TW202111048A - Adhesive sheet, intermediate laminate, method for manufacturing intermediate laminate, and method for manufacturing finished laminate - Google Patents

Abstract

An adhesive sheet 1 comprises a base material 2 and an adhesive layer 3 disposed on one side of the base material 2. The adhesive layer 3 is formed from an adhesive composition, the visible light transmissivity at wavelength 550 nm of which can decrease in response to an external stimulus, and which is capable of an irreversible state change from a high-adhesive-strength state to a low-adhesive-strength state in response to an external stimulus.

Description

Adhesive sheet, intermediate laminate, intermediate laminate manufacturing method, and product laminate manufacturing method

The present invention relates to an adhesive sheet, an intermediate laminate, a method for manufacturing an intermediate laminate, and a method for manufacturing a product laminate. In detail, it relates to an adhesive sheet, an intermediate laminate obtained by using the adhesive sheet, A method of manufacturing the intermediate laminate, and a method of manufacturing a product laminate obtained by using the intermediate laminate.

Previously, from the viewpoint of surface protection and impact resistance imparting, it has been known to attach a reinforcing film to the surface of an electronic component.

As such a reinforcing film, there is known a reinforcing film provided with an adhesive layer containing a photocurable composition, which increases the adhesive force with the adherend by light-curing the adhesive layer after being bonded to the adherend (for example, Refer to Patent Document 1).

If this kind of reinforcing film is attached to the adherend, the adhesive force is small before the adhesive layer is light-cured, so secondary processing is easy. On the other hand, after the adhesive layer is light-cured, the adhesive force becomes High, so it can reinforce the adherend. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 6467551

[The problem to be solved by the invention]

On the other hand, there is a demand that it is not desired to leave all of the reinforcing film and to peel off a part of the reinforcing film.

In this case, light is irradiated to the portion to be left (hereinafter referred to as the residual portion), and light is not irradiated to the portion to be peeled (hereinafter referred to as the peeled portion). In this way, the adhesive force of the remaining part is strong, so it can remain directly, and the adhesive force of the peeled part is low, so it can be peeled off.

On the other hand, when peeling off the peeled part, firstly, the boundary between the remaining part and the peeled part is cut off, and the peeled part is peeled from the edge of the peeled part as a starting point. However, the residual part and the peeled part cannot be distinguished visually. It is impossible to visually distinguish the above-mentioned boundary defects.

The present invention is to provide an adhesive sheet that can leave or remove only an arbitrary part by applying external stimuli to an arbitrary part after being attached to an adherend, an intermediate laminate obtained by using the adhesive sheet, and manufacture the intermediate A method of a laminate, and a method of manufacturing a product laminate obtained by using the intermediate laminate. [Technical means to solve the problem]

The present invention [1] is an adhesive sheet comprising a substrate and an adhesive layer disposed on one surface of the substrate; and the adhesive layer includes an adhesive composition that transmits visible light at a wavelength of 550 nm The rate can be reduced by external stimuli, and the above-mentioned external stimuli can irreversibly change state to a state with higher adhesion and a state with lower adhesion.

The present invention [2] includes the adhesive sheet as described in [1] above, wherein the external stimulus is active energy beam irradiation.

The present invention [3] includes the adhesive sheet as described in [1] or [2], wherein the adhesive layer comprises a first adhesive composition, and the visible light transmittance of the first adhesive composition at a wavelength of 550 nm It can be reduced by active energy beam irradiation, and the state can be irreversibly changed from a state with high adhesive force to a state with low adhesive force by active energy beam irradiation; the first adhesive composition includes a polymer, The first light hardener, a photopolymerization initiator, a compound that develops color by reaction with an acid, and a photoacid generator.

The present invention [4] includes the adhesive sheet as described in [3] above, wherein the shear storage elastic modulus G'of the adhesive layer before the state change at 25°C is 6×10 ⁴ Pa or more and 9×10 ⁴ Pa Hereinafter, the shear storage elastic modulus G'of the adhesive layer 3 at 25°C after the state change is 2.00×10 ⁶ Pa or more and 5.00×10 ⁶ Pa or less.

The present invention [5] includes the adhesive sheet as described in [1] or [2], wherein the adhesive layer comprises a second adhesive composition, and the visible light transmittance of the second adhesive composition at a wavelength of 550 nm It can be reduced by active energy beam irradiation, and the state can be irreversibly changed from a state with low adhesive force to a state with high adhesive force by active energy beam irradiation; the second adhesive composition described above includes a polymer, The second light hardener, a photopolymerization initiator, a compound that develops color by reaction with an acid, and a photoacid generator.

The present invention [6] includes the adhesive sheet as described in [5] above, wherein the shear storage elastic modulus G'of the adhesive layer at 25°C before the state change is 1×10 ⁴ Pa or more and 1.2×10 ⁵ Below Pa, the shear storage elastic modulus G'of the adhesive layer at 25°C after the state change is 1.5×10 ⁵ Pa or more and 2.0×10 ⁶ Pa or less.

The present invention [7] is an intermediate laminate comprising: an adhesive sheet having a substrate and an adhesive layer arranged on one side of the substrate, and an adherend arranged on one side of the adhesive sheet; and the above-mentioned adhesive The layer contains an adhesive composition, the visible light transmittance of the adhesive composition at a wavelength of 550 nm can be reduced by external stimuli and can be moved to a state of higher adhesive force and a state of lower adhesive force by the external stimulus. The state changes irreversibly; the above-mentioned adhesive layer has: a high-adhesive area including an adhesive composition in a state with a higher adhesive force, and a low-adhesion area including an adhesive composition in a state with a lower adhesive force; the above-mentioned high-adhesion area And the visible light transmittance of any one of the aforementioned low adhesion regions at a wavelength of 550 nm is less than the other.

The present invention [8] includes the intermediate laminate as described in [7] above, wherein the adhesive layer includes a first adhesive composition whose visible light transmittance at a wavelength of 550 nm can be activated by The energy beam is irradiated, and the state can be changed irreversibly from a state with high adhesive force to a state with low adhesive force by irradiation with active energy beam. The high-adhesion area includes the first adhesive combination before the state change The low adhesion area includes the first adhesive composition after the state change, the visible light transmittance at a wavelength of 550 nm in the low adhesion area is less than the visible light transmittance at a wavelength of 550 nm in the high adhesion area.

The present invention [9] includes the intermediate laminate as described in [7] above, wherein the adhesive layer includes a second adhesive composition whose visible light transmittance at a wavelength of 550 nm can be activated by The energy beam is irradiated to decrease, and the state can be changed irreversibly from the state of low adhesive force to the state of high adhesive force by the irradiation of active energy beam, and the low-adhesion area includes the second adhesiveness before the state change The composition; the high-adhesion area includes the second adhesive composition after the state change, the visible light transmittance of the high-adhesion area at a wavelength of 550 nm is less than the visible light transmittance of the low-adhesion area at a wavelength of 550 nm.

The present invention [10] is a method for manufacturing an intermediate laminate. The method includes the following steps: preparing an adhesive sheet having a substrate and an adhesive layer, the adhesive layer is disposed on one side of the substrate and includes an adhesive composition, The visible light transmittance of the adhesive composition at a wavelength of 550 nm can be reduced by external stimuli and can be irreversibly changed to a state with higher adhesive force and a state with lower adhesive force by the external stimulus; An adherend is arranged on one side of the adhesive sheet; and the external stimulus is applied to a part of the adhesive layer, and a stimulus part provided with the external stimulus and a non-irritated part not provided with the external stimulus are formed on the adhesive layer, by Either one of the above-mentioned stimulating part and the above-mentioned non-stimulating part becomes a high-adhesion area with a high adhesive force, and the other becomes a low-adhesive area with a low adhesive force, and the above-mentioned stimulating part is at a wavelength of 550 nm The visible light transmittance below is lower than the visible light transmittance of the non-irritating part at a wavelength of 550 nm.

The present invention [11] includes the method for manufacturing an intermediate laminate as described in [10] above, wherein the adhesive layer includes a first adhesive composition whose visible light transmittance at a wavelength of 550 nm can be It is reduced by external stimuli, and the state can be irreversibly changed from a state with high adhesive force to a state with low adhesive force by the external stimulus, the stimulating part becomes the low adhesion area, and the non-irritating part becomes The above-mentioned high adhesion area.

The present invention [12] includes the method for manufacturing an intermediate laminate as described in [10] above, wherein the adhesive layer includes a second adhesive composition, and the visible light transmittance of the second adhesive composition at a wavelength of 550 nm can be It is reduced by external stimuli, and the state can be irreversibly changed from a state with low adhesive force to a state with high adhesive force due to the external stimulus, the stimulating part becomes the high adhesion area, and the non-irritating part becomes The above low adhesion area.

The present invention [13] includes a method for manufacturing a product laminate, the method comprising the steps of preparing an intermediate laminate produced by the method for manufacturing an intermediate laminate as described in any one of [10] to [12] above Body; and the above-mentioned low-adhesion area in the above-mentioned adhesive layer is removed. [Effects of Invention]

The adhesive sheet of the present invention has an adhesive layer, and the adhesive layer contains an adhesive composition. The visible light transmittance of the adhesive composition at a wavelength of 550 nm can be reduced by external stimuli and can be adhered by external stimuli. The state of higher force and the state of lower adhesive force irreversibly change state.

If an external stimulus is applied to a part of the adhesive sheet, the visible light transmittance at a wavelength of 550 nm of the part to which the external stimulus is applied decreases, and the adhesive force changes (the adhesive force becomes higher or lower).

That is, the adhesive force of the part given external stimulus and the part not given external stimulus is different from each other, and the visible light transmittance at a wavelength of 550 nm is different from each other.

Since the visible light transmittance at a wavelength of 550 nm is different between the part given external stimulus and the part not given external stimulus, the boundary between the part given external stimulus and the part not given external stimulus can be easily distinguished visually. As a result, it is possible to easily remove the relatively low adhesive force of the part to which the external stimulus is applied and the part to which the external stimulus is not applied.

In the intermediate layered body of the present invention, the adhesive layer has a high-adhesive area in a state with higher adhesive force and a low-adhesion area in a state with lower adhesive force, and any one of the high-adhesion area and the low-adhesion area is at a wavelength The visible light transmittance at 550 nm is less than the other.

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

The manufacturing method of the intermediate laminate of the present invention includes the steps of: imparting an external stimulus to a part of the adhesive layer, forming a stimulating part to which the external stimulus is imparted and a non-stimulating part to which the external stimulus is not imparted on the adhesive layer, whereby the stimulating part and Either one of the non-irritating parts becomes a high-adhesion area with a higher adhesive force, and the other becomes a low-adhesive area with a lower adhesive force, and the visible light transmittance of the stimulated part at a wavelength of 550 nm is lower than that of the non-irritating part Part of the visible light transmittance at a wavelength of 550 nm.

Thereby, it is possible to manufacture an intermediate laminated body having an adhesive layer having a high-adhesion area and a low-adhesion area with different adhesion forces and different visible light transmittance at a wavelength of 550 nm.

The manufacturing method of the product laminate of the present invention includes the step of removing the low-adhesion area of the adhesive layer in the intermediate laminate manufactured by the manufacturing method of the intermediate laminate of the present invention.

Since the adhesive force of the low-adhesion area is low, the low-adhesion area and the corresponding base material can be easily removed from the intermediate laminate. On the other hand, it is possible to leave the high-adhesion area in the intermediate laminate and use it together with the corresponding base material to reinforce the adherend.

An embodiment of the adhesive sheet of the present invention will be described with reference to FIG. 1.

1. Adhesive sheet As shown in FIG. 1, the adhesive sheet 1 has a film shape (including a sheet shape) with a specific thickness, extends in a direction (plane direction) orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface.

Specifically, the adhesive sheet 1 includes a substrate 2 and an adhesive layer 3 arranged on one surface of the substrate 2.

Hereinafter, each layer constituting the adhesive sheet 1 will be described.

1-1. Substrate The substrate 2 is the lower layer of the adhesive sheet 1. The base material 2 is a support layer (support material) that ensures the mechanical strength of the adhesive sheet 1. In addition, the base material 2 in the intermediate layered body 5 (described later) is a reinforcing material for reinforcing the adherend 6 (described later). In addition, the substrate 2 has a film shape extending in the plane direction, and has a flat plane and a flat lower surface.

The substrate 2 includes a flexible plastic material.

Examples of such plastic materials include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, such as polymethacrylate. (Meth) acrylic resins (acrylic resins and/or methacrylic resins), such as polyolefin resins such as polyethylene, polypropylene, cycloolefin polymer (COP), such as polycarbonate resins, such as polyether sulfite resins, For example, polyarylate resins, such as melamine resins, such as polyamide resins, such as polyimide resins, such as cellulose resins, such as polystyrene resins, synthetic resins such as norene resins, and the like.

When an active energy beam (specifically, ultraviolet rays) is irradiated from the side of the substrate 2 to harden the adhesive layer 3, it is preferable that the substrate 2 has transparency to the active energy beam (specifically, ultraviolet rays). Details It will be described later.

The term “transparency” specifically means that the total light transmittance (JIS K 7375-2008) is, for example, 85% or more, and preferably 90% or more.

From the viewpoint of taking into account both the transparency to active energy beams (specifically, ultraviolet rays) and mechanical strength, as the plastic material, a polyester resin is preferable, and polyethylene terephthalate is more preferable. (PET).

The thickness of the substrate 2 is, for example, 4 μm or more. From the viewpoint of reinforcing the adherend 6 (described later), it is preferably 20 μm or more, more preferably 30 μm or more, and even more preferably 45 μm Above, it is 500 μm or less, for example, from the viewpoint of flexibility and operability, it is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 100 μm or less.

1-2. Adhesive layer The adhesive layer 3 is disposed on the entire surface of one surface of the substrate 2, and the adhesive layer 3 is the upper layer of the adhesive sheet 1.

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

The adhesive layer 3 includes an adhesive composition, the visible light transmittance of the adhesive composition at a wavelength of 550 nm can be reduced by external stimuli, and can be brought to a state of higher adhesion and lower adhesion by external stimuli The state changes irreversibly.

That is, the visible light transmittance of the adhesive composition at a wavelength of 550 nm can be reduced by the same external stimulus, and the state can be irreversibly changed to a state with higher adhesive force and a state with lower adhesive force.

Examples of the external stimulus include active energy beam irradiation such as electron beam irradiation and ultraviolet irradiation. Examples include heating, etc., preferably active energy beam irradiation, and more preferably ultraviolet irradiation.

If the external stimulus is active energy beam irradiation, it is possible to locally irradiate the active energy beam to any part in the fifth step described later.

When the external stimulus is irradiated with an active energy beam, as an adhesive composition, the visible light transmittance at a wavelength of 550 nm can be reduced by the active energy beam irradiation, and the self-adhesive force can be obtained by the active energy beam irradiation The first adhesive composition that irreversibly changes the state from a higher state to a state with a lower adhesive force, and the visible light transmittance at a wavelength of 550 nm can be reduced by active energy beam irradiation and can be irradiated by active energy beam A second adhesive composition that irreversibly changes its state from a state with low adhesive force to a state with high adhesive force.

The first adhesive composition includes a polymer, a first light curing agent, a photopolymerization initiator, a compound that develops color by reaction with an acid, and a photoacid generator.

In detail, the first adhesive composition includes a polymer as a matrix, and in order to be able to irreversibly change the state from a state with a high adhesive force to a state with a low adhesive force by the irradiation of an active energy beam, it includes The first photohardener and photopolymerization initiator, in order to reduce the transmittance of visible light at a wavelength of 550 nm by active energy beam irradiation, include a compound that develops color by reaction with an acid, and light Acid generator.

Examples of polymers include acrylic polymers, silicone polymers, urethane polymers, rubber polymers, etc., from the viewpoint of controlling optical transparency, adhesiveness, and storage elastic modulus Specifically, acrylic polymers can be cited.

The acrylic polymer can be obtained by polymerization of monomer components containing alkyl (meth)acrylate as the main component.

Alkyl (meth)acrylate is acrylate and/or methacrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylate )Butyl acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate , Isoamyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) )Octyl acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylate Base) undecyl acrylate, dodecyl (meth)acrylate, isotri(dodecyl) (meth)acrylate, tetradecyl (meth)acrylate, (meth) Isotetradecyl acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate Ester, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate and other linear or branched (meth)acrylic acid C1 -20 alkyl ester, etc., preferably methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, more preferably methyl methacrylate, butyl acrylate , 2-Ethylhexyl acrylate.

The alkyl (meth)acrylate may be used alone or in combination of two or more kinds.

As the alkyl (meth)acrylate, from the viewpoint of adjusting the glass transition temperature and the shear storage elastic modulus G', preferably methyl methacrylate and (meth)acrylic C4-12 alkyl The combined use of esters and the use of butyl (meth)acrylate alone, more preferably the combined use of methyl methacrylate and 2-ethylhexyl acrylate, and the use of butyl acrylate alone.

As the alkyl (meth)acrylate, when methyl methacrylate and C4-12 alkyl (meth)acrylate are used in combination, compared to methyl methacrylate and C4-12 (meth)acrylate The total amount of base ester is 100 parts by mass, 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 C4-12 alkyl (meth)acrylate is, for example, It is 80 parts by mass or more, and, for example, 95 parts by mass or less.

Regarding the blending ratio of the alkyl (meth)acrylate, relative to the monomer components, it is, for example, 50% by mass or more, preferably 60% by mass or more, and, for example, 97% by mass or less, preferably 80% by mass or less .

In addition, the monomer component preferably contains a functional group-containing vinyl monomer copolymerizable with the alkyl (meth)acrylate.

Examples of functional group-containing vinyl monomers include: hydroxyl-containing vinyl monomers, carboxyl-containing vinyl monomers, nitrogen-containing vinyl monomers, cyano group-containing vinyl monomers, and glycidol-containing vinyl monomers. Vinyl monomers, vinyl monomers containing sulfo groups, vinyl monomers containing phosphoric acid groups, aromatic vinyl monomers, vinyl ester monomers, vinyl ether monomers, etc.

Examples of vinyl monomers containing hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylate. 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, 4-(hydroxymethyl)acrylate (meth) Cyclohexyl)methyl and the like, preferably 2-hydroxyethyl (meth)acrylate, more preferably 2-hydroxyethyl acrylate.

Examples of vinyl monomers containing a carboxyl group include (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, and maleic acid. Diacid, fumaric acid, crotonic acid, etc., preferably, (meth)acrylic acid is used, and more preferably, acrylic acid is used.

Moreover, as a vinyl monomer containing a carboxyl group, an acid anhydride group-containing monomers, such as maleic anhydride and itaconic anhydride, can also be mentioned, for example.

Examples of nitrogen-containing vinyl monomers include: N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperidone, vinyl Pyridine, vinyl pyrrole, vinyl imidazole, vinyl azole, vinyl oxoline, N-acryloyl oxoline, N-vinyl carboxylic acid amines, N-vinyl caprolactam, etc. Preferably, N-vinylpyrrolidone can be cited.

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

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

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

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

Examples of the aromatic vinyl monomer include styrene, p-methylstyrene, o-methylstyrene, α-methylstyrene, and the like.

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 monomers can be used alone or in combination of two or more kinds. In the case of formulating a crosslinking agent (described later), from the viewpoint of introducing a crosslinked structure into the polymer, preferably, a vinyl monomer containing a hydroxyl group and a vinyl monomer containing a carboxyl group can be cited Moreover, from the viewpoint of improving cohesive force, it is preferable to include a vinyl monomer containing nitrogen, and it is more preferable to combine a vinyl monomer containing a hydroxyl group and/or a vinyl monomer containing a carboxyl group with a nitrogen-containing vinyl monomer. Vinyl monomers are used in combination, or carboxyl-containing vinyl monomers are used alone.

When a vinyl monomer containing a hydroxyl group and/or a vinyl monomer containing a carboxyl group is used in combination with a vinyl monomer containing a nitrogen, it is compared with a vinyl monomer containing a hydroxyl group and/or a vinyl monomer containing a carboxyl group. The total amount of the monomer and the nitrogen-containing vinyl monomer is 100 parts by mass, and the mixing ratio of the hydroxyl-containing vinyl monomer and/or the carboxyl-containing vinyl monomer is, for example, 40 parts by mass or more, and, for example, 60 parts by mass Hereinafter, the compounding ratio of the nitrogen-containing vinyl monomer is, for example, 40 parts by mass or more, and, for example, 60 parts by mass or less.

The blending ratio of the functional group-containing vinyl monomer relative to the monomer components is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and, for example, 30% by mass or less.

In addition, the acrylic polymer is a polymer obtained by polymerizing the above-mentioned monomer components.

When the monomer components are polymerized, for example, an alkyl (meth)acrylate and, if necessary, a vinyl monomer containing a functional group are prepared to prepare the monomer components, and the monomer components are prepared, for example, by solution polymerization, bulk polymerization, It is prepared by known polymerization methods such as emulsion polymerization.

As the polymerization method, preferably, solution polymerization is mentioned.

In solution polymerization, for example, a monomer component and a polymerization initiator are prepared in a solvent to prepare a monomer solution, and thereafter, the monomer solution is heated.

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

Examples of organic solvents include aromatic hydrocarbon solvents such as toluene, benzene, and xylene. Examples include ether solvents such as diethyl ether. Examples include ketone solvents such as acetone and methyl ethyl ketone. Examples include ethyl acetate. Ester-based solvents such as esters include, for example, amide-based solvents such as N,N-dimethylformamide, preferably ester-based solvents, and more preferably ethyl acetate.

The solvent can be used alone or in combination of two or more kinds.

The mixing ratio of the solvent relative to 100 parts by mass of the monomer components 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.

Examples of the polymerization initiator include peroxide-based polymerization initiators, azo-based polymerization initiators, and the like.

Examples of peroxide-based polymerization initiators include organic peroxides such as peroxycarbonate, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, and peroxyester. Oxide.

As an azo polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis (2,4-Dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate and other azo compounds.

As the polymerization initiator, preferably, an azo-based polymerization initiator is used, and more preferably, 2,2'-azobisisobutyronitrile is used.

The polymerization initiator may be used alone or in combination of two or more kinds.

The blending ratio of the polymerization initiator relative to 100 parts by mass of the monomer components 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 or less.

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, the monomer components are polymerized, and an acrylic polymer solution containing an acrylic polymer is obtained.

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

The weight average molecular weight of the acrylic polymer is, for example, 100,000 or more, preferably 300,000 or more and 500,000 or more, for example, 5,000,000 or less, preferably 3,000,000 or less, and more preferably 2,000,000 or less.

In addition, the above-mentioned weight average molecular weight is a value calculated by GPC (Gel Permeation Chromatograph) and calculated by polystyrene conversion.

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, for example, -10°C or lower, preferably -5°C or lower , More preferably below 0°C.

In addition, the glass transition temperature is a value described in documents, catalogs, etc., or a value calculated based on the following formula (1) (Fox formula). 1/Tg=W ₁ /Tg ₁ ＋W ₂ /Tg ₂ ＋・・・＋W _n /Tg _n (1) In the above formula (1), Tg represents the glass transition temperature of the polymer (A) (unit: K) , Tg _i (i=1, 2,...n) represents the glass transition temperature when monomer i forms a homopolymer (unit: K), W _i (i=1, 2,...n) represents the unit The mass fraction of the total monomer components of body i.

In the first adhesive composition, the blending ratio of the polymer is relative to the total of the polymer, the first photohardener, the photopolymerization initiator, the compound that develops color by reaction with acid, and the photoacid generator The amount is, for example, 70% by mass or more, and for example, 95% by mass or less, and preferably 85% by mass or less.

As the first light curing agent, from the viewpoint that the adhesive force of the adhesive layer 3 is sufficiently reduced by irradiation with active energy beams, polyfunctional (methyl) groups having a functional group number of 4 or more, preferably 5 or more and 6 or less can be mentioned. ) Acrylates, specifically, tetrafunctional (meth)acrylates such as di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. ) Acrylates, for example, hexafunctional (meth)acrylates such as dipentaerythritol poly(meth)acrylate and dipentaerythritol hexa(meth)acrylate, preferably hexafunctional (meth)acrylate, More preferably, dipentaerythritol hexaacrylate is mentioned.

The first light hardener may be used alone or in combination of two or more kinds.

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

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

In addition, the above-mentioned viscosity can be measured with a B-type viscometer. Specifically, Toki Sangyo's VISCOMETER (BH type) can be used to measure the temperature at 25°C, the rotor No. 3, the number of revolutions 10 rpm, and the measurement time of 5 minutes. The conditions are determined.

Regarding the molecular weight of the first light curing agent, from the viewpoint of compatibility, it is, for example, 1500 or less, preferably 1000 or less, and, for example, 100 or more.

In addition, it is preferable that the first light curing agent is selected to be compatible with the polymer.

As long as the first light curing agent is compatible with the polymer, the adhesive force of the adhesive layer 3 that is not irradiated with the active energy beam can be improved (described later).

Specifically, as long as the difference between the Hansen solubility parameter (HSP) of the polymer and the Hansen solubility parameter (HSP) of the first light hardener is, for example, 4 or less, preferably 3.5 or less, the first light hardener and the polymer The substances are compatible, and as a result, the adhesive force of the adhesive layer 3 that is not irradiated with the active energy beam can be improved (described later).

Furthermore, the Hansen solubility parameter (HSP) of the polymer is calculated based on the Hansen solubility parameter (HSP) of the monomers constituting the polymer.

The blending ratio of the first light hardener relative to 100 parts by mass of the polymer 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, and preferably 40 parts by mass or less.

In addition, the compounding ratio of the first light hardener is, for example, 5 relative to the total amount of the polymer, the first light hardener, the photopolymerization initiator, the compound that develops color by reaction with acid, and the photoacid generator. Mass% or more, preferably 10 mass% or more, more preferably 20 mass% or more, and, for example, 30 mass% or less.

The photopolymerization initiator promotes the curing reaction of the first photocuring agent, and can be appropriately selected depending on the type of the first photocuring agent. Examples include hydroxyketones such as 1-hydroxycyclohexyl phenyl ketone. Examples include 2,2- Benzoin ethers such as dimethoxy-1,2-diphenylethane-1-one, benzil dimethyl ketals, amino ketals, phosphine oxides, benzophenones, Contains trichloromethyl tertiary derivatives and other photo-radical initiators.

The photopolymerization initiator can be used alone or in combination of two or more kinds.

Among such photopolymerization initiators, when a polyfunctional (meth)acrylate is used as the first photohardener, a photoradical initiator is preferably used, and hydroxyketones are more preferred.

The light absorption range of the photopolymerization initiator is, for example, 300 nm or more, and for example, 450 nm or less.

The compounding ratio of the photopolymerization initiator is, for example, 0.01 parts by mass or more with respect to 100 parts by mass of the polymer, and is, for example, 1 part by mass or less, and preferably 0.5 parts by mass or less.

In addition, the compounding ratio of the photopolymerization initiator relative to the total amount of the polymer, the first photohardener, the photopolymerization initiator, the compound that develops color by reaction with acid, and the photoacid generator is, for example, 0.01 Mass% or more, and, for example, 1 mass% or less, preferably 0.5 mass% or less, and more preferably 0.1 mass% or less.

The compound that develops color by reaction with acid is a compound that changes from colorless (transparent) to colored by acid, for example, leuco pigments such as p,p',p''-tris-dimethylamino Triarylmethane-based pigments such as triphenylmethane, for example, diphenylmethane-based pigments such as 4,4-bis-dimethylaminophenyl benzhydryl benzyl ether, such as 3-diethylamino-6-methyl-7 -Fluoran-based pigments such as chlorofluorane, spiropyran-based pigments such as 3-methylspirodinaphthopyran, rose bengal pigments such as rose bengal-B-anilinolactam, etc., preferably List leuco pigments.

The compound that develops color by reaction with acid may be used alone or in combination of two or more kinds.

The compounding ratio of the compound that develops color by reaction with acid is, for example, 0.5 parts by mass or more relative to 100 parts by mass of the polymer. From the viewpoint that the visible light transmittance at a wavelength of 550 nm is further reduced due to external stimuli, it is more It is preferably 1.5 parts by mass or more, for example, 5 parts by mass or less, and more preferably 2 parts by mass or less.

In addition, the compounding ratio of the compound that develops color by reaction with acid is relative to the polymer, first light hardener, photopolymerization initiator, compound that develops color by reaction with acid, and photoacid generator The total amount is, for example, 0.1% by mass or more, for example, 5% by mass or less, and preferably 1% by mass or less.

The photoacid generator is a compound that generates an acid by irradiation with an active energy beam, and examples thereof include onium compounds.

Examples of the onium compound include iodonium and sulfonium and the like comprising a cation and ^{Cl -, Br -, I -} , ZnCl 3 -, HSO 3 -, BF 4 -, PF 6 -, AsF 6 -, SbF 6 -, CH _{^{3 SO 3 -, CF 3 SO}} 3 -, (C 6 F 5) 4 B -, (C 4 H 9) 4 B - anion of the salt such like.

As such an onium compound preferably include sulfonium comprising (cations), and _{(C 6 F 5) 4 B} - ( anion) of the salt.

Moreover, as a photoacid generator, a commercial item can also be used, for example, CPI-310B (including a _{salt of arunus and (C 6} F ₅ ) ₄ B ^- , manufactured by SAN-APRO) etc. are mentioned.

The photoacid generator can be used alone or in combination of two or more kinds.

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

In addition, the compounding ratio of the photoacid generator is, for example, 0.2 mass relative to the total amount of the polymer, the first light hardener, the photopolymerization initiator, the compound that develops color by the reaction with the acid, and the photoacid generator. % Or more, and, for example, 10% by mass or less, preferably 2% by mass or less.

In addition, when preparing the first adhesive composition, the polymer (in the case of preparing the polymer by solution polymerization, the polymer solution), the first photohardener, the photopolymerization initiator, and the The compound that develops color by reaction with acid and the photoacid generator are mixed.

In the first adhesive composition, it is preferable to formulate a crosslinking agent from the viewpoint of introducing a crosslinked structure into the polymer.

Examples of crosslinking agents include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, azoline-based crosslinking agents, aziridine-based crosslinking agents, carbodiimide-based crosslinking agents, and metal chelate. As a compound-based crosslinking agent, etc., preferably, an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent are mentioned.

Examples of the isocyanate-based crosslinking agent include: for example, aliphatic diisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; for example, lipids such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone diisocyanate. Cyclic diisocyanates; for example, aromatic diisocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate.

In addition, as the isocyanate-based crosslinking agent, derivatives of the above-mentioned isocyanate (for example, an isocyanurate modified product, a polyol modified product, etc.) can also be cited.

As the isocyanate-based crosslinking agent, commercially available products may also be used, for example, Coronaate L (trimethylolpropane adduct of toluene diisocyanate, manufactured by Tosoh), Coronate HL (trihydroxymethyl of hexamethylene diisocyanate) Methylpropane adduct, manufactured by Tosoh), Coronaate HX (isocyanurate of hexamethylene diisocyanate), Takenate D110N (trimethylolpropane adduct of xylylene diisocyanate, Mitsui Chemicals Manufacturing) and so on.

Examples of epoxy-based crosslinking agents include: N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1,3-bis(N,N-di Glycidyl amino methyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene two Alcohol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, three Methylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl isocyanurate-tris(2-hydroxyethyl) ester, resorcinol diglycidyl Glyceryl ether, bisphenol S-diglycidyl ether, etc., preferably N,N,N',N'-tetraglycidyl-m-xylylenediamine.

As the epoxy-based crosslinking agent, commercially available products may also be used, and examples thereof include Tetrad C (N,N,N',N'-tetraglycidyl-m-xylylenediamine, manufactured by Mitsubishi Gas Chemical).

The crosslinking agent can be used alone or in combination of two or more kinds.

If a crosslinking agent is formulated in the first adhesive composition, functional groups such as hydroxyl and carboxyl groups in the polymer react with the crosslinking agent to introduce a crosslinking structure into the polymer.

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

Regarding the blending ratio of the crosslinking agent, when the crosslinking agent is an isocyanate-based crosslinking agent, relative to 100 parts by mass of the polymer, for example, 0.1 parts by mass or more, preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass Parts or more, more preferably 2.0 parts by mass or more, and, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 4 parts by mass or less.

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

In addition, when blending a crosslinking agent in the first adhesive composition, a crosslinking catalyst may be blended in order to promote the crosslinking reaction.

Examples of the crosslinking catalyst include metal crosslinking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, iron triacetone acetone, butyl tin oxide, and dioctyl tin dilaurate.

The crosslinking catalyst can be used alone or in combination of two or more kinds.

The blending ratio of the crosslinking catalyst relative to 100 parts by mass of the polymer 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.

In addition, the first adhesive composition may optionally contain a silane coupling agent, an adhesiveness imparting agent, a plasticizer, a softening agent, an anti-deterioration agent, a filler, and a coloring agent within a range that does not impair the effects of the present invention. From the viewpoint of stabilization under fluorescent lamps or natural light, the ultraviolet absorber may be contained within a range that does not impair the effects of the present invention. From the viewpoint of stabilization under fluorescent lamps or natural light, Various additives such as additives such as antioxidants, surfactants, and antistatic agents are contained within the range that does not impair the effects of the present invention.

Thereby, the first adhesive composition can be obtained.

The blending ratio of the polymer relative to the first adhesive composition 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.

The blending ratio of the first light hardener relative to the first adhesive composition is, for example, 10% by mass or more, preferably 20% by mass or more, and, for example, 40% by mass or less, and preferably 30% by mass or less.

The blending ratio of the photopolymerization initiator relative to the first adhesive composition is, for example, 0.01% by mass or more, and for example, 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less.

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

The blending ratio of the photoacid generator relative to the first adhesive composition is, for example, 0.2% by mass or more, and, for example, 10% by mass or less, and preferably 2% by mass or less.

The second adhesive composition includes the above-mentioned polymer, a second light curing agent, the above-mentioned photopolymerization initiator, the above-mentioned compound that develops color by reaction with an acid, and the above-mentioned photoacid generator.

In detail, the second adhesive composition contains a polymer as a matrix, and in order to be able to irreversibly change the state from a state with a low adhesive force to a state with a high adhesive force by the irradiation of an active energy beam, it contains The second photohardener and photopolymerization initiator, in order to reduce the transmittance of visible light at a wavelength of 550 nm by active energy beam irradiation, include a compound that develops color by reaction with an acid, and light Acid generator.

The polymer may be the same as the polymer compounded in the above-mentioned first adhesive composition, preferably an acrylic polymer.

The polymer can be used alone or in combination of two or more kinds.

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

Regarding the second light curing agent, from the viewpoint that the adhesive force of the adhesive layer 3 is sufficiently improved by active energy beam irradiation, for example, a polyfunctional (meth)acrylate having a functional group number of 2 or more and 3 or less can be cited. For example, it can be listed: 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 glycol di(meth)acrylate, glycerol di(meth)acrylate and other bifunctional (meth)acrylates, such as ethoxylated isocyanuric acid tris(meth)acrylate Tri) acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate and other trifunctional (meth)acrylates, etc. Preferably, bifunctional (meth)acrylates are mentioned More preferably, polyethylene glycol diacrylate and polypropylene glycol diacrylate can be cited.

The second light hardener can be used alone or in combination of two or more kinds. In addition, by using together polyethylene glycol diacrylates with different degrees of polymerization (for example, polyethylene glycol diacrylate with a degree of polymerization of 2 or more and 6 or less and a polyethylene glycol diacrylate with a degree of polymerization of 10 or more and 16 or less) Used together) as a second light hardener to reduce adhesion.

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

The viscosity of the second light hardener at 25°C is, for example, 5 mPa·s or more, and, for example, 1000 mPa·s or less.

Regarding the molecular weight of the second light curing agent, from the viewpoint of compatibility, it is, for example, 200 or less, and, for example, 1000 or more.

In addition, it is preferable that the second light curing agent is selected to be incompatible with the polymer.

As long as the second light curing agent is incompatible with the polymer, the adhesive force of the adhesive layer 3 that is not irradiated with the active energy beam can be reduced (described later).

Specifically, as long as the difference between the Hansen solubility parameter (HSP) of the polymer and the Hansen solubility parameter (HSP) of the second light hardener is, for example, 3 or more, preferably 4 or more, the second light hardener and the polymer The substances are incompatible, and as a result, the adhesive force of the adhesive layer 3 that is not irradiated with the active energy beam can be reduced (described later).

The compounding ratio of the second light hardener is the same as the compounding ratio of the first light hardener compounded in the above-mentioned first adhesive composition.

As the photopolymerization initiator, the same as the photopolymerization initiator formulated in the above-mentioned first adhesive composition can be cited. When a polyfunctional (meth)acrylate is used as the second photocuring agent, it is more It is preferable to use a photo-radical initiator, and more preferable are hydroxyketones and benzoin ethers.

The photopolymerization initiator can be used alone or in combination of two or more kinds.

The blending ratio of the photopolymerization initiator is the same as the blending ratio of the photopolymerization initiator blended in the above-mentioned first adhesive composition.

Examples of the compound that develops color by reaction with acid include the same compound as the compound that develops color by reaction with acid, which is formulated in the first adhesive composition, and preferably includes leuco pigments. .

The compound that develops color by reaction with acid may be used alone or in combination of two or more kinds.

The compounding ratio of the compound that develops color by reaction with acid is the same as the compounding ratio of the compound that develops color by reaction with acid prepared in the first adhesive composition.

As the photoacid generator include the above-described first adhesive composition was formulated as the photoacid generator are the same, preferably comprises a sulfonium include (cations), and _{(C 6 F 5) 4 B} - ( Anion) salt.

The photoacid generator can be used alone or in combination of two or more kinds.

The blending ratio of the photoacid generator is the same as the blending ratio of the photoacid generator blended in the first adhesive composition.

In addition, when preparing the second adhesive composition, the polymer (in the case of preparing the polymer by solution polymerization, the polymer solution), the second light curing agent, the photopolymerization initiator, and the The compound that develops color by reaction with acid and the photoacid generator are mixed.

In the second adhesive composition, it is preferable to formulate a crosslinking agent from the viewpoint of introducing a crosslinked structure into the polymer.

As a crosslinking agent, the same thing as the crosslinking agent compounded in the said 1st adhesive composition is mentioned, for example, Preferably, an isocyanate type crosslinking agent is mentioned.

The crosslinking agent can be used alone or in combination of two or more kinds.

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

In addition, when a crosslinking agent is blended in the second adhesive composition, a crosslinking catalyst may be blended in order to promote the crosslinking reaction.

As the crosslinking catalyst, the same ones as the crosslinking catalyst blended in the above-mentioned first adhesive composition can be cited.

The crosslinking catalyst can be used alone or in combination of two or more kinds.

The blending ratio of the cross-linking catalyst is the same as the blending ratio of the cross-linking catalyst blended in the above-mentioned first adhesive composition.

In addition, the second adhesive composition may optionally contain various additives formulated in the above-mentioned first adhesive composition within a range that does not impair the effects of the present invention.

Thereby, the second adhesive composition can be obtained.

Relative to the second adhesive composition, the compounding ratio of the polymer, the compounding ratio of the second light hardener, the compounding ratio of the photopolymerization initiator, the compounding ratio of the compound that develops color by reaction with acid, and the photoacid The compounding ratio of the generator and the above-mentioned compounding ratio of the polymer relative to the first adhesive composition, the compounding ratio of the first light hardener, the compounding ratio of the photopolymerization initiator, the color development by reaction with acid The compounding ratio of the compound and the compounding ratio of the photoacid generator are the same.

That is, the adhesive composition (the first adhesive composition or the second adhesive composition) is mixed with a polymer, a photopolymerization initiator, a compound that develops color by reaction with an acid, and photoacid production The crosslinking agent, crosslinking catalyst, and various additives are common to each other as required, but the first adhesive composition contains the first photocuring of polyfunctional (meth)acrylate with 4 or more functional groups. On the other hand, the second adhesive composition contains a second light curing agent as a polyfunctional (meth)acrylate having a functional group number of 3 or less, and this point is different.

That is, depending on which of the first light hardener and the second light hardener is blended, the first adhesive composition or the second adhesive composition can be selectively prepared.

In addition, the adhesive layer 3 is formed from the first adhesive composition or the second adhesive composition by the method described later.

From the viewpoint of adhesion, the thickness of the adhesive layer 3 is, for example, 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more, and from the viewpoint of operability For example, it is 300 μm or less, preferably 100 μm or less, more preferably 50 μm or less, still more preferably 40 μm or less, and particularly preferably 30 μm or less.

2. Manufacturing method of adhesive sheet Next, a method of manufacturing the adhesive sheet 1 will be described with reference to FIG. 2.

The method of manufacturing the adhesive sheet 1 includes a first step of preparing a substrate 2 and a second step of arranging an adhesive layer 3 on one surface of the substrate 2.

In the first step, as shown in FIG. 2A, the base material 2 is prepared.

In the second step, as shown in FIG. 2B, an adhesive layer 3 is disposed on one surface of the substrate 2.

When disposing the adhesive layer 3 on one surface of the substrate 2, for example, the above-mentioned first adhesive composition or the second adhesive composition is coated on one surface of the substrate 2, and the solvent is dried and removed as necessary.

As the coating method of the first adhesive composition or the second adhesive composition, for example, roll coating, touch roll coating, gravure coating, reverse coating, roll brushing, spraying, dipping can be mentioned. Roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, die nozzle coating, etc.

As 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 150°C or lower, drying time For example, it is 5 seconds or more, preferably 10 seconds or more, and for example, it is 20 minutes or less, preferably 15 minutes or less, and more preferably 10 minutes or less.

In this way, the adhesive layer 3 is formed on one surface of the base material 2, and the adhesive sheet 1 having the base material 2 and the adhesive layer 3 arranged on one surface of the base material 2 can be obtained.

Furthermore, when the first adhesive composition or the second adhesive composition contains a cross-linking agent, it should be removed simultaneously with the drying or after the solvent is dried (in an area of the adhesive layer 3, the layer peeling film 4 ( After (described later)), crosslinking is preferably performed by aging.

The aging conditions can be appropriately set depending on the type of crosslinking agent. The aging temperature is, for example, 20°C or more, and, for example, 160°C or less, preferably 50°C or less, and the aging time is 1 minute or more, preferably 12 hours or more. More preferably, it is 1 day or more, and, for example, it is 7 days or less.

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

The visible light transmittance of the first adhesive composition at a wavelength of 550 nm can be reduced by active energy beam irradiation, and can be irreversibly changed from a state of high adhesive force to a state of low adhesive force by active energy beam irradiation Make status changes.

That is, if the adhesive layer 3 formed of such a first adhesive composition is irradiated with an active energy beam, acid is generated from the photoacid generator, and the compound that develops color by the reaction with the acid is developed by the acid. Color (coloring), whereby the visible light transmittance of the adhesive layer 3 at a wavelength of 550 nm after the active energy beam (after the state change) is lower than the wavelength 550 of the adhesive layer 3 before the active energy beam (before the state change) The visible light transmittance in nm, and the adhesive force of the adhesive layer 3 after the active energy beam (after the state change) is lower than the adhesive force of the adhesive layer 3 before the active energy beam (before the state change).

Therefore, in the fifth step described later, if an active energy beam is irradiated to a part of the adhesive layer 3, the adhesive layer 3 containing the first adhesive composition that has not been irradiated with the active energy beam becomes the high-adhesion area 10, and the irradiation The adhesive layer 3 containing the first adhesive composition of the overactive energy beam becomes the low adhesive area 11. In addition, the visible light transmittance of the low adhesion region 11 at a wavelength of 550 nm is lower than the visible light transmittance of the high adhesion region 10 at a wavelength of 550 nm.

Thereby, the adhesive layer 3 has a high-adhesion area 10 with a larger visible light transmittance at a wavelength of 550 nm and a low-adhesion area 11 with a lower visible light transmittance at a wavelength of 550 nm.

In addition, the adhesive force of the adhesive layer 3 (the adhesive force of the high-adhesion region 10) before the active energy beam is irradiated (before the state change) is, for example, 5 N/25 mm or more, preferably 8 N/25 mm or more, more preferably It is 10 N/25 mm or more, more preferably 12 N/25 mm or more.

In addition, the adhesive layer 3 before the state change includes a portion where the active energy beam is not irradiated and the state is not changed (the same applies hereinafter).

Furthermore, the adhesive force of the adhesive layer 3 (adhesive force of the low-adhesion region 11) after the active energy beam is irradiated (after the state change) is, for example, 4 N/25 mm or less, preferably 3 N/25 mm or less.

As long as the adhesive force of the high-adhesion area 10 is greater than the above lower limit, the high-adhesion area 10 can be left in the state of being attached to the adherend 6 and used together with the corresponding base material 2 to reinforce the adherend 6.

Moreover, as long as the adhesive force of the low-adhesion region 11 is equal to or less than the above upper limit, the low-adhesion region 11 can be easily removed from the intermediate laminate 5 together with the corresponding base material 2.

Furthermore, the details of the above-mentioned adhesive force are described in the examples described later. The adhesive sheet 1 can be attached to the polyimide film at 25°C and the peeling speed is 300 mm/min for 180° Measured by peeling test.

Furthermore, the shear storage elastic modulus G'of the adhesive layer 3 at 25°C before the active energy beam is irradiated (before the state change) is, for example, 6×10 ⁴ Pa or more, preferably 7×10 ⁴ Pa or more, and , For example, 9×10 ⁴ Pa or less, preferably 8×10 ⁴ Pa or less.

In addition, the shear storage elastic modulus G'of the adhesive layer 3 at 25°C after being irradiated with the active energy beam (after the state change) is, for example, 2.00×10 ⁶ Pa or more, preferably 2.50×10 ⁶ Pa or more, More preferably, it is 3.0×10 ⁶ Pa or more, and, for example, it is 5.00×10 ⁶ Pa or less.

Furthermore, the aforementioned shear storage elastic modulus G'can be measured by dynamic viscoelasticity measurement under the conditions of a frequency of 1 Hz, a heating rate of 5°C/min, and a temperature range of -50°C to 150°C.

In addition, the visible light transmittance at a wavelength of 550 nm of the adhesive layer 3 before the active energy beam is irradiated (before the state change) is, for example, 85% or more, and for example, 99% or less.

In addition, the visible light transmittance at a wavelength of 550 nm of the adhesive layer 3 after being irradiated with the active energy beam (after the state change) is, for example, 80% or less, and for example, 30% or more.

In addition, the visible light transmittance at the wavelength of 550 nm of the adhesive layer 3 before the active energy beam (before the state change) and the visible light at the wavelength of 550 nm of the adhesive layer 3 (after the state change) after the active energy beam is irradiated Transmittance difference (the visible light transmittance of the adhesive layer 3 before the active energy beam (before the state change) at a wavelength of 550 nm-the wavelength of the adhesive layer 3 after the active energy beam is irradiated (after the state change) 550 nm The visible light transmittance below) is, for example, 5% or more, preferably 10% or more.

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

In addition, the average transmittance at 300 nm to 700 nm of the adhesion layer 3 before the active energy beam is irradiated (before the state change) is, for example, 80% or more, and for example, 99% or less.

In addition, the average transmittance of the adhesive layer 3 from 300 nm to 700 nm after being irradiated with the active energy beam (after the state change) is, for example, 75% or less, and for example, 30% or more.

In addition, the above-mentioned transmittance measurement method will be described in detail in the examples described later (the same shall apply hereinafter).

In addition, the haze value of the adhesive layer 3 before the active energy beam is irradiated (before the state change) is, for example, 3% or less, preferably 1% or less.

In addition, the haze value of the adhesive layer 3 after being irradiated with the active energy beam (after the state change) is, for example, 5% or less, preferably 3% or less.

On the other hand, the visible light transmittance of the second adhesive composition at a wavelength of 550 nm can be reduced by irradiation with an active energy beam, and can be irradiated with an active energy beam to increase the adhesive force from a state with a low adhesive force. The state changes irreversibly.

That is, if the adhesive layer 3 formed of such a second adhesive composition is irradiated with active energy beams, an acid is generated from the photoacid generator, and the acid is a compound that develops color by reaction with the acid Color development (coloring), whereby the visible light transmittance at a wavelength of 550 nm of the adhesive layer 3 after being irradiated with the active energy beam (after the state change) is lower than that of the adhesive layer 3 before the active energy beam (before the state change) Visible light transmittance at a wavelength of 550 nm, and the adhesive force of the adhesive layer 3 (after the state change) after irradiated with the active energy beam is greater than the adhesive force of the adhesive layer 3 before the active energy beam (before the state change) .

Therefore, in the fifth step described later, if a part of the adhesive layer 3 is irradiated with an active energy beam, the adhesive layer 3 containing the second adhesive composition that is not irradiated with the active energy beam becomes the low-adhesion area 11. The adhesive layer 3 containing the second adhesive composition that has been irradiated with the active energy beam becomes a high adhesive area 10. In addition, the visible light transmittance at a wavelength of 550 nm in the high adhesion region 10 is lower than the visible light transmittance at a wavelength of 550 nm in the low adhesion region 11.

Thereby, the adhesive layer 3 has a high adhesion area 10 with a small visible light transmittance at a wavelength of 550 nm and a low adhesion area 11 with a large visible light transmittance at a wavelength of 550 nm.

In addition, the adhesive force of the adhesive layer 3 (the adhesive force of the low-adhesion region 11) before the active energy beam is irradiated (before the state change) is, for example, 4 N/25 mm or less, preferably 1 N/25 mm or less.

Furthermore, the adhesive force of the adhesive layer 3 (adhesive force of the high-adhesion region 10) after the active energy beam is irradiated (after the state change) is, for example, 5 N/25 mm or more, preferably 8 N/25 mm or more, and more It is preferably 10 N/25 mm or more, and more preferably 12 N/25 mm or more.

As long as the adhesive force of the low-adhesion region 11 is equal to or less than the above upper limit, the low-adhesion region 11 can be easily removed from the intermediate laminate 5 together with the corresponding base material 2.

In addition, as long as the adhesive force of the high-adhesion area 10 is greater than the above lower limit, the high-adhesion area 10 can be left in the state of being attached to the adherend 6, and used together with the corresponding base material 2 for the adherence 6 Reinforcement.

In addition, the shear storage elastic modulus G'of the adhesive layer 3 at 25°C before the active energy beam is irradiated (before the state change) is, for example, 1×10 ⁴ Pa or more, preferably 5×10 ⁴ Pa or more, and , For example, 1.2×10 ⁵ Pa or less, preferably 1×10 ⁵ Pa or less.

In addition, the shear storage elastic modulus G'of the adhesive layer 3 at 25°C after being irradiated with the active energy beam (after the state change) is, for example, 1.00×10 ⁵ Pa or more, preferably 1.5×10 ⁵ Pa or more, Also, for example, it is 2.0×10 ⁶ Pa or less, preferably 1.0×10 ⁶ Pa or less.

In addition, the visible light transmittance at a wavelength of 550 nm of the adhesive layer 3 before the active energy beam is irradiated (before the state change) is, for example, 85% or more, and for example, 99% or less.

In addition, the visible light transmittance at a wavelength of 550 nm of the adhesive layer 3 after being irradiated with the active energy beam (after the state change) is, for example, 80% or less, and for example, 30% or more.

In addition, the visible light transmittance at the wavelength of 550 nm of the adhesive layer 3 before the active energy beam (before the state change) and the visible light at the wavelength of 550 nm of the adhesive layer 3 (after the state change) after the active energy beam is irradiated Transmittance difference (the visible light transmittance of the adhesive layer 3 before the active energy beam (before the state change) at a wavelength of 550 nm-the wavelength of the adhesive layer 3 after the active energy beam is irradiated (after the state change) 550 nm The visible light transmittance below) is, for example, 5% or more, preferably 10% or more.

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

In addition, the average transmittance at 300 nm to 700 nm of the adhesion layer 3 before the active energy beam is irradiated (before the state change) is, for example, 80% or more, and for example, 99% or less.

In addition, the average transmittance of the adhesive layer 3 from 300 nm to 700 nm after being irradiated with the active energy beam (after the state change) is, for example, 75% or less, and for example, 30% or more.

In addition, the haze value of the adhesive layer 3 before the active energy beam is irradiated (before the state change) is, for example, 3% or less, preferably 1% or less.

In addition, the haze value of the adhesive layer 3 after being irradiated with the active energy beam (after the state change) is, for example, 5% or less, preferably 3% or less.

In addition, as shown in FIG. 2C, the adhesive sheet 1 may also peel off the film 4 on an area of the adhesive layer 3 as needed.

In this case, the adhesive sheet 1 includes a substrate 2, an adhesive layer 3, and a release film 4 in this order.

Examples of the release film 4 include flexible plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films.

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, and more preferably 50 μm or less.

The release film 4 is preferably subjected to a mold release treatment with a silicone-based, fluorine-based, long-chain alkyl-based, aliphatic amide-based mold release agent, or a mold release treatment with silica powder.

3. Intermediate layered body As shown in FIG. 3, the intermediate laminate 5 has a film shape (including a sheet shape) having a specific thickness, extends in a direction (plane direction) orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface.

Specifically, the intermediate laminate 5 includes an adhesive sheet 1 including a base material 2 and an adhesive layer 3 arranged on one surface of the base material 2 and an adherend 6 arranged on one surface of the adhesive sheet 1.

The intermediate laminate 5 can be obtained by attaching the above-mentioned adhesive sheet 1 to the adherend 6, and the details will be described later.

In addition, the intermediate layered body 5 is an intermediate part of the product layered body 12 (described later).

Hereinafter, each layer will be described in detail.

3-1. Adhesive sheet As described above, the adhesive sheet 1 includes a base material 2 and an adhesive layer 3 arranged on one surface of the base material 2.

In addition, the adhesive layer 3 of the adhesive sheet 1 has a high-adhesive area 10 including an adhesive composition in a state with high adhesive force, and a low-adhesion area 11 including an adhesive composition in a state with low adhesive force.

In addition, the visible light transmittance of any one of the high adhesion area 10 and the low adhesion area 11 at a wavelength of 550 nm is lower than the other (in other words, the visible light transmittance of the high adhesion area 10 and the low adhesion area 11 at a wavelength of 550 nm Different from each other), the details will be described later.

Such high adhesion areas 10 and low adhesion areas 11 can be obtained by applying external stimuli (specifically, active energy beams) to a part of the adhesion layer 3, and the details will be described later.

3-2. Adhesive body The adhered body 6 is a reinforced body that is reinforced by the adhesive sheet 1, and examples thereof include optical components, electronic components, and their constituent parts.

Furthermore, 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 can be selected depending on the types of optical components, electronic components, and structural parts.

4. Manufacturing method of intermediate laminate An embodiment of the manufacturing method of the intermediate layered body 5 will be described with reference to FIGS. 4 and 5.

The manufacturing method of the intermediate laminate 5 includes the following steps: preparing an adhesive sheet 1 (the third step); arranging the adherend 6 on one side of the adhesive sheet 1 (the fourth step); and by aligning a part of the adhesive layer 3 External stimulus is provided, and a stimulating part 7 to which an external stimulus is provided and a non-stimulating part 8 to which no external stimulus is provided are formed on the adhesive layer 3, so that any one of the stimulating part 7 and the non-stimulating part 8 has a higher adhesive force The high adhesion area 10 of the state makes the other low adhesion area 11 of the state of low adhesion, and the visible light transmittance of the stimulated part 7 at a wavelength of 550 nm is lower than that of the non-stimulated part 8 at a wavelength of 550 nm Visible light transmittance (Step 5).

In the fifth step, one of the stimulating part 7 and the non-stimulating part 8 becomes the high-adhesive area 10, and the other becomes the low-adhesive area 11. According to the adhesive layer 3, it is composed of the first adhesive composition or the second adhesive composition. Which composition is formed determines which of the stimulating part 7 and the non-stimulating part 8 becomes the high-adhesion area 10 or the low-adhesion area 11.

Therefore, it is divided into the case where the adhesive layer 3 is formed from the 1st adhesive composition, and the case where the adhesive layer 3 is formed from the 2nd adhesive composition, and it demonstrates below.

In addition, in the following description, the case where the external stimulus is irradiation with an active energy beam will be described.

4-1. Manufacturing method of an intermediate laminate in which the adhesive layer is formed from the first adhesive composition (Production method 1) First, the manufacturing method (manufacturing method 1) of the intermediate laminate 5 in which the adhesive layer 3 is formed from the first adhesive composition will be described with reference to FIG. 4.

In the third step, as shown in FIG. 4A, the adhesive sheet 1 is prepared.

Then, in the fourth step, as shown in FIG. 4B, the adhesive sheet 1 is attached to the adherend 6 in such a manner that the adhesive layer 3 disposed on one surface of the substrate 2 contacts the adherend 6.

Then, in the fifth step, as shown in FIG. 4C, a part of the adhesive layer 3 is irradiated with an active energy beam to form a high-adhesion area 10 and a low-adhesion area 11.

In addition, in the following description, the adhesive sheet 1 is divided into three parts in the plane direction, and two of the two ends are regarded as non-irritating parts 8 (in other words, the adhesive sheet 1 is divided into three parts in the plane direction. Of these parts, only one of the central part is regarded as the stimulation part 7) for explanation.

In the fifth step, in the adhesive sheet 1, the stimulating part 7 is irradiated with an active energy beam, and the non-stimulating part 8 is not irradiated with an active energy beam.

Specifically, the mask 9 is not arranged in the stimulation part 7, and the mask 9 for blocking the active energy beam is arranged in the non-stimulation part 8.

If the adhesive layer 3 formed of the first adhesive composition is irradiated with active energy beam as described above, the adhesive force of the adhesive layer 3 after the active energy beam is lower than the adhesive layer 3 before the active energy beam is irradiated force.

That is, the adhesive force of the adhesive layer 3 in the stimulating part 7 is reduced. On the other hand, the adhesive force of the adhesive layer 3 in the non-stimulating part 8 is not reduced, and the adhesive force remains strong.

In this way, the adhesive force of the stimulating part 7 is relatively lower than that of the non-stimulating part 8, so the stimulating part 7 (specifically, the adhesive layer 3 including the first adhesive composition after the state change) becomes the low-adhesion area 11, which is non-irritating The part 8 (specifically, the adhesive layer 3 including the first adhesive composition before the state change) becomes the high-adhesion area 10.

In addition, in the adhesion layer 3 in the stimulating portion 7 (low adhesion region 11), acid is generated from the photoacid generator, and the compound that develops color by the reaction with the acid develops color (coloring (specifically, coloring) , In black)). As a result, the adhesion layer 3 in the stimulating portion 7 (low adhesion area 11) changes from colorless (transparent) to colored (the visible light transmittance at a wavelength of 550 nm becomes lower). In this way, the visible light transmittance of the stimulated part 7 (low adhesion area 11) at a wavelength of 550 nm is lower than the visible light transmittance of the non-stimulated part 8 (high adhesion area 10) at a wavelength of 550 nm (specifically, the stimulated part 7 (low adhesion area) The adhesion area 11) is darker than the non-irritating portion 8 (high adhesion area 10), and the boundary between the stimulation portion 7 (low adhesion area 11) and the non-irritating portion 8 (high adhesion area 10) can be easily distinguished visually.

In this way, an adhesive layer 3 having a high adhesion area 10 with a large visible light transmittance at a wavelength of 550 nm and a low adhesion area 11 with a small visible light transmittance at a wavelength of 550 nm can be obtained. In addition, an intermediate laminated body 5 provided with the adhesive sheet 1 and the adherend 6 in this order (in other words, the substrate 2, the adhesive layer 3, and the adhered body 6 in this order) can be obtained.

4-2. Manufacturing method of an intermediate laminate in which the adhesive layer is formed from the second adhesive composition (manufacturing method 2) Second, the manufacturing method (manufacturing method 2) of the intermediate laminate 5 in which the adhesive layer 3 is formed from the second adhesive composition will be described with reference to FIG. 5.

In the third step, as shown in FIG. 5A, the adhesive sheet 1 is prepared.

Then, in the fourth step, as shown in FIG. 5B, the adhesive sheet 1 is attached to the adherend 6 in such a manner that the adhesive layer 3 disposed on one surface of the substrate 2 is in contact with the adherend 6.

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

Furthermore, in the following description, the adhesive sheet 1 is divided into three parts in the plane direction, and two of the two ends are regarded as the stimulation parts 7 (in other words, the adhesive sheet 1 is divided into three parts in the plane direction Part, only one of the central parts is regarded as the non-stimulating part 8) as the description.

In the fifth step, in the adhesive sheet 1, the stimulating part 7 is irradiated with an active energy beam, and the non-stimulating part 8 is not irradiated with an active energy beam.

Specifically, the mask 9 is not arranged in the stimulation part 7, and the mask 9 for blocking the active energy beam is arranged in the non-stimulation part 8.

If the adhesive layer 3 formed by the second adhesive composition is irradiated with active energy beam as described above, the adhesive force of the adhesive layer 3 after the active energy beam is greater than the adhesive layer 3 before the active energy beam is irradiated force.

That is, the adhesive force of the adhesive layer 3 in the stimulating part 7 is increased, on the other hand, the adhesive force of the adhesive layer 3 in the non-stimulating part 8 is not increased.

In this way, the stimulating part 7 has a relatively higher adhesive force with respect to the non-stimulating part 8, so the stimulating part 7 (specifically, the adhesive layer 3 including the second adhesive composition after the state change) becomes the high-adhesive area 10, which is non-irritating The part 8 (specifically, the adhesive layer 3 including the second adhesive composition before the state change) becomes the low-adhesion area 11.

In addition, in the adhesion layer 3 in the stimulating portion 7 (high adhesion area 10), acid is generated from the photoacid generator, and the compound that develops color by the reaction with the acid develops color (coloring (specifically, coloring) , In black)). As a result, the adhesion layer 3 in the stimulation portion 7 (high adhesion area 10) changes from colorless (transparent) to colored (the visible light transmittance at a wavelength of 550 nm becomes lower). In this way, the visible light transmittance of the stimulated part 7 (high adhesion area 10) at a wavelength of 550 nm is lower than the visible light transmittance of the non-stimulated part 8 (low adhesion area 11) at a wavelength of 550 nm (specifically, the stimulated part 7 (high adhesion area) The adhesion area 10) is darker than the non-irritating portion 8 (low adhesion area 11), and the boundary between the stimulation portion 7 (high adhesion area 10) and the non-irritating portion 8 (low adhesion area 11) can be easily distinguished visually.

Thereby, an adhesive layer 3 having a high adhesion area 10 with a small visible light transmittance at a wavelength of 550 nm and a low adhesion area 11 with a large visible light transmittance at a wavelength of 550 nm can be obtained. In addition, an intermediate laminate having the adhesive sheet 1 and the adherend 6 (in other words, the substrate 2, the adhesive layer 3, and the adherend 6 in this order) can be obtained.

In the above-mentioned production method 1 and the above-mentioned production method 2, the visible light transmittance of the stimulated part 7 at a wavelength of 550 nm is lower than the visible light transmittance of the non-stimulated part 8 at a wavelength of 550 nm (in other words, the stimulated part 7 is colored, and the non-stimulated part 8 is Transparency.) is common. On the other hand, in the production method 1, the irritation portion 7 becomes the low-adhesion area 11, and in the production method 2, the non-irritating portion 8 becomes the low-adhesion area 11. This aspect is different.

In the method of manufacturing the product laminate 12 described later, the intermediate laminate 5 is first manufactured, and then the low adhesion area 11 is removed from the intermediate laminate 5 so that the high adhesion area 10 remains, thereby manufacturing the product laminate 12 (As described later), if the intermediate laminate 5 is manufactured by the manufacturing method 1, the transparent high-adhesion area 10 remains, and if the intermediate laminate 5 is manufactured by the manufacturing method 2, the colored high-adhesion area 10 remains. This point is different. .

That is, it is possible to select whether the colored or transparent high-adhesion region 10 remains by selecting either of the manufacturing method 1 and the manufacturing method 2.

5. The effect of the adhesive sheet, the intermediate laminate and the manufacturing method of the intermediate laminate In the adhesive sheet 1, the adhesive layer 3 includes an adhesive composition whose visible light transmittance at a wavelength of 550 nm can be reduced by irradiation with an active energy beam, and can be reduced by irradiation with an active energy beam. The state with higher adhesion and the state with lower adhesion change irreversibly.

If an active energy beam is irradiated to a part of the adhesive sheet 1, the visible light transmittance at a wavelength of 550 nm of the part irradiated with the active energy beam decreases, and the adhesive force changes (the adhesive force becomes higher or lower).

That is, the adhesive force of the part irradiated with the active energy beam and the part not irradiated with the active energy beam are different from each other, and the visible light transmittance at a wavelength of 550 nm is different from each other.

Since the visible light transmittance of the part irradiated with the active energy beam and the part not irradiated with the active energy beam is different at a wavelength of 550 nm, it is easy to visually distinguish the part irradiated with the active energy beam and the part not irradiated with the active energy beam. As a result of the boundary, it is possible to easily remove the relatively low adhesive force of the part irradiated with the active energy beam and the part not irradiated with the active energy beam.

In the intermediate layered body 5, the adhesive layer 3 has a high-adhesion area 10 in a state where the adhesive force is relatively high, and a low-adhesion area 11 in a state where the adhesive force is low.

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

In detail, in the above-mentioned manufacturing method of the intermediate laminate 5, when the adhesive layer is formed from the first adhesive composition, the visible light transmittance at a wavelength of 550 nm in the low adhesive region 11 is less than that of the high adhesive region 10 Visible light transmittance at 550 nm. When the adhesive layer is formed from the second adhesive composition, the visible light transmittance at a wavelength of 550 nm in the high-adhesion zone 10 is lower than that at a wavelength of 550 nm in the low-adhesion zone 11 .

Thereby, the boundary between the high adhesion area 10 and the low adhesion area 11 can be easily distinguished visually. As a result, the low-adhesion area 11 can be removed from the adherend 6 together with the corresponding base material 2. On the other hand, the high-adhesion area 10 can still be adhered to the adherend 6 and remain, and the corresponding base The material 2 is used to reinforce the adherend 6 together.

As a result, it is possible to obtain a product laminate 12 (described later) in which the adherend 6 is reinforced.

Furthermore, according to the intermediate layered body 5, it is possible to use the same external stimulus (specifically, active energy beam irradiation) to form high adhesion areas 10 with different adhesion forces and different visible light transmittances at a wavelength of 550 nm. And the low adhesion area 11, so as to have both of these.

Furthermore, according to the intermediate layered body 5, the high-adhesive area 10 is not formed by forming the high-adhesive area 10 with the adhesive composition with higher adhesion and the low-adhesive area 11 is formed with the adhesive composition with lower adhesion. As with the low-adhesive area 11, the high-adhesion area 10 and the low-adhesion area 11 can be formed by using an adhesive composition of the same composition to have both of these.

The manufacturing method of the intermediate layered body 5 includes the following steps: by irradiating a part of the adhesive layer 3 with an active energy beam, a stimulating part 7 irradiated with the active energy beam and a non-stimulating part 8 not irradiated with the active energy beam are formed on the adhesive layer 3 , So that any one of the stimulating part 7 and the non-stimulating part 8 becomes a high adhesion area 10 with a higher adhesive force, the other becomes a low adhesion area 11 with a lower adhesive force, and the wavelength of the stimulating part 7 The visible light transmittance at 550 nm is less than the visible light transmittance at the wavelength of 550 nm of the non-irritating part 8.

Thereby, it is possible to manufacture an intermediate laminate body 5 having an adhesive layer 3 having a high-adhesion region 10 and a low-adhesion region 11 having different adhesive forces and different visible light transmittances at a wavelength of 550 nm from each other.

6. Product layered body and manufacturing method of product layered body The product laminate 12 is an element in the final form or a component part of the element.

Next, an embodiment of the method of manufacturing the product layered body 12 will be described with reference to FIGS. 6 and 7.

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

Specifically, the product layered body 12 can be manufactured by a method of manufacturing a product layered body, which includes: the sixth step of preparing the intermediate layered body 5 manufactured by the above-mentioned manufacturing method of the intermediate layered body 5, and bonding The seventh step of removing the low adhesion area 11 in layer 3.

In the sixth step, the intermediate layered body 5 manufactured by the above-mentioned manufacturing method of the intermediate layered body 5 is prepared, and as described above, by selecting any one of the manufacturing method 1 and the manufacturing method 2, it is determined that the remaining high adhesion area 10 is Colored or transparent.

Therefore, the following description is divided into a case where the intermediate laminate 5 manufactured by the manufacturing method 1 is prepared and a case where the intermediate laminate 5 manufactured by the manufacturing method 2 is prepared.

6-1. Preparation of intermediate laminate 5 manufactured by manufacturing method 1 First, the manufacturing method of the product laminate 12 in the case where the intermediate laminate 5 manufactured by the manufacturing method 1 is prepared will be described with reference to FIG. 6.

In the sixth step, as shown in FIG. 6A, the intermediate laminate 5 is manufactured by the manufacturing method (manufacturing method 1) of the intermediate laminate 5 in which the adhesive layer 3 is formed from the first adhesive composition, and the 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, for example, a CO ₂ laser is used to cut the boundary between the residual portion 13 including the high adhesion area 10 and the corresponding substrate 2 and the removed portion 14 including the low adhesion area 11 and the substrate 2 corresponding to it. After that, only the removed portion 14 is peeled off with the edge of the removed portion 14 as a starting point.

At this time, the high adhesion area 10 (remaining portion 13) and the low adhesion area 11 (removed portion 14) are different from each other due to the visible light transmission at a wavelength of 550 nm (specifically, the high adhesion area 10 (remaining portion 13) is transparent , The low adhesion area 11 (removed part 14) is colored), so the above boundary can be easily distinguished visually.

In addition, since the adhesive force of the low-adhesion region 11 in the removed portion 14 is reduced, the removed portion 14 can be easily peeled from the intermediate laminate 5.

On the other hand, since the adhesive force of the high-adhesion area 10 in the residual part 13 is not reduced and has the above-mentioned higher adhesive force, the residual part 13 remains in the intermediate laminated body 5.

In addition, since the high-adhesion region 10 has the above-mentioned higher adhesive force, even if the removed portion 14 is peeled off, the end of the residual portion 13 in contact with the removed portion 14 can be suppressed from floating.

In addition, the remaining part 13 can be directly used for the reinforcement of the adherend 6.

Thereby, the product laminate 12 can be obtained.

In the product laminate 12, since the remaining portion 13 is transparent, it can be preferably used for optical elements and their constituent parts that require transparency.

6-2. Preparation of intermediate laminate 5 manufactured by manufacturing method 2 Second, the manufacturing method of the product laminate 12 when the intermediate laminate 5 manufactured by the manufacturing method 2 is prepared will be described with reference to FIG. 7.

In the sixth step, as shown in FIG. 7A, the intermediate laminate 5 is manufactured by the manufacturing method (manufacturing method 2) of the intermediate laminate 5 in which the adhesive layer 3 is formed from the second adhesive composition, and the 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, for example, a CO ₂ laser is used to cut the boundary between the residual portion 13 including the high adhesion area 10 and the corresponding substrate 2 and the removed portion 14 including the low adhesion area 11 and the substrate 2 corresponding to it. After that, only the removed portion 14 is peeled off from the edge of the removed portion 14 as a starting point.

At this time, the high adhesion area 10 (remaining portion 13) and the low adhesion area 11 (removed portion 14) are different from each other due to the visible light transmittance at a wavelength of 550 nm (specifically, the high adhesion area 10 (remaining portion 13) is colored , The low adhesion area 11 (removed part 14) is transparent), so the above boundary can be easily distinguished visually.

In addition, since the adhesive force of the low-adhesion region 11 in the removed portion 14 is reduced, the removed portion 14 can be easily peeled off from the intermediate laminate 5.

On the other hand, since the adhesive force of the high-adhesion area 10 in the residual part 13 is not reduced and has the above-mentioned higher adhesive force, the residual part 13 remains in the intermediate laminated body 5.

In addition, since the high-adhesion region 10 has the above-mentioned higher adhesive force, even if the removed portion 14 is peeled off, the end of the residual portion 13 in contact with the removed portion 14 can be suppressed from floating.

In addition, the remaining part 13 can be directly used for the reinforcement of the adherend 6.

Thereby, the product laminate 12 can be obtained.

In the product laminate 12, since the remaining part 13 is colored, it can also be used as an anti-reflection layer.

7. The effect of the manufacturing method of the product laminate The manufacturing method of the product layered body 12 includes the seventh step, which is to use the above-mentioned manufacturing method of the intermediate layered body (the manufacturing method of the intermediate layered body 5 (manufacturing method 1) in which the adhesive layer 3 is formed by the first adhesive composition) or The low-adhesion region 11 of the adhesive layer 3 in the intermediate laminate 5 manufactured by the manufacturing method (manufacturing method 2)) of the adhesive layer 3 formed by the second adhesive composition is removed.

Since the adhesive force of the low-adhesion region 11 is low, the removed portion 14 can be easily removed from the intermediate laminated body 5.

In addition, since the visible light transmittance of the high adhesion area 10 (remaining portion 13) and the low adhesion area 11 (removed portion 14) at a wavelength of 550 nm are different from each other, the difference between the remaining portion 13 and the removed portion 14 can be easily distinguished visually. boundary. As a result, the removed portion 14 can be reliably removed from the adherend 6.

On the other hand, the remaining portion 13 may remain in the intermediate layered body 5 to reinforce the adherend 6.

In addition, the residual portion 13 can impart moderate rigidity, thereby improving the operability.

Especially when the adherend 6 is an electronic component, the thickness of the component parts of the electronic component tends to become smaller as the electronic component becomes more integrated, smaller and lighter in weight, and thinner in component parts. Due to this thinning, bending or curling due to stress is likely to occur at the laminated interface of the constituent parts. In addition, due to the thinning, deflection caused by its own weight is likely to occur.

Even in this case, according to the adhesive sheet 1, the residual portion 13 can impart rigidity to the electronic component, and therefore, bending, curling, and bending caused by stress or dead weight can be suppressed, and the operability can be improved.

In addition, in the manufacturing steps of electronic components, when the components are transported or processed by an automated device, the component parts of the electronic component may come into contact with members such as the transport arm and ejector pins, which may cause the component parts to be damaged.

In particular, components with a high degree of integration, small size, light weight, and thin profile may be damaged or dimensional changes caused by the concentration of local stress during the contact or cutting process of a conveyor, etc.

Even in this case, according to the adhesive sheet 1, the residual portion 13 can impart moderate rigidity, relax and disperse the stress, and can suppress cracks, cracks, peeling, dimensional changes, and the like.

8. Variations In the above description, the case where the external stimulus is irradiation with an active energy beam has been described, but the external stimulus may also be heating.

When the external stimulus is heating, the adhesive layer 3 includes an adhesive composition, the visible light transmittance of the adhesive composition at a wavelength of 550 nm can be reduced by heating, and the adhesive force can be increased by heating The state and the state with low adhesion force irreversibly change state.

As such an adhesive composition, the visible light transmittance at a wavelength of 550 nm can be reduced by heating, and the state can be irreversibly changed from a state with a low adhesive force to a state with a high adhesive force by heating. The third adhesive composition.

The third adhesive composition includes the above-mentioned polymer, an organosiloxane-containing component, the above-mentioned compound that develops color by reaction with an acid, and a thermal acid generator.

Examples of components containing organosiloxane include: acrylic polymers having organosiloxane skeletons, urethane-based polymers, polyether-based polymers, polyester-based polymers, and polycarbonate-based polymers. From the viewpoint of control of adhesive force, acrylic polymers having an organosiloxane skeleton are preferable from the viewpoint of control of adhesive force, polybutadiene-based polymers, and the like.

The thermal acid generator is a compound that generates an acid by heating, and examples thereof include aryl sulfonium salts and aryl iodonium salts. [Example]

Examples and comparative examples are shown below to further specifically explain the present invention. Furthermore, the present invention is not limited in any way by the examples and comparative examples. In addition, specific numerical values such as the blending ratio (content ratio), physical property values, and parameters used in the following description can be replaced with the blending ratios (content ratio), physical property values, etc. corresponding to those described in the above-mentioned "embodiment". The upper limit value (the value defined in the form of "below" and "not reached") or the lower limit value (the value defined in the form of "above" or "exceeding") shall be recorded accordingly for the parameters.

Furthermore, "parts" and "%" are quality standards as long as they are not specifically mentioned.

1. Details of components The components used in each example and each comparative example are 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-isophthalene Methylamine (4-functional epoxy compound, manufactured by Mitsubishi Gas Chemical) 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, manufactured by BASF Irgacure 651: 2,2-dimethoxy-1,2-diphenylethane-1-one BLACK ND1: leuco dye, Yamada Chemical Industry Manufacture of CPI-310B: Contains _{the salt of alum and (C 6} F ₅ ) ₄ B ^- , photoacid generator, manufactured by SAN-APRO

2. Preparation of polymer Synthesis example 1 9 parts by weight of methyl methacrylate (MMA), 63 parts by weight of 2-ethylhexyl acrylate (2EHA), and acrylic acid hydroxy 13 parts by weight of ethyl ester (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, Nitrogen gas was introduced, and nitrogen replacement was performed for about 1 hour while stirring. After that, it was heated to 60° C. and reacted for 7 hours to obtain a solution of an acrylic polymer having a weight average molecular weight (Mw) of 1,200,000.

Synthesis Example 2 Add 95 parts of n-butyl acrylate (BA) and 5 parts of acrylic acid (AA) as monomer components to a reaction vessel equipped with a thermometer, agitator, reflux condenser and nitrogen introduction tube. While introducing nitrogen, flow in nitrogen while stirring. Perform nitrogen replacement for 2 hours. 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 an acrylic acid with a weight average molecular weight (Mw) of 600,000 Polymer solution.

3. Preparation of adhesive composition Preparation example 1 (adjustment of the first adhesive composition) To the acrylic polymer solution of Synthesis Example 1, 2.5 parts by mass of Takenate D110N (trimethylolpropane addition of xylylene diisocyanate) was added as a crosslinking agent relative to 100 parts by weight of the solid content of the polymer. 75% ethyl acetate solution, manufactured by Mitsui Chemicals), A-DPH (dipentaerythritol hexaacrylate) as a light hardening agent, 30 parts by mass relative to 100 parts by weight of the solid content of the polymer, relative to polymer 100 parts by weight of the solid content is 0.1 parts by mass of Irgacure 184 (1-hydroxycyclohexyl phenyl ketone, manufactured by BASF Corporation) as a photopolymerization initiator, and 1 part by weight relative to 100 parts by weight of the solid content of the polymer Parts of BLACK ND1 (leuco dye) as a compound that develops color by reaction with acid, 2 parts by mass of CP-310B as a photoacid generator relative to 100 parts by weight of the solid content of the polymer, and It mixes uniformly, and prepares an adhesive composition (1st adhesive composition).

Preparation example 2 (adjustment of the second adhesive composition) Except that the light hardener was changed to APG700 (polypropylene glycol #700 (n=12) diacrylate), an adhesive composition (second adhesive composition) was prepared in the same manner as in Preparation Example 1.

Preparation Example 3～Preparation Example 10 Except for changing the preparation formula according to the description in Table 1, the treatment was performed in the same manner as in Preparation Example 1 to produce an adhesive composition.

4. Manufacture of adhesive sheet Example 1 On the upper surface of a polyethylene terephthalate film (thickness 75 μm) as a substrate, the adhesive composition of Preparation Example 1 was coated by a groove roll so that the thickness after drying became 25 μm. Then, the solvent was removed by drying at 130°C for 1 minute. Thereby, an adhesive layer is formed on one surface of the substrate. Furthermore, the release-treated surface of the release film (a polyethylene terephthalate film with a thickness of 25 μm with the surface subjected to a silicone release treatment) was attached to one surface of the adhesive layer. After that, an aging treatment was carried out for 4 days in an environment of 25° C. to carry out the cross-linking reaction between the polymer and the cross-linking agent. Thus, an adhesive sheet is manufactured.

Example 2 to Example 7, Comparative Example 1 to Comparative Example 3 Except for changing the adhesive composition according to the description in Table 1, the treatment was performed in the same manner as in Example 1 to produce an adhesive sheet.

5. Evaluation (Transmittance) For the adhesive sheet of each embodiment and each comparative example, the transmittance at 550 nm before and after irradiating LED (Light Emitting Diode) (365 nm, 4000 mJ/□), and 300 nm～700 nm The average transmittance below is measured.

The results are shown in Table 1.

(Adhesion) A polyimide film with a thickness of 25 μm was attached to a glass plate via a double-sided tape ("No. 531" manufactured by Nitto Denko) to obtain a polyimide film substrate for measurement. Then, the peeling film was removed from the adhesive sheet of each Example and each comparative example, and the adhesive sheet and the polyimide film substrate for measurement were bonded together at 25 degreeC using a hand roller, and the sample for measurement was prepared.

Then, the sample for measurement was left for 30 minutes under the conditions of 25° C. and a relative humidity of 50%, and then the adhesive force (adhesive force before UV irradiation) was measured.

Separately prepare a measurement sample in the same procedure as above, and place the measurement sample at 25°C and a relative humidity of 50% for 30 minutes. After that, irradiate the substrate side of the adhesive sheet with an LED (365 nm, 4000 mJ/□), and then placed for 30 minutes under the conditions of 25°C and 50% relative humidity, and then the adhesion (adhesion after UV irradiation) was measured.

The adhesion force is measured by holding the end of the test sample (the end of the adhesive sheet) with a chuck, and performing 180° peeling of the reinforcing film at a tensile speed of 300 mm/min, and measuring the peel strength. The results are shown in Table 1.

[Table 1] Table 1 Example, Comparative Example No. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example 1 Comparative example 2 Comparative example 3 Preparation Example No. Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 Preparation Example 9 Preparation Example 10 Adhesive composition polymer Acrylic polymer of Synthesis Example 1 100 100 100 100 - - - 100 100 100 Acrylic polymer of Synthesis Example 2 - - - - 100 100 100 - - - 1st light hardener A-DPH 30 - - - - - - 30 - - 2nd light hardener APG700 - 30 30 30 - - - - 30 - A200 - - - - 30 30 30 - - - A600 - - - - - - 5 - - - Photopolymerization initiator Irgacure 184 0.1 0.1 0.1 0.1 - - - 0.1 0.1 - Irgacure 651 - - - - 0.2 0.2 0.2 - - - A compound that develops color by reaction with acid BLACK ND1 1 1 2 2 2 2 2 - - 1 Photoacid generator CPI-310B 2 2 5 7 7 7 7 - - 2 Crosslinking agent Isocyanate-based crosslinking agent Takenate D110N 2.5 2.5 2.5 2.5 - - - 2.5 2.5 2.5 Epoxy crosslinking agent Tetrad C - - - - 0.5 0.2 0.5 - - - Evaluation 300~700 nm average transmittance (%) Before UV irradiation 84 84 84 84 83 83 83 84 84 84 After UV irradiation 72 70 19 17 twenty three 19 twenty three 84 84 50 550 nm transmittance (%) Before UV irradiation 90 90 90 90 89 89 90 90 90 90 After UV irradiation 78 78 16 13 17 12 18 90 90 65 Adhesion (N/25 mm) Before UV irradiation 12.1 0.72 1.85 2.42 0.19 0.34 0.13 13.5 0.74 11.9 After UV irradiation 2.88 14.01 14.24 15.33 8.45 12.36 7.81 2.79 12.71 12.7

In addition, the above-mentioned invention is provided as an exemplary embodiment of the present invention, but this is only an example and is not interpreted in a limited manner. Variations of the present invention as understood by those in the technical field are included in the scope of the patent application described below. [Industrial availability]

The adhesive sheet of the present invention can be preferably used as a reinforcing adhesive sheet for bonding to the surface of various components such as optical components or electronic components.

In addition, the intermediate laminate, the manufacturing method of the intermediate laminate, and the manufacturing method of the product laminate of the present invention can be particularly preferably used in various components such as optical components and electronic components.

1: Adhesive sheet 2: Substrate 3: Adhesive layer 4: Peel off the film 5: Intermediate layered body 6: Adhered body 7: stimulation part 8: Non-stimulating part 9: Mask 10: High adhesion area 11: Low adhesion area 12: Product layered body 13: Residual part 14: Remove part

Fig. 1 is a schematic view showing an embodiment of the adhesive sheet of the present invention. Fig. 2 is a schematic diagram showing an embodiment of the method of manufacturing an adhesive sheet. Fig. 2A shows the first step of preparing the substrate, Fig. 2B shows the second step of layering an adhesive layer on one of the substrates, and Fig. 2C shows the adhesive The step of peeling off the film layer by layer. Fig. 3 is a schematic diagram showing an embodiment of the intermediate laminate of the present invention. Fig. 4 is a schematic diagram showing an embodiment of the method for manufacturing an intermediate laminate of the present invention when the adhesive layer is formed of the first adhesive composition, Fig. 4A shows the third step of preparing an adhesive sheet, and Fig. 4B Shows the fourth step of arranging the adherend on one surface of the adhesive sheet. FIG. 4C shows the fifth step of irradiating a part of the adhesive layer with active energy beams to form high adhesion areas and low adhesion areas. Fig. 5 is a schematic view showing an embodiment of the method for manufacturing an intermediate laminate of the present invention when the adhesive layer is formed of the second adhesive composition, Fig. 5A shows the third step of preparing an adhesive sheet, and Fig. 5B Shows the fourth step of arranging the adherend on one surface of the adhesive sheet. FIG. 5C shows the fifth step of irradiating a part of the adhesive layer with active energy beams to form high adhesion areas and low adhesion areas. 6 is a schematic diagram showing one embodiment of the production method of the product laminate of the present invention when the intermediate laminate is prepared by the production method of the intermediate laminate using the first adhesive composition to form the adhesive layer, FIG. 6A It shows the sixth step of preparing the intermediate laminate, and FIG. 6B shows the seventh step of removing the low adhesion area in the adhesive layer. 7 is a schematic diagram showing one embodiment of the production method of the product laminate of the present invention when the intermediate laminate is prepared by the production method of the intermediate laminate using the second adhesive composition to form the adhesive layer, FIG. 7A It shows the sixth step of preparing the intermediate laminate, and FIG. 7B shows the seventh step of removing the low adhesion area in the adhesion layer.

1: Adhesive sheet

2: Substrate

3: Adhesive layer

Claims (13)

An adhesive sheet, characterized in that it has a substrate and an adhesive layer arranged on one side of the substrate; and The adhesive layer includes an adhesive composition. The visible light transmittance of the adhesive composition at a wavelength of 550 nm can be reduced by an external stimulus, and can be brought to a state with a higher adhesive force and a higher adhesive force by the external stimulus. The low state changes state irreversibly. The adhesive sheet of claim 1, wherein the above-mentioned external stimulus is irradiation of active energy beams. The adhesive sheet of claim 1 or 2, wherein the adhesive layer comprises a first adhesive composition, and the visible light transmittance of the first adhesive composition at a wavelength of 550 nm can be reduced by irradiation with an active energy beam, and The state can be irreversibly changed from a state with a higher adhesive force to a state with a lower adhesive force by the irradiation of the active energy beam, The above-mentioned first adhesive composition includes a polymer, a first light curing agent, a photopolymerization initiator, a compound that develops color by reaction with an acid, and a photoacid generator. Such as the adhesive sheet of claim 3, wherein the shear storage elastic modulus G'of the adhesive layer at 25°C before the state change is 6×10 ⁴ Pa or more and 9×10 ⁴ Pa or less, and the adhesive layer after the state change 3 Shear storage elastic modulus G'at 25°C is ^{above 2.00×10 6} Pa and below 5.00×10 ⁶ Pa. The adhesive sheet of claim 1 or 2, wherein the adhesive layer includes a second adhesive composition, and the visible light transmittance of the second adhesive composition at a wavelength of 550 nm can be reduced by irradiation with an active energy beam, and The state can be irreversibly changed from the state with lower adhesive force to the state with higher adhesive force by the irradiation of active energy beam, and The second adhesive composition described above includes a polymer, a second light curing agent, a photopolymerization initiator, a compound that develops color by reaction with an acid, and a photoacid generator. Such as the adhesive sheet of claim 5, wherein the shear storage elastic modulus G'of the adhesive layer at 25°C before the state change is 1×10 ⁴ Pa or more and 1.2×10 ⁵ Pa or less, and the above after the state change The shear storage elastic modulus G'of the adhesive layer at 25°C is 1.5×10 ⁵ Pa or more and 2.0×10 ⁶ Pa or less. An intermediate laminate, comprising: an adhesive sheet having a substrate and an adhesive layer arranged on one surface of the substrate, and an adherend arranged on one surface of the adhesive sheet; and The adhesive layer includes an adhesive composition. The visible light transmittance of the adhesive composition at a wavelength of 550 nm can be reduced by an external stimulus, and can be brought to a state with a higher adhesive force and a higher adhesive force by the external stimulus. The low state changes the state irreversibly; The above-mentioned adhesive layer has: a high-adhesion area including an adhesive composition in a state with a higher adhesive force, and a low-adhesion area including an adhesive composition in a state with a lower adhesive force; The visible light transmittance of any one of the high adhesion area and the low adhesion area at a wavelength of 550 nm is smaller than the other. The intermediate laminate of claim 7, wherein the adhesive layer includes a first adhesive composition, and the visible light transmittance of the first adhesive composition at a wavelength of 550 nm can be reduced by irradiation with an active energy beam, and can be reduced by Irradiated by the active energy beam, the state changes irreversibly from the state with higher adhesive force to the state with lower adhesive force, and The high-adhesion area includes the first adhesive composition before the state change, The low adhesion area includes the first adhesive composition after the state change, The visible light transmittance at a wavelength of 550 nm in the low adhesion area is smaller than the visible light transmittance at a wavelength of 550 nm in the high adhesion area. The intermediate laminate of claim 7, wherein the adhesive layer includes a second adhesive composition, and the visible light transmittance of the second adhesive composition at a wavelength of 550 nm can be reduced by irradiation with an active energy beam, and can be reduced by Irradiated by the active energy beam, the state changes irreversibly from the state with lower adhesive force to the state with higher adhesive force, and The low adhesion area includes the second adhesive composition before the state change, The high-adhesion area includes the second adhesive composition after the state change, The visible light transmittance at a wavelength of 550 nm in the high adhesion region is less than the visible light transmittance at a wavelength of 550 nm in the low adhesion region. A method for manufacturing an intermediate laminate, which is characterized by comprising the following steps: preparing an adhesive sheet having a substrate and an adhesive layer, the adhesive layer is disposed on one side of the substrate, and includes an adhesive composition, the adhesive composition The visible light transmittance at a wavelength of 550 nm can be reduced by external stimuli, and the state can be irreversibly changed to a state with higher adhesion and a state with lower adhesion by the aforementioned external stimuli; Arranging the adherend on one side of the above-mentioned adhesive sheet; and The external stimulus is imparted to a part of the adhesive layer, and the stimulating part to which the external stimulus is imparted and the non-stimulating part to which the external stimulus is not imparted are formed on the adhesive layer, whereby any of the stimulating part and the non-stimulating part One becomes a high-adhesion area with a higher adhesive force, and the other becomes a low-adhesive area with a lower adhesive force, and the visible light transmittance of the stimulating part at a wavelength of 550 nm is lower than that of the non-stimulating part at a wavelength of 550. Visible light transmittance in nm. The method for manufacturing an intermediate laminate of claim 10, wherein the adhesive layer comprises a first adhesive composition, and the visible light transmittance of the first adhesive composition at a wavelength of 550 nm can be reduced by external stimuli, and The state changes irreversibly from the state with higher adhesive force to the state with lower adhesive force by the above-mentioned external stimuli, The above-mentioned stimulus part becomes the above-mentioned low adhesion area, The non-irritating part becomes the high adhesion area. The method for manufacturing an intermediate laminate of claim 10, wherein the adhesive layer includes a second adhesive composition, and the visible light transmittance of the second adhesive composition at a wavelength of 550 nm can be reduced by external stimuli, and can be The state changes irreversibly from the state with low adhesive force to the state with high adhesive force due to the above-mentioned external stimuli, The above-mentioned stimulus part becomes the above-mentioned high adhesion area, The non-irritating part becomes the low adhesion area. A method for manufacturing a product laminate, characterized by comprising the steps of: preparing an intermediate laminate manufactured by the method for manufacturing an intermediate laminate according to any one of claims 10 to 12; and The low adhesion area in the adhesion layer is removed.

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