WO2023027092A1 - 積層体 - Google Patents
積層体 Download PDFInfo
- Publication number
- WO2023027092A1 WO2023027092A1 PCT/JP2022/031804 JP2022031804W WO2023027092A1 WO 2023027092 A1 WO2023027092 A1 WO 2023027092A1 JP 2022031804 W JP2022031804 W JP 2022031804W WO 2023027092 A1 WO2023027092 A1 WO 2023027092A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- pressure
- less
- weight
- adhesive sheet
- Prior art date
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- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
Definitions
- the present invention relates to a laminate including a core and adhesive sheets arranged on each surface of the core.
- pressure-sensitive adhesives also called pressure-sensitive adhesives; the same shall apply hereinafter
- pressure-sensitive adhesives are widely used in various industrial fields such as home electric appliances, automobiles, and OA equipment as bonding means with good workability and high adhesion reliability.
- pressure-sensitive adhesives are widely used for purposes such as joining, fixing, and protecting members in smartphones and other mobile electronic devices.
- Patent Documents 1 and 2 are cited as technical documents relating to adhesive tapes used for fixing members of portable electronic devices.
- the pressure-sensitive adhesive that is applied to the above-mentioned complicated shape is required to have the ability to follow the shape well and adhere to it.
- the adhesive for fixing a member having a complicated surface shape (which may be a curved surface shape) exhibits a good fixing function while maintaining a state in which the complicated shape is followed without gaps. There is a need to. If the adhesive does not adhere to the curved surface of the adherend and a gap is formed between the adherend and the adherend, water may enter through the gap and water resistance may be impaired.
- the adhesive is required to have the ability to protect the adherend.
- mobile electronic devices tend to be easily subjected to impacts and loads from the outside due to their portability.
- the performance of suppressing deformation (distortion) of a member, etc., placed on the back side of the body is required.
- the adherend is a flexible printed wiring board to which an electronic component is fixed, the electronic component may be deformed and damaged by an external impact or the like, if the adhesive is poor in protecting the adherend. malfunction may occur. Therefore, the pressure-sensitive adhesive is required to have the performance of suppressing deformation (distortion) of other members due to impact or the like (such performance is hereinafter referred to as "distortion resistance").
- the present invention has been created in view of the above circumstances, and an object of the present invention is to provide a structure (laminated body) capable of achieving both conformability to a complicated shape and resistance to distortion.
- the inventors adopted a laminate composed of two or more constituent elements laminated at least including an adhesive layer, thereby improving both the followability to a complicated shape and the above-mentioned strain resistance. found to get.
- a laminate comprising a core, a first adhesive sheet arranged on one surface of the core, and a second adhesive sheet arranged on the other surface of the core.
- the first adhesive sheet and the second adhesive sheet each include an adhesive layer.
- the product (E A ⁇ T A ) of Young's modulus E A [MPa] and thickness T A [ ⁇ m] of the core is 500,000 or more.
- one or both of the first pressure-sensitive adhesive sheet and the second pressure-sensitive adhesive sheet have a storage elastic modulus G' at 25°C (85°C) of less than 0.05 MPa.
- one or both of the first pressure-sensitive adhesive sheet and the second pressure-sensitive adhesive sheet have a storage elastic modulus G' at 120°C (120°C) of less than 0.03 MPa.
- the thickness TA of the core is 10 ⁇ m or more and 300 ⁇ m or less. According to such a configuration, it becomes easier to achieve thinning of the laminate and excellent strain resistance.
- the Young's modulus EA of the core is 3000 MPa or higher. According to such a configuration, it becomes easier to achieve thinning of the laminate and excellent strain resistance.
- the laminate has a light transmittance C total of 10% or less.
- a laminate is used in products including a light source such as a backlight module, and tends to be excellent in suppressing light leakage from the light source (light shielding property) and imparting design properties.
- the laminate has a total thickness T total of 50 ⁇ m or more and 400 ⁇ m or less. Such laminates tend to have excellent conformability to complex shapes.
- the laminate disclosed here can be preferably used for electronic equipment.
- the laminate disclosed herein utilizes the features of being excellent in conformability to complex shapes and in distortion resistance, and includes members having complex shapes, and is subject to impact and load from the outside. It is preferably used for portable electronic devices that are easy to wear. Since the laminate disclosed herein has a limited thickness, from this point of view as well, it is preferably used in portable electronic devices that are becoming thinner and lighter.
- FIG. 1 is a schematic cross-sectional view showing the configuration of a laminate according to one embodiment
- FIG. FIG. 4 is a schematic cross-sectional view showing the configuration of a laminate according to another embodiment
- FIG. 4 is a schematic cross-sectional view showing the configuration of a laminate according to another embodiment
- It is a schematic diagram explaining the method of a strain resistance test.
- the term “adhesive” refers to a material that exhibits a soft solid (viscoelastic) state in a temperature range around room temperature and has the property of easily adhering to an adherend under pressure, as described above. .
- the adhesive as used herein generally has a complex tensile modulus E * (1 Hz), as defined in "C. A. Dahlquist, “Adhesion: Fundamentals and Practice", McLaren & Sons, (1966) P. 143". It may be a material having properties satisfying ⁇ 10 7 dyne/cm 2 (typically, a material having the above properties at 25°C).
- the laminate disclosed herein includes a non-releasable core, a first adhesive sheet disposed on one surface of the core, and a second adhesive sheet disposed on the other surface of the core.
- Including sheet the first adhesive sheet is an adhesive sheet containing an adhesive layer
- the second adhesive sheet is also an adhesive sheet containing an adhesive layer.
- the first pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive sheet with a substrate in the form of having pressure-sensitive adhesive layers on both sides of a non-releasable substrate (supporting substrate). It may be a material-less pressure-sensitive adhesive sheet.
- the second pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive sheet with a substrate having a pressure-sensitive adhesive layer on both sides of a non-releasable substrate (supporting substrate), and has a non-releasable substrate. It may be a substrate-less pressure-sensitive adhesive sheet.
- the concept of laminate here can include what is called a pressure-sensitive adhesive sheet with a substrate. Further, the concept of the laminate as used herein may include what is called an adhesive sheet, adhesive tape, adhesive label, adhesive film, and the like.
- the laminate disclosed herein is typically in the form of a sheet, may be in the form of a roll, or may be in the form of a sheet. Alternatively, it may be a laminated body processed into various shapes.
- FIG. 1 shows a configuration example of a laminate in which both the first pressure-sensitive adhesive sheet and the second pressure-sensitive adhesive sheet are double-sided pressure-sensitive adhesive sheets without a base material (double-sided pressure-sensitive adhesive sheet without a base material).
- a laminate 1 shown in FIG. are provided respectively.
- the first adhesive sheet 11 is composed of an adhesive layer.
- the second adhesive sheet 12 is also composed of an adhesive layer.
- the laminate 1 before use (before being attached to an adherend) is spirally wound with the front surface 21A and the back surface 21B superimposed on the release liner 21, which is a release surface.
- the adhesive surface 12A of the second adhesive sheet 12 is protected by the front surface 21A of the release liner 21, and the adhesive surface 11A of the first adhesive sheet 11 is protected by the back surface 21B of the release liner 21.
- the adhesive surface 11A and the adhesive surface 12A may be protected by two separate release liners.
- the first pressure-sensitive adhesive sheet is a double-sided adhesive type substrate-less pressure-sensitive adhesive sheet (base-less double-sided pressure-sensitive adhesive sheet), and the second pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive type pressure-sensitive adhesive sheet with a substrate (double-sided pressure-sensitive adhesive sheet with substrate).
- FIG. 2 shows a configuration example of the laminate in the case of .
- the laminate 1 shown in FIG. 2 includes a core 15, and a first adhesive sheet 11 and a second adhesive sheet 12 are attached to the first surface 15A and the second surface 15B (both of which are non-releasable) of the core 15. are provided respectively.
- the first adhesive sheet 11 is composed of an adhesive layer.
- the second adhesive sheet 12 includes a substrate 35, and adhesive layers 32 and 34 are provided on the first surface and the second surface (both of which are non-releasable) of the substrate 35, respectively.
- the laminate 1 before use (before being attached to an adherend) is spirally wound with the front surface 21A and the back surface 21B superimposed on the release liner 21, which is a release surface.
- the release liner 21 which is a release surface.
- the surface (adhesive surface 34A) of the adhesive layer 34 is protected by the front surface 21A of the release liner 21, and the adhesive surface 11A of the first adhesive sheet 11 is protected by the back surface 21B of the release liner 21.
- the adhesive surface 11A and the adhesive surface 34A may be protected by two separate release liners.
- FIG. 3 shows a configuration example of a laminate in which both the first pressure-sensitive adhesive sheet and the second pressure-sensitive adhesive sheet are double-sided pressure-sensitive adhesive sheets with a substrate (double-sided pressure-sensitive adhesive sheet with a substrate).
- a laminate 1 shown in FIG. are provided respectively.
- the first adhesive sheet 11 includes a substrate 25, and adhesive layers 36 and 38 are provided on the first surface and the second surface (both of which are non-releasable) of the substrate 25, respectively.
- the second adhesive sheet 12 includes a substrate 35, and adhesive layers 32 and 34 are provided on the first surface and the second surface (both of which are non-releasable) of the substrate 35, respectively.
- FIG. 1 shows a configuration example of a laminate in which both the first pressure-sensitive adhesive sheet and the second pressure-sensitive adhesive sheet are double-sided pressure-sensitive adhesive sheets with a substrate (double-sided pressure-sensitive adhesive sheet with a substrate).
- a laminate 1 shown in FIG. are provided respectively.
- the first adhesive sheet 11 includes a substrate 25, and adhesive layers 36
- the laminate 1 before use (before being attached to an adherend) is spirally wound with the front surface 21A and the back surface 21B superimposed on the release liner 21, which is a release surface.
- the release liner 21 which is a release surface.
- the surface of the adhesive layer 34 (adhesive surface 34A) is protected by the front surface 21A of the release liner 21, and the surface of the adhesive layer 36 (adhesive surface 36A) is protected by the back surface 21B of the release liner 21.
- the adhesive surface 34A and the adhesive surface 36A may be protected by two separate release liners.
- the core disclosed here is a support member that supports the first adhesive sheet and the second adhesive sheet.
- the core body is characterized in that the product of Young's modulus and thickness is equal to or greater than a predetermined value. Specifically, the value EA calculated by multiplying the Young's modulus value EA of the core when the unit is MPa and the thickness value TA of the core when the unit is ⁇ m. xTA is 500,000 or more. The use of such a core tends to improve the strain resistance of the laminate.
- E A ⁇ T A is 70 ⁇ 10 4 or more, more preferably 90 ⁇ 10 4 or more (eg 100 ⁇ 10 4 or more, 110 ⁇ 10 4 or more or 120 ⁇ 10 4 or more) and more preferably 130 ⁇ 10 4 or more.
- the upper limit of E A ⁇ TA is not particularly limited. From the viewpoint of thinning and weight reduction of the laminate, it is preferably 1500 ⁇ 10 4 or less, more preferably 1000 ⁇ 10 4 or less (for example, 800 ⁇ 10 4 or more, 600 ⁇ 10 4 or more, or 500 ⁇ 10 4 or less), more preferably 400 ⁇ 10 4 or less.
- the Young's modulus EA of the core is not particularly limited as long as the product of it and the thickness TA of the core is equal to or greater than a predetermined value.
- the Young's modulus EA of the core is preferably 3000 MPa or more, more preferably 5000 MPa or more (for example, 7000 MPa or more, 8000 MPa or more, or 9000 MPa or more). It is preferably 10000 MPa or more.
- the Young's modulus EA of the core is preferably 60,000 MPa or more, more preferably 70,000 MPa or more (for example, 90,000 MPa or more, 100,000 MPa or more, or 130,000 MPa or more), More preferably, it is 150000 MPa or more.
- the upper limit of the Young's modulus EA of the core is not particularly limited. From the viewpoint of workability and handleability, the Young's modulus EA of the core is preferably 650000 MPa or less, more preferably 400000 MPa or less (for example, it may be 300000 MPa or less, may be 280000 MPa or less, and may be 250000 MPa or less. may be
- the thickness TA of the core is not particularly limited as long as the product of the thickness TA of the core and the Young's modulus EA of the core is equal to or greater than a predetermined value.
- the thickness TA of the core is preferably 10 ⁇ m or more, more preferably 12 ⁇ m or more (for example, 15 ⁇ m or more), and still more preferably 20 ⁇ m or more.
- the upper limit of the thickness TA of the core is not particularly limited. From the viewpoint of thinning and weight reduction of the laminate, the thickness TA of the core is preferably 500 ⁇ m or less (for example, 300 ⁇ m or less), more preferably 270 ⁇ m or less, or 250 ⁇ m or less. 150 ⁇ m or less.
- the material of the core included in the laminate disclosed here is not particularly limited.
- the core metal foil, resin film, foam film, paper, cloth, composites thereof, and the like can be used.
- a metal foil can be preferably used as the core.
- Common metal foils such as stainless steel foil, aluminum foil, copper foil, titanium foil, and zinc foil can be used as the metal foil.
- stainless steel foil, aluminum foil, and copper foil can be preferably used from the viewpoint of cost and workability.
- the metal foil may have the form of a single layer, or may have a multi-layered structure of two, three or more layers.
- it may be a plated foil in which different kinds of metals are plated on the surface of a metal foil.
- it may have a multi-layer structure including a metal layer and a layer made of another material (eg, paper).
- a core containing a resin film as a base film can be preferably used.
- the base film is typically an independently shape-maintainable (independent) member.
- the core in the technique disclosed here can be substantially composed of such a base film.
- the core may contain an auxiliary layer in addition to the base film. Examples of the auxiliary layer include an undercoat layer, an antistatic layer, a colored layer, etc. provided on the surface of the base film.
- a core having a colored layer disposed on the surface of the base polymer can be preferably used.
- the colorant contained in the colored layer the same colorant as used in the pressure-sensitive adhesive sheet described later can be preferably employed.
- the above resin film is a film containing a resin material as a main component (a component contained in the resin film in excess of 50% by weight).
- resin films include polyolefin resin films such as polyethylene (PE), polypropylene (PP), and ethylene/propylene copolymer; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and the like.
- the resin film may be a rubber-based film such as a natural rubber film or a butyl rubber film. Among them, from the viewpoint of handleability and workability, a polyester film is preferred, and a PET film is particularly preferred.
- the resin film may have a single-layer structure, or may have a multi-layer structure of two layers, three layers or more. From the viewpoint of shape stability, the resin film preferably has a single-layer structure. In the case of a multilayer structure, at least one layer (preferably all layers) is preferably a layer having a continuous structure of the resin (for example, polyester resin).
- the method for producing the resin film is not particularly limited, and a conventionally known method may be appropriately adopted. For example, conventionally known general film forming methods such as extrusion molding, inflation molding, T-die casting, and calender roll molding can be employed as appropriate.
- the core including the resin film may contain fillers (inorganic fillers, organic fillers, etc.), colorants, dispersants (surfactants, etc.), anti-aging agents, antioxidants, etc.
- Various additives such as agents, ultraviolet absorbers, antistatic agents, lubricants and plasticizers may be blended.
- the blending ratio of various additives is usually less than about 30% by weight (for example, less than about 20% by weight, preferably less than about 10% by weight).
- a foam film can be used as the core material.
- the foam film used for the core is a film having a portion with cells (cell structure), typically a film containing at least one stratified foam (foam layer).
- foam layer typically a film containing at least one stratified foam (foam layer).
- a preferred example of the foam film in the technology disclosed herein is a foam film composed of a single (one) foam layer.
- paper or cloth is used as the core material.
- paper that can be used for the core include Japanese paper, kraft paper, glassine paper, woodfree paper, synthetic paper, top coat paper, and the like.
- fabrics include woven fabrics and non-woven fabrics obtained by spinning various fibrous materials alone or by blending them.
- the fibrous substance include cotton, staple fiber, manila hemp, pulp, rayon, acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, and polyolefin fiber.
- the nonwoven fabric referred to here is a concept that refers to a nonwoven fabric for adhesive sheets that is mainly used in the field of adhesive tapes and other adhesive sheets, and is typically a nonwoven fabric that is produced using a general paper machine. (sometimes referred to as so-called "paper").
- the term "resin film” as used herein is typically a non-porous resin sheet, which is distinguished from, for example, non-woven fabrics (that is, does not include non-woven fabrics).
- the resin film may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film.
- the surface of the substrate on which the pressure-sensitive adhesive layer is to be provided may be subjected to surface treatment such as application of an undercoat, corona discharge treatment, plasma treatment, or the like.
- the surface of the core may be subjected to conventionally known surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of a primer, and the like.
- a surface treatment can be a treatment for improving the adhesion between the core and the adhesive sheet (adhesive layer), in other words, the anchoring property of the adhesive sheet (adhesive layer) to the core.
- ⁇ Adhesive sheet> (25°C storage modulus)
- the pressure-sensitive adhesive sheet (one or both of the first pressure-sensitive adhesive sheet and the second pressure-sensitive adhesive sheet; the same shall apply hereinafter) contained in the laminate disclosed herein has a storage elastic modulus G' at 25°C of the pressure-sensitive adhesive sheet (25°C) is characterized by being less than 0.20 MPa.
- G' storage elastic modulus
- the G' (25°C) is preferably less than 0.19 MPa, more preferably less than 0.18 MPa, still more preferably less than about 0.17 MPa (e.g., less than 0.15 MPa), particularly preferably less than 0.14 MPa, It may be less than 0.1 MPa.
- the lower limit of the G' (25 ° C.) is not particularly limited, but from the viewpoint of adhesion, the G' (25 ° C.) is preferably 0.02 MPa or more, more preferably 0.035 MPa or more. 0.05 MPa or more, 0.1 MPa or more, or 0.12 MPa or more.
- the PSA sheet may have a storage modulus G'(85°C) at 85°C of less than 0.08 MPa.
- G' storage modulus
- the G′ (85° C.) is preferably less than 0.07 MPa, more preferably less than 0.06 MPa, even more preferably less than about 0.05 MPa (for example, less than 0.045 MPa).
- the lower limit of the G' (85 ° C.) is not particularly limited, but from the viewpoint of adhesion, the G' (85 ° C.) is usually 0.01 MPa or more, preferably 0.02 MPa or more. Yes, it may be 0.03 MPa or more, or 0.04 MPa or more.
- the storage modulus G'(120°C) at 120°C of the PSA sheet can be less than 0.04 MPa.
- the G′ (120° C.) is preferably less than 0.035 MPa, more preferably less than 0.033 MPa, still more preferably less than 0.03 MPa (for example, less than 0.028 MPa).
- the lower limit of the G' (120 ° C.) is not particularly limited, but from the viewpoint of adhesion, the G' (120 ° C.) is usually 0.01 MPa or more, preferably 0.015 MPa or more. , more preferably 0.02 MPa or more, and still more preferably 0.023 MPa or more.
- the viscoelastic properties of the above-mentioned pressure-sensitive adhesive sheet can be obtained by adjusting the monomer composition of the base polymer contained in the pressure-sensitive adhesive layer and, if necessary, by appropriately adjusting the type and amount of the tackifying resin based on the contents described in this specification. It can be adjusted by selecting, appropriately setting the pressure-sensitive adhesive composition containing other components (such as a cross-linking agent) as necessary, polymer polymerization conditions, pressure-sensitive adhesive layer manufacturing conditions, and the like.
- other components such as a cross-linking agent
- the 25° C. storage modulus, 85° C. storage modulus and 120° C. storage modulus of the PSA sheet can be determined by dynamic viscoelasticity measurement. Specifically, a test piece having a thickness of about 2 mm is prepared by stacking a plurality of adhesive sheets to be measured. This test piece was punched into a disk shape with a diameter of 7.9 mm. A dynamic viscoelasticity measurement is performed under the conditions to obtain a 25°C storage modulus, an 85°C storage modulus and a 120°C storage modulus.
- ⁇ Measurement mode Shear mode ⁇ Temperature range: -70°C to 150°C ⁇ Temperature increase rate: 5°C/min ⁇ Measurement frequency: 1Hz It is also measured by the above method in the examples described later.
- the thickness T B of the pressure-sensitive adhesive sheet (not including a release liner) disclosed herein is suitably 3 ⁇ m or more, preferably 5 ⁇ m or more, more preferably over 10 ⁇ m, and still more preferably 15 ⁇ m or more.
- the thickness T B of the pressure-sensitive adhesive sheet can be, for example, 500 ⁇ m or less, preferably 350 ⁇ m or less, and preferably 270 ⁇ m or less (for example, 250 ⁇ m or less) from the viewpoint of thinning.
- the thickness T B1 of the substrate-less pressure-sensitive adhesive sheet is usually appropriately 3 ⁇ m or more, preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more. , more preferably 15 ⁇ m or more.
- the thickness T B1 of the substrate-less pressure-sensitive adhesive sheet is usually appropriately 200 ⁇ m or less, and from the viewpoint of thinning, it is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less (e.g., 60 ⁇ m or less), and still more preferably 50 ⁇ m or less. .
- the thickness T B2 of the pressure-sensitive adhesive sheet with a substrate is preferably more than 10 ⁇ m, more preferably 20 ⁇ m or more, and still more preferably 25 ⁇ m or more, Especially preferably, it is 30 ⁇ m or more.
- the thickness T B2 of the pressure-sensitive adhesive sheet with a substrate is usually suitably 500 ⁇ m or less, preferably 300 ⁇ m or less, more preferably 270 ⁇ m or less (for example, 260 ⁇ m or less), and 150 ⁇ m or less from the viewpoint of thinning. good too.
- the light transmittance CB of the adhesive sheet is not particularly limited.
- the light transmittance CB is 20% or less (preferably 10% or less, more preferably 5% or less, especially (preferably 1.5% or less) may be used.
- the lower limit of the light transmittance CB is not particularly limited, and may be substantially 0%, that is, the detection limit or less, 1% or more, 5% or more, or 15% or more.
- the light transmittance C B of the adhesive sheet may be greater than 30%, may be greater than 50%, or may be 70% or more (eg, 75% or more).
- the light transmittance CB of the pressure-sensitive adhesive sheet can be measured by the following method. Also in the examples described later, it is measured by the following method.
- the light transmittance CB [%] of the adhesive sheet is the light transmittance in the thickness direction of the adhesive sheet peeled off from the release liner (light transmittance at a wavelength of 550 nm). is measured using a transmissometer.
- a spectrophotometer manufactured by Hitachi apparatus name “U4150 type spectrophotometer” or an equivalent thereof is used.
- the type of adhesive that constitutes the adhesive layer contained in the adhesive sheet is not particularly limited.
- the adhesives include acrylic polymers, rubber polymers (natural rubber, synthetic rubber, mixtures thereof, etc.), polyester polymers, urethane polymers, polyether polymers, silicone polymers, which can be used in the field of adhesives. It may contain one or more of various rubber-like polymers such as polyamide-based polymers and fluorine-based polymers as an adhesive polymer (in the sense of a structural polymer that forms an adhesive, hereinafter also referred to as "base polymer").
- a pressure-sensitive adhesive containing an acrylic polymer or a rubber-based polymer as a base polymer can be preferably employed.
- a pressure-sensitive adhesive having an acrylic polymer as a base polymer (acrylic pressure-sensitive adhesive) is preferable.
- the technique disclosed here is preferably implemented in a mode using an acrylic pressure-sensitive adhesive.
- a pressure-sensitive adhesive layer composed of an acrylic pressure-sensitive adhesive that is, a pressure-sensitive adhesive sheet having an acrylic pressure-sensitive adhesive layer will be mainly described below. It is not intended to be limited to
- the “base polymer” of the adhesive refers to the main component of the rubber-like polymer contained in the adhesive, and is not to be construed as being limited to anything other than this.
- the term “rubber-like polymer” refers to a polymer that exhibits rubber elasticity in a temperature range around room temperature.
- the term “main component” refers to a component contained in an amount exceeding 50% by weight unless otherwise specified.
- acrylic polymer refers to a polymer containing monomer units derived from a monomer having at least one (meth)acryloyl group in one molecule as monomer units constituting the polymer.
- a monomer having at least one (meth)acryloyl group in one molecule is also referred to as "acrylic monomer”.
- an acrylic polymer in this specification is defined as a polymer containing monomeric units derived from an acrylic monomer.
- a typical example of an acrylic polymer is an acrylic polymer containing more than 50% by weight of the acrylic monomer in the total monomer components used to synthesize the acrylic polymer.
- (meth)acryloyl is a generic term for acryloyl and methacryloyl.
- (meth)acrylate is a generic term for acrylate and methacrylate, and
- (meth)acrylic is generic for acrylic and methacrylic.
- the acrylic polymer used as the polymer includes, for example, an alkyl (meth)acrylate as a main monomer, and may further include a sub-monomer copolymerizable with the main monomer. things are preferred.
- the main monomer refers to a component that accounts for more than 50% by weight of the monomer composition in the monomer raw material.
- alkyl (meth)acrylate for example, a compound represented by the following formula (1) can be preferably used.
- CH2 C( R1 ) COOR2 (1)
- R 1 in the above formula (1) is a hydrogen atom or a methyl group.
- R 2 is a chain alkyl group having 1 to 20 carbon atoms. Hereinafter, such a carbon atom number range may be expressed as "C 1-20 ".
- an alkyl (meth)acrylate in which R 2 is a C 1-14 (for example, C 1-10 , typically C 4-8 ) chain alkyl group is used as the main monomer.
- Alkyl (meth)acrylates in which R 2 is a butyl group or a 2-ethylhexyl group are preferred.
- an alkyl acrylate in which R 1 is a hydrogen atom and R 2 is a C 4-8 chain alkyl group (hereinafter also simply referred to as C 4-8 alkyl acrylate) is used as the main monomer. preferably.
- alkyl (meth)acrylates in which R 2 is a C 1-20 chain alkyl group include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) ) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acryl
- alkyl (meth)acrylates may be used singly or in combination of two or more.
- Suitable examples of alkyl (meth)acrylates include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
- Particularly preferred alkyl (meth)acrylates include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
- the ratio of the alkyl (meth)acrylate to the monomer components constituting the acrylic polymer is typically more than 50% by weight, and can be, for example, 70% by weight or more, and may be 85% by weight or more, or 90% by weight. % by weight or more.
- the upper limit of the ratio of alkyl (meth)acrylate is not particularly limited, but it is preferably 99.5% by weight or less (for example, 99% by weight or less), or properties based on submonomers such as carboxy group-containing monomers (for example, aggregation 98% by weight or less (for example, less than 97% by weight) from the viewpoint of preferably exerting force).
- the acrylic polymer may be obtained by polymerizing substantially only alkyl (meth)acrylate.
- the proportion of C 4-8 alkyl acrylate in the alkyl (meth)acrylate contained in the monomer component is preferably 70% by weight or more, It is more preferably 90% by weight or more.
- the monomer component constituting the acrylic polymer contains at least one of BA and 2EHA, and the total amount of BA and 2EHA in the alkyl (meth)acrylate contained in the monomer component is 75 wt. % or more (usually 85 wt% or more, for example 90 wt% or more, further 95 wt% or more).
- the technology disclosed herein can be practiced, for example, in a mode in which the alkyl (meth)acrylate contained in the monomer component is BA alone, 2EHA alone, BA and 2EHA, and the like.
- the monomer component constituting the acrylic polymer contains 50% by weight or more of C 1-6 alkyl (meth)acrylate.
- the polymerization ratio of C 1-6 alkyl (meth)acrylate in the acrylic polymer is preferably 50% by weight or more.
- the ratio of C 1-6 alkyl (meth)acrylate in the monomer component is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 92% by weight or more ( for example greater than 95% by weight).
- the upper limit of the ratio of C 1-6 alkyl (meth)acrylate in the monomer component is not particularly limited, and is usually 99% by weight or less, and 98% by weight or less in relation to the proportion of other copolymerizable monomers used. 97% by weight or less is preferable, and it may be less than 95% by weight.
- the C 1-6 alkyl (meth)acrylates may be used singly or in combination of two or more.
- the C 1-6 alkyl (meth)acrylate is preferably a C 1-6 alkyl acrylate, more preferably a C 2-6 alkyl acrylate, and even more preferably a C 4-6 alkyl acrylate.
- the C 1-6 alkyl (meth)acrylate is preferably a C 1-4 alkyl acrylate, more preferably a C 2-4 alkyl acrylate.
- Preferred examples of C 1-6 alkyl (meth)acrylates include BA.
- the monomer component constituting the acrylic polymer contains 50% by weight or more of C 7-10 alkyl (meth)acrylate.
- the copolymerization ratio of C 7-10 alkyl (meth)acrylate in the acrylic polymer is preferably 50% by weight or more.
- the ratio of C 7-10 alkyl (meth)acrylate in the monomer component may be greater than 60% by weight, may be greater than 70% by weight, and more preferably greater than 80% by weight. , more preferably 90% by weight or more, particularly preferably 92% by weight or more (for example, 95% by weight or more).
- the upper limit of the ratio of C 7-10 alkyl (meth)acrylate in the monomer component is not particularly limited, and is usually 99% by weight or less, and the relationship with the ratio of other copolymerizable monomers (eg, acidic group-containing monomers). Therefore, it is suitable that the content is 97% by weight or less, and preferably 96% by weight or less.
- the C 7-10 alkyl (meth)acrylates can be used singly or in combination of two or more. Suitable examples of C 7-10 alkyl (meth)acrylates include C 7-10 alkyl acrylates such as 2EHA, isooctyl acrylate, isononyl acrylate. Among them, 2EHA is preferable.
- the acrylic polymer in the technology disclosed here may be copolymerized with a sub-monomer.
- the content of the functional group-containing monomer in the monomer component is not particularly limited.
- the content of the functional group-containing monomer in the monomer component can be, for example, 0.1% by weight or more, and should be 0.5% by weight or more. is suitable, and it may be 1% by weight or more.
- the content of the functional group-containing monomer in the monomer component is appropriately 40% by weight or less, and is 20% by weight or less. is preferable, and it may be 10% by weight or less (for example, 5% by weight or less).
- an acidic group-containing monomer is used as a monomer copolymerizable with the main monomer alkyl (meth)acrylate.
- the acidic group-containing monomer can improve cohesiveness based on its polarity and exhibit good bonding strength to polar adherends.
- a cross-linking agent such as an isocyanate-based or epoxy-based cross-linking agent, the acidic group (typically a carboxyl group) becomes a cross-linking point of the acrylic polymer.
- a carboxy group-containing monomer is preferably used as the acidic group-containing monomer.
- carboxy group-containing monomers include ethylenically unsaturated monocarboxylic acids such as acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth)acrylate, crotonic acid and isocrotonic acid; maleic acid, itaconic acid and citraconic acid; ethylenically unsaturated dicarboxylic acids such as and anhydrides thereof (maleic anhydride, itaconic anhydride, etc.).
- the acidic group-containing monomer may also be a monomer having a metal salt (for example, an alkali metal salt) of a carboxy group. Among them, AA and MAA are preferred, and AA is more preferred.
- the content of an acidic group-containing monomer (typically a carboxy group-containing monomer) in the monomer component is 1.
- a content of 0% by weight or more is appropriate.
- the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is preferably 1.5% by weight or more, more preferably 2.0% by weight or more, still more preferably 2.5% by weight or more, and particularly preferably 3.0% by weight. % or more.
- the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is 4.0% by weight or more, may be more than 5.0% by weight, or may be 6.0% by weight or more. , 6.5% by weight or more.
- the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is usually 20% by weight or less, and preferably 10% by weight from the viewpoint of improving the adhesion to the adherend and thus the followability. less than, more preferably less than 8.0 wt%, more preferably less than 7.0 wt%, particularly preferably less than 6.0 wt%, even less than 5.0 wt% (e.g. less than 4.0 wt%) good.
- the acrylic polymer preferably used in the technology disclosed herein can be a copolymer obtained by copolymerizing an alkyl (meth)acrylate as a main monomer and an acidic group-containing monomer as a sub-monomer.
- the proportion of copolymer components other than the alkyl (meth)acrylate and the acidic group-containing monomer may be less than 10% by weight, less than 3% by weight, or less than 1% by weight.
- the monomer component constituting the acrylic polymer may be substantially free of functional group-containing monomers other than the above acidic group-containing monomers.
- An acrylic polymer substantially composed of an alkyl (meth)acrylate and an acidic group-containing monomer can maximize the effects of the alkyl (meth)acrylate and the acidic group-containing monomer.
- the monomer component forming the acrylic polymer may contain, for example, a hydroxyl group-containing monomer as a functional group-containing monomer other than the above-mentioned acidic group-containing monomer.
- the proportion of the hydroxyl group-containing monomer in the monomer component may be, for example, about 0.01% by weight or more and less than 1% by weight, may be less than 0.5% by weight, or may be less than 0.1% by weight. .
- the monomer component that constitutes the acrylic polymer may contain other copolymerization components other than the sub-monomers described above for the purpose of improving the cohesive force.
- copolymerization components include vinyl ester monomers such as vinyl acetate; aromatic vinyl compounds such as styrene; ) acrylate; aryl (meth)acrylate (e.g. phenyl (meth)acrylate), aryloxyalkyl (meth)acrylate (e.g. phenoxyethyl (meth)acrylate), arylalkyl (meth)acrylate (e.g. benzyl (meth)acrylate), etc.
- Aromatic ring-containing (meth)acrylates olefinic monomers; chlorine-containing monomers; isocyanate group-containing monomers such as 2-(meth)acryloyloxyethyl isocyanate; alkoxy such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate group-containing monomers; vinyl ether-based monomers such as methyl vinyl ether and ethyl vinyl ether;
- the above-mentioned other copolymerization components can be used singly or in combination of two or more.
- the amount of such other copolymerization components may be appropriately selected according to the purpose and application and is not particularly limited, but from the viewpoint of appropriately exhibiting the effects of use, it is suitable to be 0.05% by weight or more. , 0.5% by weight or more.
- the content of other copolymerization components in the monomer component is suitably 20% by weight or less, and 10% by weight or less (for example, 5% by weight or less). good too.
- the technology disclosed herein can also be preferably practiced in a mode in which the monomer component does not substantially contain other copolymerization components.
- the monomer component does not substantially contain other copolymerization components means that other copolymerization components are not used at least intentionally, and other copolymerization components are, for example, 0.01 wt% or less. To some extent, unintentional inclusion is acceptable.
- Acrylic polymers are polyfunctional having at least two polymerizable functional groups (typically radically polymerizable functional groups) having unsaturated double bonds such as (meth)acryloyl groups and vinyl groups as other monomer components. It may contain a monomer. By using a polyfunctional monomer as the monomer component, the cohesive force of the pressure-sensitive adhesive layer can be increased.
- Polyfunctional monomers can be used as cross-linking agents. Polyfunctional monomers are not particularly limited, and examples include 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and neopentyl glycol di(meth)acrylate. etc.
- a polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
- the amount of polyfunctional monomer used is not particularly limited, and can be appropriately set so that the purpose of use of the polyfunctional monomer is achieved.
- the amount of the polyfunctional monomer used can be approximately 3% by weight or less, preferably approximately 2% by weight or less, and more preferably approximately 1% by weight or less (for example, approximately 0.5% by weight or less) based on the above monomer components.
- the lower limit of the amount used when using a polyfunctional monomer is not particularly limited as long as it is greater than 0% by weight. Usually, by setting the amount of the polyfunctional monomer used to about 0.001% by weight or more (for example, about 0.01% by weight or more) of the monomer component, the effect of using the polyfunctional monomer can be appropriately exhibited.
- the composition of the monomer components constituting the acrylic polymer is designed so that the glass transition temperature (Tg) of the acrylic polymer is approximately ⁇ 15° C. or lower (for example, approximately ⁇ 70° C. or higher and ⁇ 15° C. or lower). is appropriate.
- Tg of the acrylic polymer refers to the Tg determined by the Fox formula based on the composition of the monomer components.
- the Fox equation is a relational expression between the Tg of a copolymer and the glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below.
- Tg is the glass transition temperature of the copolymer (unit: K)
- Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio based on weight)
- Tgi is the content of the monomer i. It represents the glass transition temperature (unit: K) of a homopolymer.
- the glass transition temperature of the homopolymer used for calculating the Tg the value described in the known materials shall be used.
- the monomers listed below the following values are used as the glass transition temperatures of the homopolymers of the monomers.
- the Tg of the acrylic polymer is advantageously about ⁇ 25° C. or less, preferably about ⁇ 35° C. or less, more preferably about ⁇
- the temperature is 40° C. or lower, more preferably -45° C. or lower, and may be -50° C. or lower, or -55° C. or lower.
- the Tg of the acrylic polymer is usually about -75°C or higher, preferably about -70°C or higher.
- the Tg of the acrylic polymer may be ⁇ 60° C. or lower, or ⁇ 62° C. or lower (eg, ⁇ 64° C. or lower).
- the Tg of the acrylic polymer may be about ⁇ 65° C. or higher, or about ⁇ 60° C. or higher (for example, about ⁇ 55° C. or higher).
- the Tg of the acrylic polymer can be adjusted by appropriately changing the monomer composition (that is, the types and usage ratios of the monomers used in synthesizing the polymer).
- the weight average molecular weight Mw of the base polymer disclosed herein is preferably about 30 ⁇ 10 4 or more, more preferably 40 ⁇ 10 4 or more (e.g. 45 ⁇ 10 4 or more), still more preferably It is about 50 ⁇ 10 4 or more, particularly preferably about 55 ⁇ 10 4 or more (for example, about 58 ⁇ 10 4 or more). Moreover, the above Mw is usually about 300 ⁇ 10 4 or less, and about 200 ⁇ 10 4 or less is suitable. From the viewpoint of improving flexibility, Mw is preferably about 100 ⁇ 10 4 or less, and may be about 70 ⁇ 10 4 or less (for example, about 65 ⁇ 10 4 or less).
- the base polymer one or more of the various polymers exemplified as the rubber-like polymer can be used.
- an acrylic polymer obtained by a solution polymerization method preferably has Mw within the above range.
- the dispersion (Mw/Mn) of the base polymer (preferably acrylic polymer) disclosed herein is not particularly limited.
- the dispersity (Mw/Mn) here means the dispersity (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
- the dispersity (Mw/Mn) of the base polymer is 50 or less, may be less than 45, may be less than 40 (e.g., 38 or less), may be less than 35, or may be less than 32. .
- the lower limit of Mw/Mn is not particularly limited, and may be, for example, 3.0 or more, 5.0 or more, or 7.0 or more.
- the lower limit of Mw/Mn is not particularly limited, and may be, for example, 3.0 or more, 5.0 or more, or 7.0 or more.
- Mw, Mn and Mw/Mn are polymerization conditions (time, temperature, etc.), non-volatile matter (monomer component) concentration during polymerization, amount of polymerization initiator used, use of chain transfer agent, polymerization based on chain transfer constant It can be adjusted by selecting a solvent or the like.
- Mw and Mn are obtained from values converted to standard polystyrene obtained by GPC (gel permeation chromatography).
- GPC gel permeation chromatography
- the method for obtaining the base polymer is not particularly limited, and various known polymer synthesis methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization can be used. can be appropriately adopted polymerization method.
- a solution polymerization method can be preferably employed.
- the polymerization temperature at the time of solution polymerization can be appropriately selected according to the type of monomer and solvent used, the type of polymerization initiator, etc. ° C.).
- the solvent (polymerization solvent) used for solution polymerization can be appropriately selected from conventionally known organic solvents (toluene, ethyl acetate, etc.).
- the initiator used for polymerization may be a conventionally known polymerization initiator (for example, an azo polymerization initiator such as 2,2'-azobisisobutyronitrile (AIBN) or a peroxide polymerization initiator). initiator, etc.).
- the amount of the polymerization initiator used may be a normal amount, for example, about 0.005 to 1 part by weight (typically about 0.01 to 1 part by weight) per 100 parts by weight of the monomer component. ).
- the adhesive layer in the technology disclosed herein can contain a tackifying resin. Thereby, the peel strength of the adhesive sheet can be increased.
- tackifying resins include phenol-based tackifying resins, terpene-based tackifying resins, modified terpene-based tackifying resins, rosin-based tackifying resins, hydrocarbon-based tackifying resins, epoxy-based tackifying resins, polyamide-based tackifying resins, One or more selected from tackifier resins such as elastomer-based tackifier resins and ketone-based tackifier resins can be used.
- phenol-based tackifying resins terpene-based tackifying resins, and modified terpene-based tackifying resins are preferable, and phenol-based tackifying resins (preferably terpene phenolic resins) are more preferable.
- phenolic tackifying resins include terpene phenolic resins, hydrogenated terpene phenolic resins, alkylphenolic resins and rosin phenolic resins.
- Terpene phenol resin refers to a polymer containing a terpene residue and a phenol residue, a copolymer of terpenes and a phenol compound (terpene-phenol copolymer resin), and a homopolymer or copolymer of terpenes is a concept that includes both phenol-modified (phenol-modified terpene resin).
- terpenes constituting such a terpene phenol resin include monoterpenes such as ⁇ -pinene, ⁇ -pinene, and limonene (including d-, l- and d/l-forms (dipentene)).
- a hydrogenated terpene phenol resin refers to a hydrogenated terpene phenol resin having a structure obtained by hydrogenating such a terpene phenol resin. It is sometimes called a hydrogenated terpene phenolic resin.
- Alkylphenol resins are resins obtained from alkylphenols and formaldehyde (oily phenolic resins). Examples of alkylphenol resins include novolac and resole types.
- Rosin phenolic resins are typically rosins or phenol-modified products of the various rosin derivatives described above (including rosin esters, unsaturated fatty acid-modified rosins, and unsaturated fatty acid-modified rosin esters).
- rosin phenol resins include rosin phenol resins obtained by a method of adding phenol to rosins or various rosin derivatives described above with an acid catalyst and thermally polymerizing the mixture.
- terpene-based tackifying resins include polymers of terpenes (typically monoterpenes) such as ⁇ -pinene, ⁇ -pinene, d-limonene, l-limonene and dipentene. It may be a homopolymer of one kind of terpenes, or a copolymer of two or more kinds of terpenes.
- terpene homopolymer includes ⁇ -pinene polymer, ⁇ -pinene polymer, dipentene polymer and the like.
- modified terpene resins include those obtained by modifying the above terpene resins. Specific examples include styrene-modified terpene resins and hydrogenated terpene resins.
- rosin-based tackifying resins here includes both rosins and rosin derivative resins.
- rosins include unmodified rosins (fresh rosins) such as gum rosin, wood rosin and tall oil rosin; homogenized rosin, polymerized rosin, other chemically modified rosins, etc.);
- the rosin derivative resin is typically a derivative of the above rosins.
- the term "rosin-based resin” as used herein includes derivatives of unmodified rosin and derivatives of modified rosin (including hydrogenated rosin, disproportionated rosin and polymerized rosin).
- rosin esters such as undenatured rosin esters, which are esters of undenatured rosin and alcohols, and denatured rosin esters, which are esters of denatured rosin and alcohols; Saturated fatty acid-modified rosins; for example, unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; rosin alcohols obtained by reducing the carboxy group of rosin esters modified with fatty acids; for example, rosins or metal salts of the various rosin derivatives described above; Specific examples of rosin esters include methyl esters, triethylene glycol esters, glycerin esters and pentaerythritol esters of unmodified rosins or modified rosins (hydrogenated rosins, disproportionated rosins, polymerized rosins, etc.).
- hydrocarbon tackifying resins examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic/aromatic petroleum resins (styrene-olefin copolymers, etc. ), aliphatic/alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone-based resins, and coumarone-indene-based resins.
- the softening point of the tackifying resin is not particularly limited. From the viewpoint of improving cohesive strength, a tackifier resin having a softening point (softening temperature) of about 80° C. or higher (preferably about 100° C. or higher) can be preferably used. For example, a phenol-based tackifying resin (terpene phenol resin, etc.) having such a softening point can be preferably used. In some embodiments, terpene phenolic resins with softening points of about 135° C. or higher (or even about 140° C. or higher) can be used. There is no particular upper limit for the softening point of the tackifying resin. A tackifying resin having a softening point of about 200° C.
- the softening point of the tackifying resin can be measured based on the softening point test method (ring and ball method) specified in JIS K2207.
- the tackifying resin contains one or more phenolic tackifying resins (typically terpene phenolic resins).
- the technology disclosed herein can be preferably implemented in a mode in which, for example, about 25% by weight or more (more preferably about 30% by weight or more) of the total amount of tackifying resin is 100% by weight is a terpene phenol resin.
- About 50% by weight or more of the total amount of tackifying resin may be the terpene phenolic resin, and about 70% by weight or more (eg, about 80% by weight or more) may be the terpene phenolic resin.
- Substantially all of the tackifying resin eg, about 95-100 wt%, or even about 99-100 wt%) may be a terpene phenolic resin.
- the tackifying resin may include a tackifying resin having a hydroxyl value higher than 20 mgKOH/g. Among them, a tackifying resin having a hydroxyl value of 30 mgKOH/g or more is preferable. Hereinafter, a tackifying resin having a hydroxyl value of 30 mgKOH/g or more may be referred to as a "high hydroxyl value resin".
- a tackifying resin containing such a high hydroxyl value resin e.g., a phenolic tackifying resin, preferably a terpene phenolic resin
- the upper limit of the hydroxyl value of the high hydroxyl value resin is not particularly limited. From the viewpoint of compatibility with the base polymer, the hydroxyl value of the high hydroxyl value resin is suitably about 200 mgKOH/g or less, preferably about 100 mgKOH/g or less, and may be about 70 mgKOH/g or less. , approximately 65 mg KOH/g or less. High hydroxyl value resin can be used individually by 1 type or in combination of 2 or more types.
- a value measured by a potentiometric titration method specified in JIS K0070:1992 can be adopted.
- a specific measuring method is as follows. [Method for measuring hydroxyl value] 1.
- Reagent (1) As the acetylation reagent, approximately 12.5 g (approximately 11.8 mL) of acetic anhydride is taken, pyridine is added to bring the total amount to 50 mL, and the mixture is thoroughly stirred and used. Alternatively, take about 25 g (about 23.5 mL) of acetic anhydride, add pyridine to bring the total amount to 100 mL, and use the mixture after thorough stirring.
- Hydroxyl value [(BC) x f x 28.05]/S + D here
- B Amount (mL) of 0.5 mol/L potassium hydroxide ethanol solution used in the blank test
- C Amount (mL) of 0.5 mol/L potassium hydroxide ethanol solution used for the sample
- f factor of 0.5 mol/L potassium hydroxide ethanol solution
- S weight of sample (g)
- D acid value
- 28.05 1 ⁇ 2 of the molecular weight of potassium hydroxide, 56.11; is.
- the amount (total amount) of the tackifying resin used is not particularly limited, and can be appropriately set, for example, in the range of about 1 to 100 parts by weight with respect to 100 parts by weight of the base polymer. .
- the amount of the tackifying resin to be used with respect to 100 parts by weight of the base polymer is suitably 5 parts by weight or more, and 10 parts by weight or more. , and may be 15 parts by weight or more.
- the amount of tackifying resin to be used with respect to 100 parts by weight of the base polymer is preferably 50 parts by weight or less, and may be 40 parts by weight or less. Well, it may be 30 parts by weight or less.
- the adhesive composition used for forming the adhesive layer may contain a cross-linking agent as needed.
- the type of cross-linking agent is not particularly limited, and can be appropriately selected from conventionally known cross-linking agents.
- examples of such cross-linking agents include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, and metal alkoxide-based cross-linking agents.
- Cross-linking agents metal chelate-based cross-linking agents, metal salt-based cross-linking agents, carbodiimide-based cross-linking agents, hydrazine-based cross-linking agents, amine-based cross-linking agents, silane coupling agents, and the like.
- isocyanate-based cross-linking agents isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and melamine-based cross-linking agents are preferable, isocyanate-based cross-linking agents and epoxy-based cross-linking agents are more preferable, and isocyanate-based cross-linking agents are particularly preferable. .
- the pressure-sensitive adhesive layer in the technology disclosed herein contains the cross-linking agent in the form after the cross-linking reaction, the form before the cross-linking reaction, the form after the cross-linking reaction, the intermediate or composite form thereof, and the like. can contain The cross-linking agent is typically contained in the pressure-sensitive adhesive layer exclusively in the form after the cross-linking reaction.
- a polyfunctional isocyanate meaning a compound having an average of two or more isocyanate groups per molecule, including those having an isocyanurate structure
- the isocyanate-based cross-linking agents may be used singly or in combination of two or more.
- polyfunctional isocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.
- aliphatic polyisocyanates include 1,2-ethylene diisocyanate; tetramethylene diisocyanates such as 1,2-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate and 1,4-tetramethylene diisocyanate; - hexamethylene diisocyanates such as hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate; 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate and the like.
- alicyclic polyisocyanates include isophorone diisocyanate; cyclohexyl diisocyanates such as 1,2-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate and 1,4-cyclohexyl diisocyanate; 1,2-cyclopentyl diisocyanate, 1,3 - cyclopentyl diisocyanate such as cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and the like.
- aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate.
- polyfunctional isocyanates examples include polyfunctional isocyanates having an average of 3 or more isocyanate groups per molecule.
- Such tri- or more functional isocyanates are polymers (typically dimers or trimers) of di- or tri- or more functional isocyanates, derivatives (for example, polyhydric alcohols and two or more molecules of polyfunctional isocyanates). addition reaction products), polymers, and the like.
- polyfunctional isocyanates such as reaction products with methylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate and polyester polyisocyanate can be mentioned.
- polyfunctional isocyanates include “Duranate TPA-100” (trade name) manufactured by Asahi Kasei Chemicals, "Coronate L” (trade name), “Coronate HL”, “Coronate HK” (trade name) and “Coronate HK” (trade names) manufactured by Tosoh Corporation. HX”, “Coronate 2096", and the like.
- the amount of the isocyanate-based cross-linking agent used is not particularly limited. For example, it can be about 0.1 part by weight or more with respect to 100 parts by weight of the base polymer. From the viewpoint of compatibility between cohesive strength and adhesion, impact resistance, etc., the amount of the isocyanate-based cross-linking agent used relative to 100 parts by weight of the base polymer can be, for example, more than 0.3 parts by weight, preferably 0.5 parts by weight. It is at least 0.75 parts by weight, more preferably at least 1.0 parts by weight (for example, at least 1.2 parts by weight).
- the amount of the isocyanate-based cross-linking agent used is appropriately 10 parts by weight or less, preferably 7 parts by weight, per 100 parts by weight of the base polymer. Less than 5 parts by weight, more preferably less than 4.5 parts by weight, particularly preferably less than 4 parts by weight.
- an isocyanate-based cross-linking agent and at least one cross-linking agent having a different type of cross-linkable functional group from the isocyanate-based cross-linking agent are used in combination as the cross-linking agent.
- a cross-linking agent other than an isocyanate-based cross-linking agent that is, a cross-linking agent having a different type of cross-linkable reactive group from the isocyanate-based cross-linking agent; hereinafter also referred to as a “non-isocyanate cross-linking agent”
- an isocyanate cross-linking agent can be used in combination with a system cross-linking agent.
- non-isocyanate-based cross-linking agent that can be used in combination with the isocyanate-based cross-linking agent is not particularly limited, and can be appropriately selected from the above-described cross-linking agents.
- the non-isocyanate-based cross-linking agents may be used singly or in combination of two or more.
- an epoxy-based cross-linking agent can be employed as the non-isocyanate-based cross-linking agent.
- an isocyanate-based cross-linking agent and an epoxy-based cross-linking agent in combination it is easy to achieve both cohesiveness and impact resistance.
- the epoxy-based cross-linking agent a compound having two or more epoxy groups in one molecule can be used without particular limitation.
- An epoxy-based cross-linking agent having 3 to 5 epoxy groups in one molecule is preferred.
- Epoxy-based cross-linking agents may be used singly or in combination of two or more.
- epoxy-based cross-linking agents include, but are not limited to, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl ) cyclohexane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether and the like.
- Commercially available epoxy-based cross-linking agents include Mitsubishi Gas Chemical Co., Ltd.'s trade name "TETRAD-C” and trade name “TETRAD-X”, DIC's trade name "Epiclon CR-5L", and Nagase ChemteX Corp. and "TEPIC-G” manufactured by Nissan Chemical Industries, Ltd. under the trade name of "Denacol EX-512".
- the amount of epoxy-based cross-linking agent used is not particularly limited.
- the amount of the epoxy-based cross-linking agent used is, for example, more than 0 parts by weight and about 1 part by weight or less (typically about 0.001 to 0.5 parts by weight) with respect to 100 parts by weight of the base polymer. can be done.
- the amount of the epoxy-based cross-linking agent to be used is preferably about 0.005 parts by weight or more per 100 parts by weight of the base polymer.
- the amount of the epoxy-based cross-linking agent used is appropriately about 0.2 parts by weight or less with respect to 100 parts by weight of the base polymer. It is preferably 0.1 part by weight or less, more preferably less than about 0.05 part by weight.
- the total amount (total amount) of the cross-linking agent used is not particularly limited. For example, it can be about 10 parts by weight or less, preferably about 0.005 to 10 parts by weight, more preferably about 0.01 to 5 parts by weight, based on 100 parts by weight of the base polymer (preferably acrylic polymer). can be selected from a range of
- the pressure-sensitive adhesive layer disclosed herein may or may not contain a coloring agent that can help reduce light transmittance.
- a coloring agent that can help reduce light transmittance.
- Conventionally known pigments and dyes can be used as the colorant.
- As the color of the coloring agent colored is preferable.
- the color of the coloring agent can be, for example, black, gray, red, blue, yellow, green, yellow-green, orange, purple, gold, silver, pearlescent, and the like.
- a colored coloring agent can impart light-shielding properties and design properties.
- the coloring agent may or may not contain a colorless coloring agent in combination with a colored coloring agent.
- the pressure-sensitive adhesive layer according to one typical aspect disclosed herein may be substantially free of colorless coloring agents.
- colored is a meaning including black and metallic color.
- the pressure-sensitive adhesive layer may have a multilayer structure including a colored layer containing a coloring agent.
- the pressure-sensitive adhesive layer may contain the colorant in a substantially dispersed state (it may be in a dissolved state).
- pigments and dyes can be used as the coloring agent.
- pigments include zinc carbonate, zinc oxide, zinc sulfide, talc, kaolin, calcium carbonate, titanium oxide, silica, lithium fluoride, calcium fluoride, barium sulfate, alumina, zirconia, iron oxide, and iron hydroxide.
- Chromium oxide type Spinel type firing type, Chromic acid type, Chromium vermillion type, Prussian blue type, Aluminum powder type, Bronze powder type, Silver powder type, Inorganic pigment such as calcium phosphate, Phthalocyanine type, Azo type, Condensed azo type , azo lake-based, anthraquinone-based, perylene/perinone-based, indigo-based, thioindigo-based, isoindolinone-based, azomethine-based, dioxazine-based, quinacridone-based, aniline black-based, triphenylmethane-based, and carbon black-based organic pigments. be done.
- Inorganic pigment such as calcium phosphate, Phthalocyanine type, Azo type, Condensed azo type , azo lake-based, anthraquinone-based, perylene/perinone-based, indigo-based, thioindigo-based, isoindolinone-based
- dyes examples include azo dyes, anthraquinone, quinophthalone, styryl, diphenylmethane, triphenylmethane, oxazine, triazine, xanthan, methane, azomethine, acridine, and diazine. Colorants may be used singly or in appropriate combination of two or more.
- the pressure-sensitive adhesive layer contains a black colorant.
- a black colorant As the black colorant contained in the adhesive layer, an organic or inorganic colorant (pigment, dye, etc.) can be used. Specific examples of black colorants include carbon black (furnace black, channel black, acetylene black, thermal black, lamp black, pine smoke, etc.), graphite, copper oxide, manganese dioxide, aniline black, perylene black, titanium black, and cyanine.
- Carbon black is preferred.
- As the carbon black particles it is also possible to use surface-modified carbon black particles having functional groups such as carboxyl groups, amino groups, sulfonic acid groups, silicon-containing groups (e.g., alkoxysilyl groups and alkylsilyl groups). .
- Such surface-modified carbon black particles are also called self-dispersing carbon black, and the addition of a dispersant becomes unnecessary or the amount thereof can be reduced.
- the carbon black particles may be used singly or in combination of two or more.
- the black colorant is not particularly limited, and a particulate colorant (pigment) can be preferably used.
- a black colorant eg, a black pigment such as carbon black
- the upper limit of the average particle size of the black colorant is not particularly limited, and is usually about 500 nm or less, preferably about 300 nm or less, more preferably about 250 nm or less, for example 200 nm or less (for example, about 120 nm or less).
- the "average particle size” in this specification means the particle size at 50% of the integrated value in the particle size distribution measured based on the particle size distribution measuring device based on the laser scattering/diffraction method (50% volume mean particle diameter; hereinafter sometimes abbreviated as D50 ).
- the amount of the coloring agent (solid content) used in the pressure-sensitive adhesive layer is not particularly limited, and the amount can be appropriately adjusted so as to impart the desired light-shielding properties.
- the amount of the black colorant used is usually about 0.1 to 30% by weight of the total weight of the adhesive layer, for example 0.1 to 25% by weight (typically 0.1 to 30% by weight). 20% by weight).
- the pressure-sensitive adhesive layer may contain an antirust agent.
- Rust inhibitors are not particularly limited, and include azole rust inhibitors, amine compounds, nitrites, ammonium benzoate, ammonium phthalate, ammonium stearate, ammonium palmitate, ammonium oleate, ammonium carbonate, and dicyclohexylamine benzoate. acid salts, urea, urotropine, thiourea, phenyl carbamate, cyclohexylammonium-N-cyclohexylcarbamate (CHC) and the like.
- the rust preventives can be used singly or in combination of two or more.
- an azole-based rust inhibitor can be preferably used.
- a five-membered ring aromatic compound containing two or more heteroatoms, in which at least one of the heteroatoms is a nitrogen atom is preferably used as an active ingredient.
- compounds that can be used as azole rust inhibitors include benzotriazole rust inhibitors containing benzotriazole compounds as active ingredients.
- benzotriazole compounds include 1,2,3-benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, carboxybenzotriazole and the like.
- the content of the rust inhibitor is not particularly limited, and can be, for example, 0.01 parts by weight or more (typically 0.05 parts by weight or more) with respect to 100 parts by weight of the base polymer. From the viewpoint of obtaining a better metal corrosion prevention effect, the content may be 0.1 parts by weight or more, 0.3 parts by weight or more, or 0.5 parts by weight or more. On the other hand, from the viewpoint of increasing the cohesive strength of the pressure-sensitive adhesive, the content of the rust inhibitor is preferably less than 8 parts by weight with respect to 100 parts by weight of the base polymer. It may be less than part.
- the pressure-sensitive adhesive composition may optionally contain adhesive agents such as leveling agents, cross-linking aids, plasticizers, softeners, fillers, antistatic agents, anti-aging agents, ultraviolet absorbers, antioxidants, light stabilizers, and the like.
- adhesive agents such as leveling agents, cross-linking aids, plasticizers, softeners, fillers, antistatic agents, anti-aging agents, ultraviolet absorbers, antioxidants, light stabilizers, and the like.
- Various additives common in the pharmaceutical field may be included. As for the various additives mentioned above, conventionally known ones can be used in a conventional manner, and since they do not particularly characterize the present invention, detailed description thereof will be omitted.
- the pressure-sensitive adhesive layer (layer made of pressure-sensitive adhesive) disclosed herein is a water-based pressure-sensitive adhesive composition, a solvent-based pressure-sensitive adhesive composition, a hot-melt pressure-sensitive adhesive composition, and active energy rays such as ultraviolet rays and electron beams. It may be a pressure-sensitive adhesive layer formed from an active energy ray-curable pressure-sensitive adhesive composition that is cured by irradiation.
- the water-based pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in the form of containing a pressure-sensitive adhesive (adhesive layer-forming component) in a water-based solvent (aqueous solvent), typically water-dispersed.
- the solvent-type adhesive composition refers to an adhesive composition in the form of containing an adhesive in an organic solvent.
- the organic solvent contained in the solvent-based pressure-sensitive adhesive composition one or two or more of the organic solvents (toluene, ethyl acetate, etc.) exemplified as the organic solvent (toluene, ethyl acetate, etc.) that can be used in the above solution polymerization can be used without particular limitation.
- the technology disclosed herein can be preferably practiced in a mode comprising a pressure-sensitive adhesive layer formed from a solvent-based pressure-sensitive adhesive composition.
- a solvent-based pressure-sensitive adhesive layer formed from a solvent-based pressure-sensitive adhesive composition the effects of the technique disclosed herein are preferably achieved.
- the adhesive layer disclosed here can be formed by a conventionally known method.
- a method of forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive composition to a surface having releasability (release surface) and drying can be employed.
- a pressure-sensitive adhesive sheet having a substrate for example, a method (direct method) of forming a pressure-sensitive adhesive layer by directly applying (typically applying) a pressure-sensitive adhesive composition to the substrate and drying it can be employed.
- a method of applying a pressure-sensitive adhesive composition to a surface having releasability (release surface) and drying to form a pressure-sensitive adhesive layer on the surface and transferring the pressure-sensitive adhesive layer to a substrate transfer method.
- the release surface for example, the surface of a release liner, which will be described later, can be preferably used.
- the pressure-sensitive adhesive layer disclosed herein is typically formed continuously, but is not limited to such a form. It may be a formed pressure-sensitive adhesive layer.
- the adhesive composition can be performed using a conventionally known coater such as a gravure roll coater, a die coater, and a bar coater.
- the adhesive composition may be applied by impregnation, curtain coating, or the like.
- the drying temperature can be, for example, about 40 to 150.degree. C., preferably about 60 to 130.degree.
- After drying the pressure-sensitive adhesive composition it may be further aged for the purpose of adjusting migration of components in the pressure-sensitive adhesive layer, progressing the crosslinking reaction, relaxing strain that may exist in the pressure-sensitive adhesive layer, and the like.
- the adhesive layer disclosed herein may have a single layer structure or a multilayer structure of two or more layers. From the viewpoint of productivity and the like, the pressure-sensitive adhesive layer preferably has a single-layer structure.
- the thickness of the adhesive layer is not particularly limited.
- the thickness of the pressure-sensitive adhesive layer is usually about 300 ⁇ m or less, suitably about 150 ⁇ m or less, preferably about 100 ⁇ m or less, more preferably about 70 ⁇ m or less, and about 60 ⁇ m or less (for example, 55 ⁇ m or less). good too.
- a pressure-sensitive adhesive layer with a limited thickness can well meet demands for thinning and weight reduction.
- the lower limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, but from the viewpoint of adhesiveness and conformability to an adherend, it is, for example, about 3 ⁇ m or more, and about 10 ⁇ m or more is suitable.
- the thickness of the adhesive layer is approximately 20 ⁇ m or greater, more preferably approximately 30 ⁇ m or greater, and may be approximately 40 ⁇ m or greater.
- the thickness of each pressure-sensitive adhesive layer may be the same or different.
- the gel fraction of the pressure-sensitive adhesive layer disclosed herein can be, for example, 20% or more on a weight basis, and usually 30% or more is suitable. % is preferred. By increasing the gel fraction of the pressure-sensitive adhesive layer within an appropriate range, the conformability to the adherend can be improved.
- the gel fraction is more preferably 45% or higher, still more preferably 50% or higher, particularly preferably 55% or higher, and may be 60% or higher.
- the gel fraction of the pressure-sensitive adhesive layer is suitably 90% or less, preferably 70% or less (for example, 65% or less), and may be less than 60%. .
- the "gel fraction of the pressure-sensitive adhesive layer” refers to a value measured by the following method.
- the gel fraction can be grasped as the weight ratio of ethyl acetate-insoluble matter in the pressure-sensitive adhesive layer.
- Weight Wg 1 An adhesive sample of about 0.1 g (weight Wg 1 ) is wrapped in a porous polytetrafluoroethylene membrane (weight Wg 2 ) having an average pore size of 0.2 ⁇ m, and the opening is tied with a string (weight Wg 3 ).
- porous polytetrafluoroethylene (PTFE) membrane trade name "Nitoflon (registered trademark) NTF1122” available from Nitto Denko Corporation (average pore size 0.2 ⁇ m, porosity 75%, thickness 85 ⁇ m) or equivalent use the product.
- This package was immersed in 50 mL of ethyl acetate and kept at room temperature (typically 23° C.) for 7 days to elute only the sol component in the adhesive layer outside the film. The adhering ethyl acetate is wiped off, the packet is dried at 130° C. for 2 hours, and the weight (Wg 4 ) of the packet is measured.
- the gel fraction FG of the pressure-sensitive adhesive layer is obtained by substituting each value into the following formula. A similar method is adopted in the examples described later.
- Gel fraction F G (%) [(Wg 4 -Wg 2 -Wg 3 )/Wg 1 ] ⁇ 100
- the adhesive sheet disclosed herein may contain a substrate (supporting substrate).
- the structure and material of the substrate disclosed herein are not particularly limited.
- the base material is typically a film-like base material (also referred to as "base film").
- base film a base film containing a resin film can be preferably used.
- the base film is typically an independently shape-maintainable (independent) member.
- the base film in the technique disclosed here can be substantially composed of such a base film.
- the base film may contain an auxiliary layer in addition to the base film. Examples of the auxiliary layer include a colored layer, a reflective layer, an undercoat layer, an antistatic layer, etc. provided on the surface of the base film.
- the resin film is a film containing a resin material as a main component (for example, a component contained in the resin film in excess of 50% by weight).
- resin films include polyolefin resin films such as polyethylene (PE), polypropylene (PP), and ethylene/propylene copolymer; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and the like.
- polyurethane resin film vinyl chloride resin film; vinyl acetate resin film; polyimide resin film; polyamide resin film;
- the resin film may be a rubber-based film such as a natural rubber film or a butyl rubber film. Among them, from the viewpoint of handleability and workability, a polyester film is preferred, and a PET film is particularly preferred.
- the base film may be colored with a colored layer arranged on the surface of the base film (preferably resin film).
- a base film having a structure including a colored layer in this way can impart light-shielding properties and design properties.
- the base film may or may not contain a colorant.
- the colored layer may be arranged on either one surface of the base film, or may be arranged on both surfaces. In the configuration in which the colored layers are arranged on both surfaces of the base film, the configurations of the colored layers may be the same or different.
- Such a colored layer can typically be formed by coating a base film with a colored layer-forming composition containing a coloring agent and a binder.
- a coloring agent Conventionally known pigments and dyes can be used as the colorant.
- the color of the coloring agent colored is preferred.
- the color of the coloring agent can be, for example, black, gray, red, blue, yellow, green, yellow-green, orange, purple, gold, silver, pearlescent, and the like.
- a colored coloring agent can impart light-shielding properties and design properties.
- the coloring agent may or may not contain a colorless coloring agent in combination with a colored coloring agent.
- a base film according to a typical aspect disclosed herein may be substantially free of a colorless colorant.
- colored is a meaning including black and metallic color.
- the term “colorless” is meant to include white.
- binder materials known in the field of paints or printing can be used without particular limitation. Examples include polyurethane, phenol resin, epoxy resin, urea melamine resin, polymethyl methacrylate, and the like.
- the composition for forming a colored layer may be, for example, a solvent type, an ultraviolet curable type, a heat curable type, or the like.
- the formation of the colored layer can be carried out by adopting means conventionally used for forming the colored layer without particular limitation. For example, a method of forming a colored layer (printed layer) by printing such as gravure printing, flexographic printing, and offset printing can be preferably employed.
- the colored layer may have a single layer structure consisting entirely of one layer, or may have a multilayer structure including two, three or more sub-colored layers.
- a colored layer having a multi-layer structure including two or more sub-colored layers can be formed, for example, by repeatedly applying (for example, printing) a composition for forming a colored layer.
- the colors and blending amounts of the colorants contained in each sub-colored layer may be the same or different.
- the thickness of the entire colored layer is usually suitably about 1 ⁇ m to 10 ⁇ m, preferably about 1 ⁇ m to 7 ⁇ m, and can be, for example, about 1 ⁇ m to 5 ⁇ m.
- the thickness of each sub-colored layer is preferably about 1 ⁇ m to 2 ⁇ m.
- the base film may contain a coloring agent.
- a base film containing a coloring agent in this way can impart light-shielding properties and design properties.
- Conventionally known pigments and dyes can be used as the colorant to be contained in the base film.
- the base film is a base film containing a black colorant, more specifically a resin film into which a black colorant is kneaded.
- the base film in which the black colorant is kneaded means that the black colorant is mixed in the main constituent material of the base film (the material most contained in the base film, typically a resin material). It refers to a base film that has been coated.
- the black colorant is substantially dispersed in the base film.
- An organic or inorganic colorant can be used as the black colorant contained in the base film.
- black colorants include carbon black (furnace black, channel black, acetylene black, thermal black, lamp black, pine smoke, etc.), graphite, copper oxide, manganese dioxide, aniline black, perylene black, titanium black, and cyanine.
- Black activated carbon, ferrite (non-magnetic ferrite, magnetic ferrite, etc.), magnetite, chromium oxide, iron oxide, molybdenum disulfide, chromium complexes, anthraquinone colorants, and the like.
- carbon black is preferred.
- the black colorant is not particularly limited, and a particulate colorant (pigment) can be preferably used.
- a black colorant eg, a black pigment such as carbon black
- the upper limit of the average particle size of the black colorant is not particularly limited, and is usually about 500 nm or less, preferably about 300 nm or less, more preferably about 250 nm or less, for example 200 nm or less (for example, about 120 nm or less).
- the amount of the coloring agent used in the base film is not particularly limited, and the amount can be appropriately adjusted so as to impart the desired light-shielding properties.
- the amount of the black colorant used is usually about 0.1 to 30% by weight of the total weight of the base film, for example 0.1 to 25% by weight (typically 0.1 to 30% by weight). 20% by weight).
- the base film disclosed herein may contain coloring agents (pigments and dyes) other than black coloring agents.
- non-black colorants include, for example, white colorants.
- White colorants include, for example, titanium oxide (titanium dioxide such as rutile-type titanium dioxide and anatase-type titanium dioxide), zinc oxide, aluminum oxide, silicon oxide, zirconium oxide, magnesium oxide, calcium oxide, tin oxide, barium oxide, Cesium oxide, yttrium oxide, magnesium carbonate, calcium carbonate (light calcium carbonate, heavy calcium carbonate, etc.), barium carbonate, zinc carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, aluminum silicate, magnesium silicate , calcium silicate, barium sulfate, calcium sulfate, barium stearate, zinc oxide, zinc sulfide, talc, silica, alumina, clay, kaolin, titanium phosphate, mica, gypsum, white carbon, diatomaceous earth, be
- the amount of the non-black colorant used in the base film is not particularly limited, and the amount can be appropriately adjusted so as to impart the desired light-shielding properties.
- the amount of the non-black colorant used is usually about 0.1 to 30% by weight of the resin film, for example 0.1 to 25% by weight (typically 0.1 to 20% by weight). % by weight).
- the base film may contain fillers (inorganic fillers, organic fillers, etc.), dispersants (surfactants, etc.), anti-aging agents, antioxidants, ultraviolet absorbers, antistatic agents, Various additives such as lubricants and plasticizers may be added.
- the blending ratio of various additives is usually about less than 30% by weight (for example, less than 20% by weight, typically less than 10% by weight).
- the base film may have a single-layer structure, or may have a multi-layer structure of two layers, three layers or more. From the viewpoint of shape stability, the substrate film preferably has a single-layer structure. In the case of a multilayer structure, at least one layer (preferably all layers) is preferably a layer having a continuous structure of the resin (for example, polyester resin).
- the method for producing the substrate film is not particularly limited, and any conventionally known method may be appropriately adopted. For example, conventionally known general film forming methods such as extrusion molding, inflation molding, T-die casting, and calender roll molding can be employed as appropriate.
- the thickness of the base material disclosed here is not particularly limited.
- the thickness of the substrate is usually 3 ⁇ m or more, preferably 5 ⁇ m or more (for example, 10 ⁇ m or more). In some embodiments, the thickness of the substrate may be 20 ⁇ m or greater, 30 ⁇ m or greater, 40 ⁇ m or greater, 100 ⁇ m or greater, 200 ⁇ m or greater.
- the thickness of the substrate is usually 500 ⁇ m or less, preferably 400 ⁇ m or less, more preferably 300 ⁇ m or less from the viewpoint of weight reduction. In some aspects, the thickness of the substrate may be 250 ⁇ m or less, 200 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, or 50 ⁇ m or less.
- the thickness of the substrate may be the total thickness of the base film and the colored layer.
- the surface of the base film may be subjected to conventionally known surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of a primer, and the like.
- a surface treatment can be a treatment for improving the adhesion between the base film and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer to the base film.
- the back surface of the substrate film may be subjected to release treatment as necessary.
- the release treatment for example, a general silicone-based, long-chain alkyl-based, fluorine-based, etc.
- release agent is typically applied to a thin film of about 0.01 ⁇ m to 1 ⁇ m (eg, 0.01 ⁇ m to 0.1 ⁇ m). It can be a treatment to give. By performing such a peeling treatment, it is possible to obtain effects such as facilitating the unwinding of the adhesive sheet wound into a roll.
- a release liner can be used in the formation of the adhesive layer, the production of the adhesive sheet, the production of the laminate, the storage of the laminate before use, distribution, shape processing, and the like.
- the release liner is not particularly limited.
- a release liner having a release treatment layer on the surface of a liner substrate such as a resin film or paper, a fluoropolymer (such as polytetrafluoroethylene), or a polyolefin resin (PE,
- a release liner or the like made of a low-adhesive material such as PP can be used.
- the release treatment layer may be formed by surface-treating the liner base material with a release treatment agent such as a silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide release agent.
- the laminate disclosed herein preferably has step followability at a pass level in a step waterproof test measured by the method described in Examples below.
- a laminate that satisfies the above characteristics tends to maintain a state in which it follows a complicated shape without gaps.
- the laminate disclosed herein preferably has an acceptable level of strain resistance (that is, does not cause strain) in a strain deformation test measured by the method described in Examples below.
- a laminate that satisfies the above characteristics has excellent deformation resistance against a load applied substantially in the thickness direction (Z-axis direction) of the laminate, and suppresses the occurrence of distortion in the adherend. It's easy to do.
- the total thickness T total of the laminate (not including the release liner) disclosed herein is not particularly limited.
- the total thickness T total of the laminate can be, for example, 1000 ⁇ m or less, and from the viewpoint of thinning, the total thickness T total of the laminate is preferably 500 ⁇ m or less (eg, 400 ⁇ m or less), more preferably 350 ⁇ m or less. and more preferably 300 ⁇ m or less. According to the technology disclosed herein, even if the total thickness T total of the laminate is sufficiently small, it tends to exhibit good strain resistance.
- the lower limit of the total thickness T total of the laminate is not particularly limited, but is usually 20 ⁇ m or more, preferably 30 ⁇ m or more, more preferably 40 ⁇ m or more, still more preferably 50 ⁇ m or more, and even 60 ⁇ m or more. Well, it may be 70 ⁇ m or more, or it may be 80 ⁇ m or more.
- the light transmittance C total of the laminate is not particularly limited.
- the light transmittance C total of the laminate is preferably 20% or less, more preferably 10% or less, from the viewpoint of imparting design properties and improving the light-shielding property of the laminate. , more preferably 5% or less, particularly preferably 1.5% or less.
- the lower limit of the light transmittance C total is not particularly limited, and may be substantially 0%, that is, the detection limit or less, 1% or more, 5% or more, or 15% or more.
- the light transmittance C total of the laminate can be measured by the following method. Also in the examples described later, it is measured by the following method.
- the light transmittance C total [%] of the laminate is the light transmittance in the thickness direction of the laminate peeled off from the release liner (light transmittance at a wavelength of 550 nm). is measured using a transmissometer.
- a spectrophotometer manufactured by Hitachi apparatus name “U4150 type spectrophotometer” or an equivalent thereof is used.
- the laminate disclosed herein has excellent conformability to complicated shapes and resistance to distortion. Taking advantage of such characteristics, the laminate can be used in various applications requiring deformation resistance and strain resistance. For example, it is suitable for fixing members of various portable electronic devices having members having a bent shape. In addition, since portable electronic devices may be subjected to external impacts and loads, the use of the pressure-sensitive adhesive sheet disclosed herein is highly advantageous in suppressing the occurrence of distortion of adherends.
- Non-limiting examples of the above portable electronic devices include mobile phones, smartphones, tablet computers, notebook computers, various wearable devices (for example, wrist wear type worn on the wrist like a wristwatch, Eyewear type including glasses type (monocular type and binocular type, including head-mounted type), clothes type attached to shirts, socks, hats, etc. in the form of accessories, earphones ear-wear type, etc.), digital cameras, digital video cameras, audio equipment (portable music players, IC recorders, etc.), calculators (calculators, etc.), portable game devices, electronic dictionaries, electronic notebooks, electronic books, vehicle-mounted information equipment, portable radios, portable televisions, portable printers, portable scanners, portable modems, etc.
- the term “portable” means not only being able to be simply carried, but also having a level of portability that allows an individual (a typical adult) to carry it relatively easily. shall mean.
- the pressure-sensitive adhesive sheet disclosed herein is preferably used for fixing a member such as a cover glass having a three-dimensional shape (typically a curved surface shape) constituting the portable electronic device. . It is also suitable for fixing the surface of an adherend having steps. Since the pressure-sensitive adhesive sheet disclosed herein is excellent in followability to an adherend, it can adhere well to the above three-dimensional shape and complicated shape having steps. While exhibiting a good fixing function by closely adhering to the surface of the adherend having such a three-dimensional shape and steps, for example, it is suitable for products that require waterproofness (for example, electronic devices such as portable electronic devices). It can provide excellent waterproofness.
- the laminate disclosed herein is preferably used in mobile electronic devices for fixing members such as flexible printed wiring boards constituting the mobile electronic devices. Since the laminate disclosed herein has excellent conformability to a complicated shape, it can be reliably adhered to an adherend having a bent shape such as the flexible printed wiring board. Moreover, it is possible to suppress the occurrence of distortion in the electronic components fixed to the flexible printed wiring board or the like.
- the laminate disclosed here can be used in the form of bonding materials processed into various external shapes to fix members constituting the portable electronic device as described above.
- it can be preferably used for electronic equipment (typically portable electronic equipment) equipped with an organic EL display device or a liquid crystal display device.
- an electronic device having a display part such as a touch panel display (typically a mobile electronic device such as a smartphone), and the adhesive sheet disclosed herein is used for fixing members of the device having a large-screen display part. is preferably used.
- the laminate disclosed herein may be used to fix a member such as a cover member or an organic EL unit.
- the laminate disclosed herein is preferably used as a component of the display device as described above.
- Matters disclosed by this specification include the following. [1] a core body; a first pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer disposed on one surface of the core; and a second pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer disposed on the other surface of the core, wherein
- the product (E A ⁇ T A ) of Young's modulus E A [MPa] and thickness T A [ ⁇ m] of the core is 500000 or more
- the thickness T B of one or both of the first adhesive sheet and the second adhesive sheet is greater than 10 ⁇ m
- the storage elastic modulus G′ at 25° C. (25° C.) is less than 0.20 MPa. laminate.
- the pressure-sensitive adhesive layer contained in one or both of the first pressure-sensitive adhesive sheet and the second pressure-sensitive adhesive sheet is an acrylic pressure-sensitive adhesive layer containing an acrylic polymer as a base polymer, the above [1] to [ 3] The pressure-sensitive adhesive sheet according to any one of the above items.
- the Young's modulus E A of the core is 3000 MPa or more.
- terpene phenol resin B as a tackifying resin, 3 parts of an isocyanate cross-linking agent and 0.01 part of an epoxy cross-linking agent are added to 100 parts of the acrylic polymer E contained in the solution. was added and mixed with stirring to prepare a pressure-sensitive adhesive composition E.
- terpene phenol resin B tackifier resin B
- trade name "YS Polystar T-115" manufactured by Yasuhara Chemical Co., Ltd., softening point of about 115°C, hydroxyl value of 30 to 60 mgKOH/g
- terpene phenol resin B tackifier resin B
- trade name "YS Polystar T-115" manufactured by Yasuhara Chemical Co., Ltd., softening point of about 115°C, hydroxyl value of 30 to 60 mgKOH/g
- terpene phenol resin A as tackifier resin A, 2 parts of isocyanate cross-linking agent and 0.01 of epoxy cross-linking agent are added to 100 parts of acrylic polymer A contained in the solution. and mixed with stirring to prepare a pressure-sensitive adhesive composition A.
- terpene phenol resin A the trade name "YS Polystar S-145" (manufactured by Yasuhara Chemical Co., Ltd., softening point of about 145° C., hydroxyl value of 70 to 110 mgKOH/g) was used.
- isocyanate-based cross-linking agent trade name "Coronate L” (manufactured by Tosoh Corporation, 75% ethyl acetate solution of trimethylolpropane/tolylene diisocyanate trimer adduct) was used.
- epoxy-based cross-linking agent trade name "TETRAD-C” (manufactured by Mitsubishi Gas Chemical Co., Ltd., 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) was used.
- the isocyanate-based cross-linking agent and the epoxy-based cross-linking agent were the same as those described above when preparing other pressure-sensitive adhesive compositions below.
- Table 1 summarizes the composition of the adhesive compositions E, E black , F, G, H and A and the weight average molecular weight of the base polymer.
- Adhesive composition E was applied to the release surface of a 38 ⁇ m thick polyester release liner (trade name “Diafoil MRF”, manufactured by Mitsubishi Polyester Co., Ltd.) and dried at 100° C. for 2 minutes to form a 15 ⁇ m thick adhesive. formed a layer.
- a substrate-less double-sided PSA sheet having a thickness of 15 ⁇ m, one side of which was protected by the polyester release liner, was obtained.
- Two sheets of the substrate-less double-sided pressure-sensitive adhesive sheet were prepared and used as the first pressure-sensitive adhesive sheet and the second pressure-sensitive adhesive sheet of this example.
- the adhesive surface of the first adhesive sheet was attached to one surface of a stainless steel sheet (SUS 304BA) having a thickness of 20 ⁇ m as a core. Also, the adhesive surface of the second adhesive sheet was attached to the other surface of the stainless steel sheet (SUS 304BA). In this manner, the first and second adhesive sheets are arranged on both sides of the core, and the two release liners protect the adhesive surface of the first adhesive sheet and the adhesive surface of the second adhesive sheet. A laminated body was produced, and this was used as the laminated body of this example.
- Example 2 to 4 In the same manner as in Example 1, except that the thickness of the first adhesive sheet (adhesive layer), the thickness of the second adhesive sheet (adhesive layer) and/or the core body are as shown in Table 1. , to obtain the laminate of this example.
- Example 5 Two sheets of a 38 ⁇ m thick polyester release liner (trade name “Diafoil MRF”, manufactured by Mitsubishi Polyester Co., Ltd.) were prepared.
- the adhesive composition E was applied to the release surface of each release liner and dried at 100° C. for 2 minutes to form an adhesive layer having a thickness of 10 ⁇ m.
- a multi-layer structure support with a total thickness of about 10 ⁇ m consisting of a 5 ⁇ m thick transparent PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) and a black printed layer provided on one side of the PET film.
- a substrate was prepared.
- the black printed layer was formed by printing using an ink composition containing a black colorant and using a gravure printing method.
- a thick film having an adhesive layer on the first surface and the second surface of the black printed PET film is obtained.
- a double-sided pressure-sensitive adhesive sheet with a substrate having a thickness of 30 ⁇ m was produced. Two sheets of the double-sided pressure-sensitive adhesive sheet with the base material were prepared and used as the first pressure-sensitive adhesive sheet and the second pressure-sensitive adhesive sheet of this example.
- a laminate of this example was produced using the same method as in Example 1, except that the first and second pressure-sensitive adhesive sheets of this example were used.
- the pressure-sensitive adhesive layer formed on each release liner has a thickness of 45 ⁇ m, and a 50 ⁇ m-thick PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) kneaded with a black pigment is used as a support base material.
- a 140 ⁇ m-thick double-sided pressure-sensitive adhesive sheet with a substrate was produced in the same manner as in Example 5 except that the pressure-sensitive adhesive sheets were the first and second pressure-sensitive adhesive sheets of this example.
- a laminate of this example was produced using the same method as in Example 1, except that the first and second pressure-sensitive adhesive sheets of this example were used.
- Example 7 A substrate-less double-sided PSA sheet with a thickness of 20 ⁇ m was produced using the same method as in Example 1, except that the thickness of the PSA layer was 20 ⁇ m, and used as the first PSA sheet of this example.
- Example 5 except that the pressure-sensitive adhesive layer formed on each release liner had a thickness of 50 ⁇ m, and a transparent PET film having a thickness of 160 ⁇ m (trade name “Lumirror”, manufactured by Toray Industries, Inc.) was used as the supporting substrate.
- a double-faced PSA sheet with a substrate having a thickness of 260 ⁇ m was prepared in the same manner as in , and used as the second PSA sheet of this example.
- a laminate of this example was produced using the same method as in Example 1, except that the first and second adhesive sheets of this example were used.
- Example 8> A substrate-less double-sided pressure-sensitive adhesive sheet with a thickness of 20 ⁇ m was prepared using the same method as the first and second pressure-sensitive adhesive sheets of Example 1, except that the thickness of the pressure-sensitive adhesive layer was 20 ⁇ m. 1 adhesive sheet.
- Example 8 Except that the thickness of the pressure-sensitive adhesive layer formed on each release liner was 12.5 ⁇ m, and a transparent PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) with a thickness of 235 ⁇ m was used as the supporting substrate. In the same manner as in Example 5, a double-sided pressure-sensitive adhesive sheet with a substrate having a thickness of 260 ⁇ m was produced as the second pressure-sensitive adhesive sheet of Example 8.
- a laminate of this example was produced using the same method as in Example 1, except that the first and second adhesive sheets of this example were used.
- Example 9 A laminate of this example was produced in the same manner as in Example 1, except that an aluminum sheet with a thickness of 20 ⁇ m (trade name “A1N30H-O”, manufactured by Takeuchi Metal Foil & Powder Co., Ltd.) was used as the core. bottom.
- an aluminum sheet with a thickness of 20 ⁇ m (trade name “A1N30H-O”, manufactured by Takeuchi Metal Foil & Powder Co., Ltd.) was used as the core. bottom.
- Example 10 A laminate of this example was produced in the same manner as in Example 1, except that a 20 ⁇ m thick copper sheet (trade name “C1020R-H”, manufactured by Takeuchi Metal Foil & Powder Co., Ltd.) was used as the core. bottom.
- a 20 ⁇ m thick copper sheet (trade name “C1020R-H”, manufactured by Takeuchi Metal Foil & Powder Co., Ltd.) was used as the core. bottom.
- Example 11 A laminate of this example was produced in the same manner as in Example 1, except that a 125 ⁇ m thick transparent PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) was used as the core.
- a 125 ⁇ m thick transparent PET film trade name “Lumirror”, manufactured by Toray Industries, Inc.
- Example 12 A substrate-less double-sided PSA sheet with a thickness of 15 ⁇ m was produced in the same manner as in Example 1, except that PSA composition E black was used instead of PSA composition E. 1 and 2 pressure-sensitive adhesive sheets.
- a laminate of this example was produced using the same method as in Example 11, except that the first and second pressure-sensitive adhesive sheets of this example were used.
- Example 13> A 30 ⁇ m-thick substrate-less double-sided pressure-sensitive adhesive sheet was produced in the same manner as in Example 2, except that the pressure-sensitive adhesive composition F was used instead of the pressure-sensitive adhesive composition E. and a second adhesive sheet.
- a laminate of this example was produced using the same method as in Example 1, except that the first and second pressure-sensitive adhesive sheets of this example were used.
- Example 14> A 30 ⁇ m-thick substrate-less double-sided pressure-sensitive adhesive sheet was produced in the same manner as in Example 2, except that the pressure-sensitive adhesive composition G was used instead of the pressure-sensitive adhesive composition E. and a second adhesive sheet.
- a laminate of this example was produced using the same method as in Example 1, except that the first and second pressure-sensitive adhesive sheets of this example were used.
- Example 15 A 30 ⁇ m-thick substrate-less double-sided pressure-sensitive adhesive sheet was produced in the same manner as in Example 2, except that the pressure-sensitive adhesive composition H was used instead of the pressure-sensitive adhesive composition E. and a second adhesive sheet.
- a laminate of this example was produced using the same method as in Example 1, except that the first and second pressure-sensitive adhesive sheets of this example were used.
- Example 16> A 10 ⁇ m-thick substrate-less double-sided pressure-sensitive adhesive sheet was produced in the same manner as in Example 1, except that the thickness of the pressure-sensitive adhesive layer was 10 ⁇ m. and A laminate of this example was produced using the same method as in Example 1, except that the first and second pressure-sensitive adhesive sheets of this example were used.
- Example 17 A laminate of this example was produced in the same manner as in Example 1, except that a 100 ⁇ m thick transparent PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) was used as the core.
- a 100 ⁇ m thick transparent PET film trade name “Lumirror”, manufactured by Toray Industries, Inc.
- Example 18 A substrate with a thickness of 35 ⁇ m was prepared in the same manner as in Example 1 except that the adhesive composition A was used instead of the adhesive composition E and the thickness of the adhesive layer was 35 ⁇ m. A less double-sided pressure-sensitive adhesive sheet was prepared and used as the first pressure-sensitive adhesive sheet of this example. In addition, the same method as in Example 1 was used except that the adhesive composition F was used instead of the adhesive composition A and the thickness of the adhesive layer was 25 ⁇ m. A substrate-less double-sided pressure-sensitive adhesive sheet was produced and used as the second pressure-sensitive adhesive sheet of this example. Using the same method as in Example 1, except that the first and second pressure-sensitive adhesive sheets of this example were used and a stainless steel sheet (SUS 304BA) having a thickness of 40 ⁇ m was used as the core body, this Example laminates were produced.
- SUS 304BA stainless steel sheet having a thickness of 40 ⁇ m
- Tables 2 and 3 show the outline of the laminate of each example; light transmittance CB of the adhesive sheet of each example; light transmittance C total of the laminate; Young's modulus EA [MPa] of the core, thickness TA [ ⁇ ]m and E A ⁇ T A ; the total thickness T total of the laminate are described.
- a polycarbonate plate having a size larger than that of the acrylic plate was prepared, and a level difference tape (width 5 mm, height 20 ⁇ m) was attached to the surface of this polycarbonate plate.
- This level difference tape is used for the purpose of providing projections (level differences) on the surface of the polycarbonate plate.
- an adhesive sheet having an adhesive layer on one side of a PET substrate was used as the stepped tape.
- the acrylic plate with the window-frame-shaped laminate prepared above was placed on two parallel sides of the window-frame-shaped laminate in such a position that the first adhesive sheet side of the laminate faces the polycarbonate side.
- the central portion of the window frame-like laminate crosses the stepped tape (so that the two parallel sides of the window frame laminate intersect (perpendicularly) with the stepped tape), and crimped under the conditions of 0.2 MPa and 1 minute.
- a sample for evaluation was thus obtained.
- the window-frame-shaped laminate is adhered to the adherend (acrylic plate, polycarbonate plate, and stepped tape)
- the inside becomes a space sealed from the outside.
- step waterproofing is carried out by immersing the evaluation sample in water in the autoclave, pressurizing at 25 ° C. and 0.5 MPa for 30 minutes in the autoclave, and the inside of the evaluation sample (window frame-like laminate The presence or absence of water intrusion into the inside of the body) was visually observed.
- step followability The presence or absence of water infiltration into the evaluation sample was evaluated as step followability. When water infiltration into the evaluation sample was observed, it was judged as "P: Poor", and when it was not observed, it was judged as "G: Good”. The evaluation results are shown in Tables 2 and 3 in the step followability item.
- the step waterproof test was performed after aging the evaluation sample for 30 minutes under standard conditions (23° C., 50% RH).
- a PET film 80 having a length of 50 mm, a width of 50 mm, and a thickness of 125 ⁇ m and a stepped tape 82 having a width of 2 mm, a length of 50 mm, and a height of 8 mm are prepared.
- the stepped tape 82 was attached to the central portion so that the length direction of the PET film 80 was aligned with the direction of one side of the PET film 80 .
- the stepped tape 82 is used for the purpose of forming projections (steps) on the surface of the PET film 80 .
- the level difference tape 82 an adhesive sheet having an adhesive layer on one side of a PET base material was used.
- the laminate according to each example in which both adhesive surfaces were protected with a release liner was cut into a size of 10 mm in length and 10 mm in width, and two release liners were peeled off from the laminate, and each adhesive surface was exposed to a thickness.
- a 5 ⁇ m PET film was adhered and backed to obtain a laminate sample piece 84 .
- a commercially available silicone rubber sheet 86 having a length of 50 mm, a width of 50 mm and a thickness of 3 mm was prepared.
- a laminate sample piece 84 was placed in the center of the upper surface of a silicon rubber sheet 86 so that the direction of one side of the laminate sample piece 84 and the direction of one side of the silicon rubber sheet 86 were aligned.
- the PET film 80 was placed above the silicon rubber sheet 86 with the stepped tape 82 facing downward. At this time, the PET film 80 was arranged at a position overlapping the silicon rubber sheet 86 when viewed from above. Then, as shown in FIG. 4B, a load of 40 N was applied from above the PET film 80 toward the silicon rubber sheet 86 for 10 seconds under an environment of 25° C. and 50% RH. After that, as shown in FIG. 4C, the PET film 80 was pulled upward, and the silicon rubber sheet 86 from which the laminate sample piece 84 was removed was left for 24 hours in an environment of 25° C. and 50% RH.
- the strain height of the silicon rubber sheet 86 was measured using a surface shape measuring device (model number "Wyko NT9100", manufactured by Veeco), and the strain height was evaluated as the strain resistance of the laminate.
- a surface shape measuring device model number "Wyko NT9100", manufactured by Veeco
- the value (ab) obtained by subtracting is taken as the strain height c.
- the strain height c was 3 ⁇ m or less, it was determined as “G: Good”, and when the strain height c was greater than 3 ⁇ m, it was determined as “P: Poor”.
- the evaluation results are shown in Tables 2 and 3 in the item of strain resistance.
- the laminates of Examples 1 to 15, 17 and 18, in which the thickness T B of the first and second pressure-sensitive adhesive sheets are all larger than 10 ⁇ m have the thickness T B of the first and second pressure-sensitive adhesive sheets Compared to the laminate of Example 16, which has a thickness of 10 ⁇ m, it exhibited remarkably excellent step followability.
- the laminates of Examples 1 to 17, in which the storage elastic modulus G' (25°C) at 25°C of the first and second adhesive sheets is less than 0.20 MPa, are the storage elastic moduli of the first and second adhesive sheets.
- first adhesive sheet 12 second adhesive sheet 15 core 21 release liners 25, 35 substrates 32, 34, 36, 38 adhesive layer 50 PC board 60
- PET film 82 step tape 84 laminate sample piece 86 silicon rubber sheet
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Abstract
Description
ここに開示される積層体は、非剥離性の芯体と、該芯体の一方の表面に配置された第1の粘着シートと、該芯体の他方の表面に配置された第2の粘着シートを含む。ここで、第1の粘着シートは粘着剤層を含む粘着シートであり、第2の粘着シートもまた粘着剤層を含む粘着シートである。上記第1の粘着シートは、非剥離性の基材(支持基材)の両面に粘着剤層を有する形態の基材付き粘着シートであってもよく、非剥離性の基材を有しない基材レス粘着シートであってもよい。また、上記第2の粘着シートは、非剥離性の基材(支持基材)の両面に粘着剤層を有する形態の基材付き粘着シートであってもよく、非剥離性の基材を有しない基材レス粘着シートであってもよい。
ここに開示される芯体は、第1の粘着シートと第2の粘着シートを支持する支持部材である。ここに開示される技術において、上記芯体は、ヤング率と厚さの積が所定値以上であることを特徴とする。具体的には、単位をMPaとするときの芯体のヤング率の値EAと、単位をμmとするときの芯体の厚さの値TAとを掛け合わせて算出される値EA×TAが500000以上である。かかる芯体を用いると、積層体の耐歪み性が向上する傾向にある。
(25℃貯蔵弾性率)
ここに開示される積層体に含まれる粘着シート(第1の粘着シートおよび第2の粘着シートの一方または両方。以下同じ。)は、粘着シートの25℃における貯蔵弾性率G´(25℃)は0.20MPa未満であることによって特徴づけられる。上記G´(25℃)が所定値未満の粘着シートを用いると、積層体の段差追従性が向上する傾向にある。上記G´(25℃)は、好ましくは0.19MPa未満、より好ましくは0.18MPa未満、さらに好ましくは凡そ0.17MPa未満(例えば0.15MPa未満)、特に好ましくは0.14MPa未満であり、0.1MPa未満であってもよい。上記G´(25℃)の下限は特に限定されないが、接着性の観点からは、上記G´(25℃)は0.02MPa以上であることが好ましく、より好ましくは0.035MPa以上であってもよく、0.05MPa以上でもよく、0.1MPa以上でもよく、0.12MPa以上でもよい。
いくつかの態様において、粘着シートの85℃における貯蔵弾性率G´(85℃)は0.08MPa未満であり得る。上記G´(85℃)が所定値未満の粘着シートを用いると、積層体の段差追従性が向上する傾向にある。上記G´(85℃)は、好ましくは0.07MPa未満、より好ましくは0.06MPa未満、さらに好ましくは凡そ0.05MPa未満(例えば0.045MPa未満)である。上記G´(85℃)の下限は特に限定されないが、接着性の観点からは、上記G´(85℃)は通常0.01MPa以上であることが適当であり、好ましくは0.02MPa以上であり、0.03MPa以上であってもよく、0.04MPa以上でもよい。
いくつかの態様において、粘着シートの120℃における貯蔵弾性率G´(120℃)は0.04MPa未満であり得る。上記G´(120℃)が所定値未満の粘着シートを用いると、積層体の段差追従性が向上する傾向にある。上記G´(120℃)は、好ましくは0.035MPa未満、より好ましくは0.033MPa未満、さらに好ましくは0.03MPa未満(例えば0.028MPa未満)である。上記G´(120℃)の下限は特に限定されないが、接着性の観点からは、上記G´(120℃)は通常は0.01MPa以上であることが適当であり、好ましくは0.015MPa以上であり、より好ましくは0.02MPa以上でもあり、さらに好ましくは0.023MPa以上でもある。
・測定モード:せん断モード
・温度範囲 :-70℃~150℃
・昇温速度 :5℃/min
・測定周波数:1Hz
後述の実施例においても上記の方法で測定される。
粘着シートの光透過率CB[%]は、剥離ライナーから剥がした粘着シートの厚さ方向の光透過率(波長550nmの光透過率)であり、JIS K 7136:2000に準拠して、市販の透過率計を使用して測定される。透過率計としては、日立製作所製の分光光度計(装置名「U4150型分光光度計」)またはその相当品が用いられる。
ここに開示される技術において、粘着シートに含まれる粘着剤層を構成する粘着剤の種類は特に限定されない。上記粘着剤は、粘着剤の分野において用いられ得るアクリル系ポリマー、ゴム系ポリマー(天然ゴム、合成ゴム、これらの混合物等)、ポリエステル系ポリマー、ウレタン系ポリマー、ポリエーテル系ポリマー、シリコーン系ポリマー、ポリアミド系ポリマー、フッ素系ポリマー等の各種ゴム状ポリマーの1種または2種以上を粘着性ポリマー(粘着剤を形づくる構造ポリマーという意味で、以下「ベースポリマー」ともいう。)として含むものであり得る。粘着性能やコスト等の観点から、アクリル系ポリマーまたはゴム系ポリマーをベースポリマーとして含む粘着剤を好ましく採用し得る。なかでもアクリル系ポリマーをベースポリマーとする粘着剤(アクリル系粘着剤)が好ましい。ここに開示される技術は、アクリル系粘着剤を用いる態様で好ましく実施される。
また、「(メタ)アクリロイル」とは、アクリロイルおよびメタクリロイルを包括的に指す意味である。同様に、「(メタ)アクリレート」とはアクリレートおよびメタクリレートを、「(メタ)アクリル」とはアクリルおよびメタクリルを、それぞれ包括的に指す意味である。
ここに開示される技術において、ポリマーとして用いられるアクリル系ポリマーとしては、例えば、アルキル(メタ)アクリレートを主モノマーとして含み、該主モノマーと共重合性を有する副モノマーをさらに含み得るモノマー原料の重合物が好ましい。ここで主モノマーとは、上記モノマー原料におけるモノマー組成の50重量%超を占める成分をいう。
CH2=C(R1)COOR2 (1)
ここで、上記式(1)中のR1は水素原子またはメチル基である。また、R2は炭素原子数1~20の鎖状アルキル基である。以下、このような炭素原子数の範囲を「C1-20」と表すことがある。粘着剤の貯蔵弾性率等の観点から、R2がC1-14(例えばC1-10、典型的にはC4-8)の鎖状アルキル基であるアルキル(メタ)アクリレートを主モノマーとすることが適当である。R2がブチル基または2-エチルヘキシル基であるアルキル(メタ)アクリレートが好ましい。また、粘着特性の観点から、R1が水素原子であってR2がC4-8の鎖状アルキル基であるアルキルアクリレート(以下、単にC4-8アルキルアクリレートともいう。)を主モノマーとすることが好ましい。
1/Tg=Σ(Wi/Tgi)
なお、上記Foxの式において、Tgは共重合体のガラス転移温度(単位:K)、Wiは該共重合体におけるモノマーiの重量分率(重量基準の共重合割合)、Tgiはモノマーiのホモポリマーのガラス転移温度(単位:K)を表す。
2-エチルヘキシルアクリレート -70℃
n-ブチルアクリレート -55℃
2-ヒドロキシエチルアクリレート -15℃
4-ヒドロキシブチルアクリレート -40℃
酢酸ビニル 32℃
アクリル酸 106℃
メタクリル酸 228℃
ここに開示される技術における粘着剤層には、粘着付与樹脂を含有させることができる。これにより、粘着シートの剥離強度を高めることができる。粘着付与樹脂としては、フェノール系粘着付与樹脂、テルペン系粘着付与樹脂、変性テルペン系粘着付与樹脂、ロジン系粘着付与樹脂、炭化水素系粘着付与樹脂、エポキシ系粘着付与樹脂、ポリアミド系粘着付与樹脂、エラストマー系粘着付与樹脂、ケトン系粘着付与樹脂等の粘着付与樹脂から選択される1種または2種以上を用いることができる。なかでも、フェノール系粘着付与樹脂、テルペン系粘着付与樹脂、変性テルペン系粘着付与樹脂が好ましく、フェノール系粘着付与樹脂(好適にはテルペンフェノール樹脂)がより好ましい。
テルペンフェノール樹脂とは、テルペン残基およびフェノール残基を含むポリマーを指し、テルペン類とフェノール化合物との共重合体(テルペン-フェノール共重合体樹脂)と、テルペン類の単独重合体または共重合体をフェノール変性したもの(フェノール変性テルペン樹脂)との双方を包含する概念である。このようなテルペンフェノール樹脂を構成するテルペン類の好適例としては、α-ピネン、β-ピネン、リモネン(d体、l体およびd/l体(ジペンテン)を包含する。)等のモノテルペン類が挙げられる。水素添加テルペンフェノール樹脂とは、このようなテルペンフェノール樹脂を水素化した構造を有する水素添加テルペンフェノール樹脂をいう。水添テルペンフェノール樹脂と称されることもある。
アルキルフェノール樹脂は、アルキルフェノールとホルムアルデヒドから得られる樹脂(油性フェノール樹脂)である。アルキルフェノール樹脂の例としては、ノボラックタイプおよびレゾールタイプのものが挙げられる。
ロジンフェノール樹脂は、典型的には、ロジン類または上記の各種ロジン誘導体(ロジンエステル類、不飽和脂肪酸変性ロジン類および不飽和脂肪酸変性ロジンエステル類を包含する。)のフェノール変性物である。ロジンフェノール樹脂の例には、ロジン類または上記の各種ロジン誘導体にフェノールを酸触媒で付加させ熱重合する方法等により得られるロジンフェノール樹脂が含まれる。
[水酸基価の測定方法]
1.試薬
(1)アセチル化試薬としては、無水酢酸約12.5g(約11.8mL)を取り、これにピリジンを加えて全量を50mLにし、充分に攪拌したものを使用する。または、無水酢酸約25g(約23.5mL)を取り、これにピリジンを加えて全量を100mLにし、充分に攪拌したものを使用する。
(2)測定試薬としては、0.5mol/L水酸化カリウムエタノール溶液を使用する。
(3)その他、トルエン、ピリジン、エタノールおよび蒸留水を準備する。
2.操作
(1)平底フラスコに試料約2gを精秤採取し、アセチル化試薬5mLおよびピリジン10mLを加え、空気冷却管を装着する。
(2)上記フラスコを100℃の浴中で70分間加熱した後、放冷し、冷却管の上部から溶剤としてトルエン35mLを加えて攪拌した後、蒸留水1mLを加えて攪拌することにより無水酢酸を分解する。分解を完全にするため再度浴中で10分間加熱し、放冷する。
(3)エタノール5mLで冷却管を洗い、取り外す。次いで、溶剤としてピリジン50mLを加えて攪拌する。
(4)0.5mol/L水酸化カリウムエタノール溶液を、ホールピペットを用いて25mL加える。
(5)0.5mol/L水酸化カリウムエタノール溶液で電位差滴定を行う。得られた滴定曲線の変曲点を終点とする。
(6)空試験は、試料を入れないで上記(1)~(5)を行う。
3.計算
以下の式により水酸基価を算出する。
水酸基価(mgKOH/g)=[(B-C)×f×28.05]/S+D
ここで、
B: 空試験に用いた0.5mol/L水酸化カリウムエタノール溶液の量(mL)、
C: 試料に用いた0.5mol/L水酸化カリウムエタノール溶液の量(mL)、
f: 0.5mol/L水酸化カリウムエタノール溶液のファクター、
S: 試料の重量(g)、
D: 酸価、
28.05: 水酸化カリウムの分子量56.11の1/2、
である。
ここに開示される技術において、粘着剤層の形成に用いられる粘着剤組成物は、必要に応じて架橋剤を含んでもよい。架橋剤の種類は特に制限されず、従来公知の架橋剤から適宜選択して用いることができる。そのような架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、メラミン系架橋剤、過酸化物系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、ヒドラジン系架橋剤、アミン系架橋剤、シランカップリング剤等が挙げられる。なかでも、イソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、メラミン系架橋剤が好ましく、イソシアネート系架橋剤、エポキシ系架橋剤がより好ましく、イソシアネート系架橋剤が特に好ましい。架橋剤を適切に選定して使用することにより、粘着剤層の凝集力を得て、被着体への追従性や接着力等を改善することができる。なお、ここに開示される技術における粘着剤層は、上記架橋剤を、架橋反応後の形態、架橋反応前の形態、部分的に架橋反応した形態、これらの中間的または複合的な形態等で含有し得る。上記架橋剤は、典型的には、専ら架橋反応後の形態で粘着剤層に含まれている。
脂肪族ポリイソシアネート類の具体例としては、1,2-エチレンジイソシアネート;1,2-テトラメチレンジイソシアネート、1,3-テトラメチレンジイソシアネート、1,4-テトラメチレンジイソシアネート等のテトラメチレンジイソシアネート;1,2-ヘキサメチレンジイソシアネート、1,3-ヘキサメチレンジイソシアネート、1,4-ヘキサメチレンジイソシアネート、1,5-ヘキサメチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、2,5-ヘキサメチレンジイソシアネート等のヘキサメチレンジイソシアネート;2-メチル-1,5-ペンタンジイソシアネート、3-メチル-1,5-ペンタンジイソシアネート、リジンジイソシアネート等が挙げられる。
ここに開示される粘着剤層は、光透過性低減に役立ち得る着色剤を含有してもよく、上記着色剤を含有しなくてもよい。着色剤としては、従来公知の顔料や染料を用いることができる。着色剤の色としては有色が好ましい。着色剤の色は、例えば、黒色、灰色、赤色、青色、黄色、緑色、黄緑色、橙色、紫色、金色、銀色、パール色等であり得る。有色系着色剤は、遮光性、意匠性を付与させ得る。着色剤は、有色系着色剤と組み合わせるかたちで無色系着色剤を含んでもよく、含まなくてもよい。ここに開示される典型的な一態様に係る粘着剤層は、無色系着色剤を実質的に含まないものであり得る。なお、本明細書において「有色」とは黒色や金属色を含む意味である。また、「無色」とは白色を含む意味である。粘着剤層は、着色剤を含有する着色層を含む多層構造を有していてもよい。あるいは、粘着剤層は着色剤を実質的に分散状態(溶解した状態であり得る。)で含むものであってもよい。
いくつかの態様に係る粘着剤層は防錆剤を含み得る。防錆剤としては、特に限定されず、アゾール系防錆剤、アミン化合物、亜硝酸塩類、安息香酸アンモニウム、フタル酸アンモニウム、ステアリン酸アンモニウム、パルミチン酸アンモニウム、オレイン酸アンモニウム、炭酸アンモニウム、ジシクロヘキシルアミン安息香酸塩、尿素、ウロトロピン、チオ尿素、カルバミン酸フェニル、シクロヘキシルアンモニウム-N-シクロヘキシルカルバメート(CHC)等が挙げられる。防錆剤は、1種を単独でまたは2種以上を組み合わせて用いることができる。
粘着剤組成物には、必要に応じて、レベリング剤、架橋助剤、可塑剤、軟化剤、充填剤、帯電防止剤、老化防止剤、紫外線吸収剤、酸化防止剤、光安定剤等の粘着剤の分野において一般的な各種の添加剤が含まれていてもよい。上記各種添加剤については、従来公知のものを常法により使用することができ、特に本発明を特徴づけるものではないので、詳細な説明は省略する。
架橋反応の促進、製造効率向上等の観点から、粘着剤組成物の乾燥は加熱下で行うことが好ましい。乾燥温度は、例えば40~150℃程度とすることができ、60~130℃程度とすることが好ましい。粘着剤組成物を乾燥させた後、さらに、粘着剤層内における成分移行の調整、架橋反応の進行、粘着剤層内に存在し得る歪の緩和等を目的としてエージングを行ってもよい。
特に限定するものではないが、ここに開示される粘着剤層のゲル分率は、重量基準で、例えば20%以上とすることができ、通常は30%以上とすることが適当であり、35%よりも大きいことが好ましい。粘着剤層のゲル分率を適度な範囲で高くすることにより、被着体への追従性を向上することができる。ここに開示される技術では、上記ゲル分率は、より好ましくは45%以上、さらに好ましくは50%以上、特に好ましくは55%以上であり、60%以上であってもよい。一方、被着体への追従性の観点から、粘着剤層のゲル分率は、90%以下が適当であり、70%以下(例えば65%以下)が好ましく、60%未満であってもよい。
[ゲル分率測定方法]
約0.1gの粘着剤サンプル(重量Wg1)を平均孔径0.2μmの多孔質ポリテトラフルオロエチレン膜(重量Wg2)で巾着状に包み、口をタコ糸(重量Wg3)で縛る。上記多孔質ポリテトラフルオロエチレン(PTFE)膜としては、日東電工社から入手可能な商品名「ニトフロン(登録商標)NTF1122」(平均孔径0.2μm、気孔率75%、厚さ85μm)またはその相当品を使用する。
この包みを酢酸エチル50mLに浸し、室温(典型的には23℃)で7日間保持して粘着剤層中のゾル成分のみを上記膜外に溶出させた後、上記包みを取り出して外表面に付着している酢酸エチルを拭き取り、該包みを130℃で2時間乾燥させ、該包みの重量(Wg4)を測定する。粘着剤層のゲル分率FGは、各値を以下の式に代入することにより求められる。後述の実施例においても同様の方法が採用される。
ゲル分率FG(%)=[(Wg4-Wg2-Wg3)/Wg1]×100
ここに開示される粘着シートは基材(支持基材)を含んでもよい。ここに開示される基材の構造や材料は、特に限定されない。基材は、典型的にはフィルム状基材(「基材フィルム」ともいう。)である。基材フィルムとしては、ベースフィルムとして樹脂フィルムを含むものを好ましく用いることができる。上記ベースフィルムは、典型的には、独立して形状維持可能な(非依存性の)部材である。ここに開示される技術における基材フィルムは、このようなベースフィルムから実質的に構成されたものであり得る。あるいは、上記基材フィルムは、上記ベースフィルムの他に、補助的な層を含むものであってもよい。上記補助的な層の例としては、上記ベースフィルムの表面に設けられた着色層、反射層、下塗り層、帯電防止層等が挙げられる。
ここに開示される技術において、粘着剤層の形成、粘着シートの作製、積層体の作製、使用前の積層体の保存、流通、形状加工等の際に、剥離ライナーを用いることができる。剥離ライナーとしては、特に限定されず、例えば、樹脂フィルムや紙等のライナー基材の表面に剥離処理層を有する剥離ライナーや、フッ素系ポリマー(ポリテトラフルオロエチレン等)やポリオレフィン系樹脂(PE、PP等)の低接着性材料からなる剥離ライナー等を用いることができる。上記剥離処理層は、例えば、シリコーン系、長鎖アルキル系、フッ素系、硫化モリブデン等の剥離処理剤により上記ライナー基材を表面処理して形成されたものであり得る。
ここに開示される積層体は、後述の実施例に記載の方法で測定される段差防水試験において合格レベルの段差追従性を有することが好ましい。上記特性を満足する積層体は、複雑な形状に隙間なく追従した状態を維持しやすい。
積層体の光透過率Ctotal[%]は、剥離ライナーから剥がした積層体の厚さ方向の光透過率(波長550nmの光透過率)であり、JIS K 7136:2000に準拠して、市販の透過率計を使用して測定される。透過率計としては、日立製作所製の分光光度計(装置名「U4150型分光光度計」)またはその相当品が用いられる。
ここに開示される積層体は、複雑な形状への追従性と耐歪み性に優れる。このような特徴を活かして、上記積層体は、耐変形性および耐歪み性が要求される各種用途に利用され得る。例えば、折り曲げ形状を有する部材を有する各種携帯電子機器の部材固定用途に好適である。また、携帯電子機器は、外部から衝撃や荷重が付加されることがあるため、ここに開示される粘着シートを用いて、被着体の歪みの発生を抑制する利点は大きい。上記携帯電子機器の非限定的な例には、携帯電話、スマートフォン、タブレット型パソコン、ノート型パソコン、各種ウェアラブル機器(例えば、腕時計のように手首に装着するリストウェア型、クリップやストラップ等で体の一部に装着するモジュラー型、メガネ型(単眼型や両眼型。ヘッドマウント型も含む。)を包含するアイウェア型、シャツや靴下、帽子等に例えばアクセサリの形態で取り付ける衣服型、イヤホンのように耳に取り付けるイヤウェア型等)、デジタルカメラ、デジタルビデオカメラ、音響機器(携帯音楽プレーヤー、ICレコーダー等)、計算機(電卓等)、携帯ゲーム機器、電子辞書、電子手帳、電子書籍、車載用情報機器、携帯ラジオ、携帯テレビ、携帯プリンター、携帯スキャナ、携帯モデム等が含まれる。なお、この明細書において「携帯」とは、単に携帯することが可能であるだけでは充分ではなく、個人(標準的な成人)が相対的に容易に持ち運び可能なレベルの携帯性を有することを意味するものとする。
〔1〕 芯体と、
該芯体の一方の表面に配置された、粘着剤層を含む第1の粘着シートと、
該芯体の他方の表面に配置された、粘着剤層を含む第2の粘着シートと、を備える積層体であって、
上記芯体のヤング率EA[MPa]と厚さTA[μm]の積(EA×TA)は500000以上であり、
上記第1の粘着シートおよび上記第2の粘着シートの一方または両方の厚さTBは、10μmより大きく、かつ、25℃における貯蔵弾性率G′(25℃)が0.20MPa未満である、積層体。
〔2〕 上記第1の粘着シートおよび上記第2の粘着シートの一方または両方は、
85℃における貯蔵弾性率G′(85℃)は0.05MPa未満である、上記〔1〕に記載の積層体。
〔3〕 上記第1の粘着シートおよび上記第2の粘着シートの一方または両方は、
120℃における貯蔵弾性率G′(120℃)は0.03MPa未満である、上記〔1〕または〔2〕に記載の積層体。
〔4〕 上記第1の粘着シートおよび上記第2の粘着シートの一方または両方に含まれる粘着剤層は、ベースポリマーとしてアクリル系ポリマーを含むアクリル系粘着剤層である、上記〔1〕~〔3〕のいずれかに記載の粘着シート。
〔5〕 上記芯体の厚さTAは、20μm以上270μm以下である、上記〔1〕~〔4〕のいずれかに記載の積層体。
〔6〕 上記芯体のヤング率EAは、3000MPa以上である、上記〔1〕~〔5〕のいずれかに記載の積層体。
〔7〕 光透過率Ctotalが10%以下である、上記〔1〕~〔6〕のいずれかに記載の積層体。
〔8〕 上記積層体の総厚さTtotalは50μm以上400μm以下である、上記〔1〕~〔7〕のいずれかに記載の積層体。
〔9〕 携帯電子機器において部材の固定に用いられる、上記〔1〕~〔8〕のいずれかに記載の積層体。
攪拌機、温度計、窒素ガス導入管、還流冷却器および滴下ロートを備えた反応容器に、モノマー成分としてのBA95部およびAA5部と、重合溶媒としての酢酸エチル233部とを仕込み、窒素ガスを導入しながら2時間撹拌した。このようにして重合系内の酸素を除去した後、重合開始剤として0.2部の2,2’-アゾビスイソブチロニトリル(AIBN)を加え、60℃で8時間溶液重合してアクリル系ポリマーEの溶液を得た。このアクリル系ポリマーEのMwは約60×104であった。
攪拌機、温度計、窒素ガス導入管、還流冷却器および滴下ロートを備えた反応容器に、モノマー成分としてのBA95部およびAA5部と、重合溶媒としての酢酸エチル233部とを仕込み、窒素ガスを導入しながら2時間撹拌した。このようにして重合系内の酸素を除去した後、重合開始剤として0.2部の2,2’-アゾビスイソブチロニトリル(AIBN)を加え、60℃で8時間溶液重合してアクリル系ポリマーEの溶液を得た。このアクリル系ポリマーEのMwは約60×104であった。
攪拌機、温度計、窒素ガス導入管、還流冷却器および滴下ロートを備えた反応容器に、モノマー成分としてのBA70部、2EHA30部およびAA3部と、重合溶媒としての酢酸エチル233部とを仕込み、窒素ガスを導入しながら2時間撹拌した。このようにして重合系内の酸素を除去した後、重合開始剤として0.08部の2,2’-アゾビスイソブチロニトリル(AIBN)を加え、60℃で8時間溶液重合してアクリル系ポリマーFの溶液を得た。このアクリル系ポリマーFのMwは約40×104であった。
攪拌機、温度計、窒素ガス導入管、還流冷却器および滴下ロートを備えた反応容器に、モノマー成分としての2EHA100部およびAA2部と、重合溶媒としての酢酸エチル233部とを仕込み、窒素ガスを導入しながら2時間撹拌した。このようにして重合系内の酸素を除去した後、重合開始剤として0.02部の過酸化ベンゾイル(日本油脂社製、商品名「ナイパーBW」)を加え、60℃で8時間溶液重合してアクリル系ポリマーGの溶液を得た。このアクリル系ポリマーGのMwは約40×104であった。
攪拌機、温度計、窒素ガス導入管、還流冷却器および滴下ロートを備えた反応容器に、モノマー成分としての2EHA95部およびAA5部と、重合溶媒としての酢酸エチル233部とを仕込み、窒素ガスを導入しながら2時間撹拌した。このようにして重合系内の酸素を除去した後、重合開始剤として0.03部の過酸化ベンゾイル(日本油脂社製、商品名「ナイパーBW」)を加え、60℃で8時間溶液重合してアクリル系ポリマーHの溶液を得た。このアクリル系ポリマーHのMwは約120×104であった。
攪拌機、温度計、窒素ガス導入管、還流冷却器および滴下ロートを備えた反応容器に、モノマー成分としてのn-ブチルアクリレート(BA)95部およびアクリル酸(AA)5部と、重合溶媒としての酢酸エチル233部とを仕込み、窒素ガスを導入しながら2時間撹拌した。このようにして重合系内の酸素を除去した後、重合開始剤として0.2部の2,2’-アゾビスイソブチロニトリル(AIBN)を加え、60℃で8時間溶液重合してアクリル系ポリマーAの溶液を得た。このアクリル系ポリマーAのMwは約60×104であった。
(粘着シートの作製)
厚さ38μmのポリエステル製剥離ライナー(商品名「ダイアホイルMRF」、三菱ポリエステル社製)の剥離面に粘着剤組成物Eを塗布し、100℃で2分間乾燥させて、厚さ15μmの粘着剤層を形成した。このようにして、片面が上記ポリエステル製剥離ライナーで保護された厚さ15μmの基材レス両面粘着シートを得た。上記基材レス両面粘着シートを2枚用意し、本例の第1の粘着シートと第2の粘着シートとした。
第1の粘着シートの粘着面を芯体としての厚さ20μmのステンレス鋼シート(SUS 304BA)の一方の面に貼り付けた。また、第2の粘着シートの粘着面を上記ステンレス鋼シート(SUS 304BA)の他方の面に貼り付けた。このようにして、芯体の両面に第1および第2の粘着シートがそれぞれ配置され、かつ2枚の剥離ライナーで第1の粘着シートの粘着面と第2の粘着シートの粘着面が保護された積層体を作製し、これを本例の積層体とした。
第1の粘着シート(粘着剤層)の厚さ、第2の粘着シート(粘着剤層)および/または芯体の厚さを表1のようにしたことの他は、例1と同様にして、本例の積層体を得た。
厚さ38μmのポリエステル製剥離ライナー(商品名「ダイアホイルMRF」、三菱ポリエステル社製)を2枚用意した。各剥離ライナーの剥離面に粘着剤組成物Eを塗布し、100℃で2分間乾燥させて、厚さ10μmの粘着剤層を形成した。支持基材として、厚さ5μmの透明なPETフィルム(商品名「ルミラー」、東レ社製)と該PETフィルムの片面に設けられた黒色印刷層とからなる合計厚さ約10μmの多層構造の支持基材を用意した。上記黒色印刷層は、黒色着色剤を含むインク組成物を用い、グラビア印刷法を利用して印刷を行うことにより形成した。上記支持基材の第一面および第二面に各剥離ライナー上に形成された粘着剤層を貼り合わせることにより、黒色印刷PETフィルムの第一面および第二面に粘着剤層を有する、厚さ30μmの基材付き両面粘着シートを作製した。上記基材付き両面粘着シートを2枚用意し、本例の第1の粘着シートと第2の粘着シートとした。本例の第1および第2の粘着シートを用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
各剥離ライナー上に形成する粘着剤層の厚さを45μmとし、さらに支持基材として、黒色顔料を練りこんだ厚さ50μmのPETフィルム(商品名「ルミラー」、東レ社製)を使用したこと以外は例5と同様にして、厚さ140μmの基材付き両面粘着シートを作製し、本例の第1および第2の粘着シートとした。本例の第1および第2の粘着シートを用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
粘着剤層の厚さを20μmとしたこと以外は例1と同様の方法を用いて、厚さ20μmの基材レス両面粘着シートを作製し、本例の第1の粘着シートとした。
粘着剤層の厚さを20μmとしたこと以外は例1の第1および第2の粘着シートと同様の方法を用いて、厚さ20μmの基材レス両面粘着シートを作製し、本例の第1の粘着シートとした。
芯体として厚さ20μmのアルミニウムシート(商品名「A1N30H-O」、竹内金属箔粉社製)を用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
芯体として厚さ20μmの銅シート(商品名「C1020R-H」、竹内金属箔粉社製)を用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
芯体として厚さ125μmの透明なPETフィルム(商品名「ルミラー」、東レ社製)を用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
粘着剤組成物Eの代わりに粘着剤組成物Eblackを用いたことの他は、例1と同様の方法を用いて、厚さ15μmの基材レス両面粘着シートを作製し、本例の第1および第2の粘着シートとした。本例の第1および第2の粘着シートを用いたことの他は、例11と同様の方法を用いて、本例の積層体を作製した。
粘着剤組成物Eの代わりに粘着剤組成物Fを用いたことの他は、例2と同様の方法を用いて、厚さ30μmの基材レス両面粘着シートを作製し、本例の第1および第2の粘着シートとした。本例の第1および第2の粘着シートを用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
粘着剤組成物Eの代わりに粘着剤組成物Gを用いたことの他は、例2と同様の方法を用いて、厚さ30μmの基材レス両面粘着シートを作製し、本例の第1および第2の粘着シートとした。本例の第1および第2の粘着シートを用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
粘着剤組成物Eの代わりに粘着剤組成物Hを用いたことの他は、例2と同様の方法を用いて、厚さ30μmの基材レス両面粘着シートを作製し、本例の第1および第2の粘着シートとした。本例の第1および第2の粘着シートを用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
粘着剤層の厚さを10μmにしたことの他は、例1と同様の方法を用いて、厚さ10μmの基材レス両面粘着シートを作製し、本例の第1および第2の粘着シートとした。本例の第1および第2の粘着シートを用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
芯体として厚さ100μmの透明なPETフィルム(商品名「ルミラー」、東レ社製)を用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
粘着剤組成物Eの代わりに粘着剤組成物Aを用いたことと、粘着剤層の厚さを35μmにしたことの他は、例1と同様の方法を用いて、厚さ35μmの基材レス両面粘着シートを作製し、本例の第1の粘着シートとした。また、粘着剤組成物Aの代わりに粘着剤組成物Fを用いたことと、粘着剤層の厚さを25μmにしたことの他は、例1と同様の方法を用いて、厚さ25μmの基材レス両面粘着シートを作製し、本例の第2の粘着シートとした。
本例の第1および第2の粘着シートを用いたことと、芯体として厚さ40μmのステンレス鋼シート(SUS 304BA)を用いたことの他は、例1と同様の方法を用いて、本例の積層体を作製した。
[段差防水試験]
剥離ライナーで両粘着面が保護された各例に係る積層体を、24.5mm×24.5mmの正方形状の外縁を有し、幅2mmの窓枠状(額縁状)にカットして、窓枠状積層体を得た。この窓枠状積層体の第2の粘着シート側の剥離ライナーを剥がし、露出した粘着面を、50mm×50mmの正方形で、厚さ2mmのアクリル板に貼り付けて、窓枠状積層体付きアクリル板を作製した。窓枠状積層体付きアクリル板から第1の粘着シート側の剥離ライナーを剥がした。
上記アクリル板よりも大きいサイズを有するポリカーボネート板を用意し、このポリカーボネート板の表面に、段差テープ(幅5mm、高さ20μm)を貼り付けた。この段差テープは、ポリカーボネート板の表面に凸(段差)を設ける目的で用いられるものである。ここでは、段差テープとして、PET基材の片面に粘着剤層を有する粘着シートを使用した。そして、このポリカーボネート板上に上記で作製した窓枠状積層体付きアクリル板を、該積層体の第1の粘着シート側がポリカーボネート側を向くような姿勢で、窓枠状積層体の平行する二辺の中央部が段差テープを横切るように(窓枠状積層体の上記平行する二辺が段差テープと交差(直交)するように)配置し、0.2MPa、1分間の条件で圧着した。このようにして評価用サンプルを得た。得られた評価用サンプルは、窓枠状積層体が被着体(アクリル板、ポリカーボネート板および段差テープ)に密着している場合、その内側は外部から密閉された空間となる。
段差防水性の評価は、評価用サンプルを、オートクレーブ内にて水中に沈め、上記オートクレーブ内にて、25℃、0.5MPaの加圧を30分間実施し、評価用サンプル内部(窓枠状積層体内側)への浸水の有無を目視で観察することにより行った。評価用サンプル内部への浸水の有無を、段差追従性として評価した。評価用サンプル内部への浸水が観察された場合は「P:不良」、観察されなかった場合は「G:良好」と判定した。評価結果を表2および表3の段差追従性の項目に示した。
なお、上記段差防水試験は、評価用サンプルを標準状態(23℃、50%RH)で30分間エージングしてから行った。
図4Aに示すように、縦50mm、横50mm、厚さ125μmのPETフィルム80と、幅2mm、長さ50mm、高さ8mmの段差テープ82を用意し、段差テープ82をPETフィルム80の表面の中央部に、段差テープ82の長さ方向とPETフィルム80の一辺の方向とを一致させるようにして貼りつけた。段差テープ82は、PETフィルム80の表面に凸(段差)を設ける目的で用いられるものである。ここでは、段差テープ82として、PET基材の片面に粘着剤層を有する粘着シートを使用した。次いで、剥離ライナーで両粘着面が保護された各例に係る積層体を縦10mm、横10mmのサイズにカットし、積層体から2枚の剥離ライナーを剥がして露出した各粘着面にそれぞれ厚さ5μmのPETフィルムを貼り付けて裏打ちし、積層体試料片84とした。また、縦50mm、横50mm、厚さ3mmの市販のシリコンゴムシート86を用意した。積層体試料片84をシリコンゴムシート86の上面の中央部に、積層体試料片84の一辺の方向とシリコンゴムシート86の一辺の方向とを一致させるようにして配置した。
11 第1の粘着シート
12 第2の粘着シート
15 芯体
21 剥離ライナー
25,35 基材
32,34,36,38 粘着剤層
50 PC板
60 PETフィルム
70 積層体試料片
80 PETフィルム
82 段差テープ
84 積層体試料片
86 シリコンゴムシート
Claims (8)
- 芯体と、
該芯体の一方の表面に配置された、粘着剤層を含む第1の粘着シートと、
該芯体の他方の表面に配置された、粘着剤層を含む第2の粘着シートと、を備える積層体であって、
前記芯体のヤング率EA[MPa]と厚さTA[μm]の積(EA×TA)は500000以上であり、
前記第1の粘着シートおよび前記第2の粘着シートの一方または両方は、厚さTBが10μmより大きく、かつ、25℃における貯蔵弾性率G′(25℃)が0.20MPa未満である、積層体。 - 前記第1の粘着シートおよび前記第2の粘着シートの一方または両方は、
85℃における貯蔵弾性率G′(85℃)が0.05MPa未満である、請求項1に記載の積層体。 - 前記第1の粘着シートおよび前記第2の粘着シートの一方または両方は、
120℃における貯蔵弾性率G′(120℃)が0.03MPa未満である、請求項1または2に記載の積層体。 - 前記芯体の厚さTAは、10μm以上300μm以下である、請求項1から3のいずれか一項に記載の積層体。
- 前記芯体のヤング率EAは、3000MPa以上である、請求項1から4のいずれか一項に記載の積層体。
- 光透過率Ctotalが10%以下である、請求項1から5のいずれか一項に記載の積層体。
- 前記積層体の総厚さTtotalは50μm以上400μm以下である、請求項1から6のいずれか一項に記載の積層体。
- 携帯電子機器において部材の固定に用いられる、請求項1から7のいずれか一項に記載の積層体。
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JP2012062342A (ja) * | 2010-09-14 | 2012-03-29 | Nitto Denko Corp | 両面粘着シート |
JP2018028051A (ja) * | 2016-08-10 | 2018-02-22 | 日東電工株式会社 | 粘着シート |
JP2018145340A (ja) * | 2017-03-08 | 2018-09-20 | リンテック株式会社 | 粘着フィルム |
WO2019087277A1 (ja) * | 2017-10-31 | 2019-05-09 | 株式会社寺岡製作所 | 粘着テープ |
JP2021134226A (ja) * | 2020-02-21 | 2021-09-13 | 株式会社巴川製紙所 | 両面粘着シート |
JP2022133053A (ja) * | 2021-03-01 | 2022-09-13 | Mccアドバンスドモールディングス株式会社 | 防食用ラミネートフィルムおよび防食テープ |
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JP2012062342A (ja) * | 2010-09-14 | 2012-03-29 | Nitto Denko Corp | 両面粘着シート |
JP2018028051A (ja) * | 2016-08-10 | 2018-02-22 | 日東電工株式会社 | 粘着シート |
JP2018145340A (ja) * | 2017-03-08 | 2018-09-20 | リンテック株式会社 | 粘着フィルム |
WO2019087277A1 (ja) * | 2017-10-31 | 2019-05-09 | 株式会社寺岡製作所 | 粘着テープ |
JP2021134226A (ja) * | 2020-02-21 | 2021-09-13 | 株式会社巴川製紙所 | 両面粘着シート |
JP2022133053A (ja) * | 2021-03-01 | 2022-09-13 | Mccアドバンスドモールディングス株式会社 | 防食用ラミネートフィルムおよび防食テープ |
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