanamine resin; Precipitation particles obtained by granulating catalyst residues can be mentioned, but are not limited thereto. The particle diameter of these particle|grains and content in a co-polyester film can be suitably determined according to the objective. A single component may be sufficient as the particle|grains to contain, and two or more components may be used simultaneously. In addition, various stabilizers, lubricants, antistatic agents and the like may be appropriately added.

As for the average particle diameter of the particle|grains contained in a co-polyester film, 0.1-5.0 micrometers is preferable. When the average particle diameter of the said particle|grains is less than 0.1 micrometer, the sliding property of a film may become inadequate and workability|operativity may fall. On the other hand, when the average particle diameter of the said particle|grains exceeds 5.0 micrometers, the smoothness of the film surface may be impaired.

As for content of the particle|grains contained in a co-polyester film, 0.01 to 0.3 weight% is preferable. When content of the said particle|grains is less than 0.01 weight%, the sliding property of a film may become inadequate and workability|operativity may fall. On the other hand, when content of the said particle|grains exceeds 0.3 weight%, the smoothness of the film surface may be impaired.

It does not specifically limit as a method of adding particle|grains in a co-polyester film, A well-known method is employable. For example, it can be added in any step of producing the polyester, but is preferably added as a slurry dispersed in ethylene glycol or the like in the step of esterification or before the start of the polycondensation reaction after completion of the ester exchange reaction and polycondensation. You may advance a sum reaction. In addition, a method of blending a polyester raw material with a slurry of particles dispersed in ethylene glycol or water using a kneading extruder equipped with a vent, or a method of blending dried particles and a polyester raw material using a kneading extruder , a method of precipitating particles in a polyester manufacturing process system, or the like.

The intrinsic viscosity of the copolyester is usually 0.40 to 1.10 dl/g, preferably 0.45 to 0.90 dl/g, and 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, and when the intrinsic viscosity exceeds 1.10 dl/g, the melt viscosity becomes high and an excessive load is applied to the extruder in some cases.

Next, although the manufacture example of a co-polyester film is demonstrated concretely, it is not limited at all to the following manufacture examples.

First, the method of using the co-polyester raw material mentioned above and cooling and solidifying the molten sheet extruded from die|dye 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 increase the adhesion between the sheet and the rotating cooling drum, and an electrostatic application adhesion method and/or a liquid application adhesion method is preferably employed.

Next, the obtained unstretched sheet is preferably stretched in at least one axial direction, and more preferably biaxially stretched in the biaxial direction. For example, as biaxial stretching, in the case of sequential biaxial stretching, the unstretched sheet is stretched in one direction by a roll or tenter type stretching machine in the machine direction. Extending temperature is 70-120 degreeC normally, Preferably it is 75-110 degreeC, and a draw ratio is 2.5-7.0 times normally, Preferably it is 3.0-6.0 times. Next, it extends in a direction perpendicular to the stretching direction (machine direction) of one end. Extending temperature is 70-170 degreeC normally, and a draw ratio is 3.0-7.0 times normally, Preferably it is 3.5-6.0 times. Then, heat treatment is performed under tension or less than 30% relaxation at a temperature of 150 to 270° C. to obtain a biaxially oriented film. In the above-mentioned biaxial stretching, the method of performing extending|stretching in one direction in two or more steps is also employable. In that case, it is preferable to finally carry out so that the draw ratio of two directions may become the said range, respectively.

Moreover, simultaneous biaxial stretching can also be employ|adopted regarding manufacture of a co-polyester film. Simultaneous biaxial stretching is a method in which the unstretched sheet is oriented by stretching it at the same time in the machine direction and the width direction in a temperature controlled state at usually 70 to 120°C, preferably 75 to 110°C. As a draw ratio, Preferably it is 4 to 50 times in area magnification, More preferably, it is 7 to 35 times, More preferably, it is 10 to 25 times. Then, heat treatment is performed under tension or less than 30% relaxation at a temperature of 150 to 250° C. to obtain a biaxially oriented film. Regarding the simultaneous biaxial stretching apparatus employing the above-described stretching method, conventionally known stretching methods such as a screw method, a pantograph method, and a linear drive method can be adopted.

(coating layer)

In this application film, it is important to provide an application layer in at least single side|surface of a co-polyester film. Although limitation in particular is not carried out as an application layer, A mold release layer, an antistatic layer, an oligomer sealing layer, an easily adhesive layer, a primer layer, etc. are mentioned concretely. Especially, in manufacturing the adhesive sheet and the laminated|stacked adhesive sheet laminated body, 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 application layer which comprises an application film, a mold release layer is demonstrated below.

Although a curable silicone resin, a fluorine-type resin, polyolefin resin etc. are mentioned specifically, the kind of resin used for a mold release layer, Among these, a curable silicone resin is preferable. The curable silicone resin may also be a type containing a curable silicone resin as a main component, and within the scope not impairing the gist of the present invention, a modified silicone type by graft polymerization with an organic resin such as a urethane resin, an epoxy resin, or an alkyd resin, etc. may be used.

As the kind of the curable silicone resin, any curing reaction type, such as addition type, condensation type, ultraviolet curing type, electron beam curing type, and solvent-free type, can be used. For example, Shin-Etsu Chemical Co., Ltd. KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-856, X-62-2422, X-62-2461, X-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; Momentive Performance Materials YSR-3022, TPR-6700, TPR-6720, TPR-6721, TPR6500, TPR6501, UV9300, UV9425, XS56-A2775, XS56-A2982, UV9430, TPR6600, TPR6604, TPR6605; Toray Dow Corning Co., Ltd. SRX357, SRX211, SD7220, SD7292, LTC750A, LTC760A, LTC303E, SP7259, BY24-468C, SP7248S, BY24-452, DKQ3-202, DKQ3-203, DKQ3-204, DKQ3-205, DKQ3-210 and the like are exemplified. Moreover, in order to adjust the peelability of a mold release layer, etc., you may use together a peeling control agent.

Curing conditions at the time of forming a mold release layer on a co-polyester film are not specifically limited. In the case of providing the release layer by offline coating, it is usually good to perform heat treatment at 120 to 200 ° C. for 3 to 40 seconds, preferably at 100 to 180 ° C. for 3 to 40 seconds as a reference. Moreover, you may use together heat processing and active energy ray irradiation, such as ultraviolet irradiation, as needed. In addition, as an energy source for hardening by active energy ray irradiation, a conventionally well-known apparatus and an energy source can be used. The coating amount (after drying) of the release layer is usually in the range of 0.005 to 1 g/m2, preferably 0.005 to 0.5 g/m2, more preferably 0.01 to 0.2 g/m2 in terms of coatability. When the coating amount (after drying) is less than 0.005 g/m 2 , it may be inferior to stability in terms of coatability and difficult to obtain a uniform coating film. On the other hand, in the case of applying a thick coating exceeding 1 g/m 2 , the coating film adhesion and curability of the release layer itself may be deteriorated.

As a method of providing the release layer on the co-polyester film, a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, and curtain coating can be used. Regarding the coating method, there is an example of description in "Coating method" (Maki Bookstore, Yuji Harasaki, published in 1979).

Moreover, in order to provide an application layer, such as a corona treatment, a plasma treatment, and ultraviolet irradiation treatment, to a co-polyester film previously, you may surface-treat.

(applied film)

The thickness of this application film is 9 micrometers - 250 micrometers normally, Preferably they are 12 micrometers - 125 micrometers, More preferably, they are 25 micrometers - 75 micrometers.

When the said thickness is less than 9 micrometers, the film tension becomes inadequate, and problems, such as a wrinkle being easy to enter at the time of a slit, may arise. On the other hand, when it exceeds 250 micrometers, the followability to the molded article which has a curved shape may become inadequate, for example.

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 said storage elastic modulus E' is 1.5x10 ⁹ Pa or less, when laminating|stacking with an adhesive sheet, a concave shape, a convex shape, or an uneven|corrugated shape can be formed in the adhesive sheet surface. In order for storage elastic modulus E' in 100 degreeC to satisfy the said range, it can satisfy by adjusting the kind and content of the copolymerization component contained in a co-polyester film.

On the other hand, although limitation in particular is not carried out as a lower limit, 1.0x10 ⁷ Pa or more is preferable, and 1.0x10 ⁸ Pa or more is more preferable.

The shrinkage rate after heating at 120 degreeC for 5 minutes of this application film is 3.0 % or less, and 2.5 % or less is preferable. When the shrinkage ratio is 3.0% or less, sufficient dimensional stability is obtained. Therefore, when laminating with an adhesive sheet, a concave shape, a convex shape, or an uneven shape can be formed on the adhesive sheet surface. Moreover, since generation|occurrence|production of wrinkles at the time of processing can be suppressed, wrinkles are not transferred to an adhesive sheet, but the adhesive sheet which has a sufficient external appearance can be manufactured.

Among them, 3.0% or less is preferable and, as for the shrinkage rate in the machine direction (MD) after heating at 120 degreeC for 5 minutes, 2.5% or less is preferable. On the other hand, although limitation in particular is not carried out as a minimum, 0.1 % or more is preferable and 0.5 % or more is more preferable.

Further, the shrinkage ratio 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, as a lower limit, -1.0 % or more is preferable, and -0.5 % or more is more preferable.

From the viewpoint of preventing contamination due to adhesion of oligomers (cyclic trimers) to the mold during molding processing, after heat treatment (180° C. for 10 minutes), the amount of oligomer extracted from the coating layer surface is 1.0. It is preferably x10 ^-3 mg/cm 2 or less, and more preferably 5.0 x 10 ^-4 mg/cm 2 or less.

When the extraction amount of the oligomer exceeds the range, contamination due to adhesion of the oligomer to the mold may become severe during molding. As an example, in a process in which heating is performed several times continuously, since mold contamination is promoted by deposition of the precipitated oligomer, control of the amount of oligomer precipitated during heating becomes important. For the above reason, the smaller the amount of the oligomer extracted, the more preferable.

[Method for producing this adhesive sheet laminate]

As an example of the manufacturing method of this adhesive sheet laminated body, the method of sandwiching the adhesive composition with two sheets of the coating part I or II, and forming an adhesive material layer using a laminator is mentioned, for example. Moreover, as another method, the method of apply|coating an adhesive composition to the coating part I or II, and forming an adhesive material layer is mentioned. However, it is not limited to such a manufacturing method.

As a method of apply|coating an adhesive composition, conventionally well-known coating methods, such as reverse roll coating, gravure coating, bar coating, and doctor blade coating, are mentioned, for example.

[This molded adhesive sheet laminate]

Using this PSA sheet laminate, a shaped pressure-sensitive adhesive sheet laminate 1 (referred to as “this shaped pressure-sensitive adhesive sheet laminate 1”) having an uneven shape on the surface of the pressure-sensitive adhesive layer can be produced as follows.

As shown in Fig. 3, this molded pressure-sensitive adhesive sheet laminate 1 includes a pressure-sensitive adhesive layer 2, a covering portion I that is laminated so as to be peelable on one side of the front and back sides of the pressure-sensitive adhesive layer 2, and the pressure-sensitive adhesive layer ( 2) on the front and back sides of the other side is provided with the coating part II, which is laminated so as to be peelable,

The pressure-sensitive adhesive layer 2 has concave portions, convex portions, or uneven portions (referred to as “adhesive sheet surface uneven portion 2B”) on the front and back surfaces 2A, and the front and back surfaces 2C are flat. is cotton,

The coating part I is in close contact with the front and back one side surfaces 2A of the adhesive material layer 2, and is concave, convex, or uneven on the front and back one side surfaces 3A (referred to as “coated surface unevenness 3B”). a convex portion, a concave portion, or a concave-convex portion (“protective sheet It is provided with a back surface uneven part (3D)";

The coating part II can be set as the thing provided with the structure which consists of a flat surface along 2C of front and back other side surfaces of the said adhesive material layer 2 .

In addition, as shown in FIG. 3, 2 C of front and back other side surfaces can also be set as a flat surface, and can also be formed so that 2 C of front and back other side surfaces may be provided with a recessed part, a convex part, or an uneven|corrugated part.

As shown in FIG. 2, this molded adhesive sheet laminated body 1 provided with such a structure is this adhesive sheet laminated body by press molding, vacuum molding, pressure forming, or roll molding, It can manufacture by shaping|molding an uneven|corrugated shape integrally with respect to a sheet|seat laminated body.

By manufacturing in this way, the pressure-sensitive adhesive sheet surface concavo-convex portion 2B of the pressure-sensitive adhesive layer 2, the coated surface concave-convex portion 3B of the covering portion I, and the protective sheet back surface concavo-convex portion 3D correspond to the same location, respectively. It can be done by making

The pressure-sensitive adhesive layer 2 can be used, for example, as a double-sided pressure-sensitive adhesive sheet for bonding two image display device structural members (each referred to as "adherent body") constituting an image display device.

That is, the pressure-sensitive adhesive sheet surface concavo-convex portion 2B in the pressure-sensitive adhesive layer 2 is a concave portion, convex portion, or concave-convex portion (“to It can be formed in the same outline shape so as to conform to the complex surface concavo-convex portion”). Therefore, it can be made to fit the adhesive sheet surface uneven|corrugated part 2B in this shaped adhesive sheet laminated body 1 with respect to the to-be-adhered body surface uneven|corrugated part in the image display apparatus structural member as a to-be-adhered body.

Here, as the image display device, for example, a smart phone equipped with a liquid crystal display device (LCD), an organic EL display device (OLED), electronic paper, a microelectromechanical system (MEMS) display, a plasma display (PDP), etc. , tablet terminals, mobile phones, televisions, game machines, personal computers, car navigation systems, ATMs, fish finder, and the like. However, it is not limited to these.

In addition, the image display apparatus structural member as a to-be-adhered body is a member which comprises these image display apparatuses, For example, a surface protection panel, a touch panel, an image display panel, etc. are mentioned, This shaped adhesive sheet laminated body 1 ) can be used for bonding together any two to-be-adhered bodies chosen from a surface protection panel, a touch panel, and an image display panel, for example. For example, it can be used in order to bond together a surface protection panel and a touchscreen, or a touchscreen and an image display panel. However, the adherend is not limited to these.

<Production method>

Here, the detail of the manufacturing method of this shaping|molding adhesive sheet laminated body 1 is demonstrated.

As mentioned above, as shown in FIG. 2, it can manufacture by shaping|molding the uneven|corrugated shape integrally with respect to this adhesive sheet laminated body 1 by heating and shape|molding this this adhesive sheet laminated body.

At this time, as a shaping|molding process method, press molding, vacuum forming, air pressure forming, shaping by roll, shaping by lamination, etc. can be suggested, for example. Among them, press molding is particularly preferable from the viewpoint of formability and workability.

A more detailed specific example is demonstrated.

This pressure-sensitive adhesive sheet laminate is preheated with a heater, and the pressure-sensitive adhesive sheet laminate is transferred to a press molding machine at a stage where it has been warmed to a predetermined temperature, and is pressed with a mold simulating the concavo-convex shape corresponding to the printed step shape of the adherend in advance. By cooling while processing, the mold shape can be transcribe|transferred to the single side|surface of this adhesive sheet laminated body, and the this shape adhesive sheet laminated body 1 by which the uneven|corrugated shape was carried out in single side|surface can be manufactured.

At this time, it is preferable that the preheating of this adhesive sheet laminated body heats to the temperature at which an adhesive material layer softens, specifically, to 70-120 degreeC.

The material of the mold used for the concavo-convex shaping is not particularly limited. For example, resin-type materials, such as a silicone resin and a fluororesin, metallic materials, such as stainless steel and aluminum, etc. are mentioned. Among them, since high-precision moldability is required for the uneven shaping of an adherend, a metal mold capable of controlling the temperature during molding is particularly preferable.

In addition, cooling after press working may be cooled after mold opening, and a metal mold|die may be cooled, and you may make it cool simultaneously with a press.

In the present invention, conditions for molding such as press pressure and press time are not particularly specified, and may be appropriately adjusted depending on the size and shape to be molded, the material to be used, and the like.

Moreover, you may cut using a Thompson blade, a rotary blade, etc. after a shaping|molding process.

[Method for producing this shaped adhesive sheet laminate]

Next, a pressure-sensitive adhesive layer and a covering portion I formed by laminating peelably on one surface of the pressure-sensitive adhesive layer is provided, and on one surface of the pressure-sensitive adhesive layer, concave portions, convex portions, or uneven portions (referred to as “adhesive material layer surface unevenness”) ), the especially preferable aspect of the manufacturing method of the shaping|molding adhesive sheet laminated body provided with the structure formed by shaping is demonstrated.

In the present invention related to the present manufacturing method 1 and the present manufacturing method 2, which will be described later, it is possible to form the surface uneven portions of the pressure-sensitive adhesive layer matching the uneven portions on the surface of the present adherend with high precision on the surface of the pressure-sensitive adhesive material layer, and preferably continuously. It is to propose a method for manufacturing a new shaped pressure-sensitive adhesive sheet laminate.

As an example of the embodiment of the present invention, a pressure-sensitive adhesive layer and a covering portion I formed by laminating peelably on one surface of the pressure-sensitive adhesive layer is provided, and a concave portion, convex portion, or uneven portion (“adhesive material layer”) is provided on one surface of the pressure-sensitive adhesive material layer. A method for manufacturing a shaped pressure-sensitive adhesive sheet laminate having a configuration in which the surface uneven portion is shaped), comprising: a pressure-sensitive adhesive layer; In the manufacturing method for producing a shaped adhesive sheet laminate by heating a laminate and molding the heated adhesive sheet laminate together with cooling, the adhesive sheet laminate is heated and the storage elastic modulus E' (MS ) is 1.0×10 ⁶ to 2.0×10 ⁹ Pa, starting molding, and ending molding when the storage modulus E′ (MF) of the coating part I is 5.0×10 ⁷ to 1.0×10 ¹⁰ Pa. A new manufacturing method (referred to as "the present manufacturing method 1") of a new shaped pressure-sensitive adhesive sheet laminate is proposed.

In this manufacturing method 1, also, in the manufacturing method of the said new shaped adhesive sheet laminated body, when shaping|molding a heated adhesive sheet laminated body, it is proposed to shape|mold using a cooled mold.

According to the present manufacturing method 1, for example, after heating the pressure-sensitive adhesive sheet laminate, the coating part I starts molding in a predetermined state, and the coating part I ends molding in the predetermined state, so that the adherend is A concave-convex shape matching the concavo-convex portion of the surface can be formed with high precision on the surface of the adhesive material layer.

Further, when the heated pressure-sensitive adhesive sheet laminate is molded, if it is molded using a cooled mold, cooling can be performed simultaneously with the molding and can be finished at the same time, so that the above-mentioned manufacturing method can be continuously performed.

<This manufacturing method 1>

In this manufacturing method 1, the manufacturing method (referred to as "the present manufacturing method") of the shaping adhesive sheet laminated body which concerns on an example of this embodiment heats the adhesive sheet laminated body mentioned later (heating process), The heated adhesion It is a manufacturing method provided with the process of cooling (forming and cooling process) together with shape|molding of a sheet|seat laminated body.

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 processing 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 the starting member in the present manufacturing method 1 may include a pressure-sensitive adhesive layer and a covering portion I formed by laminating peelably on one surface of the pressure-sensitive adhesive layer, and may include another member. For example, as shown in FIG. 1 , an adhesive material layer, a coating part I formed so as to be peelably laminated on one side of the front and back sides of the adhesive layer, and a coating part II formed by being peelably laminated on the other side of the adhesive material layer on the front and back sides. One PSA sheet laminate can be exemplified. However, whether or not the covering part II is provided is arbitrary, and it is good also as a structure in which the covering part II is not laminated|stacked.

In addition, it is as above-mentioned about the detail of an adhesive sheet laminated body.

(heating process)

In this manufacturing method 1, it is preferable to heat the said adhesive sheet laminated body, and to set it as the state in which the storage elastic modulus E'(M) of the coating part I is 1.0x10 ⁶ -2.0x10 ⁹ Pa.

If the storage elastic modulus E'(M) of the coating part I is within the above range, it becomes possible to deform the coating part I to a degree suitable for molding, and also to shape the desired concave-convex shape on the surface of the pressure-sensitive adhesive material layer with good precision. do.

From this point of view, the pressure-sensitive adhesive sheet laminate is preferably heated so that the storage elastic modulus E' (M) of the coating portion I is 1.0×10 ⁶ to 2.0×10 ⁹ Pa, and among them, 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, heating the adhesive sheet laminate and setting the storage modulus E'(M) of the coating part I to a state of 1.0×10 ⁶ to 1.0×10 ⁹ Pa or 1.0×10 ⁶ to 5.0×10 ⁸ more preferably, among them, 5.0×10 ⁶ to 2.0×10 ⁹ Pa, or 5.0×10 ⁶ to 1.0×10 ⁹ Pa, more preferably 1.0×10 ⁷ to 1.0×10 ⁹ Pa, Alternatively, it is most preferable to set it as 1.0×10 ⁷ to 5.0×10 ⁸ .

Here, in order to adjust the storage elastic modulus E' (M) of the coating part I by heating the adhesive sheet laminate to be within the above range, depending on the composition, gel fraction, weight average molecular weight, etc. of the composition constituting the coating part I, It can be adjusted by adjusting the heating temperature. However, it is not limited to this method.

Further, by heating the adhesive sheet laminate, the storage elastic modulus E'(M) of the coating part I is 1.0×10 ⁶ to 2.0×10 ⁹ Pa, and the storage elastic modulus G'(S) of the adhesive material layer is 1.0× It is still more preferable to set it as the state of less than 10 ⁴ Pa.

If the storage elastic modulus E'(M) of the coating part I is adjusted to the above range, in addition to that the effects as described above can be obtained, if the storage elastic modulus G'(S) of the pressure-sensitive adhesive layer is less than 1.0×10 ⁴ Pa , sufficient moldability can be imparted to the pressure-sensitive adhesive layer.

From this point of view, the pressure-sensitive adhesive sheet laminate is heated, so that the storage elastic modulus E'(M) of the coating part I is in the above range, and the storage elastic modulus G'(S) of the pressure-sensitive adhesive layer is less than 1.0×10 ⁴ Pa , in particular, it is preferably in a state of 5.0×10 ¹ Pa or more or 5.0×10 ³ Pa or less, and particularly preferably in a state of 1.0×10 ² Pa or more or 1.0×10 ³ Pa or less.

From the above, by heating the adhesive sheet laminate, the storage elastic modulus E'(M) of the coating part I is a state in the said range, and the storage elastic modulus G'(S) of the adhesive material layer is 5.0x10 ¹ Pa or more 1.0 ×10 ⁴ Pa or more, or 5.0 × 10 ¹ Pa or more and 5.0 × 10 ³ Pa or less is more preferable, and among them, 1.0 × 10 ² Pa or more and less than 1.0 × 10 ⁴ Pa, or 1.0 × 10 ² More preferably, it is set to be in a state of Pa or more and 5.0×10 ³ Pa or less, and most preferably in a state of 1.0×10 ² Pa or more and 1.0×10 ³ Pa or less.

Here, the storage elastic modulus G'(S) of an adhesive material layer can be adjusted by adjusting a heating temperature according to the component, a gel fraction, a weight average molecular weight, etc. of the composition which comprises an adhesive material layer. However, it is not limited to such a method.

In addition, 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. Incidentally, the loss tangent tan δ of the pressure-sensitive adhesive layer will be described later.

When the value of the loss tangent tanδ of the pressure-sensitive adhesive layer is 1.0 or more, it is preferable because it has flexibility to the extent that it can 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 tanδ of the pressure-sensitive adhesive layer is 1.0 or more, and among them, 1.5 or more or 20 or less, and more particularly, 3.0 or more or 10 or less. it is more preferable However, the upper limit is not limited thereto.

In this manufacturing method 1, it is preferable to heat the adhesive sheet laminated body so that the surface temperature of the coating part I may become 70-180 degreeC.

If the surface temperature of the coating part I is 70°C or higher, the adhesive layer is sufficiently softened, and the coating part I can be sufficiently deformable, and if it is 180°C or lower, wrinkles due to heat shrinkage or heat Since harmful effects, such as decomposition|disassembly of an adhesive material layer, can be suppressed, it is preferable.

From this point of view, it is preferable to heat the pressure-sensitive adhesive sheet laminate so that the surface temperature of the coating portion I is 70 to 180°C, and among them, 75°C or more or 150°C or less, and especially 80°C or more or 120°C or less It is more preferable to become

As a heating method of the pressure-sensitive adhesive sheet laminate, for example, a method in which the pressure-sensitive adhesive sheet laminate is placed between upper and lower heating plates having a heating element such as an electric heater therein and heated from the top and bottom, a method of directly sandwiching with a heating plate, heating The method using a roll, the method of immersing in hot water, etc. are mentioned. However, it is not limited to these methods.

(Forming/cooling process)

At this process, the adhesive sheet laminated body heated as mentioned above is shape|molded, and it cools together with shape|molding of an adhesive sheet laminated body. That is, the pressure-sensitive adhesive sheet laminate in a state in which the pressure-sensitive adhesive layer and the coating portion I are laminated and integrated are molded as they are. Accordingly, the coating part I is molded by the mold, and the pressure-sensitive adhesive layer is also molded through the coating part I at the same time.

At this process, after shape|molding the heated adhesive sheet laminated body, you may cool, and you may cool simultaneously with shaping|molding. For example, by pressing with a cooled die, molding and cooling can be performed simultaneously and can be completed simultaneously. Thereby, as described later, the present manufacturing method 1 can be continuously carried out.

The molding method is not particularly limited as long as the concavo-convex shape can be integrally formed on the pressure-sensitive adhesive sheet laminate. For example, press forming, vacuum forming, air pressure forming, shaping by a roll, compression molding, shaping by lamination, and the like can be given. Among them, press molding is particularly preferable from the viewpoint of formability and workability.

The material of the mold is not particularly limited. For example, resin-type materials, such as a silicone resin and a fluororesin, metallic materials, such as stainless steel and aluminum, etc. are mentioned. Among them, since high-precision moldability is required for concave-convex shaping of an adherend, a metal mold capable of controlling the temperature during molding is particularly preferable.

As the cooling means of the mold, a cooling means usually used can be employed. For example, the cooling means by water cooling or compressed air is mentioned.

For example, as shown in Fig. 2, the mold has a predetermined concave-convex shape on the inner wall surface of at least one of a pair of molds to be opened and closed, for example, a bonded surface of an adherend to which a pressure-sensitive adhesive layer is adhered (the Adhesive by providing a concave-convex shape corresponding to the concave or convex or concave and convex portions in the “joint surface”), and press-molding, vacuum-forming, air-forming or roll molding the pressure-sensitive adhesive sheet laminate using the mold. The concave-convex shape may be transferred to the sheet laminate to shape it.

In this process, as mentioned above, it is preferable to start shaping|molding in the state whose storage elastic modulus E' (MS) of the coating|covering part I in an adhesive sheet laminated body is 1.0x10 ⁶ -2.0x10 ⁹ Pa. .

Here, in the case of molding using a mold, for example, "starting molding" means closing the mold, ie, starting pressurization of the pressure-sensitive adhesive sheet laminate with the mold.

When the storage modulus E' (MS) of the coating part I is in the range of 1.0×10 ⁶ to 2.0×10 ⁹ Pa, it becomes possible to deform the coating part I to a degree suitable for molding, and also It becomes possible to shape the concavo-convex shape with good precision.

From this point of view, it is preferable to start molding the pressure-sensitive adhesive sheet laminate in a state where the storage modulus E' (MS) of the coating part I is 1.0×10 ⁶ to 2.0×10 ⁹ Pa, and among them, 5.0×10 ⁶ Pa or more. Alternatively, it is still more preferable to start molding in a state of 1.0×10 ⁹ Pa or less, particularly, in a state of 1.0×10 ⁷ Pa or more or 5.0×10 ⁸ Pa or less.

From the above, the storage elastic modulus E' (MS) of the coating part I starts shaping|molding of the adhesive sheet laminated body in the state which is 1.0×10 ⁶ to 1.0×10 ⁹ Pa or 1.0×10 ⁶ to 5.0×10 ⁸ Pa. More preferably, it is more preferable to start molding in a state of 5.0×10 ⁶ to 1.0×10 ⁹ Pa, or 5.0×10 ⁶ to 5.0×10 ⁸ Pa, and more preferably 1.0×10 ⁷ to 1.0 It is most preferable to start molding in the state of ×10 ⁹ Pa, or 1.0 × 10 ⁷ to 5.0 × 10 ⁸ Pa.

In addition, the storage elastic modulus E' (MS) of the coating part I is 1.0×10 ⁶ to 2.0×10 ⁹ Pa, and the adhesive sheet is laminated in a state where the storage elastic modulus G' (SS) of the pressure-sensitive adhesive layer is less than 1.0×10 ⁴ Pa It is still more preferable to start shaping the sieve.

In addition to that the effect as described above can be obtained when molding is started in a state where the storage modulus E' (MS) of the coating part I is within the above range, the storage modulus G' (SS) of the pressure-sensitive adhesive layer is 1.0×10 ⁴ When molding is started in a state of less than Pa, the pressure-sensitive adhesive layer can be molded in a state having more sufficient moldability.

From this point of view, the storage modulus E' (MS) of the coating part I is in the above range, and the storage modulus G' (SS) of the pressure-sensitive adhesive layer is less than 1.0×10 ⁴ Pa, in particular, the G' (SS ) is more preferably 5.0×10 ¹ Pa or more or 5.0×10 ³ Pa or less, and more preferably starts molding in a state where it is 1.0×10 ² Pa or more or 1.0×10 ³ Pa or less.

From the above, the storage elastic modulus E' (MS) of the coating part I is in the state of the said range, and the storage elastic modulus G' (SS) of the adhesive material layer is 5.0 × 10 ¹ Pa or more and less than 1.0 × 10 ⁴ Pa, or, It is more preferable to start molding in a state of 5.0×10 ¹ Pa or more and 5.0×10 ³ Pa or less, and among them, 1.0×10 ² Pa or more and 1.0×10 ⁴ Pa or more, or 1.0×10 ² Pa or more and 5.0×10 It is more preferable to start molding in a state of ³ Pa or less, and it is most preferable to start molding in a state of 1.0×10 ² Pa or more and 1.0×10 ³ Pa or less.

In addition, it is preferable to start molding in a state where the surface temperature of the coating part I is 70 to 180°C.

If the surface temperature of the coating part I is 70°C or higher, the pressure-sensitive adhesive layer is sufficiently softened, and the coating part I can be sufficiently deformable, and if it is 180°C or lower, wrinkles due to heat shrinkage or heat It is preferable because harmful effects such as decomposition of the pressure-sensitive adhesive layer can be suppressed.

Therefore, it is preferable to start molding in a state where the surface temperature of the coating part I is 70 to 180°C, and it is more preferable to set it to 75°C or more or 150°C or less, and especially 80°C or more or 120°C or less. Do.

On the other hand, in this step, it is preferable to end the molding in a state where the storage elastic modulus E' (MF) of the coating part I is 5.0×10 ⁷ to 1.0×10 ¹⁰ Pa.

Here, "finishing shaping|molding" means ending applying a shaping|molding pressure with respect to an adhesive sheet laminated body, and in the case of metal mold|die shaping|molding, it means opening a metal mold|die.

The storage modulus E' (MF) of the coating part I is preferably in the range of 5.0×10 ⁷ Pa or more and 1.0×10 ¹⁰ Pa or less from the viewpoint of excellent shape stability after molding.

From this point of view, it is preferable to end the molding in a state where the storage modulus E' (MF) of the coating part I is 5.0×10 ⁷ to 1.0×10 ¹⁰ Pa, and among them, 1.0×10 ⁸ Pa or more or 8.0×10 It is still more preferable to end the molding in a state of ⁹ Pa or less, particularly, in a state of 1.0×10 ⁹ Pa or more or 5.0×10 ⁹ Pa or less.

From the above, in this step, molding is finished in a state where the storage elastic modulus E' (MF) of the coating part I is 5.0×10 ⁷ to 8.0×10 ⁹ Pa, or 5.0×10 ⁷ to 5.0×10 ⁹ Pa. More preferably, it is more preferable to finish molding in a state of 1.0×10 ⁸ to 8.0×10 ⁹ Pa, or 1.0×10 ⁸ to 5.0×10 ⁹ Pa, among others, and 1.0×10 ⁹ to 8.0× It is most preferable to finish molding in a state of 10 ⁹ Pa, or 1.0×10 ⁹ to 5.0×10 ⁹ Pa.

In addition, it is further preferable to terminate molding when the storage elastic modulus E' (MF) of the coating part I is in the above range, and the storage elastic modulus G' (SF) of the pressure-sensitive adhesive layer is 1.0 × 10 ⁴ Pa or more. desirable.

In addition to that the effect as described above can be obtained when molding is finished in a state where the storage modulus E' (MF) of the coating part I is within the above range, the storage modulus G' (SF) of the pressure-sensitive adhesive layer is 1.0×10 When molding is finished in a state of ⁴ Pa or more, the molded adhesive layer can maintain its shape.

From this point of view, when the storage elastic modulus E' (MF) of the coating part I is in the above range, and the storage elastic modulus G' (SF) of the pressure-sensitive adhesive layer is 1.0×10 ⁴ Pa or more, the molding is terminated Preferably, among them, the storage elastic modulus G' (SF) of the adhesive layer is 5.0×10 ⁴ Pa or more or 5.0×10 ⁷ Pa or less, especially 1.0×10 ⁴ Pa or more or 1.0×10 ⁷ Pa or less. It is more preferable to end

In addition, it is preferable to finish molding in a state where the surface temperature of the coating portion I is lower than 50°C. For example, in the case of press molding, it is preferable to mold-open a metal mold|die in the state which surface temperature became less than 50 degreeC.

If the surface temperature of the coated part I is less than 50° C. and the storage elastic modulus E' (MF) of the coated part I is in the range of 5.0×10 ⁷ to 1.0×10 ¹⁰ Pa, it is deformed when the molded article is taken out after the molding is finished, or the coated portion It is preferable because it can suppress that the curvature accompanying thermal contraction of I can be suppressed.

From this point of view, it is preferable to end the molding in a state in which the surface temperature of the coating part I is less than 50°C, especially in a state in which it is 0°C or more or 45°C or less, and especially in a state in which it is 10°C or more or 40°C or less. Do.

In addition, it is preferable that the storage elastic modulus E' (MS) of the coating part I at the start of the molding and the storage elastic modulus E' (MF) of the coating part I at the end of the molding satisfy the following relational expression (1).

(One)… E'(MF)/E'(MS)≥1.3

Here, if the storage elastic modulus E' (MS) of the coating part I and the storage elastic modulus E' (MF) of the coating part I at the end of the molding satisfy the above relational expression (1), at the start of molding, when the storage elastic modulus E' (MS) Moreover, it is preferable because it has hardness enough to maintain the shape|molded shape after completion|finish of shaping|molding.

From this point of view, it is preferable that E'(MF)/E'(MS)≥1.3, and among them, 100≥E'(MF)/E'(MS) or E'(MF)/E'(MS)≥1.3 It is more preferable that it is 3.0, and among these, it is especially preferable that 50≧E'(MF)/E'(MS) or E'(MF)/E'(MS)≧5.0. However, the upper limit of E'(MF)/E'(MS) is not limited thereto.

In addition, it is preferable that the storage modulus E' (MF) of the coating part I at the end of the molding and the storage modulus G' (SF) of the pressure-sensitive adhesive layer at the end of the molding satisfy the following relational expression (2).

(2)… E'(MF)/G'(SF)≤1.0×10 ⁷

Here, when the storage elastic modulus E' (MF) of the coating part 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 above relation (2), the molded adhesive material layer This shape can be maintained.

From this point of view, it is preferable that E'(MF)/G'(SF)≤1.0×10 ⁷ , and among them, 1.0≤E'(MF)/G'(SF) or E'(MF)/G'( SF) ≤ 5.0×10 ⁶ , more preferably 1.0×10 ¹ ≤ E'(MF)/G'(SF) or E'(MF)/G'(SF) ≤ 1.0×10 ⁶ .

Although it is repeated, in this manufacturing method 1, you may press mold with a metal mold|die, and you may cool after mold opening, or you may make it cool at the same time as press molding by cooling a metal mold|die. In this way, if the mold is cooled and cooled simultaneously with press molding, cooling can be completed simultaneously with molding. Therefore, since a shaping adhesive sheet laminated body can be conveyed to the next process immediately after completion|finish of shaping|molding and cooling, a shaping adhesive sheet laminated body can be manufactured continuously.

In the case of cooling at the same time as molding the mold, it is preferable that the surface temperature of the mold is 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 obtained molded product is with good precision, and from the viewpoint of suppressing warpage accompanying heat shrinkage in the cooling process after molding. desirable.

Therefore, it is preferable that the surface temperature of a metal mold|die is 0-50 degreeC, Especially, it is more preferable that it is 10 degreeC or more or 40 degrees C or less, and especially 15 degreeC or more or 30 degrees C or less.

In addition, conditions related to press molding, such as a press pressure and a press time, are not specifically limited, What is necessary is just to adjust suitably according to the dimension and shape to shape|mold, the material to be used, etc.

(etc)

The shaping adhesive sheet laminate obtained in the said shaping|molding and cooling process may be wound up as it is, may be heat-processed, and may be cut to a predetermined|prescribed size and shape.

When cutting, the method of cutting using a Thompson blade, a rotary blade, etc. is mentioned, for example.

In this manufacturing method 1, it is preferable to continuously manufacture a shaping adhesive sheet laminated body.

For example, the pressure-sensitive adhesive sheet laminate is conveyed to a heating unit such as a heater, and the heating unit stops conveying for a predetermined period of time and heats or heats while conveying, and then transfers the heated pressure-sensitive adhesive sheet laminate to a forming unit. For example, it is conveyed to a molding die, and in the molding unit, for example, by pressing with a cooled die, cooling is performed at the same time as molding, and if necessary, it is conveyed to the next unit, so that a shaped pressure-sensitive adhesive sheet laminate can be continuously produced. there is.

<This manufacturing method 2>

As an example of the embodiment of the present invention, a pressure-sensitive adhesive layer and a covering portion I formed by laminating peelably on one surface of the pressure-sensitive adhesive layer is provided, and a concave portion, convex portion, or uneven portion (“adhesive material layer”) is provided on one surface of the pressure-sensitive adhesive material layer. A method for manufacturing a shaped pressure-sensitive adhesive sheet laminate having a configuration in which the surface uneven portion is shaped), wherein the pressure-sensitive adhesive sheet includes a pressure-sensitive adhesive layer and a covering portion I that is peelably laminated on one surface of the pressure-sensitive adhesive layer. In the manufacturing method of heating a laminated body, and shaping|molding the heated adhesive sheet laminated body with a metal mold|die to manufacture a shaped adhesive sheet laminated body, the adhesive sheet laminated body is heated, and the surface temperature of the coating part I is 70-180 degreeC. A manufacturing method of a shaped pressure-sensitive adhesive sheet laminate, characterized in that molding is started in the phosphorus state, and the shaped pressure-sensitive adhesive sheet laminate is taken out from the mold after the surface temperature of the coating part I becomes less than 60°C (referred to as “this manufacturing method 2”) called) is suggested.

According to the present manufacturing method 2, the pressure-sensitive adhesive sheet laminate is heated, molding is started in a state where the surface temperature of the coating part I is 70 to 180° C., and after the surface temperature of the coating part I becomes less than 60° C., it is molded from the mold. By taking out the pressure-sensitive adhesive sheet laminate, for example, a concave-convex shape corresponding to the concavo-convex portion on the surface of the adherend can be formed with high precision on the surface of the pressure-sensitive adhesive material layer.

This manufacturing method 2 is a manufacturing method provided with the process of heating the adhesive sheet laminated body mentioned later (heating process), and shape|molding the heated adhesive sheet laminated body, and cooling (molding/cooling process).

The present manufacturing method 2 may include other steps as long as the heating step and the forming/cooling step are included. For example, you may provide processes, such as a heat processing 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 manufacturing method 2 may include a pressure-sensitive adhesive layer and a covering portion I formed by laminating peelably on one surface of the pressure-sensitive adhesive layer, and may include another member. For example, as shown in FIG. 1 , an adhesive material layer, a coating part I formed so as to be peelably laminated on one side of the front and back sides of the adhesive layer, and a coating part II formed by being peelably laminated on the other side of the adhesive material layer on the front and back sides. One PSA sheet laminate can be exemplified. However, whether or not the covering part II is provided is arbitrary, and it is good also as a structure in which the covering part II is not laminated|stacked.

In addition, about the detail of an adhesive sheet laminated body, it is as above.

(heating process)

In this process, the said adhesive sheet laminated body is heated so that the surface temperature of the coating part I may become 70-180 degreeC.

If the surface temperature of the coating part I is 70°C or higher, the adhesive layer is sufficiently softened, and the coating part I can be sufficiently deformable, and if it is 180°C or lower, wrinkles due to heat shrinkage or heat Since harmful effects, such as decomposition|disassembly of an adhesive material layer, can be suppressed, it is preferable.

From this point of view, it is preferable to heat the pressure-sensitive adhesive sheet laminate so that the surface temperature of the coating portion I is 70 to 180°C, and among them, 75°C or more or 150°C or less, and especially 80°C or more or 120°C or less It is more preferable to become

From the above, it is more preferable to heat the said adhesive sheet laminated body and make the surface temperature of the coating part I become 70-150 degreeC, or 70-120 degreeC, Especially, 75-150 degreeC, or 75 It is more preferable to be set to be ~120 °C, and it is most preferably set to be 80 to 150 °C, or 80 to 120 °C.

As a heating method of the pressure-sensitive adhesive sheet laminate, for example, a method in which the pressure-sensitive adhesive sheet laminate is placed between upper and lower heating plates having a heating element such as an electric heater therein and heated from the top and bottom, a method of directly sandwiching with a heating plate, heating The method using a roll, the method of immersing in hot water, etc. are mentioned. However, it is not limited to these methods.

(Forming/cooling process)

In this process, it is preferable to start shaping|molding of the adhesive sheet laminated body in the state which the surface temperature of the coating part I was heated to 70-180 degreeC as mentioned above. That is, it is preferable to form the pressure-sensitive adhesive sheet laminate in a state in which the pressure-sensitive adhesive layer and the coating portion I are laminated and integrated as it is. In this way, at the same time as the coating portion I is molded, the pressure-sensitive adhesive layer can also be molded through the coating portion I.

At this process, after shape|molding the heated adhesive sheet laminated body, you may cool, and you may cool simultaneously with shaping|molding. For example, by pressing with a cooled die, molding and cooling can be performed simultaneously and can be completed simultaneously. Thereby, as described later, the present manufacturing method 2 can be continuously carried out.

The molding method is not particularly limited as long as the concavo-convex shape can be integrally formed on the pressure-sensitive adhesive sheet laminate. For example, press forming, vacuum forming, air pressure forming, shaping by roll (roll forming forming), compression molding, shaping by lamination, and the like are mentioned. Among them, press molding is particularly preferable from the viewpoint of formability and workability.

In the case of molding using a mold, the material of the mold is not particularly limited. For example, resin-type materials, such as a silicone resin and a fluororesin, metallic materials, such as stainless steel and aluminum, etc. are mentioned. Among them, since high-precision moldability is required for concave-convex shaping of an adherend, a metal mold capable of controlling the temperature during molding is particularly preferable.

As the cooling means of the mold, a cooling means usually used can be employed. For example, the cooling means by water cooling or compressed air is mentioned.

For example, as shown in Fig. 2, the mold has a predetermined concave-convex shape on the inner wall surface of at least one of a pair of molds to be opened and closed, for example, a bonded surface of an adherend to which a pressure-sensitive adhesive layer is adhered (the Adhesive by providing a concave-convex shape corresponding to the concave or convex or concave and convex portions in the “joint surface”), and press-molding, vacuum-forming, air-forming or roll molding the pressure-sensitive adhesive sheet laminate using the mold. The concave-convex shape may be transferred to the sheet laminate to shape it.

As described above, it is preferable to start molding in a state where the surface temperature of the coating part I is 70 to 180°C. If the surface temperature of the coating part I is 70°C or higher, the pressure-sensitive adhesive layer is sufficiently softened, and the coating part I can be sufficiently deformable, and if it is 180°C or lower, wrinkles due to heat shrinkage or heat It is preferable because harmful effects such as decomposition of the pressure-sensitive adhesive layer can be suppressed.

Therefore, it is preferable to start molding in a state where the surface temperature of the coating part I is 70 to 180°C, and it is more preferable to set it to 75°C or more or 150°C or less, and especially 80°C or more or 120°C or less. Do.

On the other hand, in this process, it is preferable to finish shaping|molding in the state which the surface temperature of the said coating part I became less than 60 degreeC. For example, in the case of press molding, it is preferable to mold-open a metal mold|die in the state in which the surface temperature became less than 60 degreeC.

Here, "finishing shaping|molding" means ending applying a shaping|molding pressure with respect to an adhesive sheet laminated body, and in the case of metal mold|die shaping|molding, it means opening a metal mold|die.

It is preferable that the surface temperature of the coating part I is less than 60 degreeC, since it can suppress that deformation|transformation when taking out a molded object after completion|finish of shaping|molding, and the curvature accompanying thermal contraction of the coating part I can be suppressed.

From this point of view, it is preferable to end the molding in a state in which the surface temperature of the coating part I is less than 60°C, in particular, in a state in which it is 0°C or more or 50°C or less, and especially in a state in which it is 10°C or more or 40°C or less. Do.

Although this is repeated, in the present manufacturing method 2, it may be press-molded with a metal mold|die and cooled after opening a mold, or a metal mold|die may be cooled, and you may make it cool simultaneously with press molding. In this way, if the mold is cooled and cooled simultaneously with press molding, cooling can be completed simultaneously with molding. Therefore, since a shaping adhesive sheet laminated body can be conveyed to the next process immediately after completion|finish of shaping|molding and cooling, a shaping adhesive sheet laminated body can be manufactured continuously.

In the case of cooling at the same time as molding the mold, it is preferable that the surface temperature of the mold is 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 obtained molded product is with good precision, and from the viewpoint of suppressing warpage accompanying heat shrinkage in the cooling process after molding preferred in

Therefore, it is preferable that the surface temperature of a mold is less than 60 degreeC, especially, it is more preferable that it is 0 degreeC or more or 50 degrees C or less, and especially, it is 10 degrees C or more or 40 degrees C or less.

Moreover, it is preferable that the difference of the surface temperature of the coating part I at the time of the start of shaping|molding and the time of shaping|molding is 10-100 degreeC, and especially, 20 degreeC or more or 90 degrees C or less is more preferable. Since the difference in the surface temperature of the coating part I is 10 to 100°C, for example, when transferring and shaping the uneven shape to the pressure-sensitive adhesive sheet laminate, immediately after finishing and cooling the shaping pressure-sensitive adhesive sheet laminate Since it can be conveyed to a following process, a shaping adhesive sheet laminated body can be manufactured continuously.

In addition, conditions related to press molding, such as a press pressure and a press time, are not specifically limited, What is necessary is just to adjust suitably according to the dimension and shape to shape|mold, the material to be used, etc.

(etc)

The shaping adhesive sheet laminate obtained in the said shaping|molding and cooling process may be wound up as it is, may be heat-processed, and may be cut to a predetermined|prescribed size and shape.

When cutting, the method of cutting using a Thompson blade, a rotary blade, etc. is mentioned, for example.

In this manufacturing method 2, it is preferable to manufacture the shaping|molding adhesive sheet laminated body continuously.

For example, the pressure-sensitive adhesive sheet laminate is conveyed to a heating unit such as a heater, and the heating unit stops conveying for a predetermined period of time and heats or heats while conveying, and then the heated pressure-sensitive adhesive sheet laminate is formed by forming a molding unit. For example, it is conveyed to a molding die, and in the molding unit, for example, by pressing with a cooled die, cooling is performed at the same time as molding, and if necessary, it is conveyed to the next unit, so that a shaped pressure-sensitive adhesive sheet laminate can be continuously produced. there is.

<Use>

Here, an example of the use use of this shaping adhesive sheet laminated body 1 is demonstrated.

In recent years, as cellular phones, smart phones, tablet terminals, and the like become generalized, there are many cases in which the image display unit is damaged by a user accidentally dropping it or the like. In particular, when the image display device is a touch panel type, not only the display becomes difficult to see due to damage, but also the touch panel operation itself becomes impossible due to physical obstacles or intrusion of water, or it becomes a cause of malfunction. Therefore, there are cases where repair, that is, repair, is performed in which only the image display unit is replaced.

In the repair of an image display apparatus, also when loading a new image display part, an adhesive sheet is used. Usually, a repair is performed as manual work by a repair worker in many cases, and the skill of a repair worker is required. That is, when it is not an expert, when loading an image display part via an adhesive sheet, air will enter inside, or an adhesive material will protrude.

On the other hand, if this shaped pressure-sensitive adhesive sheet laminate 1 is used, it is possible to provide a high-precision step shape in advance. Thereby, the repair operation is greatly simplified, and it becomes possible to perform it even if it does not require the skill of a repair worker. Thus, the adhesive sheet laminated body of this invention can be used usefully as an object for repair of an image display apparatus.

<Explanation of Phrase>

In the present specification, when expressed as "X to Y" (X and Y are arbitrary numbers), "preferably greater than X" or "preferably greater than X" or "preferably greater than X" together with the meaning of "X or more and Y or less" unless otherwise specified It also includes the meaning of 'to be smaller than Y'.

In addition, when expressed as "X or more" (X is an arbitrary number) or "Y or less" (Y is an arbitrary number), "It is preferable that it is greater than X" or "It is preferable that it is less than Y". include

In the present invention, the boundary between the sheet and the film is not clear, and there is no need to distinguish between the two in terms of the present invention. , "film" shall be included even when referred to as "sheet".

Example

Hereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited to the examples.

[Example/Comparative Example Group 1]

<Cloth 1-I>

In Examples 1-1 to 1-3 and Comparative Example 1-1 (hereinafter, collectively referred to as “Example/Comparative Example Group 1”), in the coating portion 1-I of the PSA sheet laminate, the following Abdomen 1-A to skin 1-D were used. The value of each storage modulus is shown in Table 1.

· Coating part 1-A: A film formed 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).

Coating part 1-B: A film formed by laminating a release layer (thickness: 38 µm) made of a modified polyolefin on one side of an unstretched polyolefin film (thickness: 50 µm) made of 4-methylpentene-1.

- Coating part 1-C: The film which consists of a polyolefin film (thickness: 70 micrometers) which consists of unstretched polypropylene.

· Coating part 1-D: A film formed 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>

(Manufacture of double-sided adhesive sheet)

As the (meth)acrylic copolymer (1-a), 15 parts by mass (18 mol%) of polymethyl methacrylate macromonomer (Tg: 105° C.) having a number average molecular weight of 2400 and butyl acrylate (Tg: -55° C.) 1 kg of acrylic copolymer (1-a-1) (weight average molecular weight 230,000) formed by random copolymerization of 81 parts by mass (75 mol%) and 4 parts by mass (7 mol%) of acrylic acid (Tg: 106° C.), and a crosslinking agent As (1-b), 90 g of glycerin dimethacrylate (manufactured by Nichi Industries, Ltd., product name: GMR) (1-b-1), and as a photoinitiator (1-c), 2,4,6-trimethylbenzophenone, 15 g of a mixture of 4-methylbenzophenone (manufactured by Lanberti, product name: Ezacure TZT) (1-c-1) was uniformly mixed to prepare a resin composition 1-1 used for the pressure-sensitive adhesive layer. The glass transition temperature of the obtained resin composition was -5 degreeC.

A PET film (manufactured by Mitsubishi Resin Co., Ltd., product name: DIA Foil MRV-V06, thickness: 100 µm) obtained by release-treating the resin composition 1-1 obtained and sandwiched between two sheets of the coating part 1-A, using a laminator, the resin composition 1 It shaped into a sheet form so that the thickness of -1 might be set to 100 micrometers, and the adhesive sheet laminated body 1-1 was manufactured. Moreover, it has arrange|positioned so that the release layer side of the coating part 1-A may 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 molding machine (manufactured by Cheil Industries, Ltd., FKS-0632-20 type) to prepare a shaped pressure-sensitive adhesive sheet laminate 1-1.

That is, using an IR heater preheated to 400°C, heating until the surface of the pressure-sensitive adhesive sheet laminate 1-1 becomes 100°C, and then using a mold for molding cooled to 25°C, the clamping pressure (型締壓) is applied. ) Press molding was performed for 5 seconds on the conditions of 8 Mpa, and the shaping adhesive sheet laminated body 1-1 formed by uneven shaping on the surface was manufactured.

<Example 1-2>

Except having used the coating part 1-B instead of the said coating part 1-A, it carried out similarly to Example 1-1, and produced the adhesive sheet laminated body 1-2 and the shaped adhesive sheet laminated body 1-2.

<Example 1-3>

Except having used the covering part 1-C instead of the said covering part 1-A, it carried out similarly to Example 1-1, and produced the adhesive sheet laminated body 1-3 and the shaped adhesive sheet laminated body 1-3.

<Comparative Example 1-1>

Except having used the coating part 1-D instead of the said coating part 1-A, it carried out similarly to Example 1-1, and produced the adhesive sheet laminated body 1-4 and the shaped adhesive sheet laminated body 1-4.

<Measurement and evaluation method>

The measuring method and evaluation method of the various physical-property values of the sample obtained by Examples 1-1 to 1-3 and Comparative Example 1-1 are demonstrated.

(modulus of elasticity of the skin)

Each of the coated portions 1-A to 1-D used in Example and Comparative Example Group 1 was cut to a length of 50 mm and a width of 4 mm, and between the chucks using a dynamic viscoelastic device (DVA-200, Haitian Instrumentation and Control Co., Ltd.). The distance was measured by applying a strain of 25 mm and 1%. The measurement temperature range was -50°C to 150°C, the frequency was 1 Hz, and the temperature increase rate was 3°C/min. The value of the storage elastic modulus in 100 degreeC of the obtained data was made into E' (MA), and the value of the storage elastic modulus in 30 degreeC was made into E' (MB).

(modulus of elasticity of adhesive layer)

The pressure-sensitive adhesive layer obtained in Example and Comparative Example Group 1 was overlapped and laminated to a thickness of 1 mm, and was 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 temperature increase rate was 3°C/min.

In the obtained data, the value of the storage modulus at 100°C is G'(SA), the value of the loss modulus is G''(SA), and the value of the storage modulus at 30°C is G'(SB), the loss modulus of The value was defined as G''(SB), and the value of G''/G' under each temperature condition was defined as the loss tangent tanδ(SA,SB) of each pressure-sensitive adhesive layer.

(gel fraction)

For the gel fraction of the adhesive layer, about 0.05 g of each of the adhesive layers obtained in Example and Comparative Example Group 1 was collected, and wrapped in a pouch shape with a SUS mesh (#200) whose mass (X) was measured in advance, and the mouth of the pouch was closed. Fold closed, measure the mass (Y) of this package, immerse in 100 ml of ethyl acetate and store in the dark at 23°C for 24 hours. Then, take out the package and heat it at 70°C for 4.5 hours to remove the attached ethyl acetate. The mass (Z) of the evaporated and dried package was measured, and the obtained mass was substituted into the following formula to obtain it.

Gel fraction [%] = [(Z-X)/(Y-X)] × 100

(Formability)

In order to confirm the moldability, the molding test of Example and Comparative Example group 1 was performed using the mold to be described next. That is, as shown in Fig. 5, one of the upper and lower molds of 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. It was an aluminum plate with a thickness of 40 mm.

On the molding surface of the convex mold, 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, and the depth is 25 µm, 50 µm, There are formed concave portions having a rectangular shape (length 89 mm, width 58 mm) when viewed from four planes of 75 µm and 100 µm.

The coating portions 1-A to 1-D of the shaped pressure-sensitive adhesive sheet laminate obtained by the method described in Example and Comparative Example Group 1, obtained by shaping the unevenness, were peeled off, and the concave portion corresponding to the printing step and the convex portion corresponding to the display surface were peeled off. The height was measured in a non-contact manner using a scanning white interference microscope, respectively.

Measure the height h of the convex portion (edge portion with the concave portion) of the molded body with respect to the depth of 100 μm of the mold, and the transfer ratio derived by the following formula is defined as ○ and less than 50% as ×. evaluated.

Transfer rate (%) = h (formed body height)/100 (mold depth) x 100

(peel force)

The pressure-sensitive adhesive sheet laminate produced in Example and Comparative Example Group 1 was cut to a length of 150 mm and a width of 50 mm, and the interface between the coated 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 values obtained by making F(C) the peeling force in an environment of 30°C, and the peeling force after heating at 100°C for 5 minutes and then naturally cooling to 30°C, as F(D), respectively, are the values obtained for the coated parts 1-A to 1- It was referred to as the peeling force of D.

Table 1 shows the evaluation results of the PSA sheet laminates 1-1 to 1-4 obtained in the Examples and Comparative Examples and the shape PSA sheet laminates 1-1 to 1-4.

From the results of Table 1 and FIG. 4 and the test results performed so far, as shown in Examples 1-1 to 1-3, 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 1.0 × 10 ⁶ to 2.0 × 10 ⁹ Pa By laminating and molding the coating portion on the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is uneven with high precision. It was confirmed that the shape can be shaped.

On the other hand, as Comparative Example 1-1 shows, when a generally widely used biaxially oriented homo PET film is used as a release film, the storage modulus of the coated part exceeds 2.0×10 ⁹ Pa even in a high-temperature region, Even after molding, sufficient unevenness could not be formed on the pressure-sensitive adhesive layer.

From the above, storage elastic modulus E' (MB) in 30 degreeC is 5.0x10 ⁷ -1.0x10 ¹⁰ Pa, and storage elastic modulus E' (MA) in 100 degreeC is 1.0x10 ⁶ -2.0x It turned out that the shaping|molding adhesive sheet by which the uneven|corrugated shape was favorable can be obtained by laminating|stacking the coating part of 10 ⁹ Pa on the adhesive material layer and performing shaping|molding.

More preferably, the loss tangent tanδ (SA) at 100° C. of the pressure-sensitive adhesive layer satisfies the condition of 1.0 or more, and the loss tangent tanδ (SB) at 30° C. of the pressure-sensitive adhesive layer satisfies the condition of less than 1.0 It turned out that higher-precision shaping can be achieved by using such an adhesive sheet laminated body.

Therefore, by using the above-described pressure-sensitive adhesive sheet laminate to shape with high accuracy the unevenness corresponding to the printing step of the image display device serving as the adherend, there is no gap between the adherends, and the printed portion is narrow. ) It was confirmed that a shaped pressure-sensitive adhesive sheet laminate for an image display device that can be adhered well without overflow of the pressure-sensitive adhesive material even in an adherend such as a frame design can be manufactured.

In addition, when looking at the peeling force, when the peeling force F (D) is measured, the heating and cooling conditions, that is, heating at 100° C. for 5 minutes, and then naturally cooling to 30° C., are when manufacturing the shaped pressure-sensitive adhesive sheet laminate. It is a typical heating and cooling condition of 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, so the covering parts 1-A to 1-D in the shaped pressure-sensitive adhesive sheet laminate It was confirmed that the peeling force of is not different from the peeling force of the coating|coated parts 1-A 1-D in an adhesive sheet laminated body.

[Example/Comparative Example Group 2]

<Cloth 2-I>

Biaxial stretching as the coating part 2-I of the adhesive sheet laminated body in Examples 2-1 to 2-4 and Comparative Example 2-1 (Hereinafter, it is also collectively called "Example and Comparative Example group 2".) A film formed by laminating a release layer (thickness: 2 µm) made of a silicone compound on one side of an isophthalic acid copolymerized PET film (thickness: 75 µm) was used. The value of each storage modulus is shown in Table 2.

<Example 2-1>

(Manufacture of double-sided adhesive sheet)

As the (meth)acrylic copolymer (2-a), 15 parts by mass (18 mol%) of polymethyl methacrylate macromonomer (Tg: 105° C.) having a number average molecular weight of 2400 and butyl acrylate (Tg: -55° C.) 1 kg of acrylic copolymer (2-a-1) (weight average molecular weight 230,000) formed by random copolymerization of 81 parts by mass (75 mol%) and 4 parts by mass (7 mol%) of acrylic acid (Tg: 106° C.), and a crosslinking agent As (2-b), 90 g of glycerin dimethacrylate (manufactured by Nichi Industries, Ltd., product name: GMR) (2-b-1), and as a photoinitiator (2-c), 2,4,6-trimethylbenzophenone, 15 g of a mixture of 4-methylbenzophenone (manufactured by Lanberti, product name: Ezacure TZT) (2-c-1) was uniformly mixed to prepare a resin composition 2-1 used for the pressure-sensitive adhesive layer. The glass transition temperature of the obtained resin composition was -5 degreeC.

A PET film (manufactured by Mitsubishi Resin Co., Ltd., product name: DIA Foil MRV-V06, thickness: 100 µm) obtained by release-treating the resin composition 2-1 and sandwiched between two sheets of the coating part 2-I, the resin composition 2 using a laminator It shaped into a sheet form so that the thickness of -1 might be set to 100 micrometers, and the adhesive sheet laminated body 2-1 was manufactured. Moreover, the release layer side of the coating part 2-I was arrange|positioned so that it might contact with the resin composition 2-1.

The obtained pressure-sensitive adhesive sheet laminate 2-1 was thermoformed in the following process using a vacuum pressure molding machine (manufactured by Cheil Industries, Ltd., FKS-0632-20 type) and a mold for molding, to obtain a shaped pressure-sensitive adhesive sheet laminate 2-1 prepared.

As for the metal mold|die for shaping|molding, as shown in FIG. 5, one of the upper and lower molds is a convex mold of 270 mm in length, 170 mm in width, and 40 mm in thickness, and the upper and the other mold is 270 mm in length, 170 mm in width, and thickness. It was a 40 mm aluminum plate. On the molding surface of the convex mold, 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, and the depth is 25 µm, 50 µm, When viewed from four planes of 75 µm and 100 µm, forming recesses having a rectangular shape (length 89 mm, width 58 mm) were provided.

With the IR heater preheated to 400 degreeC, it heated and shape|molded until the surface of the coating part 2-I of the adhesive sheet laminated body 2-1 became 100 degreeC. That is, in a state where the storage elastic modulus E' (MS) of the coating part 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, the mold surface temperature is set to 30° C. Using the cooled mold for molding, press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, the storage elastic modulus E' (MF) of the coating part 2-I was 2.8×10 ⁹ Pa, and the storage elastic modulus G of the adhesive layer The mold was opened in the state of '(SF) of 6.1x10 ⁴ Pa, and the shaping|molding adhesive sheet laminated body 2-1 formed by concavo-convex shaping on the surface was manufactured.

Further, the ratio E'(MF)/E' of the storage elastic modulus E'(MS) of the coated part 2-I at the start of the molding to the storage elastic modulus E'(MF) of the coated part 2-I at the end of the molding (MS) was 13.3.

In addition, the ratio E'(MF)/G'(SF) of the storage elastic modulus E'(MF) of the coating part 2-I at the end of the molding to the storage elastic modulus G'(SF) of the pressure-sensitive adhesive layer at the end of the molding was 4.6×10 ⁴ .

In addition, the loss tangent tanδ (SS) of the pressure-sensitive adhesive layer at the start of molding was 4.8, and the loss tangent tanδ (SF) of the pressure-sensitive 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 coating part 2-I of the pressure-sensitive adhesive sheet laminate 2-2 reached 110°C. and molded. That is, in a state where the storage elastic modulus E' (MS) of the coating part 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, the mold surface temperature is set to 30° C. Using the cooled mold for molding, press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, the storage elastic modulus E' (MF) of the coating part 2-I was 2.8×10 ⁹ Pa, and the storage elastic modulus G of the adhesive layer The mold was opened in the state of '(SF) of 6.1x10 ⁴ Pa, and the shaping|molding adhesive sheet laminated body 2-2 formed by concavo-convex shaping on the surface was manufactured.

Further, the ratio E'(MF)/E' of the storage elastic modulus E'(MS) of the coated part 2-I at the start of the molding to the storage elastic modulus E'(MF) of the coated part 2-I at the end of the molding (MS) was 21.5.

In addition, the ratio E'(MF)/G'(SF) of the storage elastic modulus E'(MF) of the coating part 2-I at the end of the molding to the storage elastic modulus G'(SF) of the pressure-sensitive adhesive layer at the end of the molding was 4.6×10 ⁴ .

In addition, the loss tangent tanδ (SS) of the pressure-sensitive adhesive layer at the start of molding was 8.2, and the loss tangent tanδ (SF) of the pressure-sensitive adhesive layer at the end of molding was 0.6.

<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 coating part 2-I of the pressure-sensitive adhesive sheet laminate 2-3 reached 90°C. and molded. That is, in a state where the storage elastic modulus E' (MS) of the coating part 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, the mold surface temperature is set to 30° C. Using the cooled mold for molding, press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, the storage elastic modulus E' (MF) of the coating part 2-I was 2.8×10 ⁹ Pa, and the storage elastic modulus G of the adhesive layer The mold was opened in the state of '(SF) of 6.1x10 ⁴ Pa, and the shaping|molding adhesive sheet laminated body 2-3 formed by concavo-convex shaping on the surface was manufactured.

Further, the ratio E'(MF)/E' of the storage elastic modulus E'(MS) of the coated part 2-I at the start of the molding to the storage elastic modulus E'(MF) of the coated part 2-I at the end of the molding (MS) was 8.0.

In addition, the ratio E'(MF)/G'(SF) of the storage elastic modulus E'(MF) of the coating part 2-I at the end of the molding to the storage elastic modulus G'(SF) of the pressure-sensitive adhesive layer at the end of the molding was 4.6×10 ⁴ .

In addition, the loss tangent tanδ (SS) of the pressure-sensitive adhesive layer at the start of molding was 2.7, and the loss tangent tanδ (SF) of the pressure-sensitive 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 coating part 2-I of the pressure-sensitive adhesive sheet laminate 2-4 reached 70°C. and molded. That is, in the state where the storage elastic modulus E' (MS) of the coating part 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, the mold surface temperature is set to 25° C. Using the cooled mold for molding, press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, the storage elastic modulus E' (MF) of the coating part 2-I was 2.8×10 ⁹ Pa, and the storage elastic modulus G of the adhesive layer The mold was opened in the state of '(SF) of 6.1x10 ⁴ Pa, and the shaping|molding adhesive sheet laminated body 2-4 formed by concavo-convex shaping on the surface was manufactured.

Further, the ratio E'(MF)/E' of the storage elastic modulus E'(MS) of the coated part 2-I at the start of the molding to the storage elastic modulus E'(MF) of the coated part 2-I at the end of the molding (MS) was 1.4.

In addition, the ratio E'(MF)/G'(SF) of the storage elastic modulus E'(MF) of the coating part 2-I at the end of the molding to the storage elastic modulus G'(SF) of the pressure-sensitive adhesive layer at the end of the molding was 4.6×10 ⁴ .

Further, the loss tangent tan ? (SS) of the pressure-sensitive adhesive layer at the start of molding was 1.4, and the loss tangent tan ? (SF) of the pressure-sensitive 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 coating part 2-I of the pressure-sensitive adhesive sheet laminate 2-5 reached 60°C. and molded. That is, in a state where the storage elastic modulus E' (MS) of the coating part 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, the mold surface temperature is set to 25° C. Using the cooled mold for molding, press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, the storage elastic modulus E' (MF) of the coating part 2-I was 2.8×10 ⁹ Pa, and the storage elastic modulus G of the adhesive layer The mold was opened in the state of '(SF) of 6.1x10 ⁴ Pa, and the shaping|molding adhesive sheet laminated body 2-5 formed by concavo-convex shaping on the surface was manufactured.

Further, the ratio E'(MF)/E' of the storage elastic modulus E'(MS) of the coated part 2-I at the start of the molding to the storage elastic modulus E'(MF) of the coated part 2-I at the end of the molding (MS) was 1.2.

In addition, the ratio E'(MF)/G'(SF) of the storage elastic modulus E'(MF) of the coating part 2-I at the end of the molding to the storage elastic modulus G'(SF) of the pressure-sensitive adhesive layer at the end of the molding was 4.6×10 ⁴ .

In addition, the loss tangent tanδ (SS) of the pressure-sensitive adhesive layer at the start of molding was 1.1, and the loss tangent tanδ (SF) of the pressure-sensitive adhesive layer at the end of molding was 0.6.

<Measurement and evaluation method>

The measuring method and evaluation method of the various physical-property values of the sample obtained by Examples 2-1 to 2-4 and Comparative Example 2-1 are demonstrated.

(modulus of elasticity of the skin)

The storage modulus E' (MS) and E' (MF) of the coating part 2-I were cut to a length of 50 mm and a width of 4 mm, and the distance between the chucks was 25 mm using a dynamic viscoelastic device (DVA-200, DVA-200, Ltd.). , was measured by applying a strain of 1%. The measurement temperature range was -50°C to 150°C, the frequency was 1 Hz, and the temperature increase rate was 3°C/min.

In Examples and Comparative Examples, the value of the storage modulus at the starting temperature of each molding was E' (MS), and the value of the storage modulus at the temperature at the end of each molding was defined as E' (MF).

In addition, in Example 2-1, since the temperature at the start of shaping|molding is 100 degreeC, storage elastic modulus E' (MS) of Example 2-1 is storage elastic modulus E' (MA) in 100 degreeC.

In addition, in any of Examples and Comparative Example Group 2, since the temperature at the end of molding was 30°C, in any of Examples and Comparative Example Group 2, the E' (MF) was the storage elastic modulus at 30°C E' ( MB) is the same.

(modulus of elasticity of adhesive layer)

The pressure-sensitive adhesive layer obtained in Example and Comparative Example Group 2 was overlapped and laminated to a thickness of 1 mm, and was 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 temperature increase rate was 3°C/min.

In the obtained data, the value of the storage elastic modulus in 100 degreeC is G'(SA), the value of the loss elastic modulus is G''(SA), the value of the storage elastic modulus in 30 degreeC is G'(SB), the loss The value of the elastic modulus was defined as G''(SB), and the value of G''/G' under each temperature condition was defined as the loss tangent tanδ (SA, SB) of each adhesive layer.

On the other hand, about the storage elastic modulus G' (SA) and G' (SB) of the adhesive material layer, the adhesive material layers obtained in Example and Comparative Example group 2 were overlapped and laminated to a thickness of 1 mm, and a rheometer (manufactured by Thermo Fisher Scientific Co., Ltd.) MARSII) was used. The measurement temperature range was -50°C to 150°C, the frequency was 1 Hz, and the temperature increase rate was 3°C/min.

In the obtained data, the value of the storage modulus at the starting temperature of each molding in Example and Comparative Example Group 2 is G' (SS), and the value of the loss modulus is G'' (SS), and the temperature at the end of each molding Let the value of the storage elastic modulus be G' (SF), and the value of the loss elastic modulus be G'' (SF), and the value of G''/G' under each temperature condition is the value of each adhesive material layer. The loss tangent was called tanδ (SS, SF).

(gel fraction)

As for the gel fraction of the adhesive layer, about 0.05 g of each of the adhesive layers obtained in Example and Comparative Example Group 2 was collected, wrapped in a pouch shape with a SUS mesh (#200) whose mass (X) was measured in advance, and the mouth of the pouch After folding and closing the package, measuring the mass (Y) of this package, immersing it in 100 ml of ethyl acetate and storing it in a dark place at 23°C for 24 hours. was evaporated, the mass (Z) of the dried package was measured, and the obtained mass was obtained by substituting the following formula.

Gel fraction [%] = [(Z-X)/(Y-X)] × 100

(Formability)

The coating portion I of the shaped pressure-sensitive adhesive sheet laminate obtained in Example and Comparative Example Group 2 was peeled off, and the height of the concave portion corresponding to the printing step and the convex portion corresponding to the display surface was measured under a scanning white interference microscope, respectively. was measured using a non-contact method.

Measure the height h of the convex portion (edge portion with the concave portion) of the molded body with respect to the depth of 100 μm of the mold, and the transfer ratio derived by the following formula is defined as ○ and less than 50% as ×. evaluated.

Transfer rate (%) = h (formed body height)/100 (mold depth) x 100

(peel force)

The pressure-sensitive adhesive sheet laminate prepared in Example and Comparative Example Group 2 was cut to a length of 150 mm and a width of 50 mm, and a 180° peeling test was performed on the interface between the coating part 2-I and the pressure-sensitive adhesive layer at a test speed of 300 mm/min. did

The values obtained by making F(C) the peeling force in an environment of 30°C, and the peeling force after heating at 100°C for 5 minutes and naturally cooling to 30°C, as F(D), respectively, are the peeling force of the coated part 2-I. said

Table 2 shows 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.

As shown in Examples 2-1 to 2-4 from the results of Table 2 and Fig. 4 and the test results performed so far, the storage modulus E' (MS) of the coating part 2-I at the start of molding. is 1.0×10 ⁶ to 2.0×10 ⁹ Pa, and adjusts so that the storage elastic modulus E′ (MF) of the coated part 2-I at the end of molding is 5.0×10 ⁷ to 1.0×10 ¹⁰ Pa By performing, it was confirmed that the concavo-convex shape can be molded to the pressure-sensitive adhesive layer with high precision.

On the other hand, as Comparative Example 2-1 shows, when the storage modulus E' (MS) of the coating part 2-I at the start of molding is greater than 2.0×10 ⁹ Pa, the pressure-sensitive adhesive layer is sufficient even after thermoforming. Unable to shape irregularities.

From the above, the storage elastic modulus E' (MS) of the coating part 2-I at the time of the start of molding is 1.0×10 ⁶ to 2.0×10 ⁹ Pa, and the storage of the coating part 2-I at the end of molding It turned out that the shaping adhesive sheet by which the uneven|corrugated shape was favorable can be obtained by shaping|molding by adjusting so that elasticity modulus E' (MF) might be 5.0x10 ⁷ -1.0x10 ¹⁰ Pa.

More preferably, the loss tangent tanδ(SS) of the pressure-sensitive adhesive layer at the start of molding satisfies the condition of 1.0 or more, and the loss tangent tanδ(SF) of the pressure-sensitive adhesive layer at the end of molding satisfies the condition of less than 1.0. It turned out that shaping|molding with higher precision can be achieved by adjusting and shaping|molding so that it may satisfy.

Therefore, by using the pressure-sensitive adhesive sheet laminate as described above, the unevenness corresponding to the printing step of the image display device as the adherend is molded with high precision, so that there is no gap between the adherends, and the printed part is designed with a narrow frame design. It has confirmed that the shape adhesive sheet laminated body for image display apparatuses which can be adhered favorably without an adhesive material overflowing also in the same to-be-adhered body can be manufactured.

In addition, when looking at the peel force, when the peel force F (D) is measured, the heating and cooling conditions, that is, heating at 100° C. for 5 minutes, and then naturally cooling to 30° C., are when manufacturing the shaped pressure-sensitive adhesive sheet laminate. It is a typical heating and cooling condition of 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, so it was confirmed that the peeling force hardly changed before and after heating.

Further, the pressure-sensitive adhesive sheet laminate is heated to start molding in a state where the storage elastic modulus E' (MS) of the coated part 2-I is 1.0×10 ⁶ to 2.0×10 ⁹ Pa, and the storage elastic modulus of the coated part 2-I is started. It was found that by completing the molding in a state where E'(MF) was 5.0×10 ⁷ to 1.0×10 ¹⁰ Pa, an uneven shape matching the uneven portion on the surface of the adherend could be formed with high precision on the surface of the adhesive material layer.

[Example/Comparative Example Group 3]

<Cloth 3-I>

As the covering part 3-I of the adhesive sheet laminated body in Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-2 (Hereinafter, it is also collectively called "Example and Comparative Example group 3".) , A film formed 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. The value of each storage modulus is shown in Table 3.

<Example 3-1>

(Manufacture of double-sided adhesive sheet)

As the (meth)acrylic copolymer (3-a), 15 parts by mass (18 mol%) of polymethyl methacrylate macromonomer (Tg: 105° C.) having a number average molecular weight of 2400 and butyl acrylate (Tg: -55° C.) 1 kg of acrylic copolymer (3-a-1) (weight average molecular weight 230,000) formed by random copolymerization of 81 parts by mass (75 mol%) and 4 parts by mass (7 mol%) of acrylic acid (Tg: 106° C.), and a crosslinking agent As (3-b), 90 g of glycerin dimethacrylate (manufactured by Nichi Industries, Ltd., product name: GMR) (3-b-1), and as a photoinitiator (3-c), 2,4,6-trimethylbenzophenone, 15 g of a mixture of 4-methylbenzophenone (manufactured by Lanberti, product name: Ezacure TZT) (3-c-1) was uniformly mixed to prepare a resin composition 3-1 used for the pressure-sensitive adhesive layer. The glass transition temperature of the obtained resin composition was -5 degreeC.

A PET film (manufactured by Mitsubishi Resin Co., Ltd., product name: DIA Foil MRV-V06, thickness: 100 µm) obtained by releasing the resin composition 3-1 obtained was sandwiched between two sheets of the coating part 3-I, and the resin composition was used with a laminator. It shaped into a sheet shape so that the thickness of 3-1 might be set to 100 micrometers, and the adhesive sheet laminated body 3-1 was manufactured.

Moreover, the release layer side of the coating part 3-I was arrange|positioned so that it might 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 molding machine (manufactured by Cheil Industries, Ltd., FKS-0632-20 type) and a mold for molding, to obtain a shaped pressure-sensitive adhesive sheet laminate 3-1 prepared.

As for the metal mold|die for shaping|molding, as shown in FIG. 5, one of the upper and lower molds is a convex mold of 270 mm in length, 170 mm in width, and 40 mm in thickness, and the upper and the other mold is 270 mm in length, 170 mm in width, and thickness. It was a 40 mm aluminum plate. On the molding surface of the convex mold, 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, and the depth is 25 µm, 50 µm, When viewed from four planes of 75 µm and 100 µm, forming recesses having a rectangular shape (length 89 mm, width 58 mm) were provided.

With an IR heater preheated to 400°C, the surface of the coated part 3-I of the pressure-sensitive adhesive sheet laminate 3-1 is heated until the surface becomes 100°C, and the pressure-sensitive adhesive sheet laminate 3-1 in the heated state is subjected to a mold surface temperature Using a mold for molding cooled to 30 ° C., press molding was performed for 5 seconds under the conditions of a clamping pressure of 8 MPa, and then the mold was opened, and a shaping adhesive sheet laminate 3-1 formed by shaping the surface unevenly was prepared.

<Example 3-2>

The pressure-sensitive 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 part 3-I of the pressure-sensitive adhesive sheet laminate 3-2 reached 70°C. Then, the pressure-sensitive adhesive sheet laminate 3-1 in the heated state was press-molded for 5 seconds under the condition of a clamping pressure of 8 MPa using a molding die cooled to 30 ° C., then the mold was opened, the surface The shaping adhesive sheet laminated body 3-2 formed by concavo-convex shaping was manufactured.

<Example 3-3>

The pressure-sensitive 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 part 3-I of the pressure-sensitive adhesive sheet laminate 3-3 reached 100°C. Then, the pressure-sensitive adhesive sheet laminate 3-1 in the heated state was press-molded 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., then the mold was opened, the surface The shaping adhesive sheet laminated body 3-3 formed by concavo-convex shaping was manufactured.

<Comparative Example 3-1>

The pressure-sensitive 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 coated part 3-I of the pressure-sensitive adhesive sheet laminate 3-4 reached 60°C. Then, the pressure-sensitive adhesive sheet laminate 3-1 in the heated state was press-molded for 5 seconds under the condition of a clamping pressure of 8 MPa using a molding die cooled to 30 ° C., then the mold was opened, the surface The shaping adhesive sheet laminated body 3-4 formed by concavo-convex shaping was manufactured.

<Comparative Example 3-2>

The pressure-sensitive 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 part 3-I of the pressure-sensitive adhesive sheet laminate 3-5 reached 100°C. Then, the pressure-sensitive adhesive sheet laminate 3-1 in the heated state was press-molded 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., then the mold was opened, the surface The shaping adhesive sheet laminated body 3-5 formed by concavo-convex shaping was manufactured.

<Measurement and evaluation method>

The measuring method and evaluation method of the various physical-property values of each sample obtained in Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-2 are demonstrated.

(modulus of elasticity of the skin)

The storage modulus of the coating part 3-I was measured by cutting it to a length of 50 mm and a width of 4 mm, and using a dynamic viscoelasticity device (DVA-200, IT Instrumentation Control Co., Ltd.) with a distance between chucks of 25 mm and a strain of 1%. The measurement temperature range was -50°C to 150°C, the frequency was 1 Hz, and the temperature increase rate was 3°C/min.

In the obtained data, the value of the storage elastic modulus of the coating part 3-I in 30 degreeC was E' (MB), and the value of the storage elastic modulus of the coating part 3-I in 100 degreeC was made into E' (MA). .

(modulus of elasticity of adhesive layer)

The pressure-sensitive adhesive layer obtained in Example and Comparative Example Group 3 was overlapped and laminated to a thickness of 1 mm, and was 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 temperature increase rate was 3°C/min.

In the obtained data, the value of the storage elastic modulus in 100 degreeC is G'(SA), the value of the loss elastic modulus is G''(SA), the value of the storage elastic modulus in 30 degreeC is G'(SB), the loss The value of the elastic modulus was defined as G''(SB), and the value of G''/G' under each temperature condition was defined as the loss tangent tanδ (SA, SB) of each adhesive layer.

(Formability)

The coating portion I of the shaped pressure-sensitive adhesive sheet laminate obtained in Example and Comparative Example group 3 was peeled off, and the height of the concave portion corresponding to the printing step and the convex portion corresponding to the display surface was measured under a scanning white interference microscope, respectively. was measured using a non-contact method.

Measure the height h of the convex portion (edge portion with the concave portion) of the molded body with respect to the depth of 100 μm of the mold, and “○” for those having a transfer rate of 50% or more, and “x” for those with a transfer rate of 50% or more ' was evaluated.

Transfer rate (%) = h (formed body height)/100 (mold depth) x 100

(Bending/Bending)

The pressure-sensitive adhesive sheet laminate prepared under each molding condition of Example and Comparative Example Group 3 was cut out 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 called deflection. The height of curvature judged the thing of less than 10 mm as "(circle)" and the thing of 10 mm or more as "x", respectively.

(peel force)

The pressure-sensitive adhesive sheet laminate prepared in Example and Comparative Example Group 3 was cut to a length of 150 mm and a width of 50 mm, and a 180° peeling test was performed on the interface between the coating part 3-I and the pressure-sensitive adhesive layer at a test rate of 300 mm/min. did

The values obtained by making F(C) the peeling force in an environment of 30°C, and the peeling force after heating at 100°C for 5 minutes and then naturally cooling to 30°C as F(D) are the values obtained as the peeling force of the coated part 3-I, respectively. said

Table 3 shows the evaluation results of the shape 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 in Table 3 and the test results performed so far, as shown in Examples 3-1 to 3-3, molding was started in a state where the surface temperature of the coated part 3-I was 70 to 180 ° C. After the surface temperature of the abdomen 3-I became less than 60 ° C., it was confirmed that the concavo-convex shape could be formed on the pressure-sensitive adhesive layer with high precision by molding so that the molding was finished and the molded product was taken out from the mold.

On the other hand, as Comparative Example 3-1 shows, when the temperature of the coating part 3-I at the start of molding was less than 70°C, sufficient unevenness could not be formed in the pressure-sensitive adhesive layer even by thermoforming.

In addition, as Comparative Example 3-2 shows, when the molding is finished and the molded article is taken out from the mold, if the surface temperature of the coating part 3-I is 70° C. or higher, warpage or flexion occurs in the molded article due to thermal contraction of the sheet So I found that it wasn't good.

From the above, in order to perform uneven shaping with higher precision, molding is started in a state where the surface temperature of the coated part 3-I is 70 to 180 ° C., and after the surface temperature of the coated part 3-I becomes less than 60 ° C., molding It turned out that it is preferable to perform shaping|molding so that the molded article may be taken out from a metal mold|die by finishing.

Therefore, by using the pressure-sensitive adhesive sheet laminate as described above, irregularities corresponding to the printing steps of the image display device serving as the adherend are molded with high precision, so that there is no gap between the adherends, and the printing portion has a narrow frame design. It has confirmed that the shaping|molding adhesive sheet laminated body for image display apparatuses which can closely_bond favorably without an adhesive material overflow also in the to-be-adhered body like this can be manufactured.

In addition, when looking at the peel force, when the peel force F (D) is measured, the heating and cooling conditions, that is, heating at 100° C. for 5 minutes, and then naturally cooling to 30° C., are when manufacturing the shaped pressure-sensitive adhesive sheet laminate. It is a typical heating and cooling condition of 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, so it was confirmed that the peeling force hardly changed before and after heating.

[Example group 4]

The method for producing the polyester raw material used in the following Examples 4-1 to 4-5 (hereinafter, collectively referred to as “Example Group 4”) is as follows.

(Method for producing polyester 4-A)

100 parts of dimethyl terephthalate, 70 parts of ethylene glycol, and 0.07 parts of calcium acetate monohydrate are put into a reactor, heated and heated, and methanol is distilled off to carry out transesterification reaction. After the start of the reaction, it takes about 4 and a half hours to 230 ° C. The temperature was raised to , and the transesterification reaction was substantially completed.

Next, 0.04 parts of phosphoric acid and 0.035 parts of antimony trioxide were added, followed by polymerization according to a conventional method. That is, the reaction temperature was gradually raised and finally set to 280°C, while the pressure was gradually reduced to finally 0.05 mmHg. After 4 hours, the reaction was completed, and according to a conventional method, it was chipped to obtain polyester 4-A. The intrinsic viscosity IV of the obtained polyester chip was 0.70 dl/g.

(Method for producing polyester 4-B)

In the method for producing polyester 4-A, as the dicarboxylic acid unit, terephthalic acid was 78 mol% and isophthalic acid was 22 mol%, except that it was prepared in the same manner as in polyester 4-A, and polyester 4 -B was obtained. The intrinsic viscosity IV of the obtained polyester chip was 0.70 dl/g.

(Method for producing polyester 4-C)

When producing the polyester 4-A, 6000 ppm of amorphous silica having an average particle diameter of 3 μm was added to prepare polyester 4-C.

(Method for producing polyester 4-D)

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

[Example 4-1]

A raw material obtained by mixing the polyester 4-B, 4-A, and 4-D in a ratio of 65 wt%, 30 wt%, and 5 wt%, respectively, is melt-extruded by a melt extruder to form a single layer got a sheet

Then, on the cooled casting drum, the sheet|seat was co-extrusion-cooled and solidified, and the non-oriented sheet was obtained. Subsequently, after stretching 3.4 times at 80° C. in the machine direction (longitudinal direction), it was further stretched 3.9 times at 80° C. in the machine direction and the vertical direction (transverse direction) through a preheating process in a tenter. After biaxial stretching, it heat-processed at 185 degreeC for 3 second, after that, the 6.4% relaxation process was performed in the width direction, and the 50-micrometer-thick polyester film was obtained. The evaluation results are shown in Table 4 below.

[Example 4-2], [Example 4-3]

Except having changed into the conditions shown in following Table 4, it carried out similarly to Example 4-1, and obtained the polyester film. The evaluation results are shown in Table 4 below.

[Example 4-4]

A raw material obtained by mixing the polyesters 4-A and 4-C at a ratio of 86% by weight and 14% by weight, respectively, was used as a raw material for the surface layer, and polyester 4-B and 4-A were mixed with 45% by weight and 55% by weight. The raw materials each mixed in the ratio of weight% were used as the raw material for an intermediate|middle layer. It melt-extruded with different melt extruders, respectively, and obtained the amorphous sheet of 2 types 3 layer lamination|stacking (surface layer/intermediate layer/surface layer).

Then, the sheet was co-extruded on the cooled casting drum, and the unoriented sheet was obtained by cooling and solidifying. Subsequently, after stretching 3.4 times at 82° C. in the machine direction (MD), it was further stretched 3.9 times at 110° C. in the machine direction and the vertical direction (width direction, TD) through a preheating process in a tenter. After biaxial stretching, the heat processing for 3 second was performed at 210 degreeC, the 2.4% relaxation process was performed to the width direction after that, and the 50-micrometer-thick polyester film was obtained. The evaluation results are shown in Table 4 below.

[Example 4-5]

Except having changed into the conditions shown in following Table 4, it carried out similarly to Example 4-4, and obtained the polyester film. The evaluation results are shown in Table 4 below.

<Measurement and evaluation method>

The measuring method and evaluation method of the various physical-property values of the sample obtained in Example group 4 are demonstrated.

(1) storage modulus (E')

About the film obtained in Example group 4, the sample of 30 mm of longitudinal direction x 5 mm of width directions was collect|collected so that a longitudinal direction might become a machine direction. Next, using a dynamic viscoelastic device (“DVA-220” manufactured by Haiti Metrology Control Co., Ltd.), the sample was clamped and fixed in a chuck set at an interval of 20 mm, and then the temperature was increased from room temperature to 200° C. The storage modulus was measured at 10 Hz. From the obtained data, the storage modulus in 100 degreeC was read.

(2) Heat shrinkage

From the central position in the width direction of the film obtained in Example Group 4, a sample was cut out in a strip shape (15 mm width × 150 mm length) so that the sample longitudinal direction was in the measurement direction, in a non-tension state, 120 ° C. It heat-treated for 5 minutes in atmosphere, the length of the sample before and behind heat processing was measured, and the thermal contraction rate (%) of the film was calculated by the following formula. In addition, a in a following formula is the sample length before heat processing, and b is the sample length after heat processing.

Heat shrinkage (%) = [(a-b)/a] × 100

(3) Amount of film surface oligomers after heat treatment

The film obtained in Example Group 4 was treated with a polyester film for 10 minutes in a hot air circulation oven at 180°C under a nitrogen atmosphere. The surface of the polyester film after heat processing was made to contact with DMF (dimethylformamide) for 3 minutes, and the oligomer which precipitated on the surface was dissolved. For such operation, for example, the method described in the dissolution mechanism used for the single-sided dissolution method in the dissolution test can be employed in the self-contained standards for food containers and packaging made of synthetic resins such as polyolefin.

Subsequently, the concentration of the obtained DMF is adjusted as necessary by dilution or the like, and the amount of oligomers in the DMF is obtained by supplying it to liquid chromatography (Shimadzu LC-2010), and dividing this value by the area of the film in which the DMF is in contact with the film It was referred to as the amount of surface oligomers (mg/cm 2 ).

The amount of oligomers in DMF was calculated|required by the peak area ratio of the standard sample peak area and the measurement sample peak area (absolute calibration curve method).

The standard sample was prepared by accurately weighing an oligomer (cyclic trimer) fractionated in advance and dissolving it in the accurately weighed DMF. The concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg/ml.

(4) Forming processing aptitude

As a (meth)acrylic copolymer, 15 mass parts (18 mol%) of polymethyl methacrylate macromonomer (Tg: 105 ° C.) having a number average molecular weight of 2400 and butyl acrylate (Tg: -55 ° C.) 81 parts by mass (75 mol%) and 4 parts by mass (7 mol%) of acrylic acid (Tg: 106° C.) are randomly copolymerized with 1 kg of an acrylic copolymer (weight average molecular weight 230,000), and as a crosslinking agent, glycerin dimethacrylate (manufactured by Nichiyu Corporation, Product name: GMR) (b-1) 90 g, and 15 g of a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (manufactured by Lanberti, product name: Ezacure TZT) as a photopolymerization initiator were uniformly mixed and adhered A resin composition used for the sheet was prepared.

The obtained resin composition was sandwiched by two release films obtained from the polyester film shown in Example Group 4 from top and bottom (a combination of top and bottom shall be sandwiched between the same release films.), using a laminator, the thickness of the resin composition is 100 µm It was shaped in a sheet shape so that it might become, and the adhesive sheet laminated body was manufactured. Moreover, it has arrange|positioned so that the mold release layer side of a polyester film may contact|connect the resin composition.

The obtained pressure-sensitive adhesive sheet laminate was thermoformed by the following process using a vacuum pressure molding machine (manufactured by Cheil Industries, Ltd., FKS-0632-20 type) to prepare a shaped pressure-sensitive adhesive sheet laminate. That is, using an IR heater preheated to 400°C, heating until the surface of the pressure-sensitive adhesive sheet laminated body reaches 100°C, and then using a mold for molding cooled to 25°C, under the condition of a clamping pressure of 8 MPa for 5 seconds It press-molded and the shape adhesive sheet laminated body formed by uneven shaping|molding on the surface was manufactured.

The polyester film of the shaping pressure-sensitive adhesive sheet laminate in which the irregularities were shaped was peeled off, and the heights of the concave and convex portions of the shaping pressure-sensitive adhesive sheet were measured in a non-contact manner using a scanning white interference microscope, respectively, and the height of the shaped body was measured as h. did

Measure the height h of the convex part of the molded body with respect to the depth of 100 µm of the mold, and the transfer rate derived by the following formula is 70% or more as ○, 50% or more and less than 70% as △, and less than 50% as ×. Each was evaluated.

Transfer rate (%) = h (formed body height)/100 (mold depth) x 100

(5) Appearance of adhesive layer (wrinkle)

The external appearance of the adhesive layer laminated body before press molding obtained by the method described in (4) was evaluated by the evaluation method shown below, respectively.

<Evaluation method>

○: It is laminated without wrinkles and maintains a good appearance.

x: Wrinkles generate|occur|produce in a film, the wrinkle is transcribe|transferred to an adhesive layer, and it is a state which cannot be used as a product.

The molded pressure-sensitive adhesive sheet laminate of the present invention is suitably used for forming image display devices such as personal computers, mobile terminals (PDA), game machines, televisions (TVs), car navigation systems, touch panels, and pen tablets, for example. can

Moreover, when forming such a shaping adhesive sheet laminated body, the adhesive sheet laminated body and application film of this invention can be used suitably.

Claims (9)

A pressure-sensitive adhesive layer and a covering portion I formed so as to be peelably laminated on one surface of the pressure-sensitive adhesive layer is provided, wherein a concave portion, a convex portion, or an uneven portion (referred to as an “adhesive material layer surface unevenness”) is formed on one surface of the pressure-sensitive adhesive material layer. In the manufacturing method of the shaped adhesive sheet laminated body provided with the structure which consists of
Heating a pressure-sensitive adhesive sheet laminate having a pressure-sensitive adhesive layer and a covering portion I that is laminated to be peelable on one surface of the pressure-sensitive adhesive layer, and molding the heated pressure-sensitive adhesive sheet laminate with a mold to produce a shaped pressure-sensitive adhesive sheet laminate It is a manufacturing method,
The pressure-sensitive adhesive sheet laminate is heated to start molding in a state where the surface temperature of the coating part I is 70 to 180 ° C., and after the surface temperature of the coating part I becomes less than 60 ° C., the molded adhesive sheet laminate is taken out from the mold. A method for manufacturing a shaped pressure-sensitive adhesive sheet laminate. The method of claim 1,
A method for manufacturing a shaped pressure-sensitive adhesive sheet laminate, characterized in that the molding is performed by any one of press molding, vacuum molding, air pressure molding, roll forming molding, and compression molding. The method of claim 1,
A method for manufacturing a shaped pressure-sensitive adhesive sheet laminate, characterized in that it is continuously manufactured using the above molding method. The method of claim 1,
The coating part I is provided with a coating base layer and a release layer,
The coating base layer having a layer comprising one or more resins selected from the group consisting of unstretched polyester, stretched polyester, copolyester, unstretched polyolefin, stretched polyolefin, and copolyolefin A method for manufacturing a shaped pressure-sensitive adhesive sheet laminate. The method of claim 1,
The pressure-sensitive adhesive layer is a (meth) acrylic copolymer (a), a cross-linking agent (b) and a method for producing a shaped pressure-sensitive adhesive sheet laminate, characterized in that it is formed of a resin composition containing a photopolymerization initiator (c). The method of claim 1,
In the shaped pressure-sensitive adhesive sheet laminate, the pressure-sensitive adhesive layer includes concave portions, convex portions, or uneven portions (referred to as “adhesive material layer surface irregularities”) on one surface of the front and back sides,
The coating part I is in close contact with one surface of the front and back sides of the adhesive material layer, and has concave parts, convex parts, or uneven parts (referred to as "coated surface uneven parts") on the front and back one side surfaces, and further, the front and back sides and is provided with convex portions, concave portions, or concave-convex portions (referred to as “coated back surface concavo-convex portions”) forming concavities and convexities corresponding to the surface concavo-convex portions of the covering portion on the opposite surfaces of the front and back surfaces of the other side; A method for manufacturing a sieve. 7. The method of claim 6,
The pressure-sensitive adhesive layer is a double-sided pressure-sensitive adhesive sheet for bonding two adherends,
The pressure-sensitive adhesive sheet laminate, characterized in that the pressure-sensitive adhesive layer surface uneven portion coincides with the concave portion, the convex portion, or the uneven portion (referred to as the “adherent surface uneven portion”) on the adherend surface of any of the above-mentioned adherends. manufacturing method. 8. The method of claim 7,
The method for producing a shaped pressure-sensitive adhesive sheet laminate, wherein the any of the adherends is any one selected from the group consisting of a surface protection panel, a touch panel, and an image display panel. The method of claim 1,
A method for producing a shaped pressure-sensitive adhesive sheet laminate, comprising heating the pressure-sensitive adhesive sheet laminate and forming an uneven shape on at least one side of the pressure-sensitive adhesive sheet laminate by press molding, vacuum forming, air pressure molding or roll forming.

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