KR20220023973A - A method for manufacturing an adhesive sheet, an intermediate laminate, an intermediate laminate, and a manufacturing method for a product laminate - Google Patents

Abstract

The adhesive sheet 1 is provided with the base material 2 and the adhesion layer 3 arrange|positioned on one side of the base material 2 . The adhesive layer 3 is made of a pressure-sensitive adhesive composition in which the visible light transmittance at a wavelength of 550 nm can be reduced by an external stimulus, and the state can be irreversibly changed into a high adhesive force and a low adhesive force by an external stimulus.

Description

A method for manufacturing an adhesive sheet, an intermediate laminate, an intermediate laminate, and a manufacturing method for a product laminate

The present invention relates to a method for producing a pressure-sensitive adhesive sheet, an intermediate laminate, an intermediate laminate, and a method for producing a product laminate, in particular, an intermediate laminate obtained by using the pressure-sensitive adhesive sheet, the intermediate laminate obtained by using the pressure-sensitive adhesive sheet, and the intermediate laminate It is related with the manufacturing method of the product laminated body obtained using the method of doing this, and the intermediate|middle laminated body.

Conventionally, it is known to stick a reinforcement film on the surface of an electronic device from a viewpoint of surface protection and impact resistance provision.

As such a reinforcing film, there is known a reinforcing film in which adhesion to an adherend is increased by providing an adhesive layer made of a photocurable composition and photocuring the adhesive layer after adhesion to an adherend (for example, , see Patent Document 1).

When such a reinforcing film is attached to an adherend, rework is easy because the adhesive force is small before photocuring the pressure-sensitive adhesive layer. can

Japanese Patent No. 6467551 Publication

On the other hand, there is a desire to peel a part of the reinforcement film without leaving all of the reinforcement film.

In such a case, light is irradiated to the part to remain|survive (it is set as a residual part hereafter), and light is not irradiated to the part to peel (it is set as a peeling part hereafter). Then, since the adhesive force of a residual part is strong, it can be made to remain|survive as it is, and since the adhesive force of a peeling part is low, it can peel.

On the other hand, in order to peel the peeling part, first, the boundary between the residual part and the peeling part is cut|disconnected, and the peeling part is peeled using the edge of the peeling part as a starting point, but a residual part and a peeling part are visually distinguished. Since this cannot be done, there is a problem that the above boundary cannot be visually determined.

The present invention relates to a pressure-sensitive adhesive sheet capable of remaining or removing only an arbitrary portion by applying an external stimulus to an arbitrary portion after affixing to an adherend, an intermediate laminate obtained using the pressure-sensitive adhesive sheet, and the intermediate laminate It is to provide the manufacturing method of the product laminated body obtained using the manufacturing method and the intermediate|middle laminated body.

The present invention [1] includes a substrate and an adhesive layer disposed on one side of the substrate, wherein the adhesive layer can decrease visible light transmittance at a wavelength of 550 nm by an external stimulus, and adhesive strength by the external stimulus It is an adhesive sheet which consists of an adhesive composition which can irreversibly change state in this high state and the state with low adhesive force.

The present invention [2] includes the pressure-sensitive adhesive sheet according to the above [1], wherein the external stimulus is irradiation with an active energy ray.

In the present invention [3], the adhesive layer can decrease the visible light transmittance at a wavelength of 550 nm by irradiation with active energy ray, and from a state of high adhesion to a state of low adhesion by irradiation with active energy ray, irreversibly The [ 1] or the adhesive sheet as described in [2] is included.

In the present invention [4], the shear storage modulus G' at 25°C of the pressure-sensitive adhesive layer before state change is 6×10 ⁴ Pa or more and 9×10 ⁴ Pa or less, and shear storage at 25° C. of the pressure-sensitive adhesive layer after the change of state The adhesive sheet according to [3], wherein the elastic modulus G' is 2.00×10 ⁶ Pa or more and 5.00×10 ⁶ Pa or less, is included.

In the present invention [5], the adhesive layer can reduce the visible light transmittance at a wavelength of 550 nm by irradiation with active energy ray, and from a state of low adhesion to a state of high adhesion by irradiation with active energy ray, irreversibly The [ 1] or the adhesive sheet as described in [2] is included.

In the present invention [6], the shear storage modulus G' at 25° C. of the pressure-sensitive adhesive layer before the change of state is 1×10 ⁴ Pa or more and 1.2×10 ⁵ Pa or less, and the pressure-sensitive adhesive layer at 25° C. The adhesive sheet according to [5], wherein the shear storage modulus G' is 1.5×10 ⁵ Pa or more and 2.0×10 ⁶ Pa or less.

The present invention [7] is provided with an adhesive sheet having a substrate and an adhesive layer disposed on one side of the substrate, and an adherend disposed on one side of the adhesive sheet, wherein the adhesive layer is formed by an external stimulus. Visible light transmittance at a wavelength of 550 nm can be reduced, and the adhesive composition can be irreversibly changed in a state of high adhesive force and low adhesive force by the external stimulus, and the adhesive layer is in a state of high adhesive force. A high-adhesion region made of a pressure-sensitive adhesive composition and a low-adhesion region made of a pressure-sensitive adhesive composition with low adhesive strength, wherein either one of the high-adhesion region and the low-adhesion region has a smaller visible light transmittance at a wavelength of 550 nm than the other. , is an intermediate laminate.

In the present invention [8], the adhesive layer can reduce the visible light transmittance at a wavelength of 550 nm by irradiation with active energy ray, and from a state of high adhesion to a state of low adhesion by irradiation with active energy ray, irreversibly Consists of a state-changeable first adhesive composition, wherein the high-adhesion region consists of the first adhesive composition before the state change, and the low-adhesion region consists of the first adhesive composition after the state change, and the low-adhesion region and the intermediate laminate according to [7], wherein the visible light transmittance at a wavelength of 550 nm in the region is smaller than the visible light transmittance in the high-adhesion region at a wavelength of 550 nm.

In the present invention [9], the adhesive layer is capable of lowering the visible light transmittance at a wavelength of 550 nm by irradiation with active energy ray, and is irreversibly from a state of low adhesion to a state of high adhesion by irradiation with active energy ray. Consists of a state-changeable second adhesive composition, wherein the low-adhesion region consists of the second adhesive composition before the state change, and the high-adhesion region consists of the second adhesive composition after the state change, and the high-adhesion region and the intermediate laminate according to the above [7], wherein the visible light transmittance at a wavelength of 550 nm of the region is smaller than the visible light transmittance at a wavelength of 550 nm of the low adhesion region.

The present invention [10] is arranged on one side of a substrate and the substrate, the visible light transmittance at a wavelength of 550 nm can be reduced by an external stimulus, and a state with high adhesion and a state with low adhesion by the external stimulus, A step of preparing an adhesive sheet having an adhesive layer made of an adhesive composition capable of irreversibly changing its state, a step of arranging an adherend on one side of the adhesive sheet, and applying the external stimulus to a part of the adhesive layer, By forming the magnetic pole portion to which the external stimulus is applied and the non-stimulation portion to which the external stimulus is not applied in the adhesive layer, either one of the magnetic pole portion and the non-stimulation portion becomes a high-adhesive region with high adhesive force , the other side becomes a low-adhesion region with low adhesive force, and further comprising a step of making the visible light transmittance at a wavelength of 550 nm of the magnetic pole portion smaller than the visible light transmittance at a wavelength of 550 nm of the non-stimulating portion. manufacturing method.

According to the present invention [11], the visible light transmittance at a wavelength of 550 nm of the adhesive layer can be reduced by an external stimulus, and the state can be irreversibly changed from a high adhesive force to a low adhesive force by the external stimulus. and the method for producing the intermediate laminate according to the above [10], comprising the first adhesive composition, wherein the magnetic pole portion serves as the low adhesion region and the non-stimulation portion serves as the high adhesion region.

In the present invention [12], the visible light transmittance of the adhesive layer at a wavelength of 550 nm can be decreased by an external stimulus, and the state can be irreversibly changed from a low adhesive force to a high adhesive force by the external stimulus and the method for producing the intermediate laminate according to the above [10], comprising the second adhesive composition, wherein the magnetic pole portion serves as the high adhesion region and the non-stimulation portion serves as the low adhesion region.

In the present invention [13], the step of preparing an intermediate laminate produced by the method for producing an intermediate laminate according to any one of [10] to [12], and the low-adhesive region in the pressure-sensitive adhesive layer The manufacturing method of the product laminated body provided with the process of removing is included.

The adhesive sheet of the present invention includes an adhesive layer, and the adhesive layer is capable of lowering visible light transmittance at a wavelength of 550 nm by an external stimulus, and is irreversibly in a state of high adhesive force and low adhesive force by external stimulus. It consists of a pressure-sensitive adhesive composition that can change state.

When an external stimulus is applied to a part of this pressure-sensitive adhesive sheet, the visible light transmittance at a wavelength of 550 nm is lowered in the portion to which the external stimulus is applied, and the adhesive force is changed (adhesive force increases or decreases).

That is, the portion to which the external stimulus is applied and the portion to which the external stimulus is not applied have different adhesive strength and different visible light transmittance at a wavelength of 550 nm.

Since the visible light transmittance at a wavelength of 550 nm is different between the externally stimulated part and the externally non-stimulated part, the boundary between the externally stimulated part and the externally non-stimulated part can be visually easily discriminated. As a result, it is possible to easily remove a portion having a relatively low adhesive strength among the portion to which the external stimulus is applied and the portion to which the external stimulus is not applied.

In the intermediate laminate of the present invention, the pressure-sensitive adhesive layer includes a high-adhesion region in a high-adhesive state and a low-adhesive region in a low-adhesive state, and one of the high-adhesion region and the low-adhesion region is higher than the other. The visible light transmittance at a wavelength of 550 nm is small.

Thereby, the boundary between the high-adhesion region and the low-adhesion region can be visually easily discriminated, and as a result, the low-adhesion region can be easily removed.

In the method for manufacturing an intermediate laminate of the present invention, an external stimulus is applied to a part of an adhesive layer to form a stimulus part to which an external stimulus is applied and a non-stimulating part to which an external stimulus is not applied, in the adhesive layer, One of the non-stimulatory parts becomes a high-adhesion region in a state of high adhesion, and the other becomes a low-adhesion region in a state of low adhesion, and the visible light transmittance at a wavelength of 550 nm of the magnetic pole part is at a wavelength of 550 nm of the non-stimulating part. and a step of making it smaller than the visible light transmittance of

Thereby, while mutually different adhesive force, the intermediate|middle laminated body provided with the adhesive layer provided with the high-adhesion area|region and the low-adhesion area|region from which the visible light transmittance in wavelength 550nm differs can be manufactured.

The manufacturing method of the product laminated body of this invention is equipped with the process of removing the low-adhesion area|region of the adhesion layer in the intermediate|middle laminated body manufactured by the manufacturing method of the intermediate|middle laminated body of this invention.

Since the adhesive force in the low tack area is low, the low tack area can be easily removed from the intermediate laminate together with the corresponding substrate. On the other hand, the high-adhesion region can be used for reinforcing the adherend together with the corresponding base material by remaining in the intermediate laminate.

1 : shows the schematic of one Embodiment of the adhesive sheet of this invention.
Fig. 2 is a schematic view showing an embodiment of a method for manufacturing an adhesive sheet, in which Fig. 2A shows a first step of preparing a base material, and Fig. 2B shows an adhesive layer on one side of the base material. 2C shows the process of laminating|stacking a peeling film on one side of an adhesion layer.
3 : shows the schematic of one Embodiment of the intermediate|middle laminated body of this invention.
Fig. 4 is a schematic view showing one embodiment of a method for producing an intermediate laminate of the present invention in a case where an adhesive layer is formed of the first adhesive composition, and Fig. 4A is a product for preparing an adhesive sheet Step 3 is shown, and FIG. 4B shows a fourth step of arranging an adherend on one side of the pressure-sensitive adhesive sheet, and FIG. 4C is a portion of the pressure-sensitive adhesive layer by irradiating an active energy ray to form a high-adhesion region and a low-adhesion region. A fifth step of forming is shown.
Fig. 5 is a schematic view showing one embodiment of a method for producing an intermediate laminate of the present invention in a case where an adhesive layer is formed of a second adhesive composition, and Fig. 5A is a method for preparing an adhesive sheet Step 3 is shown, and FIG. 5B shows a fourth step of arranging an adherend on one side of the pressure-sensitive adhesive sheet, and FIG. 5C shows a part of the pressure-sensitive adhesive layer by irradiating an active energy ray to form a high-adhesion region and a low-adhesion region. A fifth step of forming is shown.
[Fig. 6] Fig. 6 is an embodiment of the manufacturing method of the product laminate of the present invention in the case of preparing the intermediate laminate by the manufacturing method of the intermediate laminate in which the adhesive layer is formed with the first adhesive composition. 6A shows the 6th process of preparing an intermediate|middle laminated body, and FIG. 6B shows the 7th process of removing the low-adhesion area|region in an adhesive layer as schematic drawing which shows a form.
7 is an embodiment of the manufacturing method of the product laminate of the present invention in the case where the intermediate laminate is prepared by the manufacturing method of the intermediate laminate in which the pressure-sensitive adhesive layer is formed with the second pressure-sensitive adhesive composition. 7A shows the 6th process of preparing an intermediate|middle laminated body, and FIG. 7B shows the 7th process of removing the low-adhesion area|region in an adhesive layer as schematic diagram showing a form.

One Embodiment of the adhesive sheet of this invention is described with reference to FIG.

1. Adhesive sheet

1 , the pressure-sensitive adhesive sheet 1 has a film shape (including a sheet shape) having a predetermined thickness, extends in a direction (plane direction) orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface. has

Specifically, the pressure-sensitive adhesive sheet 1 includes a base material 2 and an adhesion layer 3 disposed on one side of the base material 2 .

Hereinafter, each layer which comprises the adhesive sheet 1 is demonstrated.

1-1. write

The base material 2 is a lower layer of the adhesive sheet 1 . The base material 2 is a support layer (support material) which ensures the mechanical strength of the adhesive sheet 1 . In addition, the base material 2 is a reinforcing material for reinforcing the to-be-adhered body 6 (described later) in the intermediate|middle laminated body 5 (described later). In addition, the base material 2 has a film shape extending in the plane direction, and has a flat plane and a flat lower surface.

The base material 2 is made of a flexible plastic material.

As such a plastic material, for example, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, for example, (meth)acrylic resins such as polymethacrylate (acrylic resins) and/or methacrylic resin), for example polyethylene, polypropylene, polyolefin resin such as cycloolefin polymer (COP), for example polycarbonate resin, for example polyethersulfone resin, for example, polyarylate resins such as melamine resins such as polyamide resins such as polyimide resins such as cellulosic resins such as polystyrene resins such as norbornene resins. A synthetic resin etc. are mentioned.

Although described later in detail, when the adhesive layer 3 is cured by irradiating an active energy ray (specifically, ultraviolet rays) from the base 2 side, preferably, the base 2 is an active energy ray ( Specifically, it has transparency to ultraviolet rays).

Specifically, having transparency means that a total light transmittance (JIS K 7375-2008) is, for example, 85% or more, preferably 90% or more.

From a viewpoint of making transparency with respect to an active energy ray (specifically, ultraviolet-ray) and mechanical strength compatible, as a plastic material, Preferably a polyester resin, More preferably, polyethylene terephthalate (PET) is mentioned.

The thickness of the substrate 2 is, for example, 4 μm or more, from the viewpoint of reinforcing the adherend 6 (described later), preferably 20 μm or more, more preferably 30 μm or more, still more preferably 45 μm or more, Moreover, for example, 500 micrometers or less, From a viewpoint of flexibility and handling property, Preferably it is 300 micrometers or less, More preferably, it is 200 micrometers or less, More preferably, it is 100 micrometers or less.

1-2. adhesive layer

The adhesive layer 3 is arrange|positioned on the whole surface of one side of the base material 2, The adhesive layer 3 is the upper layer of the adhesive sheet 1 .

The pressure-sensitive adhesive layer 3 is a pressure-sensitive adhesive layer for bonding the pressure-sensitive adhesive sheet 1 to the adherend 6 . In addition, the adhesive layer 3 has a film shape extending in the plane direction, and has a flat plane and a flat lower surface.

The adhesive layer 3 is made of a pressure-sensitive adhesive composition in which the visible light transmittance at a wavelength of 550 nm can be reduced by an external stimulus, and the state can be irreversibly changed into a high adhesive force and a low adhesive force by an external stimulus.

That is, the pressure-sensitive adhesive composition can decrease the visible light transmittance at a wavelength of 550 nm by the same external stimulus, and can irreversibly change its state into a state with high adhesive force and a state with low adhesive force.

As an external stimulus, active energy ray irradiation, such as electron beam irradiation and ultraviolet irradiation, for example, heating etc. are mentioned, for example, Preferably active energy ray irradiation, More preferably, ultraviolet irradiation is mentioned.

If the external stimulus is active energy ray irradiation, an arbitrary part can be locally irradiated with an active energy ray in the 5th process mentioned later.

When the external stimulus is active energy ray irradiation, as an adhesive composition, the visible light transmittance at a wavelength of 550 nm can be decreased by active energy ray irradiation, and from a high adhesive force to a low adhesive force by active energy ray irradiation , The first adhesive composition capable of irreversibly changing the state, and the visible light transmittance at a wavelength of 550 nm can be reduced by irradiation with active energy ray, and from a state of low adhesion to a state of high adhesion by irradiation with active energy ray, irreversible A second pressure-sensitive adhesive composition capable of changing the state of

A 1st adhesive composition contains a polymer, a 1st photocuring agent, a photoinitiator, the compound which develops color by reaction with an acid, and a photo-acid generator.

Specifically, the first adhesive composition contains a polymer as a matrix, and in order to irreversibly change the state from a state of high adhesion to a state of low adhesion by irradiation with active energy ray, the first photocuring agent And, a photoinitiator is included, and in order to make it possible to reduce the visible light transmittance in wavelength 550nm by active energy ray irradiation, the compound which develops color by reaction with an acid, and a photo-acid generator are included.

Examples of the polymer include acrylic polymers, silicone polymers, urethane polymers, and rubber polymers, and acrylic polymers are exemplified from the viewpoint of optical transparency, adhesiveness, and control of storage modulus.

The acrylic polymer is obtained by polymerization of a monomer component containing (meth)acrylic acid alkyl ester as a main component.

(meth)acrylic acid alkyl ester is acrylic acid ester and / or methacrylic acid ester, for example, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylic acid propyl, (meth) acrylic acid butyl, (meth) Isopropyl acrylate, (meth) acrylic acid isobutyl, (meth) acrylic acid s-butyl, (meth) acrylic acid t-butyl, (meth) acrylate pentyl, (meth) acrylic acid isopentyl, (meth) acrylic acid neopentyl, (meth) Acrylic acid hexyl, (meth)acrylic acid heptyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid octyl, (meth)acrylic acid isooctyl, (meth)acrylic acid nonyl, (meth)acrylic acid isononyl, (meth)acrylic acid Decyl, (meth)acrylic acid isodecyl, (meth)acrylic acid undecyl, (meth)acrylic acid dodecyl, (meth)acrylic acid isotridodecyl, (meth)acrylic acid tetradecyl, (meth)acrylic acid isotetradecyl, (meth) linear or (meth)acrylic acid pentadecyl, (meth)acrylic acid cetyl, (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl, (meth)acrylic acid isooctadecyl, (meth)acrylic acid nonadecyl, (meth)acrylic acid eicosyl, etc.; Branched (meth)acrylic acid C1-20 alkyl ester, etc. are mentioned, Preferably (meth)acrylate, (meth)acrylic acid butyl, (meth)acrylic acid 2-ethylhexyl, More preferably, methyl methacrylate , butyl acrylate, and 2-ethylhexyl acrylate.

(meth)acrylic acid alkyl ester can be used individually or in combination of 2 or more types.

As the (meth)acrylic acid alkyl ester, from the viewpoint of adjusting the glass transition temperature and the shear storage modulus G', preferably methyl methacrylate and (meth)acrylic acid C4-12 alkyl ester in combination, (meth)acrylic acid butyl alone Use, More preferably, combined use of methyl methacrylate and 2-ethylhexyl acrylate, and single use of butyl acrylate are mentioned.

As the (meth)acrylic acid alkyl ester, when methyl methacrylate and (meth)acrylic acid C4-12 alkyl ester are used together, with respect to 100 parts by mass of the total amount of methyl methacrylate and (meth)acrylic acid C4-12 alkyl ester, The blending ratio of methyl methacrylate is, for example, 5 parts by mass or more, and for example, 20 parts by mass or less, and the blending ratio of (meth)acrylic acid C4-12 alkyl ester is, for example, , 80 parts by mass or more, and for example, 95 parts by mass or less.

The blending ratio of the (meth)acrylic acid alkyl ester is, for example, 50 mass % or more, preferably 60 mass % or more, with respect to the monomer component, and for example, 97 mass % or less, preferably 80 mass % or less. % or less.

Further, the monomer component preferably contains a vinyl monomer having a functional group copolymerizable with the (meth)acrylic acid alkyl ester.

Examples of the functional group-containing vinyl monomer include a hydroxyl group-containing vinyl monomer, a carboxyl group-containing vinyl monomer, a nitrogen-containing vinyl monomer, a cyano group-containing vinyl monomer, a glycidyl group-containing vinyl monomer, a sulfo group-containing vinyl monomer, and a phosphate group-containing vinyl monomer. A vinyl monomer, an aromatic vinyl monomer, a vinyl ester monomer, a vinyl ether monomer, etc. are mentioned.

As the hydroxyl group-containing vinyl monomer, for example, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 4-hydroxybutyl, (meth)acrylic acid 6-hydroxy Hexyl, (meth)acrylic acid 8-hydroxyoctyl, (meth)acrylic acid 10-hydroxydecyl, (meth)acrylic acid 12-hydroxylauryl, (meth)acrylic acid 4-(hydroxymethyl)cyclohexylmethyl, etc. are mentioned. and 2-hydroxyethyl (meth)acrylate, more preferably 2-hydroxyethyl acrylate.

Examples of the carboxyl group-containing vinyl monomer include (meth)acrylic acid, (meth)acrylic acid 2-carboxyethyl, (meth)acrylic acid carboxypentyl, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like, preferably is (meth)acrylic acid, more preferably acrylic acid.

Moreover, as a carboxyl group containing vinyl monomer, acid anhydride group containing monomers, such as maleic anhydride and itaconic anhydride, are mentioned, for example.

Examples of the nitrogen-containing vinyl monomer include N-vinylpyrrolidone, methyl vinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyl. Oxazole, vinylmorpholine, N-acryloylmorpholine, N-vinylcarboxylic acid amides, N-vinylcaprolactam, etc. are mentioned, Preferably N-vinylpyrrolidone is mentioned.

As a cyano group containing vinyl monomer, (meth)acrylonitrile etc. are mentioned, for example.

As a glycidyl group containing vinyl monomer, (meth)acrylic-acid glycidyl etc. are mentioned, for example.

As a sulfo group containing vinyl monomer, styrene sulfonic acid, allyl sulfonic acid, etc. are mentioned, for example.

As a phosphoric acid group containing vinyl monomer, 2-hydroxyethyl acryloyl phosphate etc. are mentioned, for example.

As an aromatic vinyl monomer, styrene, p-methylstyrene, o-methylstyrene, (alpha)-methylstyrene etc. are mentioned, for example.

As a vinyl ester monomer, vinyl acetate, vinyl propionate, etc. are mentioned, for example.

As a vinyl ether monomer, methyl vinyl ether etc. are mentioned, for example.

The functional group-containing vinyl monomer may be used alone or in combination of two or more. When a crosslinking agent (described later) is blended, from the viewpoint of introducing a crosslinked structure to the polymer, preferably a hydroxyl group-containing vinyl monomer and a carboxyl group-containing vinyl monomer are mentioned, and from the viewpoint of improving cohesive force, it is preferable Preferably, a nitrogen-containing vinyl monomer is mentioned, More preferably, a hydroxyl group-containing vinyl monomer and/or a carboxyl group-containing vinyl monomer and a nitrogen-containing vinyl monomer are used in combination, or a carboxyl group-containing vinyl monomer is used alone.

When using a hydroxyl group containing vinyl monomer and/or a carboxyl group containing vinyl monomer, and a nitrogen containing vinyl monomer together, 100 mass of total amount of a hydroxyl group containing vinyl monomer and/or a carboxyl group containing vinyl monomer, and a nitrogen containing vinyl monomer With respect to parts, the blending ratio of the hydroxyl group-containing vinyl monomer and/or the carboxyl group-containing vinyl monomer is, for example, 40 parts by mass or more, and for example, 60 parts by mass or less, and further, nitrogen-containing vinyl The compounding ratio of the monomer is, for example, 40 parts by mass or more, and is, for example, 60 parts by mass or less.

The blending ratio of the functional group-containing vinyl monomer is, for example, 5 mass % or more, preferably 10 mass % or more, more preferably 15 mass % or more, and, for example, 30 mass % with respect to the monomer component. is below.

And the acrylic polymer is a polymer formed by superposing|polymerizing the above-mentioned monomer component.

In order to polymerize the monomer component, for example, (meth)acrylic acid alkyl ester and, if necessary, a functional group-containing vinyl monomer is blended to prepare a monomer component, and this is, for example, solution polymerization, bulk polymerization, emulsion polymerization It prepares by well-known polymerization methods, such as

As a polymerization method, Preferably solution polymerization is mentioned.

In solution polymerization, a monomer component and a polymerization initiator are mix|blended with a solvent, for example, a monomer solution is prepared, and a monomer solution is heated after that.

As a solvent, an organic solvent etc. are mentioned, for example.

Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene, benzene, and xylene, ether solvents such as diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, For example, ester solvents, such as ethyl acetate, For example, amide solvents, such as N,N- dimethylformamide, are mentioned, Preferably an ester solvent is mentioned, More preferably, ethyl acetate is mentioned.

A solvent can be used individually or can use 2 or more types together.

The mixing ratio of the solvent is, for example, 100 parts by mass or more, preferably 200 parts by mass or more, and for example, 500 parts by mass or less, preferably 300 parts by mass or less with respect to 100 parts by mass of the monomer component. am.

As a polymerization initiator, a peroxide type polymerization initiator, an azo type polymerization initiator, etc. are mentioned, for example.

Examples of the peroxide-based polymerization initiator include organic peroxides such as peroxycarbonate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxyester.

As the azo polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2, Azo compounds, such as 4-dimethylvaleronitrile) and 2,2'- azobisisobutyrate dimethyl, are mentioned.

As a polymerization initiator, Preferably it is an azo type polymerization initiator, More preferably, 2,2'- azobisisobutyronitrile is mentioned.

A polymerization initiator can be used individually or can use 2 or more types together.

The mixing ratio of the polymerization initiator is, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 1 part by mass or less, preferably 0.5 parts by mass with respect to 100 parts by mass of the monomer component. is below.

The heating temperature is, for example, 50°C or more and 80°C or less, and the heating time is, for example, 1 hour or more and 8 hours or less.

Thereby, a monomer component is superposed|polymerized and the acrylic polymer solution containing an acrylic polymer is obtained.

The solid content concentration of the acrylic polymer solution is, for example, 20 mass% or more, and is, for example, 80 mass% or less.

The weight average molecular weight of the acrylic polymer is, for example, 100000 or more, preferably 300000 or more, more preferably 500000 or more, and for example, 5000000 or less, preferably 3000000 or less, more preferably 2000000 or less. am.

In addition, said weight average molecular weight is the value computed by polystyrene conversion by measuring by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the acrylic polymer is, for example, -100°C or higher, preferably -80°C or higher, more preferably -40°C or higher, and further, for example, -10°C or lower, preferably Preferably it is -5 °C or less, More preferably, it is 0 °C or less.

In addition, a glass transition temperature is a value described in literature, a catalog, etc., or is a value calculated based on following formula (1) (Fox formula).

1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +...+W _n /Tg _n (1)

In the formula (1), Tg represents the glass transition temperature (unit: K) of the polymer (A), and Tg _i (i = 1, 2, ... n) is when the monomer i formed a homopolymer. The glass transition temperature (unit: K) at the time is shown, and W _i (i=1, 2,...n) shows the mass fraction in all the monomer components of the monomer i.

In the first adhesive composition, the blending ratio of the polymer is, for example, 70% by mass or more with respect to the total amount of the compound and photoacid generator that develops color by reaction of the polymer, the first photocuring agent, the photoinitiator, and the acid, Moreover, for example, it is 95 mass % or less, Preferably it is 85 mass % or less.

As the first photocuring agent, from the viewpoint of sufficiently reducing the adhesive force of the adhesive layer 3 by irradiation with active energy ray, the number of functional groups is 4 or more, preferably 5 or more, and 6 or less polyfunctional (meth)acrylate Specifically, tetrafunctional (meth)acrylics such as ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate Rates, for example, hexaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and other hexafunctional (meth)acrylates are mentioned, Preferably hexaerythritol poly(meth)acrylate is mentioned. rate, more preferably dipentaerythritol hexaacrylate.

A 1st photocuring agent can be used individually or can use 2 or more types together.

In addition, the functional group equivalent of the first photocuring agent is, for example, 50 g/eq or more, and is, for example, 500 g/eq or less.

The viscosity of the first photocuring agent at 25°C is, for example, 100 mPa·s or more, preferably 400 mPa·s or more, more preferably 1000 mPa·s or more, still more preferably 3000 mPa·s or more, particularly preferably is 4000 mPa·s or more, most preferably 5000 mPa·s or more, moreover 6000 mPa·s or more, and is usually 8000 mPa·s or less.

In addition, the said viscosity can be measured with a B-type viscometer, and specifically, using Toki Sangyo VISCOMETER (BH type), measurement temperature 25 degreeC, rotor No. 3, rotation speed 10rpm, measurement time of 5 minutes conditions can be measured.

The molecular weight of the first photocuring agent is, from the viewpoint of compatibility, for example, 1500 or less, preferably 1000 or less, and for example, 100 or more.

Further, the first photocuring agent is preferably selected to be compatible with the polymer.

When the first photocuring agent is compatible with the polymer, it is possible to increase the adhesive force (described later) of the adhesive layer 3 to which the active energy ray is not irradiated.

Specifically, if the difference between the Hansen solubility parameter (HSP) of the polymer and the Hansen solubility parameter (HSP) of the first photocuring agent is, for example, 4 or less, preferably 3.5 or less, the first photocuring agent and the polymer are compatible , As a result, the adhesive force (described later) of the adhesive layer 3 to which the active energy ray is not irradiated can be increased.

On the other hand, the Hansen solubility parameter (HSP) of the polymer is calculated based on the Hansen solubility parameter (HSP) of the monomer constituting the polymer.

The blending ratio of the first photocuring agent is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and for example, 50 parts by mass or less, preferably 40 parts by mass with respect to 100 parts by mass of the polymer. less than wealth

In addition, the mixing ratio of the first photocuring agent is, for example, 5% by mass or more, preferably 5% by mass or more, based on the total amount of the compound and photoacid generator that develops color by reaction of the polymer, the first photocuring agent, the photopolymerization initiator, and the acid. It is 10 mass % or more, More preferably, it is 20 mass % or more, For example, it is 30 mass % or less.

The photoinitiator accelerates the curing reaction of the first photocuring agent and is appropriately selected according to the type of the first photocuring agent, for example, hydroxyketones such as 1-hydroxycyclohexylphenylketone, for example, 2 Benzoin ethers such as ,2-dimethoxy-1,2-diphenylethan-1-one, benzyl dimethyl ketals, aminoketones, acylphosphine oxides, benzophenones, trichloromethyl group-containing triazine Photoradical initiators, such as derivatives, etc. are mentioned.

A photoinitiator can be used individually or can use 2 or more types together.

Among such photoinitiators, when polyfunctional (meth)acrylate is used as the first photocuring agent, preferably a photoradical initiator, more preferably hydroxyketones are employed.

The light absorption range of a photoinitiator is, for example, 300 nm or more, and is 450 nm or less, for example.

The compounding ratio of a photoinitiator is 0.01 mass part or more with respect to 100 mass parts of polymers, and is, for example, 1 mass part or less, Preferably, it is 0.5 mass part or less.

In addition, the mixing ratio of the photoinitiator is, for example, 0.01 mass % or more with respect to the total amount of the compound and photoacid generator that develops color by reaction of the polymer, the first photocuring agent, the photoinitiator and the acid, and, further, for example For example, it is 1 mass % or less, Preferably it is 0.5 mass % or less, More preferably, it is 0.1 mass % or less.

A compound that develops color by reaction with an acid is a compound that changes color from colorless (transparent) to colored by an acid, for example, a leuco-based dye, for example, p,p',p"-tris-dimethylamino Triarylmethane-based dyes such as triphenylmethane, for example, diphenylmethane-based dyes such as 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, for example 3-diethylamino-6 -Fluoran-based dyes such as methyl-7-chlorofluoran, for example, spiropyran-based dyes such as 3-methylspirodynaphthopyran, for example, rhodamine such as rhodamine-B-anilinolactam Mineral dye etc. are mentioned, Preferably a leuco-type dye is mentioned.

The compound which develops color by reaction with an acid can be used individually or in combination of 2 or more types.

The blending ratio of the compound that develops color by reaction with an acid is, for example, 0.5 parts by mass or more with respect to 100 parts by mass of the polymer, preferably from the viewpoint of further lowering the visible light transmittance at a wavelength of 550 nm by external stimulation, It is 1.5 mass parts or more, and is 5 mass parts or less, for example, Preferably it is 2 mass parts or less.

In addition, the compounding ratio of the compound which develops color by reaction with an acid is, for example, 0.1 mass % or more with respect to the total amount of the compound and photo-acid generator which color by reaction of a polymer, a 1st photocuring agent, a photoinitiator, and an acid. and, for example, 5% by mass or less, preferably 1% by mass or less.

A photo-acid generator is a compound which generate|occur|produces an acid by active energy ray irradiation, For example, an onium compound etc. are mentioned.

Examples of the onium compound include onium cations such as iodonium and sulfonium, Cl ^- , Br ^- , I ^- , ZnCl ₃ ^- , HSO ₃ ^- , BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF and salts composed of anions such as ₆ ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (C ₆ F ₅ ) ₄ B ^- , and (C ₄ H ₉ ) ₄ B ^- .

As such an onium compound, Preferably, the salt which consists of sulfonium (onium cation) and (C ₆ F ₅ ) ₄ B ^- (anion) is mentioned.

Moreover, as a photo-acid generator, a commercial item can also be used, For example, CPI-310B (a salt which consists of sulfonium and (C ₆ F ₅ ) ₄ B ^- , the San Apro company make) etc. are mentioned.

A photo-acid generator can be used individually or can use 2 or more types together.

The blending ratio of the photoacid generator is, for example, 1 part by mass or more with respect to 100 parts by mass of the polymer, and for example, 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass. less than wealth

In addition, the compounding ratio of a photo-acid generator is 0.2 mass % or more with respect to the total amount of the compound and photo-acid generator which develop color by reaction of a polymer, a 1st photo-curing agent, a photoinitiator, and an acid, and, further, For example, it is 10 mass % or less, Preferably it is 2 mass % or less.

Then, in order to prepare the first pressure-sensitive adhesive composition, a polymer (a polymer solution when the polymer is prepared by solution polymerization), a first photocuring agent, a photopolymerization initiator, and a compound that develops color by reaction with an acid, and photoacid generation The agent is blended in the above ratio and mixed.

A crosslinking agent is preferably mix|blended with the 1st adhesive composition from a viewpoint of introduce|transducing a crosslinked structure into a polymer.

Examples of the crosslinking agent include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, a carbodiimide-based crosslinking agent, and a metal chelate-based crosslinking agent, preferably isocyanate. A system crosslinking agent and an epoxy type crosslinking agent are mentioned.

As an isocyanate type crosslinking agent, For example, aliphatic diisocyanate, such as butylene diisocyanate and hexamethylene diisocyanate, For example, cyclopentylene diisocyanate, cyclo Alicyclic diisocyanates such as hexylene diisocyanate and isophorone diisocyanate, for example 2,4-tolylene diisocyanate, 4,4'-diphenylmethane Aromatic diisocyanate, such as diisocyanate and xylylene diisocyanate, is mentioned.

Moreover, as an isocyanate type crosslinking agent, the derivative of said isocyanate (For example, isocyanurate modified body, polyol modified product, etc.) is also mentioned.

As an isocyanate type crosslinking agent, a commercial item can also be used, For example, Coronate L (trimethylol propane adduct body of tolylene diisocyanate, a dosing agent), Coronate HL (hexamethylene diamond) Trimethylolpropane adduct form of isocyanate, dosing agent), Coronate HX (isocyanurate form of hexamethylene diisocyanate), Takenate D110N (trimethylolpropane adduct form of xylylene diisocyanate) A methylol propane adduct body, the Mitsui Chemicals make) etc. are mentioned.

Examples of the epoxy-based crosslinking agent include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidyl aniline, 1,3-bis(N,N-diglycidyl Dylaminomethyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether Dill ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol Polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris ( 2-hydroxyethyl) isocyanurate, resorcin diglycidyl ether, bisphenol-S-diglycidyl ether, etc. are mentioned, Preferably N,N,N',N'- tetraglycidyl ether, etc. are mentioned. dil-m-xylenediamine is mentioned.

As the epoxy-based crosslinking agent, a commercially available product may be used, and examples thereof include tetrad C (N,N,N',N'-tetraglycidyl-m-xylenediamine, manufactured by Mitsubishi Gas Chemicals). there is.

A crosslinking agent can be used individually or can use 2 or more types together.

When a crosslinking agent is mix|blended with the 1st adhesive composition, functional groups, such as a hydroxyl group and a carboxyl group in a polymer, and a crosslinking agent react, and a crosslinked structure is introduce|transduced into a polymer.

The functional group equivalent of the crosslinking agent is, for example, 50 g/eq or more, and is, for example, 500 g/eq or less.

The mixing ratio of the crosslinking agent is, for example, 0.1 parts by mass or more, preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass or more with respect to 100 parts by mass of the polymer when the crosslinking agent is an isocyanate-based crosslinking agent. , More preferably, it is 2.0 mass parts or more, For example, it is 10 mass parts or less, Preferably it is 5 mass parts or less, More preferably, it is 4 mass parts or less.

In addition, when the crosslinking agent is an epoxy-based crosslinking agent, it is, for example, 0.1 parts by mass or more with respect to 100 parts by mass of the polymer, and for example, 2 parts by mass or less, preferably 1 part by mass or less, more preferably is 0.3 parts by mass or less from the viewpoint of improving the adhesive force.

Moreover, when mix|blending a crosslinking agent with the 1st adhesive composition, in order to accelerate|stimulate a crosslinking reaction, you may mix|blend a crosslinking catalyst.

Examples of the cross-linking catalyst include metal-based cross-linking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, nashem ferric, butyl tin oxide, and dioctyl tin dilaurate.

A crosslinking catalyst can be used individually or can use 2 or more types together.

The mixing ratio of the crosslinking catalyst is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and for example, 0.05 parts by mass or less with respect to 100 parts by mass of the polymer.

In addition, in the first adhesive composition, if necessary, for example, a silane coupling agent, a tackifier, a plasticizer, a softener, an inhibitor of deterioration, a filler, a colorant, from the viewpoint of stabilization under a fluorescent lamp or under natural light, a UV absorber, a fluorescent lamp From the viewpoint of stabilization under or under natural light, various additives such as additives such as antioxidants, surfactants and antistatic agents can be contained within a range that does not impair the effects of the present invention.

Thereby, a 1st adhesive composition is obtained.

The blending ratio of the polymer is, for example, 50% by mass or more, preferably 70% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less with respect to the first adhesive composition. .

The blending ratio of the first photocuring agent is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 40% by mass or less, preferably 30% by mass with respect to the first adhesive composition. % or less.

The blending ratio of the photoinitiator is, for example, 0.01% by mass or more with respect to the first adhesive composition, and for example, 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.1% by mass or less. is below.

The compounding ratio of the compound which develops color by reaction with an acid is, for example, 0.1 mass % or more, and for example, 5 mass % or less, preferably 1 mass % or less, with respect to the first adhesive composition.

The compounding ratio of a photo-acid generator is 0.2 mass % or more with respect to 1st adhesive composition, and is 10 mass % or less, for example, Preferably it is 2 mass % or less.

A 2nd adhesive composition contains the said polymer, the 2nd photocuring agent, the said photoinitiator, the compound which develops color by reaction of the said acid, and the said photo-acid generator.

Specifically, the second pressure-sensitive adhesive composition contains a polymer as a matrix, and is irreversibly changed from a low-adhesive state to a high-adhesive state by irradiation with an active energy ray. And, a photoinitiator is included, and in order to make it possible to reduce the visible light transmittance in wavelength 550nm by active energy ray irradiation, the compound which develops color by reaction with an acid, and a photo-acid generator are included.

As a polymer, the thing similar to the polymer mix|blended with said 1st adhesive composition is mentioned, Preferably an acrylic polymer is mentioned.

A polymer can be used individually or can use 2 or more types together.

The blending ratio of the polymer is the same as the blending ratio of the polymer to be blended in the above-described first adhesive composition.

The second photocuring agent, from the viewpoint of sufficiently improving the adhesive force of the adhesive layer 3 by irradiation with active energy ray, for example, a polyfunctional (meth)acrylate having 2 or more and 3 or less functional groups, specifically As, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate , Bisphenol A propylene oxide modified di(meth)acrylate, alkanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, pentaerythritol di(meth)acrylate, neopentyl Bifunctional (meth)acrylates such as lycol di(meth)acrylate and glycerin di(meth)acrylate, for example, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth) ) acrylate and trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, preferably bifunctional (meth)acrylate, more preferably polyethylene glycol die acrylate and polypropylene glycol diacrylate.

A 2nd photocuring agent can be used individually or can use 2 or more types together. In addition, as the second photocuring agent, polyethylene glycol diacrylate having a different polymerization degree is used in combination (for example, polyethylene glycol diacrylate having a polymerization degree of 2 or more and 6 or less, and polyethylene glycol having a polymerization degree of 10 or more and 16 or less) By using col diacrylate together), adhesive force can be made low.

In addition, the functional group equivalent of the second photocuring agent is, for example, 50 g/eq or more, and is, for example, 500 g/eq or less.

The viscosity in 25 degreeC of a 2nd photocuring agent is 5 mPa*s or more, for example, and is 1000 mPa*s or less, for example.

The molecular weight of a 2nd photocuring agent is 200 or less from a compatible viewpoint, and is 1000 or more, for example.

Further, the second photocuring agent is preferably selected that is not compatible with the polymer.

If the second photocuring agent is not compatible with the polymer, it is possible to lower the adhesive force (described later) of the adhesive layer 3 to which the active energy ray is not irradiated.

Specifically, if the difference between the Hansen solubility parameter (HSP) of the polymer and the Hansen solubility parameter (HSP) of the second photocuring agent is, for example, 3 or more, preferably 4 or more, the second photocuring agent and the polymer are not compatible As a result, the adhesive force (described later) of the adhesive layer 3 not irradiated with an active energy ray can be made low.

The blending ratio of the second photocuring agent is the same as the blending ratio of the first photocuring agent to be blended with the above-described first adhesive composition.

Examples of the photopolymerization initiator include those similar to those of the photopolymerization initiator blended with the first adhesive composition described above, and when a polyfunctional (meth)acrylate is used as the second photocuring agent, preferably a photoradical initiator, more preferably Hydroxyketones and benzoin ethers are preferably employed.

A photoinitiator can be used individually or can use 2 or more types together.

The compounding ratio of the photoinitiator is the same as that of the photoinitiator mix|blended with the above-mentioned 1st adhesive composition.

As a compound which develops color by reaction with an acid, the thing similar to the compound which develops color by reaction with the acid mix|blended with the above-mentioned 1st adhesive composition is mentioned, Preferably a leuco-type pigment|dye is mentioned.

The compound which develops color by reaction with an acid can be used individually or in combination of 2 or more types.

The blending ratio of the compound that develops color by reaction with an acid is the same as the blending ratio of the compound that develops color by reaction with the acid to be blended in the first adhesive composition described above.

Examples of the photo-acid generator include those similar to those of the photo-acid generator blended in the first adhesive composition, preferably composed of sulfonium (onium cation) and (C ₆ F ₅ ) ₄ B ⁻ (anion). salts may be mentioned.

A photo-acid generator can be used individually or can use 2 or more types together.

The compounding ratio of a photo-acid generator is the same as the compounding ratio of the photo-acid generator mix|blended with an above-mentioned 1st adhesive composition.

Then, in order to prepare the second adhesive composition, a compound that develops color by reaction of a polymer (a polymer solution when a polymer is prepared by solution polymerization), a second photocuring agent, a photoinitiator, and an acid, and photoacid generation The agent is blended in the above ratio and mixed.

A crosslinking agent is preferably mix|blended with the 2nd adhesive composition from a viewpoint of introduce|transducing a crosslinked structure into a polymer.

As a crosslinking agent, the thing similar to the crosslinking agent mix|blended with said 1st adhesive composition is mentioned, Preferably an isocyanate type crosslinking agent is mentioned.

A crosslinking agent can be used individually or can use 2 or more types together.

The blending ratio of the crosslinking agent is the same as the blending ratio of the crosslinking agent blended in the above-described first adhesive composition.

Moreover, when mix|blending a crosslinking agent with the 2nd adhesive composition, in order to accelerate|stimulate a crosslinking reaction, you may mix|blend a crosslinking catalyst.

As a crosslinking catalyst, the thing similar to the crosslinking catalyst mix|blended with the above-mentioned 1st adhesive composition is mentioned.

A crosslinking catalyst can be used individually or can use 2 or more types together.

The blending ratio of the crosslinking catalyst is the same as the blending ratio of the crosslinking catalyst blended with the above-described first adhesive composition.

In addition, the 2nd adhesive composition can contain various additives mix|blended with said 1st adhesive composition as needed in the range which does not impair the effect of this invention.

Thereby, a 2nd adhesive composition is obtained.

The blending ratio of the polymer to the second adhesive composition, the blending ratio of the second photocuring agent, the blending ratio of the photopolymerization initiator, the blending ratio of the compound that develops color by reaction with an acid, and the blending ratio of the photo-acid generator are the above-described first adhesiveness The blending ratio of the polymer to the composition, the blending ratio of the first photocuring agent, the blending ratio of the photoinitiator, the blending ratio of the compound that develops color by reaction with an acid, and the blending ratio of the photo-acid generator are the same.

That is, the pressure-sensitive adhesive composition (the first pressure-sensitive adhesive composition or the second pressure-sensitive adhesive composition) includes a blending ratio of a polymer, a photopolymerization initiator, and a compound that develops color by reaction with an acid, a photoacid generator, and a crosslinking agent blended as needed, crosslinking It is common in that it includes a catalyst and various additives, and the first adhesive composition includes a first photocuring agent that is a polyfunctional (meth)acrylate having 4 or more functional groups, while the second adhesive composition has 3 or less functional groups. It differs in that it contains the 2nd photocuring agent which is a polyfunctional (meth)acrylate.

That is, the first pressure-sensitive adhesive composition or the second pressure-sensitive adhesive composition can be selectively prepared depending on which one of the first photocuring agent and the second photocuring agent is blended.

And the adhesive layer 3 is formed from the 1st adhesive composition or the 2nd adhesive composition by the method mentioned later.

The thickness of the adhesive layer 3 is, from the viewpoint of adhesiveness, for example, 5 µm or more, preferably 10 µm or more, more preferably 15 µm or more, still more preferably 20 µm or more, and from the viewpoint of handling properties, yes For example, it is 300 micrometers or less, Preferably it is 100 micrometers or less, More preferably, it is 50 micrometers or less, More preferably, it is 40 micrometers or less, Especially preferably, it is 30 micrometers or less.

2. Manufacturing method of adhesive sheet

Next, the method of manufacturing the adhesive sheet 1 is demonstrated with reference to FIG.

The method of manufacturing this adhesive sheet 1 is equipped with the 1st process of preparing the base material 2, and the 2nd process of arrange|positioning the adhesive layer 3 on one side of the base material 2.

In a 1st process, as shown to FIG. 2A, the base material 2 is prepared.

At a 2nd process, as shown in FIG. 2B, the adhesive layer 3 is arrange|positioned on one side of the base material 2.

In order to arrange the pressure-sensitive adhesive layer 3 on one side of the substrate 2, for example, the first pressure-sensitive adhesive composition or the second pressure-sensitive adhesive composition is applied to one side of the substrate 2, and, if necessary, The solvent is dried off.

As a coating method of the 1st adhesive composition or 2nd adhesive composition, for example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brush, spray coating, dip roll coating, bar coating, knife coating, air knife coating , curtain coating, lip coating, die coating, and the like.

As the drying conditions, the drying temperature is, for example, 50°C or higher, preferably 70°C or higher, more preferably 100°C or higher, and for example, 200°C or lower, preferably 180°C or lower, more Preferably it is 150 degrees C or less, and drying time is, for example, 5 second or more, Preferably it is 10 second or more, For example, it is 20 minutes or less, Preferably, it is 15 minutes or less, More preferably, 10 minutes or less. less than a minute

Thereby, the adhesive layer 3 is formed on one side of the base material 2, and the adhesive sheet 1 provided with the base material 2 and the adhesive layer 3 arrange|positioned on one side of the base material 2). is obtained

On the other hand, when the first pressure-sensitive adhesive composition or the second pressure-sensitive adhesive composition contains a crosslinking agent, a release film 4 (described later) is laminated on one side of the pressure-sensitive adhesive layer 3 simultaneously with drying and removal or after drying of the solvent. after), preferably, crosslinking is carried out by aging.

Aging conditions are appropriately set according to the type of crosslinking agent, and the aging temperature is, for example, 20 ° C. or higher, and for example, 160 ° C. or lower, preferably 50 ° C. or lower, and the aging time is, 1 minute or longer, preferably 12 hours or longer, more preferably 1 day or longer, and for example, 7 days or shorter.

As described above, the pressure-sensitive adhesive layer 3 in the pressure-sensitive adhesive sheet 1 is formed of either the first pressure-sensitive adhesive composition or the second pressure-sensitive adhesive composition.

The first adhesive composition can decrease the visible light transmittance at a wavelength of 550 nm by irradiation with active energy ray, and can irreversibly change state from a state of high adhesion to a state of low adhesion by irradiation with active energy ray.

That is, when an active energy ray is irradiated to the pressure-sensitive adhesive layer 3 formed of the first pressure-sensitive adhesive composition as described above, an acid is generated from the photoacid generator, and a compound that develops color by reaction with the acid with the acid develops color (coloring). By doing so, the visible light transmittance at a wavelength of 550 nm of the adhesive layer 3 after irradiating with an active energy ray (after a change of state) is at a wavelength of 550 nm of the adhesive layer 3 before irradiating with an active energy ray (before a change of state) becomes smaller than the visible light transmittance of, and the adhesive force of the adhesive layer 3 after irradiation with active energy rays (after change of state) is smaller than the adhesive force of the adhesive layer 3 before irradiation with active energy rays (before change of state) .

Therefore, in the fifth step to be described later, when a part of the adhesive layer 3 is irradiated with an active energy ray, the adhesive layer 3 made of the first adhesive composition that is not irradiated with an active energy ray becomes a high adhesive region ( 10), the pressure-sensitive adhesive layer 3 made of the first pressure-sensitive adhesive composition irradiated with an active energy ray becomes the low-adhesion region 11 . In addition, the visible light transmittance at a wavelength of 550 nm of the low adhesion region 11 is smaller than the visible light transmittance at a wavelength of 550 nm of the high adhesion region 10 .

Accordingly, the adhesive layer 3 includes a high adhesion region 10 having a large visible light transmittance at a wavelength of 550 nm and a low adhesion region 11 having a small visible light transmittance at a wavelength of 550 nm.

And, the adhesive force of the adhesive layer 3 (adhesive force of the high adhesive region 10) before irradiation with active energy rays (before change of state) is, for example, 5N/25mm or more, preferably 8N/25mm or more, More preferably, it is 10 N/25 mm or more, More preferably, it is 12 N/25 mm or more.

On the other hand, the adhesion layer 3 before a change of state contains a part which does not change state without irradiating an active energy ray (the same below).

Moreover, the adhesive force of the adhesive layer 3 (adhesive force of the low adhesive region 11) after irradiating an active energy ray (after a change of state) is, for example, 4N/25mm or less, Preferably, it is 3N/25mm or less.

If the adhesive force of the high-adhesion region 10 is equal to or greater than the lower limit, the high-adhesion region 10 remains as it is adhered to the adherend 6, and together with the corresponding substrate 2, for reinforcement of the adherend 6 Available.

In addition, if the adhesive force of the low-adhesion region 11 is equal to or less than the upper limit, the low-adhesion region 11 can be easily removed from the intermediate laminate 5 together with the corresponding substrate 2 .

On the other hand, the above adhesive force is described in detail in Examples to be described later, but the adhesive sheet 1 is adhered to a polyimide film at 25° C., and 180 degrees peel test at a peeling rate of 300 mm/min. is measured by

Moreover, the shear storage modulus G' at 25 degreeC of the adhesive layer 3 before irradiation with an active energy ray (before a change of state) is, for example, 6x10 ⁴ Pa or more, Preferably 7x10 ⁴ Pa above, and for example, 9×10 ⁴ Pa or less, preferably 8×10 ⁴ Pa or less.

Moreover, the shear storage modulus G' at 25 degreeC of the adhesive layer 3 after irradiating an active energy ray (after a change of state) is, for example, 2.00×10 ⁶ Pa or more, preferably 2.50×10 ⁶ Pa or more. , more preferably 3.0×10 ⁶ Pa or more, and for example, 5.00×10 ⁶ Pa or less.

In addition, said shear storage modulus G' is measured by the dynamic viscoelasticity measurement in the conditions of a frequency of 1 Hz, a temperature increase rate of 5 degreeC/min, and the temperature range of -50 degreeC - 150 degreeC.

Moreover, the visible light transmittance in wavelength 550nm of the adhesion layer 3 before irradiation with an active energy ray (before a change of state) is, for example, 85% or more, and is 99% or less, for example.

Moreover, the visible light transmittance in wavelength 550nm of the adhesion layer 3 after irradiating an active energy ray (after a change of state) is, for example, 80 % or less, and is 30 % or more, for example.

And the visible light transmittance at wavelength 550nm of the adhesive layer 3 before irradiation with an active energy ray (before a change of state), and visible light at a wavelength of 550nm of the adhesive layer 3 after irradiating with an active energy ray (after a change of state) The difference in transmittance (visible light transmittance at a wavelength of 550 nm of the adhesive layer 3 before irradiation with active energy rays (before state change) - at a wavelength of 550 nm of the adhesion layer 3 after irradiation with active energy rays (after state change) Visible light transmittance) is, for example, 5% or more, preferably 10% or more.

If the difference is equal to or greater than the lower limit, the boundary between the high-adhesion region 10 and the low-adhesion region 11 can be visually easily determined, and as a result, the low-adhesion region 11 can be easily removed. .

Moreover, the average transmittance|permeability in 300 nm - 700 nm of the adhesion layer 3 before irradiating an active energy ray (before a state change) is 80 % or more, and is 99 % or less, for example.

Moreover, the average transmittance|permeability in 300 nm - 700 nm of the adhesion layer 3 after irradiating an active energy ray (after a state change) is 75 % or less, and is 30 % or more, for example.

On the other hand, the method for measuring the transmittance will be described in detail in the Examples to be described later (hereinafter the same).

Moreover, the haze value of the adhesion layer 3 before irradiating an active energy ray (before a state change) is 3 % or less, for example, Preferably, it is 1 % or less.

Moreover, the haze value of the adhesion layer 3 after irradiating an active energy ray (after a state change) is 5 % or less, for example, Preferably it is 3 % or less.

On the other hand, the second pressure-sensitive adhesive composition can decrease the visible light transmittance at a wavelength of 550 nm by irradiation with active energy rays, and can be irreversibly changed from a state of low adhesion to a state of high adhesion by irradiation with active energy rays. .

That is, when the pressure-sensitive adhesive layer 3 formed of the second pressure-sensitive adhesive composition is irradiated with active energy rays, an acid is generated from the photo-acid generator, and a compound that develops color by reaction with the acid by the acid is developed (coloring). ), the visible light transmittance at a wavelength of 550 nm of the adhesive layer 3 after irradiating an active energy ray (after a change of state) is a wavelength of 550 nm of the adhesive layer 3 before irradiating an active energy ray (before a change of state) becomes smaller than the visible light transmittance in , and the adhesive force of the adhesive layer 3 after irradiation with active energy rays (after change of state) is greater than the adhesive force of the adhesive layer 3 before irradiation with active energy rays (before change of state) .

Therefore, in the fifth step to be described later, when a part of the adhesive layer 3 is irradiated with active energy ray, the adhesive layer 3 made of the second adhesive composition not irradiated with active energy ray is a low-adhesion region. It becomes (11), and the adhesive layer 3 which consists of the 2nd adhesive composition irradiated with an active energy ray turns into the highly adhesive area|region 10. In addition, the visible light transmittance at a wavelength of 550 nm of the high adhesion region 10 becomes smaller than the visible light transmittance at a wavelength of 550 nm in the low adhesion region 11 .

Accordingly, the adhesive layer 3 includes a high adhesion region 10 having a small visible light transmittance at a wavelength of 550 nm and a low adhesion region 11 having a large visible light transmittance at a wavelength of 550 nm.

And the adhesive force of the adhesive layer 3 (adhesive force of the low adhesive region 11) before irradiation with an active energy ray (before change of state) is, for example, 4N/25mm or less, preferably 1N/25mm or less .

In addition, the adhesive force (adhesive force of the high adhesive region 10) of the adhesive layer 3 after irradiation with active energy rays (after state change) is, for example, 5N/25mm or more, preferably 8N/25mm or more, more Preferably it is 10N/25mm or more, More preferably, it is 12N/25mm or more.

When the adhesive force of the low-tackiness region 11 is equal to or less than the upper limit, the low-tackiness region 11 can be easily removed from the intermediate laminate 5 together with the corresponding substrate 2 .

In addition, if the adhesive force of the high-adhesion region 10 is equal to or greater than the lower limit, the high-adhesion region 10 remains as it is adhered to the adherend 6 , and the adherend 6 together with the corresponding substrate 2 is Can be used for reinforcement.

Moreover, the shear storage modulus G' at 25 degreeC of the adhesive layer 3 before irradiation with an active energy ray (before a change of state) is, for example, 1×10 ⁴ Pa or more, preferably 5×10 ⁴ Pa above, and for example, 1.2×10 ⁵ Pa or less, preferably 1×10 ⁵ Pa or less.

Moreover, the shear storage modulus G' at 25 degreeC of the adhesive layer 3 after irradiating an active energy ray (after a change of state) is, for example, 1.00×10 ⁵ Pa or more, preferably 1.5×10 ⁵ Pa or more. and, for example, 2.0×10 ⁶ Pa or less, preferably 1.0×10 ⁶ Pa or less.

Moreover, the visible light transmittance in wavelength 550nm of the adhesion layer 3 before irradiation with an active energy ray (before a change of state) is, for example, 85% or more, and is 99% or less, for example.

Moreover, the visible light transmittance in wavelength 550nm of the adhesion layer 3 after irradiating an active energy ray (after a change of state) is, for example, 80 % or less, and is 30 % or more, for example.

And the visible light transmittance at wavelength 550nm of the adhesive layer 3 before irradiation with an active energy ray (before a change of state), and visible light at a wavelength of 550nm of the adhesive layer 3 after irradiating with an active energy ray (after a change of state) The difference in transmittance (visible light transmittance at a wavelength of 550 nm of the adhesive layer 3 before irradiation with active energy rays (before state change) - at a wavelength of 550 nm of the adhesion layer 3 after irradiation with active energy rays (after state change) Visible light transmittance) is, for example, 5% or more, preferably 10% or more.

If the difference is equal to or greater than the lower limit, the boundary between the high-adhesion region 10 and the low-adhesion region 11 can be visually easily determined, and as a result, the low-adhesion region 11 can be easily removed. .

Moreover, the average transmittance|permeability in 300 nm - 700 nm of the adhesion layer 3 before irradiating an active energy ray (before a state change) is 80 % or more, and is 99 % or less, for example.

Moreover, the average transmittance|permeability in 300 nm - 700 nm of the adhesion layer 3 after irradiating an active energy ray (after a state change) is 75 % or less, and is 30 % or more, for example.

Moreover, the haze value of the adhesion layer 3 before irradiating an active energy ray (before a state change) is 3 % or less, for example, Preferably, it is 1 % or less.

Moreover, the haze value of the adhesion layer 3 after irradiating an active energy ray (after a state change) is 5 % or less, for example, Preferably it is 3 % or less.

In addition, as shown in FIG. 2C, the adhesive sheet 1 may laminate|stack the peeling film 4 on one side of the adhesive layer 3 as needed.

In such a case, the adhesive sheet 1 is equipped with the base material 2, the adhesive layer 3, and the peeling film 4 in order.

As the release film 4, flexible plastic films, such as polyethylene, a polypropylene, a polyethylene terephthalate, and a polyester film, are mentioned, for example.

The thickness of the release film 4 is, for example, 3 µm or more, preferably 10 µm or more, and for example, 200 µm or less, preferably 100 µm or less, more preferably 50 µm or less.

The release film 4 is preferably subjected to a release treatment with a release agent such as silicone, fluorine, long-chain alkyl or fatty acid amide, or a release treatment with silica powder.

3. Intermediate laminate

3 , the intermediate laminate 5 has a film shape (including a sheet shape) having a predetermined thickness, extends in a direction (planar direction) perpendicular to the thickness direction, and has a flat upper surface and a flat have a bottom

Specifically, the intermediate laminate 5 includes a base material 2 and an adhesive sheet 1 having an adhesive layer 3 disposed on one side of the base material 2 , and one side of the pressure sensitive adhesive sheet 1 . A to-be-adhered body 6 arrange|positioned is provided.

Although described later in detail, the intermediate|middle laminated body 5 is obtained by sticking the above-mentioned adhesive sheet 1 to the to-be-adhered body 6 .

In addition, the intermediate|middle laminated body 5 is an intermediate|middle component of the product laminated body 12 (described later).

Hereinafter, each layer will be described in detail.

3-1. adhesive sheet

As described above, the pressure-sensitive adhesive sheet 1 includes a substrate 2 and an adhesive layer 3 disposed on one side of the substrate 2 .

In addition, the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive sheet 1 has a high-adhesion region 10 made of the pressure-sensitive adhesive composition in a high-adhesive state, and a low-adhesion area 11 made of the pressure-sensitive adhesive composition in a low-adhesive state. be prepared

In addition, as will be described in detail later, either of the high adhesion region 10 and the low adhesion region 11 has lower visible light transmittance at a wavelength of 550 nm than the other (in other words, the high adhesion region 10 and the low adhesion region 10). The regions 11 have different visible light transmittances at a wavelength of 550 nm from each other).

The high adhesion region 10 and the low adhesion region 11 are obtained by applying an external stimulus (specifically, an active energy ray) to a part of the adhesion layer 3 , as will be described later in detail.

3-2. adherend

The to-be-adhered body 6 is a to-be-reinforced body reinforced by the adhesive sheet 1, For example, an optical device, an electronic device, its component, etc. are mentioned.

On the other hand, in FIG. 3 , the adherend 6 has a flat plate shape, but the shape of the adherend 6 is not particularly limited, and various shapes are available depending on the types of optical devices, electronic devices, and structural parts thereof. this is chosen

4. Manufacturing method of intermediate laminate

One Embodiment of the manufacturing method of the intermediate|middle laminated body 5 is demonstrated with reference to FIG.4 and FIG.5.

In the manufacturing method of this intermediate laminated body 5, the process of preparing the adhesive sheet 1 (3rd process), and the process of arrange|positioning the to-be-adhered body 6 on one side of the adhesive sheet 1 (4th process) , and an external stimulus is applied to a part of the adhesive layer 3 to form, in the adhesive layer 3, a magnetic pole portion 7 to which an external stimulus is applied and a non-stimulated portion 8 to which an external stimulus is not applied, Either one of the magnetic pole portion 7 and the non-stimulating portion 8 becomes the high-adhesive region 10 in a high-adhesive state, and the other becomes the low-adhesive region 11 in a low-adhesive state, and the magnetic pole portion A step (fifth step) of making the visible light transmittance at a wavelength of 550 nm of (7) smaller than the visible light transmittance at a wavelength of 550 nm of the non-stimulating portion 8 is provided.

In the fifth step, one of the magnetic pole portions 7 and the non-stimulating portion 8 becomes the high-adhesion region 10 and the other serves as the low-adhesion region 11, but the adhesive layer 3 is the first Whether formed by the tacky composition or the second tacky composition determines which of the irritating portion 7 and the non-irritating portion 8 will be the high tack area 10 or the low tack area 11 .

Then, it divides into the case where the adhesive layer 3 is formed by the 1st adhesive composition, and the case where the adhesive layer 3 is formed by the 2nd adhesive composition, and it demonstrates below.

In addition, in the following description, the case where an external stimulus is active energy ray irradiation is demonstrated.

4-1. Method for producing an intermediate laminate for forming a pressure-sensitive adhesive layer with the first pressure-sensitive adhesive composition (Method 1)

First, the manufacturing method (manufacturing method 1) of the intermediate|middle laminated body 5 which forms the adhesive layer 3 with a 1st adhesive composition is demonstrated with reference to FIG.

In a 3rd process, as shown to FIG. 4A, the adhesive sheet 1 is prepared.

Next, in a 4th process, as shown in FIG. 4B, the adhesive sheet 1 on the to-be-adhered body 6 so that the adhesive layer 3 arrange|positioned on one side of the base material 2, and the to-be-adhered body 6 may contact. ) is attached.

Next, in the fifth step, as shown in FIG. 4C , the high-adhesion region 10 and the low-adhesion region 11 are formed by irradiating a part of the adhesive layer 3 with an active energy ray.

On the other hand, in the following description, the non-stimulating portion 8 (in other words, the adhesive sheet 1 divided into three in the plane direction) is divided into two places at both ends of the adhesive sheet 1 divided into three in the plane direction. Only one part of the central portion of the inside will be described as the magnetic pole portion 7).

In the fifth step, in the pressure-sensitive adhesive sheet 1 , the magnetic pole portion 7 is irradiated with an active energy ray, and the non-stimulated portion 8 is not irradiated with an active energy ray.

Specifically, the mask 9 is not placed on the stimulation portion 7 , but the mask 9 that blocks active energy rays is placed on the non-stimulation portion 8 .

As described above, when the adhesive layer 3 formed of the first adhesive composition is irradiated with an active energy ray, the adhesive force of the adhesive layer 3 after irradiating the active energy ray is the adhesive layer 3 before irradiating the active energy ray. ) is smaller than the adhesive force of

That is, while the adhesive force of the adhesive layer 3 in the magnetic pole portion 7 is decreased, the decrease in adhesive strength does not occur in the adhesive layer 3 in the non-pole portion 8, and the adhesive force remains strong. .

Then, the magnetic pole part 7 has relatively low adhesive force with respect to the non-stimulated part 8, so the magnetic pole part 7 (specifically, the adhesive layer 3 made of the first adhesive composition after the change of state) Silver becomes the low-adhesion region 11 , and the non-irritating portion 8 (specifically, the adhesive layer 3 made of the first adhesive composition before the change of state) becomes the high-adhesion region 10 .

In addition, in the pressure-sensitive adhesive layer 3 in the magnetic pole portion 7 (low adhesion region 11), an acid is generated from the photo-acid generator, and a compound that develops color by reaction with the acid with the acid develops color (coloring). (specifically, black)). As a result, the adhesive layer 3 in the magnetic pole portion 7 (low adhesion region 11) changes from colorless (transparent) to colored (visible light transmittance at a wavelength of 550 nm becomes low). Then, the visible light transmittance at a wavelength of 550 nm of the magnetic pole portion 7 (low adhesion region 11) is smaller than the visible light transmittance at a wavelength of 550 nm of the non-stimulating portion 8 (high adhesion region 10) (specifically In this case, the magnetic pole portion 7 (low adhesion region 11) is darker than the non-stimulation portion 8 (high adhesion region 10), the magnetic pole portion 7 (low adhesion region 11) and The boundary of the non-stimulating portion 8 (high adhesion region 10) can be visually easily determined.

Thereby, the adhesive layer 3 provided with the high adhesion area|region 10 with a large visible light transmittance|permeability at a wavelength of 550 nm and the low adhesion area|region 11 with a small visible light transmittance|permeability at a wavelength of 550 nm is obtained. Further, an intermediate laminate 5 including the pressure-sensitive adhesive sheet 1 and the adherend 6 in order (in other words, the substrate 2, the pressure-sensitive adhesive layer 3, and the adherend 6 are provided in this order). is obtained

4-2. Method for producing an intermediate laminate for forming a pressure-sensitive adhesive layer with the second pressure-sensitive adhesive composition (Method 2)

Second, the manufacturing method (manufacturing method 2) of the intermediate|middle laminated body 5 which forms the adhesive layer 3 with the 2nd adhesive composition is demonstrated with reference to FIG.

In a 3rd process, as shown to FIG. 5A, the adhesive sheet 1 is prepared.

Next, in the fourth step, as shown in FIG. 5B , the pressure-sensitive adhesive sheet 1 is applied to the adherend 6 such that the adhesive layer 3 disposed on one side of the substrate 2 and the adherend 6 come into contact with each other. ) is attached.

Next, in the fifth step, as shown in FIG. 5C , a part of the adhesive layer 3 is irradiated with an active energy ray to form a high-adhesion region 10 and a low-adhesion region 11 .

On the other hand, in the following description, the magnetic pole part 7 (in other words, the adhesive sheet 1 divided into three parts in the plane direction) at two places of both end parts among the thing which divided the adhesive sheet 1 into 3 in the plane direction. Only one part of the central portion of the inside will be described as the non-stimulating portion 8).

In the fifth step, in the pressure-sensitive adhesive sheet 1 , the magnetic pole portion 7 is irradiated with an active energy ray, and the non-stimulated portion 8 is not irradiated with an active energy ray.

Specifically, the mask 9 is not placed on the stimulation portion 7 , but the mask 9 that blocks active energy rays is placed on the non-stimulation portion 8 .

As described above, when the adhesive layer 3 formed of the second adhesive composition is irradiated with an active energy ray, the adhesive force of the adhesive layer 3 after irradiating the active energy ray is the adhesive layer 3 before irradiating the active energy ray. ) is greater than the adhesive force of

That is, while the adhesive force of the adhesive layer 3 in the magnetic pole part 7 is improved, the improvement of adhesive force does not occur in the adhesive layer 3 in the non-pole part 8.

Then, the magnetic pole portion 7 has a relatively high adhesive force with respect to the non-stimulated portion 8, so the magnetic pole portion 7 (specifically, the adhesive layer 3 made of the second adhesive composition after a change of state) Silver becomes the high-adhesion region 10 , and the non-irritating portion 8 (specifically, the adhesive layer 3 made of the second adhesive composition before the change of state) becomes the low-adhesion region 11 .

In addition, in the pressure-sensitive adhesive layer 3 in the magnetic pole portion 7 (high-adhesion region 10), an acid is generated from the photo-acid generator, and with the acid, a compound that develops color by reaction with the acid develops color (coloring). (specifically, black)). As a result, the adhesive layer 3 in the magnetic pole portion 7 (high adhesion region 10) changes from colorless (transparent) to colored (visible light transmittance at a wavelength of 550 nm becomes low). Then, the visible light transmittance at a wavelength of 550 nm of the magnetic pole portion 7 (high adhesion region 10) becomes smaller than the visible light transmittance at wavelength 550 nm of the non-stimulating portion 8 (low adhesion region 11) (specifically In this case, the magnetic pole portion 7 (high adhesion region 10) is darker than the non-stimulation portion 8 (low adhesion region 11), the magnetic pole portion 7 (high adhesion region 10) and The boundary of the non-stimulating portion 8 (low adhesion region 11) can be visually easily determined.

Thereby, the adhesive layer 3 provided with the high adhesion area|region 10 with a small visible light transmittance|permeability at wavelength 550nm and the low adhesion area|region 11 with a large visible light transmittance|permeability at wavelength 550nm is obtained. Further, an intermediate laminate 5 including the pressure-sensitive adhesive sheet 1 and the adherend 6 in order (in other words, the substrate 2, the pressure-sensitive adhesive layer 3, and the adherend 6 are provided in this order). is obtained

In the above manufacturing method 1 and the above manufacturing method 2, the visible light transmittance at a wavelength of 550 nm of the magnetic pole portion 7 is smaller than the visible light transmittance at a wavelength of 550 nm of the non-stimulating portion 8 (in other words, the magnetic pole portion 7 is It is colored and the non-irritating portion 8 is transparent.) On the other hand, in manufacturing method 1, the stimulating part 7 becomes the low-adhesion region 11, and in manufacturing method 2, the non-irritating part 8 is low-adhesive. It is different in that it becomes the area|region 11.

Moreover, in the manufacturing method of the product laminated body 12 mentioned later, the intermediate|middle laminated body 5 is manufactured first, and the low-adhesion area|region 11 is removed from the intermediate laminated body 5 after that, and high adhesiveness is carried out. The product laminate 12 (described later) is produced by leaving the region 10, but when the intermediate laminate 5 is manufactured by the manufacturing method 1, a transparent high-adhesion region 10 remains, and the manufacturing method 2 When the intermediate laminated body 5 is manufactured by , it is different in that the colored high-adhesive region 10 remains.

That is, depending on which one of the manufacturing methods 1 and 2 is selected, it is possible to select whether to leave the colored or transparent high adhesion region 10 .

5. Effects of adhesive sheets, intermediate laminates and methods for producing intermediate laminates

In the pressure-sensitive adhesive sheet 1, the pressure-sensitive adhesive layer 3 is capable of lowering the visible light transmittance at a wavelength of 550 nm by irradiation with active energy ray, and has high adhesion and low adhesion by irradiation with active energy ray, It consists of an irreversibly changeable adhesive composition.

When a part of the pressure-sensitive adhesive sheet 1 is irradiated with an active energy ray, the visible light transmittance at a wavelength of 550 nm decreases in the portion irradiated with the active energy ray, and the adhesive force changes (adhesive force increases or decreases).

That is, the part irradiated with an active energy ray and the part which is not irradiated with an active energy ray differ in adhesive force mutually, and the visible light transmittance in wavelength 550nm differs.

Since the visible light transmittance at a wavelength of 550 nm is different between the part irradiated with the active energy ray and the part not irradiated with the active energy ray, the boundary between the part irradiated with the active energy ray and the part not irradiated with the active energy ray It can discriminate|determine visually easily, and as a result, among the part irradiated with an active energy ray, and the part which is not irradiated with an active energy ray, the part with relatively low adhesive force can be easily removed.

In the intermediate laminate (5), the pressure-sensitive adhesive layer (3) includes a high-adhesive region (10) in a high-adhesive state and a low-adhesive region (11) in a low-adhesive state.

In addition, the visible light transmittance at a wavelength of 550 nm is smaller in either one of the high-adhesion region 10 and the low-adhesion region 11 than the other.

Specifically, in the above-described method for producing the intermediate laminate 5 , when the adhesive layer is formed with the first adhesive composition, the visible light transmittance at a wavelength of 550 nm of the low adhesive region 11 is the high adhesive region (10) is smaller than the visible light transmittance at a wavelength of 550 nm, and when the adhesive layer is formed of the second adhesive composition, the visible light transmittance at a wavelength of 550 nm of the high adhesive region 10 is that of the low adhesive region 11 It becomes smaller than the visible light transmittance|permeability at a wavelength of 550 nm.

Thereby, the boundary between the high-adhesion region 10 and the low-adhesion region 11 can be visually easily determined. As a result, the low-adhesive region 11 can be removed from the adherend 6 together with the corresponding substrate 2, while the high-adhesive region 10 is left attached to the adherend 6 as it is, It can be used for reinforcement of the adherend 6 together with the corresponding base material 2 .

As a result, the product laminate 12 (described later) in which the adherend 6 is reinforced can be obtained.

Moreover, according to this intermediate laminated body 5, the high adhesion area|region 10 from which adhesive force is mutually different and the visible light transmittance at wavelength 550nm differs by the same external stimulus (specifically, active energy ray irradiation). And by forming the low-adhesion region 11, these can be shared.

Further, according to this intermediate laminate 5, by forming the high-adhesive region 10 with the high-adhesive adhesive composition and forming the low-adhesive region 11 with the low-adhesive composition, the high-adhesive region ( 10) and the low-adhesion region 11 are not shared, but by forming the high-adhesion region 10 and the low-adhesion region 11 with an adhesive composition of the same composition, they can be shared.

In the manufacturing method of the intermediate|middle laminated body 5, a part of the adhesive layer 3 is irradiated with an active energy ray, the adhesive layer 3 is irradiated with the stimulation part 7 irradiated with an active energy ray, and an active energy ray. By forming the non-stimulating portion 8, which is not stimulated, either one of the magnetic pole portion 7 and the non-stimulated portion 8 becomes the high-adhesive region 10 in a state of high adhesive force, and the other is in a state of low adhesive force. a step of making the visible light transmittance at a wavelength of 550 nm of the magnetic pole portion 7 smaller than the visible light transmittance at a wavelength of 550 nm of the non-stimulating portion 8 .

Thereby, the intermediate laminated body 5 provided with the adhesive layer 3 provided with the high-adhesion area|region 10 and the low-adhesion area|region 11 from which adhesive force is mutually different and the visible light transmittance at wavelength 550nm differs by this. can be manufactured.

6. Product laminate and manufacturing method of product laminate

The product stacked body 12 is a final device or a component of the device.

Next, one Embodiment of the manufacturing method of the product laminated body 12 is demonstrated with reference to FIG.6 and FIG.7.

The product laminate 12 is manufactured by removing the low-adhesion region 11 from the intermediate laminate 5 described above.

Specifically, the product laminate 12 includes the sixth step of preparing the intermediate laminate 5 produced by the method for manufacturing the intermediate laminate 5 described above, and the It is manufactured by the manufacturing method of the product laminated body provided with the 7th process of removing the adhesive area|region 11.

In the sixth step, the intermediate laminate 5 produced by the above-described method for manufacturing the intermediate laminate 5 is prepared. It is determined whether the high-adhesion region 10 is colored or transparent.

Then, it divides into the case where the intermediate laminated body 5 manufactured by manufacturing method 1 is prepared, and the case where the intermediate laminated body 5 manufactured by manufacturing method 2 is prepared, and it demonstrates below.

6-1. When preparing the intermediate laminate 5 manufactured by manufacturing method 1

First, the manufacturing method of the product laminated body 12 in the case of preparing the intermediate laminated body 5 manufactured by manufacturing method 1 is demonstrated with reference to FIG.

In the sixth step, as shown in Fig. 6A, the intermediate laminate 5 is manufactured by the manufacturing method (Method 1) of the intermediate laminate 5 in which the pressure-sensitive adhesive layer 3 is formed with the first adhesive composition, , an intermediate laminate 5 is prepared.

In the seventh step, as shown in FIG. 6B , the low-adhesion region 11 is removed from the intermediate laminate 5 .

Specifically, a residual portion 13 composed of the high-adhesion region 10 and the substrate 2 corresponding thereto, and the removal portion 14 composed of the low-adhesion region 11 and the substrate 2 corresponding thereto. The boundary of , for example, is cut with a CO ₂ laser or the like, and then only the removal portion 14 is peeled off with the end of the removal portion 14 as a starting point.

At this time, since the high adhesion region 10 (residual portion 13) and the low adhesion region 11 (removed portion 14) have different visible light transmittance at a wavelength of 550 nm (specifically, the high adhesion region) (10) (residual portion 13) is transparent, and low-adhesion region 11 (removed portion 14) is colored), and the above boundary can be visually easily determined.

And since the adhesive force of the low-adhesion area|region 11 in the removal part 14 is falling, the removal part 14 can be peeled easily from the intermediate|middle laminated body 5. As shown in FIG.

On the other hand, the adhesive force of the high-adhesion region 10 in the residual portion 13 is not lowered, and since it has the above-described high adhesive force, the residual portion 13 remains in the intermediate laminate 5 .

In addition, since the high-adhesion region 10 has the above-described high adhesive force, it is possible to suppress floating of the end portion of the remaining portion 13 in contact with the removal portion 14 even when the removal portion 14 is peeled off.

And the remaining part 13 can be used for reinforcement of the to-be-adhered body 6 as it is.

Thereby, the product laminated body 12 is obtained.

In the product laminate 12 , the remaining portion 13 is transparent, and therefore can be suitably used for optical devices and constituent parts thereof that require transparency.

6-2. When preparing the intermediate laminated body 5 manufactured by manufacturing method 2

Second, the manufacturing method of the product laminated body 12 in the case of preparing the intermediate laminated body 5 manufactured by manufacturing method 2 is demonstrated with reference to FIG.

In the sixth step, as shown in Fig. 7A, the intermediate laminate 5 is manufactured by the manufacturing method (Method 2) of the intermediate laminate 5 in which the pressure-sensitive adhesive layer 3 is formed with the second adhesive composition. , an intermediate laminate 5 is prepared.

In the seventh step, as shown in FIG. 7B , the low-adhesion region 11 is removed from the intermediate laminate 5 .

Specifically, a residual portion 13 composed of the high-adhesion region 10 and the substrate 2 corresponding thereto, and the removal portion 14 composed of the low-adhesion region 11 and the substrate 2 corresponding thereto. The boundary of , for example, is cut with a CO ₂ laser or the like, and then only the removal portion 14 is peeled off with the end of the removal portion 14 as a starting point.

At this time, since the high adhesion region 10 (residual portion 13) and the low adhesion region 11 (removed portion 14) have different visible light transmittance at a wavelength of 550 nm (specifically, the high adhesion region) (10) (residual portion 13) is colored, and low-adhesion region 11 (removed portion 14) is transparent), and the above boundary can be visually easily determined.

And since the adhesive force of the low-adhesion area|region 11 in the removal part 14 is falling, the removal part 14 can be peeled easily from the intermediate|middle laminated body 5. As shown in FIG.

On the other hand, the adhesive force of the high-adhesion region 10 in the residual portion 13 is not lowered, and since it has the above-described high adhesive force, the residual portion 13 remains in the intermediate laminate 5 .

In addition, since the high-adhesion region 10 has the above-described high adhesive force, it is possible to suppress floating of the end portion of the remaining portion 13 in contact with the removal portion 14 even when the removal portion 14 is peeled off.

And the remaining part 13 can be used for reinforcement of the to-be-adhered body 6 as it is.

Thereby, the product laminated body 12 is obtained.

In the product laminate 12 , the remaining portion 13 can be used as an antireflection layer because it is colored.

7. Effects of the manufacturing method of the product laminate

The manufacturing method of the product laminated body 12 is the manufacturing method of the said intermediate laminated body (the manufacturing method of the intermediate laminated body 5 which forms the adhesive layer 3 with a 1st adhesive composition (Manufacturing method 1) or the 2nd The low-adhesive region 11 of the adhesive layer 3 in the intermediate laminate 5 manufactured by the manufacturing method (Method 2)) of the intermediate laminate 5 in which the adhesive layer 3 is formed with the adhesive composition ) is provided with a seventh process of removing.

Since the adhesive force in the low-adhesion region 11 is low, the removal portion 14 can be easily removed from the intermediate laminate 5 .

Further, since the high-adhesion region 10 (remaining portion 13) and the low-adhesion region 11 (removed portion 14) have different visible light transmittance at a wavelength of 550 nm from each other, the remaining portion 13 and the removal The boundary of the portion 14 can be easily determined visually. As a result, the removal portion 14 can be reliably removed from the adherend 6 .

On the other hand, the remaining portion 13 can be made to remain in the intermediate laminate 5 to reinforce the adherend 6 .

Moreover, since moderate rigidity is provided by the residual part 13, handling property improves.

In particular, with respect to the case where the adherend 6 is an electronic device, the thickness of the component parts of the electronic device tends to be small as the electronic device becomes highly integrated, smaller and lighter, and the component components are thinner. This thickness reduction makes it easy to generate|occur|produce curvature and curl resulting from stress at the lamination|stacking interface of a component. Moreover, it becomes easy to produce the curvature by dead weight by thickness reduction.

Also in such a case, according to this adhesive sheet 1, since rigidity can be provided to an electronic device by the residual part 13, curvature, curl, curvature, etc. by stress, dead weight, etc. are suppressed, and handling performance can be improved.

Moreover, in the manufacturing process of an electronic device, when conveyance or processing by an automated apparatus is performed, the component of an electronic device may come into contact with members, such as a conveyance arm and a pin, and a component may be damaged.

In particular, in highly integrated, compact, lightweight, and thin devices, damage or dimensional change may occur due to local stress concentration during contact with a conveying device or the like or cutting processing.

Even in such a case, according to this adhesive sheet 1, moderate rigidity is provided by the remaining part 13, and stress is relieved and dispersed, and cracks, cracks, peeling, dimensional changes, etc. can be suppressed. there is.

8. Variants

Although the above description demonstrated the case where an external stimulus was active energy ray irradiation, heating may be sufficient as an external stimulus.

When the external stimulus is heating, the visible light transmittance at a wavelength of 550 nm can be reduced by heating, and the state of the adhesive layer 3 can be irreversibly changed into a state with high adhesion and a state with low adhesion by heating. It consists of a tacky composition.

Examples of such a pressure-sensitive adhesive composition include a third pressure-sensitive adhesive composition in which the visible light transmittance at a wavelength of 550 nm can be reduced by heating and can be irreversibly changed from a low adhesive strength to a high adhesive strength state by heating.

The third pressure-sensitive adhesive composition contains the above-described polymer, the organosiloxane-containing component, and a compound that develops color by reaction of the above-described acid, and a thermal acid generator.

As the organosiloxane-containing component, for example, an acrylic polymer having an organosiloxane skeleton, a urethane polymer, a polyether polymer, a polyester polymer, a polycarbonate polymer, a polybutadiene polymer, etc. From a viewpoint of control of adhesive force, Preferably, the acrylic polymer which has organosiloxane frame|skeleton is mentioned.

A thermal acid generator is a compound which generate|occur|produces an acid by heating, For example, an arylsulfonium salt, an aryliodonium salt, etc. are mentioned.

Example

Examples and comparative examples are shown below, and the present invention will be described more specifically. In addition, this invention is not limited at all to an Example and a comparative example. In addition, specific numerical values, such as a compounding ratio (content ratio), physical property value, parameter, etc. used in the following description are described in the above "Specific contents for carrying out the invention", and the corresponding compounding ratio (contains) ratio), physical properties, parameters, etc., may be substituted with the upper limit (the numerical value defined as “less than” or “less than”) or the lower limit (the numerical value defined as “more than” or “exceed”) of the description.

In addition, unless otherwise indicated, "part" and "%" are based on mass.

1. Details of ingredients

Each component used in each Example and each comparative example is described below.

Takenate D110N: 75% ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals

Tetrad C: N,N,N',N'-tetraglycidyl-m-xylylenediamine (tetrafunctional epoxy compound, manufactured by Mitsubishi Gas Chemicals)

A-DPH: dipentaerythritol hexaacrylate; functional group equivalent 96 g/eq

APG700: polypropylene glycol #700 (n=12) diacrylate; functional group equivalent 404 g/eq

A200: polyethylene glycol #200 (n=4) diacrylate; functional group equivalent 154 g/eq

A600: polyethylene glycol #600 (n=14) diacrylate; functional group equivalent 354 g/eq

Irgacure 184: 1-hydroxycyclohexyl phenyl ketone from BASF

Irgacure 651: 2,2-dimethoxy-1,2-diphenylethan-1-one

BLACK ND1: leuco dye, made by Yamada Chemical Industries, Ltd.

CPI-310B: salt consisting of sulfonium and (C ₆ F ₅ ) ₄ B ^- , photoacid generator, acid aprose

2. Preparation of polymer

Synthesis Example 1

In a reaction vessel equipped with a thermometer, a stirrer, a reflux cooling tube and a nitrogen gas introduction tube, as monomers, 9 parts by weight of methyl methacrylate (MMA), 63 parts by weight of 2-ethylhexyl acrylate (2EHA), and hydroxyethyl acrylic 13 parts by weight of rate (HEA), 15 parts by weight of N-vinylpyrrolidone (NVP), 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator, and 233 parts by weight of ethyl acetate as a solvent were introduced, nitrogen gas was flowed through It was sent and nitrogen substituted for about 1 hour, stirring. Then, it heated at 60 degreeC, made it react for 7 hours, and obtained the solution of the acrylic polymer whose weight average molecular weight (Mw) is 120000.

Synthesis Example 2

In a reaction vessel equipped with a thermometer, a stirrer, a reflux cooling tube, and a nitrogen gas introduction tube, 95 parts of n-butyl acrylate (BA) and 5 parts of acrylic acid (AA) as monomer components are charged, and nitrogen gas is introduced while nitrogen is introduced. The gas was discharged and nitrogen substituted for 2 hours while stirring. Then, 0.2 parts of 2,2'-azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and solution polymerization was carried out at 60° C. for 8 hours to obtain a solution of an acrylic polymer having a weight average molecular weight (Mw) of 600000. .

3. Preparation of adhesive composition

Preparation Example 1 (Preparation of the first adhesive composition)

To the acrylic polymer solution of Synthesis Example 1, as a crosslinking agent, Takenate D110N (75% ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals) was added 100 parts by weight of polymer solid content to 2.5 parts by mass, A-DPH (dipentaerythritol hexaacrylate) as a photocuring agent, 30 parts by mass based on 100 parts by weight of polymer solid content, as a photopolymerization initiator, Irgacure 184 (1-hydroxycyclo Hexylphenyl ketone, manufactured by BASF), 0.1 parts by mass based on 100 parts by weight of the polymer solid content, as a compound that develops color by reaction with an acid, BLACK ND1 (leuco dye), 1 part by mass based on 100 parts by weight of the polymer solid content , As a photoacid generator, 2 parts by mass of CP-310B was added with respect to 100 parts by weight of solid content of the polymer, and the mixture was uniformly mixed to prepare an adhesive composition (first adhesive composition).

Preparation Example 2 (Preparation of the second adhesive composition)

Except having changed the photocuring agent into APG700 (polypropylene glycol #700 (n=12) diacrylate), it carried out similarly to Preparation Example 1, and prepared the adhesive composition (2nd adhesive composition).

Preparation Example 3 - Preparation Example 10

Except having changed the formulation formulation according to description of Table 1, it processed similarly to Preparation Example 1, and the adhesive composition was manufactured.

4. Preparation of adhesive sheet

Example 1

On the upper surface of the polyethylene terephthalate film (thickness 75 micrometers) as a base material, the adhesive composition of Preparation Example 1 was apply|coated with the fountain roll so that the thickness after drying might be set to 25 micrometers. Then, it dried at 130 degreeC for 1 minute, and the solvent was removed. Thereby, the adhesive layer was formed in one side of a base material. Furthermore, the release-treated surface of the peeling film (the 25-micrometer-thick polyethylene terephthalate film by which the surface was silicone release-processed) was pasted together by one side of the adhesion layer. Thereafter, an aging treatment was performed for 4 days in an atmosphere of 25° C. to advance a crosslinking reaction between the polymer and the crosslinking agent. Thereby, the adhesive sheet was manufactured.

Examples 2 to 7, Comparative Examples 1 to 3

Except having changed the adhesive composition according to description of Table 1, it processed similarly to Example 1, and produced the adhesive sheet.

5. Evaluation

(transmittance)

About the adhesive sheet of each Example and each comparative example, the transmittance|permeability in 550 nm before and behind irradiating LED (365 nm, 4000 mJ/□), and the average transmittance|permeability in 300 nm - 700 nm were measured.

The results are shown in Table 1.

(adhesiveness)

The polyimide film with a thickness of 25 micrometers was affixed to the glass plate through the double-sided adhesive tape ("No. 531" manufactured by Nitto Electric Co., Ltd.), and the polyimide film board|substrate for a measurement was obtained. Next, the peeling film was removed from the adhesive sheet of each Example and each comparative example, the adhesive sheet and the polyimide film board|substrate for a measurement were bonded together at 25 degreeC using the hand roller, and the sample for a measurement was prepared.

Next, after leaving this sample for a measurement to stand for 30 minutes in 25 degreeC and 50% of relative humidity, the adhesive force (adhesive force before UV irradiation) was measured.

Separately, in the same procedure as above, a sample for measurement is prepared, and this sample for measurement is left to stand for 30 minutes at 25°C and 50% relative humidity, and then LED (365 nm, 4000 mJ) from the base side of the pressure-sensitive adhesive sheet. /□), and further, after leaving it to stand for 30 minutes in 25 degreeC and 50% of relative humidity, the adhesive force (adhesive force after UV irradiation) was measured.

The measurement of adhesive force held the edge part (end part of an adhesive sheet) of the sample for a measurement with a chuck|zipper, performed 180 degree peel of a reinforcement film at 300 mm/min of tensile speed|rate, and measured peeling strength. The results are shown in Table 1.

In addition, although the said invention was provided as embodiment of the illustration of this invention, this is only a mere illustration and should not be interpreted limitedly. Modifications of the present invention that are obvious to those skilled in the art are included in the following claims.

The adhesive sheet of this invention is used suitably as an adhesive sheet for reinforcement bonded to the surface of various devices, such as an optical device and an electronic device.

In addition, the intermediate laminated body of this invention, the manufacturing method of an intermediate laminated body, and the manufacturing method of a product laminated body are various devices, such as an optical device and an electronic device, WHEREIN: It is used suitably.

1 adhesive sheet
2 description
3 adhesive layer
5 Intermediate Laminate
6 adherend
7 stimulus part
8 non-irritating part
10 High adhesion area
11 Low tack area
12 product stack

Claims (13)

A substrate and an adhesive layer disposed on one side of the substrate,
The adhesive layer is characterized in that the visible light transmittance at a wavelength of 550 nm can be reduced by an external stimulus, and the adhesive composition can be irreversibly changed into a high adhesive force and a low adhesive force by the external stimulus. which is an adhesive sheet. The method of claim 1,
The pressure-sensitive adhesive sheet, characterized in that the external stimulus is active energy ray irradiation. The method of claim 1,
A first adhesive composition in which the adhesive layer is capable of reducing the visible light transmittance at a wavelength of 550 nm by irradiation with active energy rays, and irreversibly changing its state from a state of high adhesion to a state of low adhesion by irradiation with active energy rays is made of,
The said 1st adhesive composition contains a polymer, a 1st photocuring agent, a photoinitiator, the compound which develops color by reaction with an acid, and a photo-acid generator, The adhesive sheet characterized by the above-mentioned. 4. The method of claim 3,
The shear storage modulus G' at 25° C. of the pressure-sensitive adhesive layer before the change of state is 6×10 ⁴ Pa or more and 9×10 ⁴ Pa or less,
Shear storage elastic modulus G' at 25 degreeC of the adhesive layer after a state change is 2.00x10 ⁶ Pa or more and 5.00x10 ⁶ Pa or less, The adhesive sheet characterized by the above-mentioned. The method of claim 1,
A second adhesive composition in which the adhesive layer can reduce the visible light transmittance at a wavelength of 550 nm by irradiation with active energy ray, and irreversibly change the state from a low adhesive force to a high adhesive force by active energy ray irradiation is made of,
The said 2nd adhesive composition contains a polymer, a 2nd photocuring agent, a photoinitiator, the compound which develops color by reaction with an acid, and a photo-acid generator, The adhesive sheet characterized by the above-mentioned. 6. The method of claim 5,
The shear storage modulus G' at 25° C. of the pressure-sensitive adhesive layer before the change of state is 1×10 ⁴ Pa or more and 1.2×10 ⁵ Pa or less,
Shear storage elastic modulus G' at 25°C of the pressure-sensitive adhesive layer after the state change is 1.5×10 ⁵ Pa or more and 2.0×10 ⁶ Pa or less, The pressure-sensitive adhesive sheet. A pressure-sensitive adhesive sheet having a base material and an adhesive layer disposed on one side of the base material, and an adherend disposed on one side of the pressure-sensitive adhesive sheet,
The adhesive layer is made of an adhesive composition capable of reducing visible light transmittance at a wavelength of 550 nm by an external stimulus, and irreversibly changing the state into a high adhesive force and a low adhesive force by the external stimulus,
The pressure-sensitive adhesive layer includes a high-adhesive region made of a pressure-sensitive adhesive composition with high adhesive strength and a low-adhesive region made of a low-adhesive composition comprising a low-adhesive composition,
An intermediate laminate, characterized in that either one of the high adhesion region and the low adhesion region has a smaller visible light transmittance at a wavelength of 550 nm than the other. 8. The method of claim 7,
A first adhesive composition in which the adhesive layer is capable of reducing the visible light transmittance at a wavelength of 550 nm by irradiation with active energy rays, and irreversibly changing its state from a state of high adhesion to a state of low adhesion by irradiation with active energy rays is made of,
The high-adhesive region consists of the first adhesive composition before the change of state,
The low-adhesive region consists of the first adhesive composition after the change of state,
An intermediate laminate, characterized in that a visible light transmittance at a wavelength of 550 nm in the low adhesion region is smaller than a visible light transmittance in the high adhesion region at a wavelength of 550 nm. 8. The method of claim 7,
A second adhesive composition in which the adhesive layer can reduce the visible light transmittance at a wavelength of 550 nm by irradiation with active energy ray, and irreversibly change the state from a low adhesive force to a high adhesive force by active energy ray irradiation is made of,
The low-adhesive region consists of the second adhesive composition before the change of state,
The high-adhesive region consists of the second adhesive composition after the change of state,
The intermediate laminate according to claim 1, wherein a visible light transmittance at a wavelength of 550 nm in the high adhesion region is smaller than a visible light transmittance in the low adhesion region at a wavelength of 550 nm. Adhesiveness that is arranged on one side of the substrate and the substrate, the visible light transmittance at a wavelength of 550 nm can be reduced by an external stimulus, and the state can be irreversibly changed into a state with high adhesion and a state with low adhesion by the external stimulus A step of preparing an adhesive sheet provided with an adhesive layer made of a composition,
disposing an adherend on one side of the pressure-sensitive adhesive sheet; and
The external stimulus is applied to a part of the adhesive layer to form, in the adhesive layer, a stimulus part to which the external stimulus is applied and a non-stimulation part to which the external stimulus is not applied. One side is a high adhesion region with high adhesive force, and the other is a low adhesion region with low adhesive force, and the visible light transmittance at a wavelength of 550 nm of the magnetic pole portion is visible light at a wavelength of 550 nm of the non-stimulating portion A method for producing an intermediate laminate, comprising the step of making the transmittance smaller than the transmittance. 11. The method of claim 10,
The adhesive layer is composed of a first adhesive composition capable of reducing visible light transmittance at a wavelength of 550 nm by an external stimulus, and irreversibly changing the state from a high adhesive force to a low adhesive force by the external stimulus, ,
The magnetic pole portion becomes the low-adhesive region,
The manufacturing method of the intermediate|middle laminated body characterized by the said non-stimulation part becoming the said high-adhesion area|region. 11. The method of claim 10,
The adhesive layer is composed of a second adhesive composition capable of reducing visible light transmittance at a wavelength of 550 nm by an external stimulus, and irreversibly changing the state from a low adhesive force to a high adhesive force by the external stimulus, ,
The magnetic pole portion becomes the high-adhesive region,
The manufacturing method of the intermediate|middle laminated body characterized by the said non-stimulation part becoming the said low-adhesion area|region. The process of preparing the intermediate laminated body manufactured by the manufacturing method of the intermediate laminated body of Claim 10;
The manufacturing method of the product laminated body characterized by comprising the process of removing the said low adhesive area|region in the said adhesive layer.

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