TW202108719A - Laminate and method for producing laminate - Google Patents

Abstract

To provide a laminate that can exhibit excellent outgas resistance against any outgas generation mode. Provided is a laminate 1, in which a first adherend 2, an adhesive layer 4, and a second adherend 6 are laminated in this order, and, setting the saturated water vapor pressure at 85 DEG C as Fv, the interfacial adhesion force between the first adherend 2 and the adhesive layer 4 at 85 DEG C as Ft, the shear storage elastic modulus (G') of the adhesive layer 4 at 85 DEG C as Fi, and the interfacial adhesion force between the second adherend 6 and the adhesive layer 4 at 85 DEG C as Fb, a condition of Ft > Fv, Fi > Fv, and Fb > Fv is satisfied.

Description

Laminated body and manufacturing method of laminated body

The present invention relates to a laminated body and a method for manufacturing the laminated body.

In recent years, display devices such as liquid crystal displays (LCD) or input devices used in combination with display devices, such as touch panels, have been widely used in various fields. In the manufacture of these display devices or input devices, a transparent adhesive sheet is used for the purpose of bonding optical members, and a transparent adhesive sheet is also used for bonding the display device and the input device.

For the adhesive sheet used in this application, in addition to the adhesive performance, various characteristics are also required. For example, resin plates such as polycarbonate substrates are often used as optical members due to their excellent transparency and heat resistance. However, when an adhesive sheet is attached to the resin plate and placed in a high-temperature environment, there is an adhesive layer A situation in which air bubbles are generated, which affects optical performance. Therefore, depending on the application of the adhesive sheet, excellent resistance to outgassing may be required.

For example, Patent Document 1 to Patent Document 3 disclose an optical laminate having an adhesive layer. Patent Document 1 discloses an optical laminate in which a resin plate containing polycarbonate or acrylic is attached to an adherend via a transparent adhesive. Patent Document 2 discloses a laminate having a laminate unit having a transparent resin layer and a glass layer arranged via an adhesive layer. In addition, Patent Document 3 discloses an optical laminate having a first layer and a second layer that include a raw material capable of generating outgas, and have a bonded surface, and are arranged on the first layer. The retardation layer between the second layer and the first adhesive layer and the second adhesive layer. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-222085 [Patent Document 2] Japanese Patent Laid-Open No. 2018-1615 [Patent Document 3] Japanese Patent Laid-Open No. 2018-45567

[The problem to be solved by the invention]

When the adhesive sheet is attached to a resin plate that can generate outgassing, air bubbles may also be generated at the interface between the adhesive sheet and the resin plate, and air bubbles may also be generated in the adhesive sheet. As such, the generation method of effluent gas is not a model, and therefore it is required to develop a laminate that can exhibit excellent effluent gas resistance for any generation method. Therefore, in order to solve the problems of the prior art, the inventors of the present invention conducted studies for the purpose of providing a laminate that exhibits excellent resistance to outgassing against any method of generating outgassing. [Means to solve the problem]

In the process of studying the subject, the inventors discovered that when an adhesive sheet is attached to a resin sheet, especially polycarbonate, the moisture of the resin sheet will vaporize and expand due to heating, and the cause is The pressure generated by the expansion will generate bubbles and so on. Therefore, the inventors of the present invention have actively studied to solve the above-mentioned problems. As a result, they have found that by sequentially laminating a first adhered material, an adhesive layer, and a second adhered material in a laminate, the durability test When the saturated water vapor pressure of the temperature under the conditions (for example, 85°C) or the temperature under the harsh environment actually used is set to Fv, set the interface adhesion force between the first adhesive layer and the adhesive layer at the temperature Ft, set the shear storage elastic coefficient (G') of the adhesive layer to Fi, and set the interface adhesion between the second adhesive layer and the adhesive layer to Fb, set Ft>Fv, Fi>Fv , And Fb>Fv, to obtain a laminate with excellent resistance to outgassing in any way of producing outgassing. Specifically, the present invention has the following configuration.

[1] A laminated body, which is formed by sequentially laminating a first adhered material, an adhesive layer, and a second adhered material, and Set the saturated water vapor pressure at 85°C as Fv, Let the interface adhesion force between the first adhesive layer and the adhesive layer at 85°C measured by the following measuring method (a) be Ft, Let the shear storage elastic coefficient (G') of the adhesive layer at 85°C measured by the following measuring method (b) be Fi, When the interface adhesion between the second adhesive material and the adhesive layer at 85°C measured by the following measuring method (c) is Fb, Meet the conditions of Ft>Fv, Fi>Fv, and Fb>Fv; Measurement method (a): Coat the adhesive on the surface of the first material to be bonded of the laminate with the size of 10 mm×10 mm, and attach it to the center of the glass plate with a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm; on the side of the adhesive layer, A glass plate with a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm was bonded through an adhesive so that the two glass plates became a cross positional relationship to each other to form a measurement sample; the measurement sample was placed at 85°C, After leaving for 3 hours in an environment with a relative humidity of less than 20%, at 85°C and a relative humidity of less than 20%, use a tensile testing machine to pull each glass plate in the opposite direction of the thickness direction at a speed of 5 mm/min. Stretching, the stress at the time of peeling between the first adhesive material and the adhesive layer is measured as the interface adhesion force (Ft); when there is no peeling between the first adhesive material and the adhesive layer, the interface is closely adhered Force (Ft) is greater than the maximum tensile stress; Measurement method (b): Fix the laminate to the fixture for solid shear test using an adhesive, and measure the shear storage of the adhesive layer in the temperature range of 20°C to 120°C under the conditions of solid shear mode, frequency 1 Hz, and strain 1.0% Elasticity coefficient G', set the value of shear storage elasticity coefficient G'at 85℃ as Fi; Measurement method (c): Apply an adhesive to the surface of the second material to be bonded of a laminate with a size of 10 mm × 10 mm, and adhere to the center of a glass plate with a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm; on the side of the adhesive layer, A glass plate with a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm was bonded through an adhesive so that the two glass plates became a cross positional relationship to each other to form a measurement sample; the measurement sample was placed at 85°C, After leaving for 3 hours in an environment with a relative humidity of less than 20%, at 85°C and a relative humidity of less than 20%, use a tensile testing machine to pull each glass plate in the opposite direction of the thickness direction at a speed of 5 mm/min. Stretching, the stress when peeling between the second adhesive material and the adhesive layer is measured as the interface adhesion force (Fb); when there is no peeling between the second adhesive material and the adhesive layer, the interface is closely adhered The force (Fb) is greater than the maximum tensile stress. [2] The laminate according to [1], wherein the first adhesive material is a resin plate. [3] The laminate according to [1] or [2], wherein the first adhesive material includes a polycarbonate resin. [4] The laminate according to any one of [1] to [3], wherein the second adhesive material includes at least one selected from a glass plate and a resin plate. [5] A method for manufacturing a laminate, which is the method for manufacturing a laminate according to any one of [1] to [4], including: The bonding step of bonding the first adhesive material and the second adhesive material to the adhesive layer with post-curing properties; and The step of irradiating active energy rays from the side of the first adhesive material or the second adhesive material. [6] The method of manufacturing a laminate as described in [5], wherein The adhesive layer used in the bonding step is an adhesive layer in which the adhesive composition is made into a semi-hardened state. The adhesive composition includes a crosslinkable acrylic copolymer, a crosslinking agent, a photopolymerization initiator, a monofunctional monomer, and a multifunctional monomer. [7] The method for producing a laminate as described in [6], wherein the monofunctional monomer is lauryl acrylate. [8] The method for producing a laminate as described in [6] or [7], wherein the multifunctional monomer is a monomer having a bisphenol skeleton in one molecule. [Effects of the invention]

According to the present invention, it is possible to obtain a laminate that exhibits excellent resistance to outgassing against any method of generating outgassing.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be performed based on representative embodiments or specific examples, but the present invention is not limited to such embodiments.

(Layered body) The present invention relates to a laminate in which a first adhesive material, an adhesive layer, and a second adhesive material are sequentially laminated. As shown in FIG. 1, the laminate 1 of the present invention has a first adhesive material 2, an adhesive layer 4, and a second adhesive material 6 in this order. In addition, in the laminated body 1 of the present invention, the first material to be bonded 2 and the adhesive layer 4 are laminated in direct contact, and the adhesive layer 4 and the second to be bonded material 6 are also in direct contact. Buildup. Here, let the saturated water vapor pressure at 85°C be Fv, and the interface adhesive force between the first adhesive layer and the adhesive layer at 85°C measured by the following measuring method (a) as Ft, The shear storage elastic coefficient (G') of the adhesive layer at 85°C measured by the following measuring method (b) is set to Fi, and the first measured at 85°C measured by the following measuring method (c) When the interface adhesive force between the second adhesive material and the adhesive layer is set to Fb, the conditions of Ft>Fv, Fi>Fv, and Fb>Fv are satisfied.

Measurement method (a): The adhesive was applied to the surface of the first adhesive material of the laminate with the size of 10 mm×10 mm, and the adhesive was applied to the center of a glass plate having a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm. On the adhesive layer side, a glass plate having a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm was bonded via an adhesive so that the two glass plates were in a cross positional relationship to each other to prepare a measurement sample. After placing the measurement sample in an environment of 85°C and a relative humidity of less than 20% for 3 hours, use a tensile testing machine to separate each glass plate at a speed of 5 mm/min at 85°C and a relative humidity of less than 20%. It is stretched in the opposite direction in the thickness direction, and the stress when peeling occurs between the first adhesive layer and the adhesive layer is measured as the interface adhesion force (Ft). When there is no peeling between the first adhesive material and the adhesive layer, the interface adhesion force (Ft) is greater than the maximum tensile stress. Here, in the measurement method (a), the glass plate attached to the adhesive layer side may be coated with an adhesive on the adhesive layer exposed by removing the second adhesive material, and then the adhesive may be The bonding may be to apply an adhesive to the surface of the second material to be bonded, and to be bonded via the adhesive. Regarding the stacking order in the measurement sample, it is appropriately changed according to each situation in the flow 1 to flow 3 described later.

Measurement method (b): Fix the laminate to the fixture for solid shear test using an adhesive, and measure the shear storage of the adhesive layer in the temperature range of 20°C to 120°C under the conditions of solid shear mode, frequency 1 Hz, and strain 1.0% The elastic coefficient G', the value of the shear storage elastic coefficient G'at 85°C is set to Fi. The adhesive used at this time preferably has a glass transition temperature (Tg) of 120°C or higher so as not to affect the shear storage elasticity coefficient to be measured. As the adhesive, for example, aronalpha quick-attack multi-purpose EXTRA manufactured by KONISHI Corporation can be used.

Measurement method (c): The adhesive was applied to the surface of the second material to be bonded of the laminate with the size of 10 mm × 10 mm, and the adhesive was applied to the center of a glass plate having a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm. On the adhesive layer side, a glass plate having a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm was bonded via an adhesive so that the two glass plates were in a cross positional relationship to each other to prepare a measurement sample. After placing the measurement sample in an environment of 85°C and a relative humidity of less than 20% for 3 hours, use a tensile testing machine to separate each glass plate at a speed of 5 mm/min at 85°C and a relative humidity of less than 20%. It is stretched in the opposite direction in the thickness direction, and the stress when peeling occurs between the second adhesive layer and the adhesive layer is measured as the interface adhesion force (Fb). When there is no peeling between the second adhesive material and the adhesive layer, the interface adhesion force (Fb) is greater than the maximum tensile stress. Here, in the measurement method (c), the glass plate attached to the adhesive layer side may be coated with an adhesive on the adhesive layer exposed by removing the first adhesive material, and then the adhesive may be applied through the adhesive. The bonding may be by applying an adhesive to the surface of the first material to be bonded, and bonding through the adhesive. Regarding the stacking order in the measurement sample, it is appropriately changed according to each situation in the flow 1 to flow 3 described later.

The measurement method (a) and the measurement method (c) are specifically achieved by performing the following procedures 1 to 3 in sequence. (Process 1) After cutting the laminate to a size of 10 mm×10 mm, apply a thin layer of adhesive to one of the laminate surfaces (the surface on the side of the first adhesive material), and apply the adhesive in a thickness of 4.0 mm × width 30 mm × length 50 mm The laminated body is fixed to the center of the glass A. Then, the adhesive was applied to the other side of the laminate (the surface of the second adhesive material side) in the same manner, and the laminate was fixed to the center of the glass B having a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm. At this time, as shown in FIG. 2, the two glasses A and B are bonded so as to have a cross positional relationship with each other. In addition, the upper figure of FIG. 2 is a figure which looked at the sample for measurement from a plane direction, and the lower figure of FIG. 2 is a figure which looked at the side surface of the sample for measurement from a cross-sectional direction. As shown in FIG. 2, the glass A 10 and the glass B 20 are bonded together so that each surface of the laminated body 1 may become a cross positional relationship, and the sample for measurement is comprised. The thus-obtained measurement sample was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely harden the adhesive, and then placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours. Thereafter, using a tensile testing machine, each glass was stretched in the opposite direction in the thickness direction at a speed of 5 mm/min at 85°C and a relative humidity of less than 20% until the glass was separated. The measurement of the maximum stress σ1 and the observation of the peeling interface determine Ft and Fb using the following criteria. (1) When peeling occurs at the interface between the first adherend and the adhesive layer, set Ft=σ1 and implement the test of Flow 2 to measure Fb. (2) When peeling occurs at the interface between the second adhesive material and the adhesive layer, set Fb=σ1 and implement the test of Flow 3 to measure Ft. (3) When peeling occurs at the interface between the adhesive and the glass (or the material to be bonded), set Ft, Fb>σ1. That is, when there is no peeling at the interface between the adhered material and the adhesive layer as in the case of (3), but the glass and the laminate are separated, it is considered that the interface adhesion force (Ft) and the interface adhesion force (Fb) are greater than this The maximum tensile stress at the time. In addition, as the adhesive used for bonding the glass and the laminate, for example, an instant adhesive can be used, and specifically, aronalpha quick-attack multi-purpose EXTRA manufactured by KONISHI Corporation can be used. Here, the adhesive is not particularly limited as long as the adhesive force (the maximum stress in the measurement) between each target material and the glass is greater than the saturated water vapor pressure (Fv) at 85°C. Furthermore, the glass used in the measurement is preferably an alkali glass, and for example, a float plate glass manufactured by Standard-Test Piece (Stock) Co., Ltd. can be used.

(Process 2) In the measurement of Flow 1, the adhesive layer that peeled off and exposed at the interface between the first adhesive material and the adhesive layer was thinly coated with the adhesive and fixed to a thickness of 4.0 mm × width 30 mm × length 50 mm The center of the new glass C. At this time, the two glasses B and C are bonded together in a cross positional relationship in the same manner as described above. The thus-obtained measurement sample was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely harden the adhesive, and then placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours. Thereafter, using a tensile testing machine, each glass was stretched in the opposite direction in the thickness direction at a speed of 5 mm/min at 85°C and a relative humidity of less than 20% until the glass was separated. The measurement of the maximum stress σ2 and the observation of the peeling interface determine Fb using the following criteria. (4) When peeling occurs at the interface between the second adhesive material and the adhesive layer, set Fb=σ2. (5) When peeling occurs at the interface between the adhesive and the glass, or the adhesive and the adhesive layer, set Fb>σ2.

(Process 3) Apply the adhesive thinly to the exposed adhesive layer that peeled off at the interface between the second adhesive material and the adhesive layer in the measurement of Flow 1, and fix it to a thickness 4.0 mm × width 30 mm × length 50 mm The center of the new glass D. At this time, the two glasses A and D are bonded together in a cross positional relationship in the same manner as described above. The thus-obtained measurement sample was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely harden the adhesive, and then placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours. Thereafter, using a tensile testing machine, each glass was stretched in the opposite direction in the thickness direction at a speed of 5 mm/min at 85°C and a relative humidity of less than 20% until the glass was separated. The measurement of the maximum stress σ3 and the observation of the peeling interface determine Ft using the following criteria. (6) When peeling occurs at the interface between the first adhesive material and the adhesive layer, set Ft=σ3. (7) When peeling occurs at the interface between the adhesive and the glass, or the adhesive and the adhesive layer, set Ft>σ3.

The saturated water vapor pressure Fv at 85°C in this specification is 0.058 MPa. In addition, the saturated water vapor pressure at 85°C can be the value described in Table 1.1 Saturated Vapor Pressure of Water attached to JIS Z 8806.

In the laminate of the present invention, the saturated water vapor pressure (Fv) at 85°C and the interface adhesion force (Ft) between the first adhesive layer and the adhesive layer measured by the method described above, and the shear of the adhesive layer The relationship between the storage elastic coefficient (Fi) and the interface adhesion force (Fb) between the second adhesive layer and the adhesive layer satisfies the following conditions. Ft>Fv, Fi>Fv, and Fb>Fv In the present invention, by making Fv, Ft, Fi, and Fb satisfy the above-mentioned conditions, it is possible to exhibit excellent resistance to outgassing in any manner of generating outgassing.

Here, three error modes (error modes) as shown in Fig. 3(a) to Fig. 3(c) can be cited as the generation method of the vented gas. The error mode 1 is shown in FIG. 3( a ). In this error mode, air bubbles R are generated at the interface between the first adhesive material 2 and the adhesive layer 4. The error mode 2 is shown in FIG. 3(b). In this error mode, air bubbles R are generated in the adhesive layer 4. The error mode 3 is shown in FIG. 3(c). In this error mode, bubbles R are generated at the interface between the second adhesive material 6 and the adhesive layer 4. In the present invention, by setting Fv, Ft, Fi, and Fb as predetermined conditions, it is possible to suppress the generation of various external gases as shown in FIGS. 3(a) to 3(c). Thereby, in the laminate of the present invention, even under high temperature conditions, the adhesive layer is suppressed from floating or peeling from the adherend, and the adhesiveness of the constituent members of the laminate is improved.

The interface adhesion (Ft) between the first adhesive material and the adhesive layer may be greater than 0.058 MPa, more preferably 0.10 MPa or greater, further preferably 0.15 MPa or greater, further preferably 0.20 MPa or greater, particularly preferably 0.25 MPa or greater .

The shear storage elastic coefficient (Fi) of the adhesive layer may be greater than 0.058 MPa, more preferably 0.10 MPa or greater, and still more preferably 0.15 MPa or greater.

The interface adhesion (Fb) between the second adhesive material and the adhesive layer may be greater than 0.058 MPa, more preferably 0.10 MPa or greater, further preferably 0.15 MPa or greater, further preferably 0.20 MPa or greater, particularly preferably 0.25 MPa or greater .

The laminate of the present invention is preferably used as an optical member. That is, the laminate of the present invention is preferably an optical laminate. For example, the laminate of the present invention is preferably used as a structural member of image display devices, parts of electrical and electronic equipment such as home appliances and game consoles, and decorative parts of automobiles. Furthermore, the laminate of the present invention has excellent resistance to outgassing even under high temperature conditions, and therefore is also preferably used as an on-vehicle optical member such as an on-vehicle display.

(Being bonded) The laminate of the present invention has a first adhesive material and a second adhesive material bonded via an adhesive layer. In addition, the first adhesive material and the second adhesive material may be the same kind of adhesive material or different adhesive materials. In addition, in the present invention, at least one of the first adhesive material and the second adhesive material may be an adhesive material that generates outgassing. In this case, the laminate of the present invention can still exhibit excellent resistance to outgassing.

The first material to be bonded is preferably a resin plate. Examples of the resin constituting the resin plate include polyester, polyethylene, polypropylene, polyvinyl chloride, polyvinyl alcohol, polystyrene, polycarbonate, polyetherimide, polyimide, and fluororesin. , Polyamide, (meth)acrylic resin, polymethyl methacrylate resin, copolymer of acrylonitrile and styrene, copolymer of acrylonitrile and butadiene, styrene, etc., a mixture of these can also be used Resin. Among them, the resin plate is preferably a (meth)acrylic resin plate and a polycarbonate resin plate, and more preferably a polycarbonate resin plate. That is, the first adhesive material preferably contains a polycarbonate resin. Here, the polycarbonate resin includes a composite material of a polycarbonate resin and other components (for example, a laminate of a methyl methacrylate base material and a polycarbonate resin sheet, or a polycarbonate resin with a hard coat layer). Resin board) or, raw materials containing only polycarbonate resin, etc. The polycarbonate resin sheet is a member that is prone to outgassing especially under high temperature conditions. However, in the present invention, by setting the relationship between Fv, Ft, Fi, and Fb as predetermined conditions, even when the polycarbonate resin sheet is used As the first adhesive material, when the laminate is placed under high temperature conditions, the generation of outgassing can also be suppressed. In addition, the first adhesive material can function as a cover film or a protective film in the optical laminate.

In addition, when the first material to be bonded is a polycarbonate resin sheet, examples of the polycarbonate resin sheet include Panlite PC-1151 manufactured by Teijin Chemicals Co., Ltd., and Mitsubishi Gas Chemical Co., Ltd. Stock) manufactured by Iupilon (Iupilon) NF2000 and so on. Furthermore, as the first adhesive material, a laminated base material in which a hard coat layer is laminated on at least one surface of a polycarbonate resin plate or a polymethyl group laminated on at least one surface of a polycarbonate resin plate can also be used. Laminated base material made of methyl acrylate (PMMA) base material.

The second adhesive material preferably includes at least one selected from a glass plate and a resin plate. The second bonded material is preferably an optical member, such as a touch panel, an indium tin oxide (ITO) film, or a polarizing plate. Moreover, as a member which comprises these optical members, a glass plate and a resin plate are mentioned. The bonding surface of the second adhesive material with the adhesive layer is preferably a glass plate and a resin plate.

The thickness of each of the first adhesive material and the second adhesive material is preferably 0.5 mm or more, more preferably 0.7 mm or more, and still more preferably 1 mm or more. In addition, the thickness of each of the first adhesive material and the second adhesive material is preferably 5 mm or less, more preferably 4 mm or less, and still more preferably 3 mm or less.

(Adhesive layer) The laminate of the present invention has an adhesive layer. The adhesive layer may be a single-layer adhesive layer, or a multilayer adhesive layer formed by laminating multiple layers of adhesives.

The thickness of the adhesive layer can be appropriately set according to the application, and is not particularly limited, but is preferably 10 μm or more, and more preferably 20 μm or more. Furthermore, the thickness of the adhesive layer is preferably 1000 μm or less, more preferably 750 μm or less, and still more preferably 500 μm or less. By setting the thickness of the adhesive layer within the above range, it is possible to more effectively improve the resistance to outgassing of the laminate. Furthermore, by setting the thickness of the adhesive layer within the above-mentioned range, it is possible to sufficiently ensure the level difference followability when the adherend is a member having a level difference. Furthermore, by setting the thickness of the adhesive layer within the above-mentioned range, the adhesive layer can be easily manufactured.

The shear storage elastic coefficient (G') of the adhesive layer at 85°C measured by the measurement method (b) should be greater than 0.058 MPa, more preferably 0.10 MPa or greater, and still more preferably 0.15 MPa or greater. The shear storage elasticity (G') of the adhesive layer is measured under the conditions of solid shear mode, frequency 1 Hz, strain 1.0%, and the shear storage elasticity of the adhesive layer in the temperature range of 20°C to 120°C. Coefficient (G'), calculate the value of shear storage elastic coefficient (G') at 85°C.

The adhesive layer is preferably an acrylic adhesive layer. The acrylic adhesive layer preferably contains an acrylic copolymer. In addition, in this specification, "unit" is a repeating unit (monomer unit) constituting a polymer. "(Meth)acrylic acid" means both or either of acrylic acid and methacrylic acid.

(Adhesive composition) The adhesive layer is preferably an adhesive layer having post-curing properties before being bonded to the first adhesive material and the second adhesive material. That is, in a state before being bonded to the first adhesive material and the second adhesive material, the adhesive layer is preferably an adhesive layer in which the adhesive composition is made into a semi-cured state. In addition, when the adhesive layer is an acrylic adhesive layer, the adhesive composition contains at least an acrylic copolymer. Moreover, when the adhesive layer bonded to the first adhesive material and the second adhesive material is a semi-cured adhesive layer, the adhesive composition preferably contains a crosslinkable acrylic copolymer, Crosslinking agent, photopolymerization initiator, monofunctional monomer and multifunctional monomer.

(Acrylic Copolymer) The acrylic copolymer preferably contains a non-crosslinkable (meth)acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group. That is, the acrylic copolymer is preferably a crosslinkable acrylic copolymer. The crosslinkable acrylic copolymer preferably has transparency to a degree that does not reduce the visibility of a display device or the like.

The non-crosslinkable (meth)acrylate unit (a1) is a repeating unit derived from an alkyl (meth)acrylate. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylate. N-Butyl acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, (meth)acrylate Base) isodecyl acrylate, n-undecyl (meth)acrylate, n-dodecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Benzyl meth)acrylate and the like. These may be used individually by 1 type, and may use 2 or more types together. Among the alkyl (meth)acrylates, it is preferable to select from methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethyl (meth)acrylate in terms of increasing adhesiveness. At least one of hexyl esters.

Examples of the acrylic monomer unit (a2) having a crosslinkable functional group include a hydroxyl group-containing monomer unit, an amine group-containing monomer unit, a glycidyl group-containing monomer unit, and a carboxyl group-containing monomer unit. These monomer units may be one type or two or more types. The hydroxyl-containing monomer unit is a repeating unit derived from a hydroxyl-containing monomer. Examples of hydroxyl-containing monomers include (meth)acrylic acid hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. (Meth)acrylic acid [(mono-, di- or poly)alkylene glycol] esters such as alkyl esters, (meth)acrylate mono(diethylene glycol) esters, (meth)acrylate monocaprolactone, etc. ( Meth)acrylate lactone. Examples of the amine group-containing monomer unit include repeating units derived from amine group-containing monomers such as (meth)acrylamide and allylamine. Examples of the glycidyl group-containing monomer unit include repeating units derived from glycidyl group-containing monomers such as glycidyl (meth)acrylate. Examples of the carboxyl group-containing monomer unit include acrylic acid and methacrylic acid.

The content of the crosslinkable acrylic monomer unit (a2) in the acrylic copolymer is preferably 0.01% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 35% by mass or less.

In addition, the acrylic copolymer preferably contains a hydroxyl group-containing monomer unit. The content of the hydroxyl group-containing monomer unit is preferably 0.01% by mass or more and 40% by mass or less, and more preferably 0.5% by mass or more and 35% by mass or less with respect to the total mass of the acrylic copolymer. In addition, by setting the content of the hydroxyl group-containing monomer unit within the above range, a uniform cross-linked structure is exhibited, so the adhesive performance is improved, and the elastic modulus under high temperature conditions can be further improved.

The acrylic copolymer may further include a unit derived from a nitrogen-containing monomer. Nitrogen-containing monomers are monomers that contain nitrogen in one molecule. Examples of nitrogen-containing monomers include dimethyl acrylamide, diethyl acrylamide, acryl morpholine, hydroxyethyl acrylamide, methylol acrylamide, and methoxy methacrylic acid. Amide, ethoxymethacrylamide, dimethylaminoethylacrylamide, N-vinyl caprolactam, N-vinyl-2-pyrrolidone, dimethyl (meth)acrylate Ethyl amino ethyl, N-vinyl formamide and the like. Among them, the nitrogen-containing monomer is preferably at least one selected from acrylamide derivatives, amine group-containing monomers and nitrogen-containing heterocyclic monomers, and more preferably acrylamide derivatives. The acrylamide derivative is more preferably at least one selected from the group consisting of dimethylacrylamide, diethylacrylamide, and acrylmorpholine, and particularly preferably dimethylacrylamide.

The content of the unit derived from the nitrogen-containing monomer is preferably 1% by mass or more, and more preferably 3% by mass or more with respect to the total mass of the acrylic copolymer. Furthermore, the content of the unit derived from the nitrogen-containing monomer is preferably 20% by mass or less with respect to the total mass of the acrylic copolymer.

The acrylic copolymer may optionally contain (meth)acrylate alkoxyalkyl ester units or (meth)acrylates having an alicyclic structure. Furthermore, the acrylic copolymer may have other monomer units other than the above-mentioned monomer units. The other monomers may be those that can be copolymerized with the monomer unit, and examples thereof include (meth)acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinylpyrrolidone, vinylpyridine, and the like.

The weight average molecular weight of the acrylic copolymer is preferably 100,000 or more, more preferably 300,000 or more, still more preferably 500,000 or more, particularly preferably 600,000 or more. Furthermore, the weight average molecular weight of the acrylic copolymer is preferably 2 million or less, more preferably 1.8 million or less, and still more preferably 1.6 million or less. By setting the weight average molecular weight of the acrylic copolymer within the above-mentioned range, the coatability is excellent, and the adhesive layer easily exhibits excellent resistance to outgassing.

The weight average molecular weight of the acrylic copolymer is measured by gel permeation chromatography (GPC) and determined on a polystyrene basis. The measurement conditions of gel permeation chromatography (GPC) are as follows. Solvent: Tetrahydrofuran (THF) String: Shodex KF801, KF803L, KF800L, KF800D (manufactured by Showa Denko Co., Ltd.) Column temperature: 40℃ Sample concentration: 0.5% by mass Detector: RI-2031plus (manufactured by JASCO) Pump: RI-2080plus (manufactured by JASCO) Flow (velocity): 0.8 ml/min Injection volume: 10 μl Calibration curve: A calibration curve of 10 samples using standard polystyrene Shodex standard polystyrene (manufactured by Showa Denko Co., Ltd.) Mw=1320-2,500,000.

The content of the acrylic copolymer relative to the total mass of the adhesive composition is preferably 75% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more.

(Crosslinking agent) The adhesive composition preferably contains a crosslinking agent. The crosslinking agent can be appropriately selected in consideration of the reactivity with the crosslinkable functional group possessed by the acrylic copolymer. For example, it can be selected from known crosslinking agents such as isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds, and butylated melamine compounds. Among these, since the acrylic monomer unit (a2) having a crosslinkable functional group can be easily crosslinked, an isocyanate compound or an epoxy compound is preferable. For example, when a hydroxyl group is included as a crosslinkable functional group, it is more preferable to use an isocyanate compound in terms of the reactivity of the hydroxyl group.

As an isocyanate compound, toluene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. Examples of epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, and neopentyl glycol diglycidyl ether. Glycidyl ether, 1,6-hexanediol diglycidyl ether, tetraglycidyl xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl) cyclohexane, trihydroxy Methyl propane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc.

The content of the crosslinking agent in the adhesive composition is appropriately selected according to the desired adhesive properties, etc., relative to 100 parts by mass of the acrylic copolymer, preferably 0.01 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass Above and 3 parts by mass or less. As the crosslinking agent, one type may be used alone or two or more types may be used in combination, and when two or more types are used in combination, it is preferable that the total mass is within the above-mentioned range.

(Photopolymerization initiator) When the adhesive layer has post-curing properties, the adhesive composition preferably contains a photopolymerization initiator. Photopolymerization initiators are used for the polymerization of acrylic copolymers. The photopolymerization initiator is not particularly limited, and examples thereof include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenylketone, and 2-hydroxy-2-methyl 1-Phenylacetone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylacetone, 2-hydroxy-1-(4-(4-(2-hydroxyl (-2-methylpropanyl)benzyl)phenyl)-2-methyl-1-acetone and other alkylphenone-based photopolymerization initiators, 2,4,6-trimethylbenzyl- Diphenyl phosphine oxide or 2,4,6-trimethyl benzophenone) phenyl phosphine oxide and other phenyl phosphine oxide polymerization initiators, methyl benzoate or 4-methyl benzophenone Intramolecular dehydrogenation-type photopolymerization initiators, and oil-soluble polymerization initiators such as oxime ester-based polymerization photoinitiators or cationic polymerization photoinitiators.

The content of the photopolymerization initiator is preferably 0.1 part by mass or more and 10 parts by mass or less, and more preferably 0.4 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer. As the photopolymerization initiator, one type may be used alone or two or more types may be used in combination, and when two or more types are used in combination, it is preferable that the total mass is within the above-mentioned range.

(Monofunctional monomer) The adhesive composition preferably contains a monofunctional monomer having one reactive double bond in the molecule.

Examples of monofunctional monomers include lauryl acrylate, isobornyl acrylate, isostearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, N -Acrylic oxyethyl hexahydrophthalimide, acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, propylene morpholine, ethylene Base pyrrolidone and so on. Among them, the monofunctional monomer is preferably lauryl acrylate. Examples of commercially available monofunctional monomers include lauryl acrylate (LA) manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like.

The content of the monofunctional monomer is preferably 1 part by mass to 20 parts by mass, and more preferably 2 parts by mass to 20 parts by mass relative to 100 parts by mass of the acrylic copolymer. The said monofunctional monomer may be used individually by 1 type, or may use 2 or more types together, and when using 2 or more types together, it is preferable that the total mass is within the said range.

(Multifunctional monomer) The adhesive composition preferably contains a multifunctional monomer having two or more reactive double bonds in the molecule. The polyfunctional monomer has two or more reactive double bonds. Among them, the multifunctional monomer preferably has two or more and less than five reactive double bonds, and more preferably has two or more and less than four reactive double bonds.

Examples of multifunctional monomers include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, and di(meth)acrylate 1,4-butanediol meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol diacrylate, polybutylene glycol di(meth)acrylate , Neopentyl glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, bisphenol A dishrink (Meth)acrylates of polyols such as diacrylate of glycerol ether, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc., vinyl methacrylate Base ester and so on.

Among them, the multifunctional monomer is preferably a multifunctional monomer having a bisphenol skeleton in one molecule. By using a multifunctional monomer having a bisphenol skeleton in one molecule, the hardness of the post-curing adhesive layer can be more effectively improved. Thereby, the resistance to outgassing of the post-cured adhesive layer can be more effectively improved.

As a multifunctional monomer having a bisphenol skeleton in one molecule, for example, diacrylate of bisphenol A diglycidyl ether, diacrylate of propoxylated bisphenol A, and bisphenol F diglycidyl ether The diacrylate and so on.

As the polyfunctional monomer, commercially available products can be used. Examples of commercially available products include the bifunctional monomer M211B (bisphenol A ethylene oxide modified diacrylate) manufactured by Toagosei Co., Ltd., and the bifunctional monomer M08 (bisphenol F epoxy resin) manufactured by Toagosei Co., Ltd. Ethane modified diacrylate), the difunctional monomer A-BPP-3 (propoxylated bisphenol A diacrylate) manufactured by Shin Nakamura Chemical Company, etc.

The content of the multifunctional monomer is preferably 1 part by mass to 30 parts by mass, and more preferably 5 parts by mass to 30 parts by mass relative to 100 parts by mass of the acrylic copolymer. The said polyfunctional monomer may be used individually by 1 type, or may use 2 or more types together, and when using 2 or more types together, it is preferable that the total mass is within the said range. By setting the content of the polyfunctional monomer within the above range, the hardness of the post-curing adhesive layer can be more effectively increased, and the gas resistance of the adhesive layer can be more effectively improved.

(Solvent) The adhesive composition may also contain a solvent. That is, the adhesive composition may be a solvent-based adhesive composition.

Examples of solvents include hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; dichloromethane, trichloroethane, and trichloroethylene. , Tetrachloroethylene, dichloropropane and other halogenated hydrocarbons; methanol, ethanol, propanol, isopropanol, butanol, isobutanol, diacetone alcohol and other alcohols; diethyl ether, diisopropyl ether, dioxane, Ethers such as tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, acetic acid Esters such as amyl ester and ethyl butyrate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate And other polyols and their derivatives.

A solvent may be used individually by 1 type, and may use 2 or more types together. The content of the solvent in the adhesive composition is not particularly limited, and it can be 25 parts by mass or more and 500 parts by mass or less, and 30 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer.

(Other ingredients) The adhesive composition may contain components other than those described above within a range that does not impair the effects of the present invention. Examples of other components include components known as additives for adhesives. For example, plasticizers, antioxidants, metal corrosion inhibitors, adhesion imparting agents, silane coupling agents, ultraviolet absorbers, hindered amine compounds and other light stabilizers can be selected as needed. Furthermore, dyes or pigments may be added for the purpose of coloring. Examples of plasticizers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, and palmitic acid. Vinyl carboxylates such as vinyl ester, vinyl stearate, vinyl cyclohexane carboxylate, vinyl benzoate, or styrene. Examples of antioxidants include phenol-based antioxidants, amine-based antioxidants, lactone-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. These antioxidants may be used individually by 1 type, and may use 2 or more types together. As a metal corrosion inhibitor, a benzotriazole-based resin can be cited as a preferable example in terms of the compatibility of the adhesive or the height of the effect. Examples of the adhesion imparting agent include rosin resins, terpene resins, terpene phenol resins, coumarone-indene resins, styrene resins, xylene resins, phenol resins, petroleum resins, and the like. As the silane coupling agent, for example, mercaptoalkoxysilane compounds (for example, mercapto-substituted alkoxy oligomers, etc.) and the like can be cited. As an ultraviolet absorber, a benzotriazole type compound, a benzophenone type compound, etc. are mentioned, for example. However, when ultraviolet rays are used for active energy rays during post-curing, it is preferable to add them within a range that does not hinder the polymerization reaction.

(Method of manufacturing laminate) The present invention relates to a method of manufacturing the laminate. The manufacturing method of the laminated body preferably includes: bonding the first adhesive material and the second adhesive material to the adhesive layer having post-curing properties; and irradiating from the side of the first adhesive material or the second adhesive material Steps of active energy lines.

The adhesive layer having post-curing properties can be produced, for example, as follows. In the step of manufacturing the adhesive layer having post-curing properties, it is preferable to include a step of applying the adhesive composition to form a coating film, and heating the coating film. For example, it is preferable to apply an adhesive composition on the release sheet to form a coating film, and heat the coating film to form a cured product in a semi-cured state. By heating the coating film, the acrylic copolymer and the crosslinking agent react to form a semi-cured adhesive layer.

The application of the adhesive composition can be carried out using a known coating device. Examples of coating devices include: blade coaters, air knife coaters, roll coaters, bar coaters, gravure coaters, micro gravure coaters, bar blade coaters, and lip coaters. Cloth machine, die coater, curtain coater, etc.

In the coating step, it is preferable to apply so that the coating amount after drying becomes 10 μm/m ² or more, and it is more ^{preferable to apply so that the coating amount after drying becomes 20 μm/m 2} or more. Furthermore, it is preferable to apply so that the coating amount after drying becomes 500 μm/m ² or less, and it is more preferable to apply so as to become 300 μm/m ² or less.

The heat-drying process of the coating film can be implemented using a well-known heating apparatus, such as a heating furnace and an infrared lamp. For example, an air circulating constant temperature oven at 50°C or higher and 150°C or lower is used to dry for 10 seconds or longer and 10 minutes or shorter.

After the heating and drying step, it is preferable to set an aging treatment step in which the adhesive sheet is allowed to stand at a certain temperature for a certain period of time. The aging treatment step can be carried out by standing still for 7 days under the conditions of 23°C and 50% relative humidity, for example.

In the step of attaching the first adhesive layer and the second adhesive layer to the post-curing adhesive layer, the first adhesive layer is attached to each surface of the post-curing adhesive layer obtained by the method. One to be bonded and the second to be bonded. After bonding, you may perform autoclave treatment in order to improve adhesiveness.

After bonding the first adhesive material and the second adhesive material to both sides of the adhesive layer, it is preferable to provide a step of irradiating active energy rays from the side of the first adhesive material or the second adhesive material. By irradiating active energy rays, the semi-hardened adhesive layer is completely hardened (post-hardened). Thereby, the cohesive force of the adhesive layer is improved, and the adhesiveness to each material to be bonded is improved. In addition, by post-curing the adhesive layer, the resistance to outgassing of the entire laminate can be more effectively improved. In addition, in the laminate, when the first adhesive material is a resin plate such as a polycarbonate resin plate, the resin plate is preferably a transparent substrate, and when active energy rays are irradiated, it is preferably from the first adhesive. The material side is irradiated with active energy rays.

Examples of the active energy rays include ultraviolet rays, electron beams, visible rays, X-rays, ion beams, etc., which can be appropriately selected according to the polymerization initiator contained in the adhesive layer. Among them, in terms of versatility, ultraviolet rays or electron beams are preferred, and ultraviolet rays are particularly preferred. As the ultraviolet light source, for example, a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, etc. can be used. As the electron beam, for example, Cockcroft-Walton (Cockcroft-Walton) type, Van der Graaff (Van der Graaff) type, resonant transformer type, insulated core transformer type, linear type, dinamic type can be used. (Dynamitron) type, high-frequency type and other electron beams emitted by various electron beam accelerators. The irradiation output of ultraviolet rays is preferably such that the accumulated light amount becomes 100 mJ/cm ² to 10000 mJ/cm ² , and more preferably 500 mJ/cm ² to 5000 mJ/cm ² . In this way, by using an adhesive layer with post-curing properties and bonding in a semi-cured state with good wettability, it is possible to improve the adhesion to the first and second adhered materials and increase Ft and Fb. , And further improve Fi by post-curing. [Example]

Examples and comparative examples are listed below to more specifically illustrate the characteristics of the present invention. The materials, usage amount, ratio, processing content, processing flow, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the specific examples shown below.

(Example 1) [Production of laminated body (A-1G)] <Production of crosslinkable acrylic copolymer (A-1)> With 2-ethylhexyl acrylate (2EHA) 45% by mass, ethyl acrylate (EA) 40% by mass, 4-hydroxybutyl acrylate (4HBA) 2% by mass, N,N-dimethylacrylamide (DMAA) ) It is formulated to be 13% by mass, and 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator is dissolved in the solution. The solution was heated to 60°C for random copolymerization to obtain a crosslinkable acrylic copolymer (A-1). The weight average molecular weight of the crosslinkable acrylic copolymer (A-1) is 540,000. In addition, the weight average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) and based on polystyrene standards. The measurement conditions of gel permeation chromatography (GPC) are as follows. Solvent: Tetrahydrofuran String: Shodex KF801, KF803L, KF800L, KF800D (manufactured by Showa Denko Co., Ltd.) Column temperature: 40℃ Sample concentration: 0.5% by mass Detector: RI-2031plus (manufactured by JASCO) Pump: RI-2080plus (manufactured by JASCO) Flow (velocity): 0.8 ml/min Injection volume: 10 μl Calibration curve: A calibration curve of 10 samples using standard polystyrene Shodex standard polystyrene (manufactured by Showa Denko Co., Ltd.) Mw=1320-2,500,000.

＜Preparation of adhesive composition (A-1)＞ To 100 parts by mass of the crosslinkable acrylic copolymer (A-1), a xylylene diisocyanate compound (manufactured by Mitsui Chemicals Co., Ltd., Takenate D-110N) as a crosslinking agent is added 0.2 Parts by mass, 10 parts by mass of lauryl acrylate (LA) as a monofunctional monomer, and bisphenol A ethylene oxide modified diacrylate as a multifunctional monomer (manufactured by Toagosei Co., Ltd., Alonis ( Aronix M211B) 12 parts by mass, as a polymerization initiator, bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide (manufactured by BASF Japan (stock), Yanjiagu ( IRGACURE) 819) 1.0 part by mass, a solvent was prepared so that the solid content concentration was 35% by mass, ethyl acetate was added to obtain an adhesive composition (A-1).

<Preparation of Adhesive Layer (A-1)> The adhesive composition (A-1) prepared as described above was uniformly prepared using an applicator so that the coating amount after drying became 150 μm/m ² It is applied to a polyethylene terephthalate film (first release sheet) with a thickness of 100 μm with a release agent layer treated with a silicone-based release agent (heavy release film, manufactured by Teijin DuPont Film (stock), after removal Molded polyethylene terephthalate film) surface. After that, it was dried in an air circulation constant temperature oven at 100° C. for 3 minutes to form an adhesive layer (A-1) on the surface of the first release sheet. Then, a second release sheet (light release film, manufactured by Teijin DuPont Film (strand), manufactured by Teijin DuPont Film (strand), which is higher in release than the first release sheet with a thickness of 75 μm) was attached to the surface of the adhesive layer. Treated polyethylene terephthalate film) to obtain the first release sheet/adhesive layer (A-1)/the first release sheet in which the adhesive layer (A-1) is sandwiched by a pair of release sheets with poor release strength Adhesive sheet with a release sheet composed of two release sheets. The pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under the conditions of 23° C. and a relative humidity of 50%, and was subjected to an aging treatment.

<Production of laminated body (A-1G)> Using the adhesive sheet with a release sheet obtained as described above, a laminated body (A-1G) was produced by the following method. First, the second release sheet, which is the light release film of the adhesive sheet with a release sheet, is peeled off, and the exposed adhesive layer (A-1) is bonded to a PC board with a thickness of 1 mm (Teijin (Teijin) Stock) manufactured by Panlite PC-1151). Next, the first release sheet as the heavy release film was peeled off, and the exposed adhesive layer (A-1) was adhered to the entire surface of the glass plate having a size of 100 mm×200 mm as the second adhesive material. PC board constituting the sample / adhesive layer / glass sheet autoclave treatment (40 ℃, 0.5 MPa, 30 min), then, from the side of the glass sheet so that the integrated quantity of light to be irradiated with ultraviolet ray 3000 mJ / cm ^2, and A laminate sample with a size of 100 mm×200 mm was obtained.

(Example 2) ＜Production of laminated body (A-1P)＞ The second adhesive material was changed to 100 μm thick Cosmoshine A4300 (PET) manufactured by Toyobo Co., Ltd., and ultraviolet rays were irradiated from the PET side, except that the laminate (A-1P) was produced in the same manner as in Example 1. ).

(Example 3) <Production of crosslinkable acrylic copolymer (A-2)> It is blended with 75% by mass of n-butyl acrylate (BA) and 25% by mass of 2-hydroxyethyl acrylate (2HEA), and 2,2'-azobis(2,4) as a radical polymerization initiator -Dimethylvaleronitrile) dissolved in the solution. The solution was heated to 60°C for random copolymerization to obtain a crosslinkable acrylic copolymer (A-2). The weight average molecular weight of the crosslinkable acrylic copolymer (A-2) is 510,000.

＜Preparation of adhesive composition (A-2)＞ With respect to 100 parts by mass of the crosslinkable acrylic copolymer (A-2), 0.1 parts by mass of a toluene diisocyanate compound (manufactured by Tosoh Co., Ltd., Coronate L55) as a crosslinking agent is added , 30 parts by mass of lauryl acrylate (LA) as a monofunctional monomer, bisphenol A ethylene oxide modified diacrylate as a multifunctional monomer (manufactured by Toagosei Co., Ltd., Aronix) M211B) 6 parts by mass, as a polymerization initiator, bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide (manufactured by BASF Japan (stock), IRGACURE) 819) 1.12 parts by mass, a solvent was prepared so that the solid content concentration was 35% by mass, ethyl acetate was added to obtain an adhesive composition (A-2).

＜Production of Adhesive Layer (A-2)＞ Except that the adhesive composition (A-1) was changed to the adhesive composition (A-2), the tape peeling of the adhesive layer (A-2) with a thickness of 150 μm was obtained in the same manner as in Example 1. Adhesive piece of the piece. The pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under the conditions of 23° C. and a relative humidity of 50%, and was subjected to an aging treatment.

＜Production of laminated body (A-2G)＞ Except for changing the adhesive layer (A-1) to the adhesive layer (A-2), a laminate (A-2G) was produced in the same manner as in Example 1.

(Example 4) ＜Production of laminated body (A-2P)＞ Except that the adhesive layer (A-1) was changed to the adhesive layer (A-2), a laminate (A-2P) was produced in the same manner as in Example 2.

(Comparative example 1) <Production of laminate (A-3G)> Using the adhesive layer (A-2) produced as described above, a laminate (A-3G) was produced by the following method. First, the light release film of the adhesive sheet with a release sheet, which is the second release sheet, is peeled off, and the exposed adhesive layer (A-2) is bonded to a glass of 100 mm×200 mm as the second adhesive material. board. In the state where the glass plate/adhesive layer (A-2)/first peeling sheet is ^{laminated, ultraviolet rays are irradiated from the glass side so that the cumulative light amount becomes 3000 mJ/cm 2} , and then the first peeling sheet is peeled off, The exposed adhesive layer was pasted on the entire surface of a 1 mm thick PC board (Panlite PC-1151 manufactured by Teijin Co., Ltd.) as the first adhesive material. The laminate composed of PC board/adhesive layer (A-3)/glass plate was subjected to autoclave treatment (40°C, 0.5 MPa, 30 min) to produce laminate (A-3G).

(Comparative example 2) ＜Preparation of adhesive composition (A-4)＞ With respect to 100 parts by mass of the crosslinkable acrylic copolymer (A-1), a toluene diisocyanate compound (manufactured by Tosoh Co., Ltd., Coronate L55) 0.05 parts by mass is blended, and acrylic acid is not blended Lauryl ester, bisphenol A ethylene oxide modified diacrylate and bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide were obtained in the same manner as in Example 1 except that Adhesive composition (A-4).

<Production of Adhesive Layer (A-4)> Except that the adhesive composition (A-1) was changed to the adhesive composition (A-4), the tape peeling of the adhesive layer (A-4) with a thickness of 150 μm was obtained in the same manner as in Example 1. Adhesive piece of the piece. The pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under the conditions of 23° C. and a relative humidity of 50%, and was subjected to an aging treatment.

＜Production of laminated body (A-4G)＞ Except that the adhesive layer (A-1) was changed to the adhesive layer (A-4), and ultraviolet irradiation was not performed, a laminate (A-4G) was produced in the same manner as in Example 1.

(Comparative example 3) <Production of laminate (A-5P)> Using the adhesive layer (A-1) produced as described above, a laminate (A-5P) was produced by the following method. First, the light release film of the adhesive sheet with a release sheet, that is, the second release sheet was peeled off, and the exposed adhesive layer (A-1) was bonded to a PC board with a thickness of 1 mm (Teijin (Teijin) Stock) manufactured by Panlite PC-1151). In the state where the glass plate PC board/adhesive layer (A-1)/first release sheet is laminated, ultraviolet rays are irradiated from the ^{side of the first release sheet as the heavy release film so that the cumulative light amount becomes 3000 mJ/cm 2, which} After that, the first release sheet was peeled off, and the exposed adhesive layer was stuck on the entire surface of a PET film having a size of 100 mm×200 mm as the second adhesive material. The laminate composed of PC board/adhesive layer (A-5)/PET was autoclaved (40°C, 0.5 MPa, 30 min) to produce laminate (A-5P).

(Measurement and evaluation) <Measurement of the interface adhesive force (Ft) between the first adhesive material and the adhesive layer and the interface adhesive force (Fb) between the adhesive layer and the second adhesive material> (Process 1) After cutting the laminates produced in the Examples and Comparative Examples to a size of 10 mm×10 mm, a thin layer of instant adhesive (KONISHI (KONISHI) was applied to one of the laminate surfaces (the surface on the side of the first adhesive material). ) The company's aronalpha (aronalpha) quick-attack multi-purpose EXTRA), the laminated body is fixed to the center of the glass A with a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm. Then, the instant adhesive was applied to the other side of the laminate (the side of the second adhesive material side) in the same manner, and the laminate was fixed to the center of the glass B having a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm. At this time, as shown in FIG. 2, the two glasses A and B are bonded so as to have a cross positional relationship with each other. The thus-obtained measurement sample was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely harden the instant adhesive, and then placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours. Thereafter, using a tensile testing machine, each glass was stretched in the opposite direction in the thickness direction at a speed of 5 mm/min at 85°C and a relative humidity of less than 20% until the glass was separated. The measurement of the maximum stress σ1 and the observation of the peeling interface determine Ft and Fb using the following criteria. (1) When peeling occurs at the interface between the first adherend and the adhesive layer, set Ft=σ1 and implement the test of Flow 2 to measure Fb. (2) When peeling occurs at the interface between the second adhesive material and the adhesive layer, set Fb=σ1 and implement the test of Flow 3 to measure Ft. (3) When peeling occurs at the interface between the adhesive and the glass (or the material to be bonded) instantaneously, set Ft, Fb>σ1.

(Process 2) In the measurement of Flow 1, the adhesive layer that peeled off and exposed at the interface between the first adhesive material and the adhesive layer was thinly coated with instant adhesive, and fixed to a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm The center of the new glass C. At this time, the two glasses B and C are bonded together in a cross positional relationship in the same manner as described above. The thus-obtained measurement sample was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely harden the instant adhesive, and then placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours. Thereafter, using a tensile testing machine, each glass was stretched in the opposite direction in the thickness direction at a speed of 5 mm/min at 85°C and a relative humidity of less than 20% until the glass was separated. The measurement of the maximum stress σ2 and the observation of the peeling interface determine Fb using the following criteria. (4) When peeling occurs at the interface between the second adhesive material and the adhesive layer, set Fb=σ2. (5) When peeling occurs at the interface between the instant adhesive and glass, or the instant adhesive and the adhesive layer, set Fb>σ2.

(Process 3) In the measurement of flow 1, the adhesive layer that peeled off at the interface between the second adhesive material and the adhesive layer was exposed and applied a thin layer of instant adhesive, and fixed it to a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm The center of the new glass D. At this time, the two glasses A and D are bonded together in a cross positional relationship in the same manner as described above. The thus-obtained measurement sample was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely harden the instant adhesive, and then placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours. Thereafter, using a tensile testing machine, each glass was stretched in the opposite direction in the thickness direction at a speed of 5 mm/min at 85°C and a relative humidity of less than 20% until the glass was separated. The measurement of the maximum stress σ3 and the observation of the peeling interface determine Ft using the following criteria. (6) When peeling occurs at the interface between the first adhesive material and the adhesive layer, set Ft=σ3. (7) When peeling occurs at the interface between the instant adhesive and the glass, or the instant adhesive and the adhesive layer, set Ft>σ3.

＜Measurement of the cohesive force (Fi) of the adhesive layer＞ The laminates produced in the Examples and Comparative Examples were cut into a size of 10 mm×8 mm, and fixed to the dynamic viscoelasticity with an instant adhesive (aronalpha quick-attack multi-purpose EXTRA manufactured by KONISHI) Device Rheogel-E4000 (manufactured by UBM Co., Ltd.) is a fixture for solid shear test to measure the adhesive layer in the temperature range of 20°C to 120°C under the conditions of solid shear mode, frequency 1 Hz, and strain 1.0% Set the shear storage elastic coefficient G'at 85°C as Fi.

＜Bubble/Floating and peeling＞ The 100 mm×200 mm laminate samples produced in the Examples and Comparative Examples were placed in an environment at 85° C. and a relative humidity of less than 20%, and observed after 100 hours to evaluate the presence or absence of bubbles or floating and peeling. ○: No bubbles or floating and peeling ×: Air bubbles or floating and peeling occurred in any of the following modes Mode1: Floating occurred at the interface between the first adhesive material and the adhesive layer Mode2: Bubbles larger than 0.1 mmϕ are generated in the adhesive layer Mode3: Floating occurs at the interface between the second adhesive material and the adhesive layer

[Table 1] Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Layer composition The first to be bonded PC1151 PC1151 PC1151 PC1151 PC1151 PC1151 PC1151 Adhesive layer A-1 A-1 A-2 A-2 A-3 A-4 A-5 Second material Glass PET Glass PET Glass Glass PET Fv[MPa] 0.058 0.058 0.058 0.058 0.058 0.058 0.058 Ft[MPa] >0.5※ >0.5※ 0.36 0.36 0.043 0.86 >0.5※ Fi[MPa] 0.29 0.29 0.24 0.18 0.18 0.049 0.37 Fb[MPa] >0.5※ 0.38 >0.5※ 0.37 0.37 0.43 0.050 Bubble/floating peeling ○ ○ ○ ○ ×Mode1 ×Mode2 ×Mode3 ※The person who peeled off at the interface between the glass and the instant adhesive

In the laminated body obtained in the example, the generation of bubbles in the adhesive layer was suppressed, and the adhesive layer was suppressed from floating or peeling from each adherend.

1: Layered body 2: The first material to be bonded 4: Adhesive layer 6: The second is the next material 10: Glass A 20: Glass B R: Bubble

Fig. 1 is a cross-sectional view illustrating the structure of a laminate including the adhesive sheet of the present invention. Fig. 2 is a diagram illustrating a method of measuring the cross adhesive force of a double-sided pressure-sensitive adhesive sheet. Figs. 3(a) to 3(c) are cross-sectional views for explaining the manner in which the vented gas is generated in the laminate.

1: Layered body

2: The first material to be bonded

4: Adhesive layer

6: The second is the next material

Claims (8)

A laminated body, which is formed by sequentially laminating a first material to be bonded, an adhesive layer, and a second material to be bonded, and Set the saturated water vapor pressure at 85°C as Fv, Let the interface adhesion force between the first adhesive material and the adhesive layer at 85°C measured by the following measuring method (a) be Ft, Let the shear storage elastic coefficient (G') of the adhesive layer at 85°C measured by the following measuring method (b) be Fi, When the interface adhesive force of the second adhesive material and the adhesive layer at 85°C measured by the following measuring method (c) is Fb, Meet the conditions of Ft>Fv, Fi>Fv, and Fb>Fv; Measurement method (a): Coat the adhesive on the surface of the first material to be bonded of the laminate with the size of 10 mm×10 mm, and attach it to the center of the glass plate with a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm; on the side of the adhesive layer, A glass plate with a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm was bonded through an adhesive so that the two glass plates became a cross positional relationship to each other to form a measurement sample; the measurement sample was placed at 85°C, After leaving for 3 hours in an environment with a relative humidity of less than 20%, at 85°C and a relative humidity of less than 20%, use a tensile testing machine to pull each glass plate in the opposite direction of the thickness direction at a speed of 5 mm/min. Stretching, the stress at the time of peeling between the first adhesive material and the adhesive layer is measured as the interface adhesion force (Ft); when there is no peeling between the first adhesive material and the adhesive layer, the interface is closely adhered Force (Ft) is greater than the maximum tensile stress; Measurement method (b): Fix the laminate to the fixture for solid shear test using an adhesive, and measure the shear storage of the adhesive layer in the temperature range of 20°C to 120°C under the conditions of solid shear mode, frequency 1 Hz, and strain 1.0% Elasticity coefficient G', set the value of shear storage elasticity coefficient G'at 85℃ as Fi; Measurement method (c): Apply an adhesive to the surface of the second material to be bonded of a laminate with a size of 10 mm × 10 mm, and adhere to the center of a glass plate with a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm; on the side of the adhesive layer, A glass plate with a thickness of 4.0 mm × a width of 30 mm × a length of 50 mm was bonded through an adhesive so that the two glass plates became a cross positional relationship to each other to form a measurement sample; the measurement sample was placed at 85°C, After leaving for 3 hours in an environment with a relative humidity of less than 20%, at 85°C and a relative humidity of less than 20%, use a tensile testing machine to pull each glass plate in the opposite direction of the thickness direction at a speed of 5 mm/min. Stretching, the stress when peeling between the second adhesive material and the adhesive layer is measured as the interface adhesion force (Fb); when there is no peeling between the second adhesive material and the adhesive layer, the interface is closely adhered The force (Fb) is greater than the maximum tensile stress. The laminate according to claim 1, wherein the first adhesive material is a resin plate. The laminate according to claim 1 or 2, wherein the first adhesive material includes a polycarbonate resin. The laminate according to claim 1 or claim 2, wherein the second adherend material includes at least one selected from a glass plate and a resin plate. A method for manufacturing a laminate, which is the method for manufacturing a laminate according to any one of Claims 1 to 4, comprising: The bonding step of bonding the first adhesive material and the second adhesive material to the adhesive layer with post-curing properties; and The step of irradiating active energy rays from the side of the first adhesive material or the second adhesive material. The method of manufacturing a laminate according to claim 5, wherein The adhesive layer used in the bonding step is an adhesive layer in which the adhesive composition is made into a semi-hardened state, The adhesive composition includes a crosslinkable acrylic copolymer, a crosslinking agent, a photopolymerization initiator, a monofunctional monomer, and a multifunctional monomer. The method for manufacturing a laminate according to claim 6, wherein the monofunctional monomer is lauryl acrylate. The method for producing a laminate according to claim 6 or 7, wherein the polyfunctional monomer is a monomer having a bisphenol skeleton in one molecule.

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