WO2018173896A1 - 両面粘着シート、画像表示装置構成用部材を有する積層体、積層体形成キット及び両面粘着シートの使用 - Google Patents
両面粘着シート、画像表示装置構成用部材を有する積層体、積層体形成キット及び両面粘着シートの使用 Download PDFInfo
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- WO2018173896A1 WO2018173896A1 PCT/JP2018/010061 JP2018010061W WO2018173896A1 WO 2018173896 A1 WO2018173896 A1 WO 2018173896A1 JP 2018010061 W JP2018010061 W JP 2018010061W WO 2018173896 A1 WO2018173896 A1 WO 2018173896A1
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- WO
- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- double
- meth
- adhesive sheet
- temperature
- Prior art date
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- 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
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- 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
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- 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
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- 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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to a double-sided pressure-sensitive adhesive sheet that can be suitably used for bonding two image display device constituting members, in particular, a flexible image display device constituting member (so-called flexible member) that can be bent or bent, and the use thereof. Is.
- an image display panel such as a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), and a protection disposed on the front side (viewing side).
- a flat display panel such as a liquid crystal display panel (LCD) is mainly used for these image display panels.
- LCD liquid crystal display panel
- Patent Document 1 as a pressure-sensitive adhesive sheet that can suppress the generation of bubbles that can be visually recognized even under a reduced pressure environment as well as when bonded under normal pressure, even if foreign matter is present on the adherend surface, A pressure-sensitive adhesive sheet having physical properties that the storage shear modulus of the pressure-sensitive adhesive sheet according to the reference master curve falls within the range of 5 ⁇ 10 2 Pa to 1 ⁇ 10 4 Pa at both frequencies of 10 ⁇ 3 Hz and 10 ⁇ 5 Hz. Is disclosed.
- Patent Document 2 when a laminated body bonded through an adhesive sheet is cut, the cut end face does not become sticky with time, and even if there are irregularities on the adherend surface, there are no bubbles remaining.
- a new transparent adhesive sheet that can be attached without foaming even if the adherend is made of a material that generates outgas such as plastic, a first adhesive layer having different viscoelastic behavior and A pressure-sensitive adhesive sheet having one or more second pressure-sensitive adhesive layers and having a structure in which these layers are laminated and integrated, and a dynamic shear storage elastic modulus G ′ measured by temperature dispersion at a frequency of 1 Hz
- the transparent pressure-sensitive adhesive sheet has a value of 2 ⁇ 10 4 to 5 ⁇ 10 5 Pa at 20 ° C. and 1 ⁇ 10 4 to 1 ⁇ 10 5 Pa at 150 ° C.
- Patent Document 3 discloses a transparent double-sided pressure-sensitive adhesive sheet that is excellent in workability such as cutting workability as well as being excellent in conformity to steps and unevenness due to a printing site when bonded to an adherend.
- a transparent double-sided pressure-sensitive adhesive sheet having an intermediate resin layer (A) and a pressure-sensitive adhesive layer (B) as a front and back layer, each layer being one or more types of (meth) acrylic acid esters
- a layer comprising a (co) polymer as a base resin, and the storage shear modulus (G ′ (A)) of the intermediate resin layer (A) at a frequency of 1 Hz in a temperature range of 0 ° C. to 100 ° C. is a pressure sensitive adhesive
- a transparent double-sided PSA sheet is disclosed which is higher than the layer (B) and has an indentation hardness (Asker C2 hardness) of the entire sheet of 10 to 80.
- the image display apparatus structural member which has a level
- the thickness of the maximum thickness portion of the pressure-sensitive adhesive sheet is 250 ⁇ m or less
- the gel fraction (a) at the position in contact with the stepped portion after bonding is 10% or more, and is in contact with the flat surface portion.
- a transparent double-sided pressure-sensitive adhesive sheet for an image display device which is smaller than the gel fraction (b) of the position, is disclosed.
- an organic electroluminescence (organic EL) display is mainly used.
- the double-sided pressure-sensitive adhesive sheet used for laminating these image display device constituting members has the optical properties required for conventional flat display panels. In addition to properties and durability, it is required that bending, peeling and lifting do not occur even when a bending test is performed.
- Patent Document 5 discloses a pressure-sensitive adhesive for an optical film containing a (meth) acrylic acid ester copolymer (A), which is the (meth) acrylic acid ester.
- An optical film pressure-sensitive adhesive sheet is disclosed in which the glass transition temperature of the copolymer (A) is ⁇ 70 ° C. or higher and ⁇ 55 ° C. or lower and the weight average molecular weight is more than 1,000,000 and 2.5 million or less. .
- the double-sided pressure-sensitive adhesive sheet used for the bonding may be folded, peeled off or floated after the bending test. No bending resistance will be required, but there is no established bending test method. Thus, a double-sided pressure-sensitive adhesive sheet having high bending resistance that does not fold or peel off under conditions closer to the actual usage environment is required.
- an object of the present invention is to provide a double-sided pressure-sensitive adhesive sheet having high bending resistance that does not cause folding or peeling even in a bending test close to an actual use environment.
- Patent Document 5 when the glass transition temperature of the (meth) acrylic acid ester copolymer constituting the pressure-sensitive adhesive sheet is ⁇ 70 ° C. or higher and ⁇ 55 ° C. or lower, the pressure-sensitive adhesive has excellent adhesive strength and has bending durability. It is disclosed to become a sheet.
- the present inventor has studied in more detail the relationship between the properties of the double-sided pressure-sensitive adhesive sheet and the bending resistance.
- the thickness of the double-sided pressure-sensitive adhesive sheet is within the range of 10 ⁇ m to 150 ⁇ m
- the glass transition temperature of the (meth) acrylic acid ester copolymer constituting the sheet is ⁇ 50 ° C. or higher and ⁇ 20 ° C. or lower
- the present inventor has (3) a storage elastic modulus-temperature graph in which the double-sided pressure-sensitive adhesive sheet is plotted with temperature on the horizontal axis and logarithm of shear storage elastic modulus (G ′) on the vertical axis.
- G ′ logarithm of shear storage elastic modulus
- the gist of the present invention is as follows.
- Tg glass transition temperature
- a glass transition temperature (Tg) which is formed from a pressure-sensitive adhesive composition containing (A), has a thickness of 10 ⁇ m or more and 150 ⁇ m or less, and is defined by a Tan ⁇ peak temperature of dynamic viscoelasticity, is ⁇ 50 ° C. to ⁇
- the double-sided PSA sheet has a storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 100 ° C. in a storage elastic modulus-temperature graph in which the horizontal axis represents temperature and the vertical axis represents the logarithm of shear storage elastic modulus (G ′).
- G ′ logarithm of shear storage elastic modulus
- the (meth) acrylic acid ester (co) polymer (A) does not contain a carboxyl group-containing monomer as a (co) polymerization component, and at least a hydroxyl group-containing monomer or an amide group as a (co) polymerization component
- the (meth) acrylic acid ester (co) polymer (A) includes a (meth) acrylic acid alkyl ester in which a (meth) acryloyl group and a tertiary carbon atom are bonded as a (co) polymerization component.
- the laminate according to any one of [1] to [5].
- the storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 50 ° C. is in the range of 3.0 ⁇ 10 2 to 4.0 ⁇ 10 4 Pa, according to any one of the above [1] to [8] Laminated body.
- the image display device constituting member is a combination of two or more of the group consisting of a surface protection panel, a touch panel, an optical film, and an organic EL (Electronic Luminescent) display panel.
- the laminated body in any one of these.
- a flexible display comprising the laminate according to any one of [1] to [11].
- a double-sided pressure-sensitive adhesive sheet which is formed from a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester (co) polymer (A), and is defined by a Tan ⁇ peak temperature of dynamic viscoelasticity.
- the glass transition temperature (Tg) is in the range of ⁇ 50 ° C. to ⁇ 20 ° C.
- the storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 100 ° C. is 2.0 ⁇ 10 3 to 3.0 ⁇ .
- a double-sided pressure-sensitive adhesive sheet having a thickness in the range of 10 4 Pa and a thickness of 10 ⁇ m or more and 150 ⁇ m or less.
- the (meth) acrylic acid ester (co) polymer (A) does not contain a carboxyl group-containing monomer as a (co) polymerization component, and at least a hydroxyl group-containing monomer or an amide group as a (co) polymerization component
- the double-sided pressure-sensitive adhesive sheet according to any one of the above [13] to [16], which contains either or both of the contained monomers.
- the (meth) acrylic acid ester (co) polymer (A) includes a (meth) acrylic acid alkyl ester in which a (meth) acryloyl group and a tertiary carbon atom are bonded as a (co) polymerization component.
- the double-sided pressure-sensitive adhesive sheet according to any one of [13] to [17].
- the storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 50 ° C. is in the range of 3.0 ⁇ 10 2 to 4.0 ⁇ 10 4 Pa, according to any one of the above [13] to [20] Double-sided adhesive sheet.
- the double-sided pressure-sensitive adhesive sheet is formed from a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester (co) polymer (A), and has a thickness of 10 ⁇ m or more and 150 ⁇ m or less,
- the glass transition temperature (Tg) defined by the Tan ⁇ peak temperature of dynamic viscoelasticity is in the range of ⁇ 50 ° C. to ⁇ 20 ° C.
- the storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 100 ° C. is 2
- a laminate-forming kit characterized by being in the range of 0.0 ⁇ 10 3 to 3.0 ⁇ 10 4 Pa.
- the double-sided PSA sheet has a storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 100 ° C. in a storage elastic modulus-temperature graph in which temperature is plotted on the horizontal axis and logarithm of shear storage elastic modulus (G ′) is plotted on the vertical axis.
- G ′ logarithm of shear storage elastic modulus
- the (meth) acrylic acid ester (co) polymer (A) does not contain a carboxyl group-containing monomer as a (co) polymerization component, and as a (co) polymerization component, at least a hydroxyl group-containing monomer or an amide group
- the (meth) acrylic acid ester (co) polymer (A) includes a (meth) acrylic acid alkyl ester in which a (meth) acryloyl group and a tertiary carbon atom are bonded as a (co) polymerization component,
- the laminate-forming kit according to any one of [23] to [27].
- the storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 50 ° C. is in the range of 3.0 ⁇ 10 2 to 4.0 ⁇ 10 4 Pa, according to any one of the above [23] to [30] Laminate formation kit.
- a double-sided pressure-sensitive adhesive sheet as a method for laminating a flexible member for constituting an image display device, wherein the double-sided pressure-sensitive adhesive sheet is a base material-free and comprises a (meth) acrylic acid ester (co) polymer ( A glass transition temperature (Tg), which is formed from a pressure-sensitive adhesive composition containing A), has a thickness of 10 ⁇ m or more and 150 ⁇ m or less, and is defined by a Tan ⁇ peak temperature of dynamic viscoelasticity, is ⁇ 50 ° C. to ⁇ 20
- An image display device having a storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 100 ° C. within a range of 2.0 ⁇ 10 3 to 3.0 ⁇ 10 4 Pa.
- Use of a double-sided pressure-sensitive adhesive sheet as a method for bonding a structural flexible member.
- the double-sided PSA sheet has a storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 100 ° C. in a storage elastic modulus-temperature graph in which temperature is plotted on the horizontal axis and logarithm of shear storage elastic modulus (G ′) is plotted on the vertical axis.
- G ′ logarithm of shear storage elastic modulus
- the (meth) acrylic acid ester (co) polymer (A) does not contain a carboxyl group-containing monomer as a (co) polymerization component, and at least either a hydroxyl group-containing monomer or an amide group-containing monomer or both
- the (meth) acrylic acid ester (co) polymer (A) includes (meth) acrylic acid alkyl ester in which a (meth) acryloyl group and a tertiary carbon atom are bonded as a (co) polymerization component.
- the image display constituent member is a combination method of two or more kinds in the group consisting of a surface protection panel, a touch panel, an optical film, and an organic EL display panel, and the image display device constituent flexible member as the bonding method of the image display device constituent flexible member Use of the double-sided pressure-sensitive adhesive sheet according to any one of [32] to [40].
- the double-sided pressure-sensitive adhesive sheet of the present invention has excellent bending resistance, it can be used as a pressure-sensitive adhesive material suitable for bonding a flexible member for constituting an image display device that can be bent or curved.
- the double-sided pressure-sensitive adhesive sheet of the present invention is particularly preferably used as a double-sided pressure-sensitive adhesive sheet for an image display device having a flexible member having a base material that can be bent or bent, such as an organic EL (Electronic Luminescent) display panel. it can.
- an organic EL Electro Luminescent
- FIG. 1 is an explanatory view showing a bending test of Examples and Comparative Examples.
- (Meth) acryl means acryl and methacryl
- (meth) acryloyl means acryloyl and methacryloyl
- (meth) acrylate means acrylate and methacrylate
- (co) polymer is intended to encompass polymers and copolymers.
- the “sheet” conceptually includes a sheet, a film, and a tape.
- “storage elastic modulus G ′” means a storage elastic modulus when dynamic viscoelasticity measurement is performed in a shear mode, and is a value obtained by the method described in the examples described later.
- the double-sided pressure-sensitive adhesive sheet of the present invention (hereinafter also referred to as “the double-sided pressure-sensitive adhesive sheet”) is substrate-free and has at least the following properties (1) to (4).
- the base material-less double-sided pressure-sensitive adhesive sheet refers to a double-sided pressure-sensitive adhesive sheet having only a pressure-sensitive adhesive layer without having a base material as a support.
- the thickness is in the range of 10 ⁇ m to 150 ⁇ m.
- the glass transition temperature (Tg) defined by the Tan ⁇ peak temperature of dynamic viscoelasticity is in the range of ⁇ 50 ° C. to ⁇ 20 ° C.
- the storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 100 ° C. is in the range of 2.0 ⁇ 10 3 to 3.0 ⁇ 10 4 Pa.
- the pressure-sensitive adhesive disclosed in Patent Document 5 is set so that the glass transition temperature (Tg) is ⁇ 70 ° C. or higher and ⁇ 55 ° C. or lower, and has poor practical adhesive strength at room temperature. It is considered that the sex is not sufficient.
- Tg glass transition temperature
- the present inventors have studied to obtain a pressure-sensitive adhesive sheet having high bending resistance without extremely reducing the glass transition temperature (Tg) of the pressure-sensitive adhesive as in Patent Document 5 described above.
- Tg glass transition temperature
- the “buckling” is a phenomenon in which a pressure-sensitive adhesive sheet becomes white or a bending mark is formed around a bending line after a bending test.
- the “flow” is a phenomenon in which the adhesive sheet around the bend line appears to rise after the bend test.
- the “buckling” is mainly due to the high glass transition temperature and shear storage modulus (G ′) of the adhesive, and free molecular chains at the micro level. It was clarified that this is a kind of breakdown and yielding phenomenon of polymer structure caused by the lack of room for movement. Further, the “flow” is a phenomenon that is caused by the fact that the shear storage elastic modulus (G ′) is low and the pressure-sensitive adhesive sheet sandwiched between the upper and lower films is pushed out by bending and accumulated.
- the present inventors assume that the above two phenomena (buckling and flow) can be suppressed by adjusting the shear storage modulus (G ′) of the adhesive.
- the glass storage temperature of the pressure-sensitive adhesive is bent without being extremely lowered as in Patent Document 5 by controlling the shear storage elastic modulus in a specific temperature range. It has been found that an adhesive sheet having resistance can be obtained.
- the double-sided PSA sheet is a flexible display having a member for constituting an image display device such as a plastic panel or an organic EL (Electronic Luminescent) display panel, in particular, a flexible member for constituting a bendable or bendable image display device.
- an image display device such as a plastic panel or an organic EL (Electronic Luminescent) display panel
- a flexible member for constituting a bendable or bendable image display device In order to paste the said image display apparatus structural member, it is used suitably.
- flexible means that it can be bent or bent, and that it can be bent or bent includes a state where it is bent or bent.
- the radius of curvature that can be bent or curved is preferably 10 mm or less, and more preferably 3 mm or less.
- the present invention is applied to a flexible member having a curvature radius of 3 mm or less, the display can be folded and used.
- the image display device constituting member may be a flexible member that can be bent or bent, for example, a surface protection panel, a touch panel, an optical film, an organic film having a substrate made of a resin film or glass that can be bent or bent.
- EL Electro Luminescent
- a combination of two or more of the group consisting of EL (Electronic Luminescent) display panels can be mentioned.
- at least one image display device constituting member is preferably a flexible member, and more preferably a flexible organic EL (Electronic Luminescent) display panel.
- the surface protection panel examples include a flexible member that is made of a material such as thin glass or plastic and is protected from an external impact by being positioned on the outermost layer side, such as a cover film.
- the touch panel function may be integrated, for example, a touch-on-lens (TOL) type or a one-glass solution (OGS) type.
- the surface protection panel may have a printing step portion printed in a frame shape on the peripheral portion thereof.
- Examples of the touch panel include a flexible member in which a touch sensor is mounted on a base material such as thin glass or plastic and has a sensor function.
- an in-cell type image display panel with a touch function built into the image display panel and an on-cell type image display panel with a touch panel function built in between the polarizing plate and the organic EL shall be included in the touch panel.
- optical film examples include a flexible member that is mounted inside a flexible display such as a polarizing film, a retardation film, an optical filter, an antireflection film, a near-infrared cut film, and an electromagnetic wave shielding film and exhibits an optical function. .
- Examples of the flexible organic EL display panel include members having a configuration in which various electrode layers and organic EL elements are formed on a plastic substrate that can be bent or bent, and a sealing film and a passivation film are laminated. .
- organic EL display panel / double-sided pressure-sensitive adhesive sheet / release film touch panel / double-sided pressure-sensitive adhesive sheet / release film, surface protection panel / double-sided pressure-sensitive adhesive sheet / release film, optical film Any one of / a double-sided pressure-sensitive adhesive sheet / release film can be cited as a suitable example.
- an organic EL display panel / a double-sided pressure-sensitive adhesive sheet / touch panel an organic EL display panel / a double-sided pressure-sensitive adhesive sheet / surface protection panel
- Organic EL display panel / Double-sided PSA sheet / Touch panel / Double-sided PSA sheet / Surface protection panel Organic EL display panel / Double-sided PSA sheet / Touch panel / Double-sided PSA sheet / Surface protection panel
- Optical film / Double-sided PSA sheet / Touch panel Optical film / Double-sided PSA sheet / Touch panel / Double-sided PSA sheet / Surface protection panel, etc.
- This double-sided pressure-sensitive adhesive sheet is formed from a pressure-sensitive adhesive composition (hereinafter referred to as “this pressure-sensitive adhesive composition”) containing at least a (meth) acrylic acid ester (co) polymer (A).
- the pressure-sensitive adhesive composition may further contain a crosslinking agent (B), a photoinitiator (C), and other components, and is preferably a photocurable composition.
- the double-sided pressure-sensitive adhesive sheet may have a single layer configuration or a multilayer configuration.
- Examples of the (meth) acrylic acid ester (co) polymer (A) include, for example, a copolymer obtained by polymerizing a monomer component copolymerizable with an alkyl (meth) acrylate homopolymer. Can be mentioned. Among them, the (meth) acrylic acid ester (co) polymer (A) contains two or more copolymer components, and at least one copolymer component is an alkyl (meth) acrylate and / or the following copolymerizable monomer A. Any one of ⁇ H is preferable.
- copolymerizable monomers A to H the following copolymerizable monomers A, B, or E are particularly preferable.
- the copolymerizable monomer A is not included, and either or both of the copolymerizable monomers B and E are included.
- not containing copolymerizable monomer A means “substantially free”, not only when not completely contained, but also in (meth) acrylic acid ester (co) polymer, It includes that the copolymerizable monomer A is contained in an amount of less than 0.5% by mass, preferably less than 0.1% by mass.
- alkyl (meth) acrylates alkyl (meth) acrylates in which a (meth) acryloyl group and a tertiary carbon atom are bonded are preferable.
- the shear storage elastic modulus (G ′) on the high temperature side (100 ° C. to 150 ° C.) of the double-sided PSA sheet can be easily flattened.
- the (meth) acrylic acid ester (co) polymer (A) contains (a) a carboxyl group other than the alkyl (meth) acrylate and the alkyl (meth) acrylate copolymerizable therewith.
- Monomer hereinafter also referred to as “copolymerizable monomer A”
- hydroxyl group-containing monomer hereinafter also referred to as “copolymerizable monomer B”
- (c) amino group-containing monomer hereinafter referred to as “copolymerizable monomer C”.
- the alkyl (meth) acrylate is preferably a linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain, and a linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain.
- n-butyl (meth) acrylate isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) Acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isono (Meth) acrylate, t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, unde
- Examples of the copolymerizable monomer A include (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, and 2- (meth) acryloyloxyethyl.
- Phthalic acid 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- ( Mention may be made of (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid. These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer B include hydroxyalkyl (meta) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. ) Acrylates. These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer C include aminoalkyl (meth) acrylates such as aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminoisopropyl (meth) acrylate, and N-alkylamino. Mention may be made of N, N-dialkylaminoalkyl (meth) acrylates such as alkyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate. These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer D include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate glycidyl ether. . These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer E include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, Examples thereof include N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, maleic acid amide, and maleimide. These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer F include compounds having a vinyl group in the molecule.
- Examples of such compounds include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, functional monomers having a functional group such as a hydroxyl group, an amide group and an alkoxylalkyl group in the molecule; Polyalkylene glycol di (meth) acrylates and vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl laurate, and aromatic vinyl monomers such as styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene and other substituted styrenes Can be illustrated. These may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer G include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate and the like. These may be used alone or in combination of two or more.
- the copolymerizable monomer H is a monomer having a side chain carbon number of 20 or more when a (meth) acrylic (co) polymer is obtained by polymerization.
- a (meth) acrylic (co) polymer can be used as a graft copolymer.
- the characteristics of the main chain and side chain of the graft copolymer can be changed depending on the selection and blending ratio of the copolymerizable monomer H and other monomers.
- the skeleton component is preferably composed of an acrylic polymer or a vinyl polymer.
- the skeleton component of the macromonomer include, for example, a linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain, the copolymerizable monomer A, a copolymerizable monomer G described later, and the copolymerizable monomer. What is illustrated by B etc. is mentioned, These can be used individually or in combination of 2 or more types.
- the macromonomer has a radically polymerizable group or a functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amino group, an amide group, or a thiol group.
- a radically polymerizable group or a functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amino group, an amide group, or a thiol group.
- those having a radical polymerizable group copolymerizable with other monomers are preferable.
- One or two or more radically polymerizable groups may be contained, and one of them is particularly preferred. Even when the macromonomer has a functional group, one or two or more functional groups may be contained, and one of them is particularly preferable.
- radical polymerizable group and the functional group may be contained.
- the number average molecular weight of the copolymerizable monomer H is preferably 500 to 20,000, more preferably 800 or more and 8000 or less, and particularly preferably 1000 or more and 7000 or less.
- a generally produced monomer for example, a macromonomer manufactured by Toa Gosei Co., Ltd.
- a macromonomer manufactured by Toa Gosei Co., Ltd. can be used as appropriate.
- the (meth) acrylic acid ester (co) polymer (A) is a linear or branched alkyl (meta) having 4 to 18 carbon atoms in the side chain.
- a copolymer of monomer components containing acrylate and copolymerizable monomer A and / or copolymerizable monomer B is preferred.
- (2) a copolymer of monomer components containing the above-mentioned side chain linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms and copolymerizable monomer A is preferable.
- the Tg can be kept low, so that the selection range of the copolymerizable monomer B is widened, and bending resistance is improved. It becomes easy to balance with basic adhesive performance such as heat and whitening resistance, adhesive strength and durability.
- the (meth) acrylic acid ester (co) polymer (A) includes a copolymerizable monomer A, a linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain, and a copolymerizable monomer B and / or a copolymerizable monomer E.
- a copolymer of monomer components is preferred.
- alkyl (meth) acrylates in which a (meth) acryloyl group and a tertiary carbon atom are bonded are used as the linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain. Most preferred.
- alkyl (meth) acrylate in which the (meth) acryloyl group and a tertiary carbon atom are bonded examples include, for example, 2-ethyl hesyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, isobutyl (Meth) acrylate, isostearyl (meth) acrylate, etc. can be mentioned. These can be used alone or in combination of two or more.
- the linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain is preferably contained in an amount of 30% by mass or more and 90% by mass or less in all monomer components of the copolymer. More preferably, it is contained in the range of not less than 88% by mass, and more preferably not less than 40% by mass and not more than 85% by mass.
- the copolymerizable monomer A is 1.2% by mass to 15% by mass or less in the total monomer components of the copolymer, and particularly 1.5% by mass or more or 10% by mass or less from the viewpoint of obtaining excellent adhesive properties.
- the copolymerizable monomer B is preferably contained in an amount of 0% by mass or more and 30% by mass or less in all monomer components of the copolymer, particularly 0% by mass or more or 25% by mass or less, and more preferably 1% by mass or more. Or it is further more preferable to contain in 20 mass% or less.
- the copolymerizable monomer C is preferably contained in an amount of 0% by mass or more and 30% by mass or less in all monomer components of the copolymer, particularly 0% by mass or more or 25% by mass or less, and more preferably 0% by mass or more. Or it is further more preferable to contain in 20 mass% or less.
- the copolymerizable monomer D is preferably contained in an amount of 0% by mass or more and 30% by mass or less in all monomer components of the copolymer, particularly 0% by mass or more or 25% by mass or less, and more preferably 0% by mass or more. Or it is further more preferable to contain in 20 mass% or less.
- the copolymerizable monomer E is preferably contained in the total monomer component of the copolymer in an amount of 0% by mass to 30% by mass, more preferably 0% by mass or more or 25% by mass or less, and particularly preferably 1% by mass or more. Or it is further more preferable to contain in 20 mass% or less.
- the copolymerizable monomer F is preferably contained in an amount of 0% by mass or more and 30% by mass or less in all monomer components of the copolymer, particularly 0% by mass or more or 25% by mass or less, and more preferably 0% by mass or more. Or it is further more preferable to contain in 20 mass% or less.
- the copolymerizable monomer G is preferably contained in the total monomer component of the copolymer in an amount of 0% by mass to 70% by mass, more preferably 3% by mass or more and 65% by mass or less, and particularly preferably 5% by mass or more. Or it is more preferable to contain in the range of 60 mass% or less.
- the copolymerizable monomer H is 5% by mass or more and 30% by mass or less, particularly 6% by mass or more and 25% by mass or less, and especially 8% by mass or more or 20% by mass or less in the total monomer components of the copolymer. It is preferable to contain in the range.
- acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride
- heterocyclic basic monomers such as vinyl pyrrolidone, vinyl pyridine and vinyl carbazole
- the (meth) acrylic acid ester (co) polymer (A) has a mass average molecular weight of 100,000 to 1,500,000, more preferably 150,000 or more and 1.3 million or less, particularly 200,000 or more and 1,200,000 or less. preferable.
- this adhesive composition is a solventless type which does not contain a solvent. Since the present pressure-sensitive adhesive composition is solvent-free, there are advantages such as no solvent remaining and excellent high-temperature durability.
- the (meth) acrylic acid ester (co) polymer (A) has a mass average molecular weight of 100,000 to 900,000. It is preferable that it is 150,000 or more and 750,000 or less, and it is most preferable that it is 200,000 or more and 600,000 or less.
- the (meth) acrylic acid ester (co) polymer (A) has a mass average molecular weight in the above range, hot melt film formation is possible. From the above points, the (meth) acrylic acid ester (co) polymer (A) has a mass average molecular weight of preferably 150,000 to 750,000, more preferably 200,000 or more and 60,000 or less. Is most preferred.
- the most preferred examples of the (meth) acrylic (co) polymer (A) include, for example, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, isobutyl Monomer component (a) such as (meth) acrylate and isostearyl (meth) acrylate, (meth) acrylic acid having a carboxyl group, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxy Propylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid
- (meth) acrylic acid ester copolymers obtained by copolymerizing at least one monomer component selected from the monomer components (a) and (b) are preferable, and the monomer components (a) and (b) are preferable.
- (c) acrylic acid ester copolymers obtained by copolymerizing at least one monomer component selected from each of them are more preferred.
- one of each of the monomer components (a) and (c) is used.
- a (meth) acrylic acid ester copolymer obtained by copolymerizing the monomer components selected above is more preferable.
- the pressure-sensitive adhesive composition preferably contains a crosslinking agent (B) in addition to the (meth) acrylic acid ester (co) polymer (A).
- the storage elastic modulus G ′ of the (meth) acrylic acid ester (co) polymer (A) can be easily adjusted.
- the crosslinking agent (B) is preferably a crosslinking agent having at least double bond crosslinking.
- at least one crosslinkable functional group selected from (meth) acryloyl group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, carbodiimide group, oxazoline group, aziridine group, vinyl group, amino group, imino group, and amide group
- polyfunctional (meth) acrylate is preferably used.
- polyfunctional means what has two or more crosslinkable functional groups.
- the crosslinkable functional group may be protected with a deprotectable protecting group.
- polyfunctional (meth) acrylate examples include 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin glycidyl ether di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethacrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A poly Propoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol Lopantrioxyethyl (meth) acrylate, ⁇
- the content of the crosslinking agent (B) is 0.5 to 50 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester (co) polymer (A), particularly 1 to 40 parts by mass, Among them, the proportion is preferably 5 parts by mass or more and 30 parts by mass or less.
- crosslinking agent (B) By containing the crosslinking agent (B) in the above range, it becomes easy to balance the shape stability of the double-sided PSA sheet.
- the pressure-sensitive adhesive composition preferably contains a photoinitiator (C) in addition to the (meth) acrylic acid ester (co) polymer (A) and the crosslinking agent (B).
- the photoinitiator (C) serves as a reaction initiation assistant in the crosslinking reaction of the crosslinking agent (B) described above.
- a photoinitiator sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.
- the photoinitiator sensitive to light having a wavelength longer than 380 nm can obtain high photoreactivity, and when the sensitive light is shaped into a sheet shape of the pressure-sensitive adhesive composition, It is preferable in that it can be easily reached.
- Photoinitiators are roughly classified into two types depending on the radical generation mechanism, a cleavage type photoinitiator capable of generating a radical by cleaving the single bond of the photoinitiator itself, a photoexcited initiator, and a photoinitiator in the system. It is roughly classified into a hydrogen abstraction type photoinitiator that can form an exciplex with a hydrogen donor and transfer hydrogen of the hydrogen donor.
- the cleavage type photoinitiator decomposes to generate another compound when generating radicals by light irradiation, and once excited, it has no function as an initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive after the crosslinking reaction is completed, and it is not likely to cause unexpected light degradation or the like in the pressure-sensitive adhesive, which is preferable.
- the hydrogen abstraction type photoinitiator does not generate a decomposition product such as a cleavage type photoinitiator during radical generation reaction by irradiation with active energy rays such as ultraviolet rays, so that it is difficult to become a volatile component after completion of the reaction, and to the adherend. This is useful in that it can reduce damage.
- a hydrogen abstraction type initiator as the photoinitiator (C).
- a hydrogen abstraction type photoinitiator By using a hydrogen abstraction type photoinitiator, a cross-linking reaction between (meth) acrylate (co) polymers (A) occurs, and the high-temperature side shear storage modulus (G ′) of the double-sided PSA sheet is flattened. It becomes easy to.
- a hydrogen abstraction type photoinitiator is used when using a (meth) acrylic acid ester (co) polymer (A) having a relatively low weight average molecular weight of 100,000 to 900,000. It becomes easy to make the shear storage elastic modulus (G ′) on the high temperature side of the double-sided PSA sheet flat.
- a monomer that generates a radical active species when receiving light is used as the (co) polymer component constituting the (meth) acrylic acid ester (co) polymer (A).
- Such monomers include benzophenone structure, benzyl structure, o-benzoylbenzoate structure, thioxanthone structure, 3-ketocoumarin structure, 2-ethylanthraquinone structure, and camphorquinone structure, and (meth) acrylic acid
- numerator can be mentioned.
- 4-acryloyloxybenzophenone 4-acryloyloxyethoxybenzophenone, 4-acryloyloxy-4′-methoxybenzophenone, 4-acryloyloxyethoxy-4′-methoxybenzophenone, 4-acryloyloxy-4′- Bromobenzophenone, 4-acryloyloxyethoxy-4'-bromobenzophenone, 4-methacryloyloxybenzophenone, 4-methacryloyloxyethoxybenzophenone, 4-methacryloyloxy-4'-methoxybenzophenone, 4-methacryloyloxyethoxy-4'-methoxybenzophenone 4-methacryloyloxy-4′-bromobenzophenone, 4-methacryloyloxyethoxy-4′-bromobenzophenone and mixtures thereof It can be exemplified an acrylic monomer having benzophenone structure, such as objects.
- cleavage type photoinitiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- ⁇ 4- (2-hydroxy-2 -Methyl-propionyl) benzyl ⁇ phenyl] -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglyoxylic Acid methyl, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2 Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (
- Examples of the hydrogen abstraction type photoinitiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4- (meth) Acryloyloxybenzophenone, 4- [2-((meth) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4′-methoxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis (2-phenyl) -2-oxoacetic acid) oxybisethylene, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2, 4-dimethylthioxanthate And anthraquinone, 2-methylanth
- bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine are highly sensitive to light and dissociate as a decomposition product after reaction.
- Acylphosphine oxide photoinitiators such as oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide are preferred.
- benzophenone 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4- Methoxybenzophenone, 4- (meth) acryloyloxybenzophenone, 4- [2-((meth) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4′-methoxybenzophenone, methyl 2-benzoylbenzoate, benzoyl It is preferable to use methyl formate or the like.
- the content of the photoinitiator (C) is not particularly limited.
- 0.1 to 10 parts by weight, particularly 0.5 parts by weight or more and 5 parts by weight or less, and 1 part by weight of 100 parts by weight of the (meth) acrylic acid ester (co) polymer (A) It is preferable to contain it in the ratio above or 3 parts by mass.
- sensitizer in addition to the photoinitiator (C) component.
- the sensitizer is not particularly limited, and any sensitizer that can be used as a photoinitiator can be used without any problem. Examples include aromatic amines, anthracene derivatives, anthraquinone derivatives, coumarin derivatives, thioxanthone derivatives, phthalocyanine derivatives, aromatic ketones such as benzophenone, xanthone, thioxanthone, Michler ketone, 9,10-phenanthraquinone, and derivatives thereof. be able to.
- the present pressure-sensitive adhesive composition is blended in a normal pressure-sensitive adhesive composition.
- a normal pressure-sensitive adhesive composition may contain known components.
- tackifier resins antioxidants, light stabilizers, metal deactivators, rust inhibitors, anti-aging agents, hygroscopic agents, hydrolysis inhibitors, antistatic agents, antifoaming agents, inorganic particles, etc. It is possible to appropriately contain additives.
- the pressure-sensitive adhesive composition preferably contains a rust inhibitor, and specifically, a rust inhibitor selected from the group consisting of benzotriazole, imidazole, triazole, tetrazole, thiazole and derivatives thereof is used. It is preferable to do.
- reaction catalyst a tertiary amine compound, a quaternary ammonium compound, a tin laurate compound, etc.
- a reaction catalyst may be appropriately contained as necessary.
- This double-sided PSA sheet has a glass transition temperature (Tg) in the range of ⁇ 50 ° C. to ⁇ 20 ° C.
- Tg glass transition temperature
- the glass transition temperature (Tg) of all the pressure-sensitive adhesive layers does not have to be in the above range, and the entire pressure-sensitive adhesive layer composed of a plurality of pressure-sensitive adhesive layers, that is, the book
- the glass transition temperature of the double-sided pressure-sensitive adhesive sheet may be in the above range.
- the present inventor does not simply determine the bending durability only by the numerical value of the glass transition temperature, but the relationship with the storage elastic modulus G ′ described below is important, and further, the storage described below.
- the double-sided pressure-sensitive adhesive sheet within the range of the elastic modulus G ′, it has been found that by setting the glass transition temperature relatively high, not only bending durability but also excellent workability can be expressed.
- the glass transition temperature (Tg) of the pressure-sensitive adhesive layer is preferably ⁇ 50 ° C. to ⁇ 20 ° C., and most preferably ⁇ 30 ° C. to ⁇ 25 ° C.
- the (meth) acrylic acid ester (co) polymer (A) composed of a monomer component containing a monomer appropriately selected from the monomers described above is used. Use it.
- This double-sided PSA sheet has a storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 100 ° C. within a range of 2.0 ⁇ 10 3 to 3.0 to 10 4 Pa.
- the storage elastic modulus G ′ at a low temperature ( ⁇ 20 ° C.) is set to be relatively low, and the storage elastic modulus G ′ at a high temperature (at 85 ° C.) is set to be relatively high. It was said that the bending durability could be improved, but the present inventor made use of a projection test as described below to observe this state of the double-sided pressure-sensitive adhesive sheet after the bending test. It was discovered that fold marks could be observed in a double-sided PSA sheet design having such viscoelastic properties.
- the storage elastic modulus G ′ at a low temperature ( ⁇ 20 ° C.) is set to be relatively low and the storage elastic modulus G ′ at a high temperature (at 85 ° C.) is set to be relatively high as in the past. It has been found that by designing a double-sided pressure-sensitive adhesive sheet having viscoelastic properties in a region, not only the bending durability can be improved, but also excellent workability can be expressed.
- the temperature-time conversion rule in the polymer material in order for this double-sided pressure-sensitive adhesive sheet to have bending durability, it must have resistance to repeated bending tests of tens of thousands of times, in other words, repeated operation.
- the viscoelastic behavior of the polymer material on the long side that is, the temperature-time conversion law
- the viscoelastic behavior of the polymer material on the high temperature side is It will be related.
- the present inventors have found that the viscoelastic behavior in the region of 100 ° C. greatly contributes to the bending durability by paying attention to the viscoelastic behavior on the high temperature side of the pressure-sensitive adhesive sheet and repeatedly studying it. It is.
- the double-sided PSA sheet preferably has a storage elastic modulus G ′ of 3.0 ⁇ 10 3 to 2.0 ⁇ 10 4 at a frequency of 1 Hz and a temperature of 100 ° C., more preferably 4 ⁇ 10. Most preferably, it is 2 Pa to 1.0 ⁇ 10 4 Pa.
- the double-sided PSA sheet preferably has a storage elastic modulus G ′ of 3 ⁇ 10 2 Pa to 4 ⁇ 10 4 Pa at a frequency of 1 Hz and a temperature of 50 ° C.
- the storage elastic modulus G ′ at a temperature of 100 ° C. being in the above-mentioned range, the storage elastic modulus G ′ at a temperature of 50 ° C. is in such a range, so that the bending durability can be improved over a wide temperature range. Can be increased.
- the storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of 50 ° C. is more preferably 5.0 ⁇ 10 2 Pa to 3.0 ⁇ 10 4 Pa, and 1.0 ⁇ 10 3 Pa to 1 Most preferably, it is 0.0 ⁇ 10 4 Pa.
- the double-sided PSA sheet preferably has a storage elastic modulus G ′ at a frequency of 1 Hz and a temperature of ⁇ 20 ° C. of more than 1.5 ⁇ 10 5, and is 1.6 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa. More preferably, it is more preferably 3.0 ⁇ 10 5 to 5.0 ⁇ 10 6 Pa, and most preferably 4.3 ⁇ 10 5 to 1.0 ⁇ 10 6 Pa. If the shear storage modulus (G ′) at a temperature of ⁇ 20 ° C. (low temperature) is within the above range, it is easy to impart bending resistance without impairing the tackiness and tackiness at room temperature. , The handling properties at the time of processing and pasting can be improved.
- G ′ shear storage modulus
- the storage elastic modulus G ′ can be set within the range by adjusting the irradiation amount of ultraviolet rays to the double-sided pressure-sensitive adhesive sheet.
- the irradiation amount of ultraviolet rays is preferably set to 5000 mJ / cm 2 or less, more preferably 4000 mJ / cm 2 or less, more preferably not more 3000 mJ / cm 2 or less, most preferably 2000 mJ / cm 2 or less It is.
- the dose of ultraviolet ray is preferably set to 250 mJ / cm 2 or more, more preferably to 500 mJ / cm 2 or more, and most preferably 1000 mJ / cm 2 or more.
- the double-sided PSA sheet has a storage elastic modulus at a frequency of 1 Hz and a temperature of 100 ° C. in a storage elastic modulus-temperature graph in which the horizontal axis represents temperature and the vertical axis represents the logarithm of shear storage elastic modulus (G ′).
- G ′ shear storage elastic modulus
- the flexible display must be resistant to various bending speeds in an actual use environment. Also in the bending test, it is predicted that the angular velocity at which the double-sided pressure-sensitive adhesive sheet bends constantly changes from the start of bending to the end of bending due to the structure of the bending tester, the deflection of the film laminate, and the like. Thus, in the bending test, the double-sided PSA sheet is deformed at various speeds. For this reason, in particular, the double-sided pressure-sensitive adhesive sheet used for the flexible display is required not to cause the above-mentioned “buckling” or “flow” in various assumed speed ranges.
- the adhesive material used in the flexible display is required to have stable viscoelastic behavior in various temperature ranges.
- this inventor discovers that a double-sided adhesive sheet can be equipped with high bending tolerance by making the storage elastic modulus (G ') of the shearing of the high temperature side (temperature of 100 degreeC) into a specific range.
- G ' storage elastic modulus
- the natural logarithm is preferably closer to 0.00, preferably ⁇ 0.010 or more and 0.010 or less, more preferably ⁇ 0.007 or more and 0.007 or less, Most preferably, it is -0.003 or more and 0.003 or less.
- the thickness of this double-sided PSA sheet is 10 ⁇ m or more and 150 ⁇ m or less.
- the storage elastic modulus G ′ of the double-sided pressure-sensitive adhesive sheet is within the above range and the thickness of the double-sided pressure-sensitive adhesive sheet is within the above range.
- the thickness of the double-sided PSA sheet is more preferably 20 ⁇ m or more and 120 ⁇ m or less, and most preferably 25 ⁇ m or more and 100 ⁇ m or less.
- the (meth) acrylic acid ester (co) polymer (A) and the crosslinking agent (B), the photoinitiator (C) and other optional components are mixed in a predetermined amount as necessary, and the pressure-sensitive adhesive composition is prepared. Make it.
- mixing methods are not particularly limited, and the mixing order of each component is not particularly limited.
- a heat treatment step may be put in the production of the present pressure-sensitive adhesive composition, and in this case, it is desirable to perform heat treatment after mixing each component of the present pressure-sensitive adhesive composition in advance. You may use what concentrated various mixing components into the masterbatch.
- the apparatus at the time of mixing is not restrict
- this adhesive composition can be used as a solvent-free system which does not contain a solvent as above-mentioned. By using it as a solvent-free system, the solvent does not remain, and the heat resistance and light resistance can be improved.
- the present adhesive composition prepared as described above is cured by, for example, irradiating ultraviolet rays to form a single-layer or multilayer sheet-shaped adhesive layer (adhesive layer after curing).
- An adhesive sheet can be manufactured.
- Dose of ultraviolet light as described above, it is preferable to be 5000 mJ / cm 2 or less, more preferably 4000 mJ / cm 2 or less, still more preferably 3000 mJ / cm 2 or less.
- this pressure-sensitive adhesive composition comprises a monomer component constituting the (meth) acrylic (co) polymer (A) and, if necessary, a crosslinking agent (B), a photoinitiator (C) and other optional components.
- a (meth) acrylic (co) polymer (A) is produced by irradiating light and allowing the polymerization reaction to proceed. Can also be used.
- the double-sided pressure-sensitive adhesive sheet can be used in addition to directly applying the pressure-sensitive adhesive composition to an adherend to form a single-layer or multilayer sheet-like pressure-sensitive adhesive layer (cured pressure-sensitive adhesive layer). It can also be set as the double-sided adhesive sheet with a release film which shape
- Examples of the material of the release film include a polyester film, a polyolefin film, a polycarbonate film, a polystyrene film, an acrylic film, a triacetyl cellulose film, and a fluororesin film.
- a polyester film and a polyolefin film are particularly preferable.
- the thickness of the release film is not particularly limited. Among these, from the viewpoint of processability and handling properties, it is preferably 25 ⁇ m to 500 ⁇ m, more preferably 38 ⁇ m or more and 250 ⁇ m or less, and particularly preferably 50 ⁇ m or more or 200 ⁇ m or less.
- this double-sided pressure-sensitive adhesive sheet employs a method of directly extruding the pressure-sensitive adhesive composition or a method of molding by pouring into a mold without using an adherend or a release film as described above. You can also
- the laminate of the present invention having a flexible member for configuring an image display device (hereinafter also referred to as “the present laminate”) is a laminate of the double-sided pressure-sensitive adhesive sheet having the above-described characteristics and a flexible member for configuring an image display device. It has a configuration.
- the above-described flexible member can be exemplified, among others, a surface protection panel, a touch panel, an optical film, and a substrate having a base material made of a resin film or glass that can be bent or curved, and the like.
- a combination of two or more of the group consisting of organic EL (Electronic Luminescent) display panels is preferable.
- it is preferable that at least one flexible member for constructing an image display device is a flexible member, and in particular, a flexible organic EL (Electronic Luminescent) display panel is preferable.
- an organic EL display panel / this double-sided adhesive sheet / release film, a touch panel / this double-sided adhesive sheet / release film, a surface protection panel / this double-sided adhesive sheet / release film, an optical film / A double-sided pressure-sensitive adhesive sheet / release film can be cited as a suitable example.
- an organic EL display panel / a double-sided pressure-sensitive adhesive sheet / touch panel an organic EL display panel / a double-sided pressure-sensitive adhesive sheet / a surface protection panel
- Organic EL display panel / double-sided pressure-sensitive adhesive sheet / touch panel / double-sided pressure-sensitive adhesive sheet / surface protective panel Organic EL display panel / double-sided pressure-sensitive adhesive sheet / touch panel / double-sided pressure-sensitive adhesive sheet / surface protective panel, optical film / double-sided pressure-sensitive adhesive sheet / touch panel, optical film / double-sided pressure-sensitive adhesive sheet / touch panel / double-sided pressure-sensitive adhesive sheet / surface protective panel Either can be mentioned as a suitable example.
- this laminated body has a curved surface shape. Specifically, the case where the external shape of this laminated body is circular arc shape or another curved surface can be mentioned.
- a laminate including a surface protection panel having an arc shape, a catenary line shape, a parabola shape, a Bezier curve shape, a spline curve shape, a deflection curve, and other curved surface shapes can be given.
- this double-sided pressure-sensitive adhesive sheet has high bending durability, it can be suitably used for bonding two flexible members for constituting an image display device that can be bent or bent.
- the above-described flexible member can be exemplified, among others, a surface protection panel, a touch panel, an optical film, and a substrate having a base material made of a resin film or glass that can be bent or curved, and the like.
- a combination of two or more of the group consisting of organic EL display panels is preferable.
- it is preferable that at least one flexible member for constructing an image display device is a flexible member, and in particular, a flexible organic EL (Electronic Luminescent) display panel is preferable.
- the laminate forming kit of the present invention for forming the laminate (hereinafter also referred to as “this kit”) includes a flexible member for constituting an image display device and a double-sided pressure-sensitive adhesive sheet for bonding to the flexible member. And the double-sided pressure-sensitive adhesive sheet is the double-sided pressure-sensitive adhesive sheet described above.
- the laminate forming kit for forming the laminate is a set of materials for forming the laminate, and is a combination in a state where the materials are not joined to each other.
- the above-described flexible member can be exemplified, among others, a surface protection panel, a touch panel, an optical film, and a substrate having a base material made of a resin film or glass that can be bent or curved, and the like.
- a combination of two or more of the group consisting of organic EL (Electronic Luminescent) display panels is preferable.
- it is preferable that at least one flexible member for constructing an image display device is a flexible member, and in particular, a flexible organic EL (Electronic Luminescent) display panel is preferable.
- a thin flat product with an extremely small thickness and an arbitrarily limited maximum thickness usually supplied in the form of a roll (Japanese Industrial Standard JISK6900).
- JISK6900 Japanese Industrial Standard
- the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
- the thickness of the double-sided PSA sheets 1 to 16 produced in Examples and Comparative Examples is less than 500 ⁇ m, it was adjusted by laminating the PSA layers until each became 500 ⁇ m.
- the double-sided PSA sheets 1 to 16 produced in Examples and Comparative Examples were laminated until the PSA layer had a thickness of 1 mm, and this was used as a sample for measuring the glass transition temperature.
- a copper thin film having a thickness of 50 mm was formed on a glass substrate (45 mm ⁇ 45 mm) to produce a glass substrate for a copper thin film discoloration test.
- the release film on one side of the pressure-sensitive adhesive sheets produced in the above Examples and Comparative Examples was peeled off, and a PET film (trade name “Cosmo Shine A4100”, 125 ⁇ m, manufactured by Toyobo Co., Ltd.) was attached to the exposed surface with a hand roller.
- a PET film trade name “Cosmo Shine A4100”, 125 ⁇ m, manufactured by Toyobo Co., Ltd.
- the remaining release film was peeled off, and the pressure-sensitive adhesive sheet was attached to a copper glass substrate for copper thin film discoloration test with a hand roller.
- the sample for copper thin film discoloration test (glass substrate for copper thin film discoloration test with adhesive sheet) is stored for about 1 hour in an environment of 85 ° C. and 85% RH, and after storage, the color of the sample for copper thin film discoloration test is stored. The change was visually confirmed, and the case where the gray color derived from the copper thin film remained was judged as ⁇ (good, good), and the one that was almost transparent was judged as x (bad, poor).
- Acrylic ester copolymer A 100 parts by weight of the product name “Ezacure TZT” (4-methylbenzophenone) manufactured by Nippon Sebel Hegner as photoinitiator: 0.6 parts by weight, and Osaka Organic Chemical as a crosslinking monomer Trade name “Biscoat V260 (1,9-nonanediol diacrylate)” manufactured by the company was added in an amount of 1.0 part by weight to obtain an ultraviolet curable pressure-sensitive adhesive composition 1.
- Ezacure TZT (4-methylbenzophenone) manufactured by Nippon Sebel Hegner as photoinitiator: 0.6 parts by weight
- Osaka Organic Chemical as a crosslinking monomer
- Trade name “Biscoat V260 (1,9-nonanediol diacrylate)” manufactured by the company was added in an amount of 1.0 part by weight to obtain an ultraviolet curable pressure-sensitive adhesive composition 1.
- the acrylic ester copolymer polymer A was composed of n-butyl acrylate: 78.4% by mass, 2-ethylhexyl acrylate: 19.6% by mass, and acrylic acid: 2.0% by mass. According to GPC measurement, Mw of the acrylate copolymer polymer A is 413,000, Mn is 145,000, Mw / Mn is 2.9, and the theoretical Tg is ⁇ 57 ° C. is there.
- the pressure-sensitive adhesive composition 1 is sandwiched between a release film made of polyethylene terephthalate (PET) having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, and hot-melt molded into a sheet shape having a thickness of 0.1 mm.
- PET polyethylene terephthalate
- the double-sided pressure-sensitive adhesive sheet 1 was obtained by irradiating the release film with ultraviolet rays having an integrated light quantity of 1000 mJ / cm 2 .
- Example 2 The pressure-sensitive adhesive composition 1 used in Example 1 was sandwiched between a polyethylene terephthalate release film having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, hot-melt molded into a sheet having a thickness of 0.1 mm, and high-pressure mercury The double-sided pressure-sensitive adhesive sheet 2 was obtained by irradiating ultraviolet rays with an integrated light amount of 500 mJ / cm 2 through the release film using a lamp.
- Example 3 The pressure-sensitive adhesive composition 1 used in Example 1 was sandwiched between a polyethylene terephthalate release film having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, hot-melt molded into a sheet having a thickness of 0.1 mm, and high-pressure mercury The double-sided pressure-sensitive adhesive sheet 3 was obtained by irradiating ultraviolet rays with an integrated light amount of 1500 mJ / cm 2 through the release film using a lamp.
- Example 4 The pressure-sensitive adhesive composition 1 used in Example 1 was sandwiched between a polyethylene terephthalate release film having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, and hot-melt molded into a sheet having a thickness of 0.075 mm.
- the double-sided pressure-sensitive adhesive sheet 4 was obtained by irradiating ultraviolet rays with an integrated light quantity of 1000 mJ / cm 2 through the release film using a lamp.
- Example 5 The pressure-sensitive adhesive composition 1 used in Example 1 was sandwiched between a polyethylene terephthalate release film having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, and hot-melt molded into a sheet having a thickness of 0.025 mm.
- the double-sided pressure-sensitive adhesive sheet 5 was obtained by irradiating ultraviolet rays with an integrated light quantity of 1000 mJ / cm 2 through the release film using a lamp.
- Acrylic ester copolymer B 100 parts by weight, photo-initiator “Ezacure TZT” (4-methylbenzophenone): 0.6 parts by weight as a photoinitiator and Osaka Organic Chemical as a crosslinking monomer Trade name “Biscoat V260 (1,9-nonanediol diacrylate)” manufactured by the company: 1.0 part by weight and trade name “BT-120” (1,2,3- Benzotriazole): 0.5 part was added to obtain UV curable adhesive composition 2.
- the pressure-sensitive adhesive composition 2 is sandwiched between a release film made of polyethylene terephthalate (PET) having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, and is hot-melt molded into a sheet shape having a thickness of 0.1 mm.
- PET polyethylene terephthalate
- the double-sided pressure-sensitive adhesive sheet 6 was obtained by irradiating the release film with ultraviolet rays having an integrated light quantity of 1000 mJ / cm 2 .
- Example 7 A double-sided PSA sheet 7 was obtained in the same manner as in Example 2 except that the PSA composition 2 was used.
- Example 8 The pressure-sensitive adhesive composition 2 used in Example 6 was sandwiched between a polyethylene terephthalate release film having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, and hot-melt molded into a sheet having a thickness of 0.1 mm, and high-pressure mercury A double-sided pressure-sensitive adhesive sheet 8 was obtained by irradiating ultraviolet rays with an integrated light quantity of 2000 mJ / cm 2 through the release film using a lamp.
- Example 9 A double-sided PSA sheet 9 was obtained in the same manner as in Example 4 except that the PSA composition 2 was used.
- Example 10 A double-sided PSA sheet 10 was obtained in the same manner as in Example 5 except that the PSA composition 2 was used.
- Acrylic ester copolymer C 100 parts by weight of the product name “Ezacure TZT” (4-methylbenzophenone): 1.5 parts by weight as a photoinitiator, and a organic monomer as a crosslinking monomer.
- the pressure-sensitive adhesive composition 3 is sandwiched between a release film made of polyethylene terephthalate (PET) having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, hot-melt molded into a sheet shape having a thickness of 100 ⁇ m, and a high-pressure mercury lamp is used.
- PET polyethylene terephthalate
- the double-sided PSA sheet 11 was obtained by irradiating the release film with ultraviolet rays having an integrated light quantity of 1000 mJ / cm 2 .
- Example 1 The pressure-sensitive adhesive composition 1 used in Example 1 was sandwiched between a polyethylene terephthalate release film having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, hot-melt molded into a sheet having a thickness of 0.1 mm, and high-pressure mercury
- the double-sided pressure-sensitive adhesive sheet 12 was obtained by irradiating ultraviolet rays with an integrated light amount of 250 mJ / cm 2 through the release film using a lamp.
- Example 2 The pressure-sensitive adhesive composition 1 used in Example 1 was sandwiched between a polyethylene terephthalate release film having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, hot-melt molded into a sheet having a thickness of 0.1 mm, and high-pressure mercury
- the double-sided pressure-sensitive adhesive sheet 13 was obtained by irradiating ultraviolet rays with an integrated light amount of 2500 mJ / cm 2 through the release film using a lamp.
- Acrylic ester copolymer D 100 parts by weight, UV curing type by adding 0.15 parts by weight of a product name “Ezacure TZT” (4-methylbenzophenone) manufactured by Nippon Siebel Hegner as a photoinitiator Of PSA composition 4 was obtained.
- Ezacure TZT (4-methylbenzophenone) manufactured by Nippon Siebel Hegner
- the acrylic ester copolymer polymer D is composed of 75 parts by mass of 2-ethylhexyl acrylate (homopolymer Tg-70 ° C.), 20 parts by mass of vinyl acetate (homopolymer Tg + 32 ° C.), and acrylic acid (homopolymer). Tg + 106 ° C.) 5 parts by mass, and the acrylic ester copolymer polymer according to GPC measurement has a Mw of 446000, Mn of 97800, and Mw / Mn of 4.6. The theoretical Tg is ⁇ 50 ° C.
- the pressure-sensitive adhesive composition 4 is sandwiched between a polyethylene terephthalate release film having a thickness of 75 ⁇ m and a thickness of 100 ⁇ m, hot-melt molded into a sheet having a thickness of 0.1 mm, and the high-pressure mercury lamp is used to form the pressure-sensitive adhesive composition 4.
- the double-sided pressure-sensitive adhesive sheet 14 was obtained by irradiating the release film with ultraviolet rays having an integrated light quantity of 2000 mJ / cm 2 .
- This pressure-sensitive adhesive solution is applied to the release surface of a 38 ⁇ m-thick silicone release PET film using a hot melt coater so as to have a thickness of 100 ⁇ m, and is adhered and laminated to the 50 ⁇ m-thick silicone release PET film.
- the film was aged for 7 days at room temperature (23 ° C.) and sufficiently crosslinked to obtain a double-sided PSA sheet 15.
- Acrylic ester copolymer D 100 parts by mass of UV curing resin pentaerythritol acrylate (trade name “PETIA” manufactured by Daicel Cytec Co., Ltd.) 20 parts by mass as a crosslinking monomer and 4-methylbenzophenone as a photoinitiator
- a resin composition for an intermediate resin layer was prepared by mixing 1.5 parts by mass.
- the resin composition for intermediate resin layer was heated and melted on a 75 ⁇ m-thick polyethylene terephthalate film that had been peeled off, and coated with an applicator to a thickness of 50 ⁇ m. The film was coated.
- An intermediate resin layer (A-1) was produced by irradiating the polyethylene terephthalate film with ultraviolet rays having an integrated light quantity of 2000 mJ / cm 2 by a high pressure mercury lamp to crosslink the intermediate layer resin composition.
- a pressure-sensitive adhesive composition was prepared by mixing 2.0 parts by mass of 4-methylbenzophenone as a photoinitiator as a photoinitiator with 100 parts by mass of the acrylic ester copolymer D. This pressure-sensitive adhesive composition was heated and melted and subjected to a release treatment, on a polyethylene terephthalate film having a thickness of 75 ⁇ m, applied in a sheet shape so as to have a thickness of 25 ⁇ m, and subjected to a release treatment. A polyethylene terephthalate film having a thickness of 38 ⁇ m was coated.
- the pressure-sensitive adhesive layer (B-1) was produced by irradiating the polyethylene terephthalate film with ultraviolet rays having an accumulated light quantity of 2000 mJ / cm 2 by a high-pressure mercury lamp to crosslink the pressure-sensitive adhesive composition.
- the pressure sensitive adhesive layer (B-1 ′) was formed in the same manner as the pressure sensitive adhesive layer (B-1) except that the coated substrate was changed to a polyethylene terephthalate film having a thickness of 50 ⁇ m which had been subjected to a release treatment. Produced.
- the PET film on both sides of the intermediate resin layer (A-1) is peeled and removed sequentially, and the PET film on one side of the pressure sensitive adhesive layers (B-1) and (B-1 ′) is peeled off to expose the adhesive film.
- the surfaces were sequentially bonded to both surfaces of (A-1) with a laminator to prepare a multilayer double-sided pressure-sensitive adhesive sheet 16 (thickness: 100 ⁇ m).
- the double-sided pressure-sensitive adhesive sheet 12 of Comparative Example 1 has a storage elastic modulus G ′ that is not within a predetermined range and is too low, and thus peeling occurred in the bending test result.
- the double-sided pressure-sensitive adhesive sheet 13 of Comparative Example 2 has a storage elastic modulus G ′ that is not within a predetermined range and is too high.
- the double-sided pressure-sensitive adhesive sheet 14 of Comparative Example 3 and the double-sided pressure-sensitive adhesive sheet 15 of Comparative Example 4 did not fall within the predetermined range and were too high, so that bending occurred in the bending test result.
- the double-sided pressure-sensitive adhesive sheet 16 of Comparative Example 5 has a glass transition temperature that is not within a predetermined range and is too high.
- a phenomenon such as bulging in the vicinity of the bent portion was also observed in the bending test result.
- a double-sided pressure-sensitive adhesive sheet suitable for laminating a flexible member that can be bent or bent, and the double-sided pressure-sensitive adhesive sheet is bonded to a flexible display without being folded or peeled off. It can also be applied to.
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Abstract
Description
このように、より実使用環境下に近い条件下において、折れや剥がれが発生することのない、高い折り曲げ耐性を有する両面粘着シートが求められる。
本発明の両面粘着シート(以下「本両面粘着シート」とも称する。)は、基材レスであって、少なくとも次の(1)~(4)の特性を有する。
なお、基材レスの両面粘着シートとは、支持体となる基材を有さず、粘着剤層だけを有する両面粘着シートをいう。
また、「流れ」とは、屈曲試験後に屈曲線の周辺の粘着シートが盛り上がって見える現象である。
また、前記「流れ」は、せん断貯蔵弾性率(G’)が低く、上下のフィルムによって挟まれた粘着シートが屈曲により押し出され、これが蓄積することによって生じる現象であることを明らかにした。
これらの中でも、少なくとも1つの画像表示装置構成用部材が、フレキシブル部材であることが好ましく、とりわけ、フレキシブル有機EL(Electronic Luminescent)ディスプレイパネルであることが好ましい。
本両面粘着シートは、少なくとも(メタ)アクリル酸エステル(共)重合体(A)を含有する粘着剤組成物(以下「本粘着剤組成物」という。)から形成される。
上記(メタ)アクリル酸エステル(共)重合体(A)としては、例えばアルキル(メタ)アクリレートの単独重合体の他、これと共重合可能なモノマー成分を重合することにより得られる共重合体を挙げることができる。
中でも、(メタ)アクリル酸エステル(共)重合体(A)が、2成分以上の共重合成分を含み、少なくとも1つの共重合成分が、アルキル(メタ)アクリレート及び/又は下記共重合性モノマーA~Hの何れかであることが好ましい。
(2)また、上記共重合性モノマーAを含まず、共重合性モノマーB又はEの何れかもしくは両方を含むことが特に好ましい。共重合性モノマーB又はEの何れか若しくは両方を含むことで、耐腐食特性、接着性及び耐湿熱白化特性の兼備が可能となる。
なお、「共重合性モノマーAを含まない」とは、“実質的に含まない”の意であり、完全に含まない場合のみならず、(メタ)アクリル酸エステル(共)重合体中に、共重合性モノマーAが0.5質量%未満、好ましくは、0.1質量%未満で含むことを包含する。
(3)さらに、上記アルキル(メタ)アクリレートの中でも、(メタ)アクリロイル基と3級炭素原子が結合したアルキル(メタ)アクリートが好ましい。このようなアルキル(メタ)アクリレートを用いることで、本両面粘着シートの高温側(100℃~150℃)のせん断貯蔵弾性率(G’)をフラット化し易くなる。
これらは1種又は2種以上を組み合わせてもよい。
(メタ)アクリル酸エステル(共)重合体(A)が、重合性モノマーAを含むことにより、Tgを低く維持することができるため、共重合性モノマーBの選択の幅が広がり、折り曲げ耐性と、耐湿熱白化性や接着力、耐久性などの基本的な粘着性能とのバランス化が容易になる。
なお、本粘着剤組成物が無溶剤系であって、ホットメルトによって製膜する場合、上記(メタ)アクリル酸エステル(共)重合体(A)の質量平均分子量は、10万~90万であることが好ましく、中でも15万以上或いは75万以下であることがより好ましく、20万以上或いは60万以下であることがもっとも好ましい。
(メタ)アクリル酸エステル(共)重合体(A)の質量平均分子量が、上記範囲にあることで、ホットメルト製膜が可能となる。
以上の点から、(メタ)アクリル酸エステル(共)重合体(A)の質量平均分子量は、中でも15万~75万であることがより好ましく、その中でも20万以上或いは6万以下であることが最も好ましい。
本粘着剤組成物は、上記(メタ)アクリル酸エステル(共)重合体(A)の他、架橋剤(B)を含有するものであることが好ましい。
本粘着剤組成物は、上記(メタ)アクリル酸エステル(共)重合体(A)及び架橋剤(B)の他、光開始剤(C)を含有するものであることが好ましい。
本粘着剤組成物は、上述した(メタ)アクリル酸エステル(共)重合体(A)、架橋剤(B)及び光開始剤(C)の他にも、通常の粘着組成物に配合されている公知の成分を含有してもよい。例えば粘着付与樹脂、酸化防止剤、光安定化剤、金属不活性化剤、防錆剤、老化防止剤、吸湿剤、加水分解防止剤、帯電防止剤、消泡剤、無機粒子などの各種の添加剤を適宜含有させることが可能である。本粘着剤組成物は、中でも、防錆剤を含有することが好ましく、具体的には、ベンゾトリアゾール、イミダゾール、トリアゾール、テトラゾール、チアゾール及びこれらの誘導体からなる群より選択される防錆剤を使用することが好ましい。
本両面粘着シートは、ガラス転移温度(Tg)が、-50℃~-20℃の範囲内にある。
なお、本両面粘着シートが多層の場合、各層全ての粘着剤層のガラス転移温度(Tg)が上記範囲にある必要はなく、複数の粘着剤層から構成された粘着剤層全体、すなわち、本両面粘着シートのガラス転移温度が上記範囲にあれば良い。
本両面粘着シートは、周波数1Hz、温度100℃における貯蔵弾性率G’が、2.0×103~3.0~104Paの範囲内にあるものである。
すなわち、本両面粘着シートが、折り曲げ耐久性を有するには、何万回レベルの繰り返し折り曲げ試験、言い換えると、繰り返し動作に対する耐性を備えなければならない。
このように、高分子材料が繰り返し動作に対する耐性を具備する為には、高分子材料の長時間側の粘弾性挙動、すなわち温度-時間換算則では、高分子材料の高温側の粘弾性挙動が関係してくることになる。
そして、本発明者らは、本粘着シートの高温側の粘弾性挙動に着目して、検討を重ねることにより、温度100℃の領域における粘弾性挙動が折り曲げ耐久性に大きく寄与することを見出したのである。
温度-20℃(低温)でのせん断貯蔵弾性率(G’)が上記の範囲内にあれば、室温での粘着性やタック性を損なうことなく折り曲げ耐性を付与しやすいため、接着力や耐久性、加工時や貼合時のハンドリング性が向上する等の利点を有することができる。
また、上記と同様の理由から、紫外線の照射量は、250mJ/cm2以上とすることが好ましく、500mJ/cm2以上とすることがさらに好ましく、1000mJ/cm2以上とすることが最も好ましい。
フレキシブルディスプレイは、実使用環境下においては、様々な折り曲げ速度に対する耐性を具備しなければならない。
また、屈曲試験においても、屈曲開始から屈曲終了時までは屈曲試験機の構造、フィルム積層体のたわみ等によって、両面粘着シートが屈曲する角速度は常に変化していることが予測される。
このように、屈曲試験においては、両面粘着シートは、さまざまな速度で変形する。このため特に、フレキシブルディスプレイに用いられる両面粘着シートには、想定される様々な速度領域において、上述した「座屈」や「流れ」が生じないことが求められる。
本両面粘着シートの厚みは、10μm以上150μm以下である。
本両面粘着シートの製造方法としては、公知の製造方法を採用することができる。以下に、その一例を示す。
また、本粘着剤組成物は、上述のとおり、溶剤を含まない無溶剤系として使用することできる。無溶剤系として使用することで溶剤が残存せず、耐熱性及び耐光性が高まるという利点も備えることができる。
画像表示装置構成用フレキシブル部材を有する本発明の積層体(以下「本積層体」とも称する。)は、上述した特性を有する本両面粘着シートと、画像表示装置構成用フレキシブル部材とが積層された構成を有するものである。
これらの中でも、少なくとも1つの画像表示装置構成用フレキシブル部材が、フレキシブル部材であることが好ましく、とりわけ、フレキシブル有機EL(Electronic Luminescent)ディスプレイパネルであることが好ましい。
さらに、本積層体は、曲面形状を有していることが好ましい。具体的には、本積層体の外形が円弧状やその他の曲面である場合を挙げることができる。さらに具体的には、円弧状、懸垂線状、放物線状、ベジェ曲線状、スプライン曲線状、たわみ曲線、その他の曲面形状を有する、表面保護パネルを備えた積層体を挙げることができる。
画像表示装置構成用フレキシブル部材の貼合において、上述した本両面粘着シートを用いると、該部材を折り曲げて使用した場合であっても、粘着材がはみ出したり、凝集破壊したりすることなく、また、両面粘着シートに折れ痕が付くこともない。
これらの中でも、少なくとも1つの画像表示装置構成用フレキシブル部材が、フレキシブル部材であることが好ましく、とりわけ、フレキシブル有機EL(Electronic Luminescent)ディスプレイパネルであることが好ましい。
本積層体を形成するための本発明の積層体形成キット(以下、「本キット」とも称する)は、画像表示装置構成用フレキシブル部材と、該フレキシブル部材に貼合するための両面粘着シートとを有し、該両面粘着シートが上述した本両面粘着シートであることを特徴とするものである。
本積層体を形成するための積層体形成キットとは、本積層体を形成するための材料一式の意味であり、材料同士は接合されていない状態での組み合わせである。
これらの中でも、少なくとも1つの画像表示装置構成用フレキシブル部材が、フレキシブル部材であることが好ましく、とりわけ、フレキシブル有機EL(Electronic Luminescent)ディスプレイパネルであることが好ましい。
本明細書において「X~Y」(X,Yは任意の数字)と表現する場合、特にことわらない限り「X以上Y以下」の意と共に、「好ましくはXより大きい」或いは「好ましくはYより小さい」の意も包含する。
また、「X以上」(Xは任意の数字)或いは「Y以下」(Yは任意の数字)と表現した場合、「Xより大きいことが好ましい」或いは「Y未満であることが好ましい」旨の意図も包含する。
一般的に「シート」とは、JISにおける定義上、薄く、その厚さが長さと幅のわりには小さく平らな製品をいい、一般的に「フィルム」とは、長さ及び幅に比べて厚さが極めて小さく、最大厚さが任意に限定されている薄い平らな製品で、通常、ロールの形で供給されるものをいう(日本工業規格JISK6900)。しかし、シートとフィルムの境界は定かでなく、本発明において文言上両者を区別する必要がないので、本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。
なお、以下の実施例及び比較例において、下記の物性測定、処理については、下記条件で行った。
(1)実施例及び比較例で作製した両面粘着シート1~16を、50mm×100mmに裁断し、PETフィルム厚み0.38mm×50mm×100mmに貼合する。
(2)貼合したサンプルをPET(0.1mm×50mm×100mm)と貼合した積層体を作製する。
(3)PET38μmを内側として、作製された積層体を、折り曲げ試験機DLDMLH-FS(ユアサシステム製)を用いて、次の試験条件で試験を行う。
・曲率半径r=3mm
・試験速度=60rpm
・試験回数=10万回
(4)試験後の積層体を目視観察し、両面粘着シートに折れ痕のついているものと、被着体に両面粘着シートの剥がれがあるものを「×」、目視観察で変化のないものを「○」として評価した。
投影機とスクリーンの間に折り曲げ試験後のサンプルを設置し、スクリーンに映った折り曲げ試験後のサンプルに歪みの有無で、両面粘着シートに折れ痕のついているものと、被着体からの両面粘着シートの剥がれを判別した。
実施例及び比較例で作製した両面粘着シート1~16の貯蔵弾性率G’は、レオメトリックス社製の粘弾性測定装置「ダイナミックアナライザー RDAII」を用いて剪断法により、次の条件で測定した。
・治具:Φ25mmパラレルプレート
・歪み:0.5%
・周波数:1Hz
・温度:-70~200℃(-70℃から昇温速度3℃/minで測定)
・試料厚さ:500μm
・治具:Φ25mmパラレルプレート
・歪み:0.5%
・周波数:1Hz
ガラス基板(45mm×45mm)上に、厚さ50Åの銅薄膜を形成し、銅薄膜変色試験用ガラス基板を作製した。
アクリル酸エステル共重合体ポリマーA:100重量部に対し、光開始剤として日本シイベルヘグナー社製の商品名「エザキュア TZT」(4-メチルベンゾフェノン):0.6重量部と、架橋モノマーとして大阪有機化学社製の商品名「ビスコートV260(1,9-ノナンジオールジアクリレート)」:1.0重量部とを添加して紫外線硬化型の粘着剤組成物1を得た。
実施例1で使用した粘着剤組成物1を、厚さ75μmと厚さ100μmのポリエチレンテレフタレート製の離型フィルムとの間に挟んで、厚み0.1mmのシート状にホットメルト成形し、高圧水銀ランプを用いて、該離型フィルム越しに積算光量500mJ/cm2の紫外線を照射させて両面粘着シート2を得た。
実施例1で使用した粘着剤組成物1を、厚さ75μmと厚さ100μmのポリエチレンテレフタレート製の離型フィルムとの間に挟んで、厚み0.1mmのシート状にホットメルト成形し、高圧水銀ランプを用いて、該離型フィルム越しに積算光量1500mJ/cm2の紫外線を照射させて両面粘着シート3を得た。
実施例1で使用した粘着剤組成物1を、厚さ75μmと厚さ100μmのポリエチレンテレフタレート製の離型フィルムとの間に挟んで、厚み0.075mmのシート状にホットメルト成形し、高圧水銀ランプを用いて、該離型フィルム越しに積算光量1000mJ/cm2の紫外線を照射させて両面粘着シート4を得た。
実施例1で使用した粘着剤組成物1を、厚さ75μmと厚さ100μmのポリエチレンテレフタレート製の離型フィルムとの間に挟んで、厚み0.025mmのシート状にホットメルト成形し、高圧水銀ランプを用いて、該離型フィルム越しに積算光量1000mJ/cm2の紫外線を照射させて両面粘着シート5を得た。
アクリル酸エステル共重合体ポリマーB:100重量部に対し、光開始剤として日本シイベルヘグナー社製の商品名「エザキュア TZT」(4-メチルベンゾフェノン):0.6重量部と、架橋モノマーとして大阪有機化学社製の商品名「ビスコートV260(1,9-ノナンジオールジアクリレート)」:1.0重量部と、防錆剤として城北化学社製の商品名「BT-120」(1,2,3-ベンゾトリアゾール):0.5部とを添加して紫外線硬化型の粘着剤組成物2を得た。
前記粘着剤組成物2を用いた以外は、実施例2と同様にして両面粘着シート7を得た。
実施例6で使用した粘着剤組成物2を、厚さ75μmと厚さ100μmのポリエチレンテレフタレート製の離型フィルムとの間に挟んで、厚み0.1mmのシート状にホットメルト成形し、高圧水銀ランプを用いて、該離型フィルム越しに積算光量2000mJ/cm2の紫外線を照射させて両面粘着シート8を得た。
前記粘着剤組成物2を用いた以外は、実施例4と同様にして両面粘着シート9を得た。
前記粘着剤組成物2を用いた以外は、実施例5と同様にして両面粘着シート10を得た。
アクリル酸エステル共重合体ポリマーC:100重量部に対し、光開始剤として日本シイベルヘグナー社製の商品名「エザキュア TZT」(4-メチルベンゾフェノン):1.5重量部と、架橋モノマーとして大阪有機化学社製の商品名「ビスコートV260(1,9-ノナンジオールジアクリレート)」:1.5重量部とを添加して紫外線硬化型の粘着剤組成物3を得た。
実施例1で使用した粘着剤組成物1を、厚さ75μmと厚さ100μmのポリエチレンテレフタレート製の離型フィルムとの間に挟んで、厚み0.1mmのシート状にホットメルト成形し、高圧水銀ランプを用いて、該離型フィルム越しに積算光量250mJ/cm2の紫外線を照射させて両面粘着シート12を得た。
実施例1で使用した粘着剤組成物1を、厚さ75μmと厚さ100μmのポリエチレンテレフタレート製の離型フィルムとの間に挟んで、厚み0.1mmのシート状にホットメルト成形し、高圧水銀ランプを用いて該離型フィルム越しに積算光量2500mJ/cm2の紫外線を照射させて両面粘着シート13を得た。
アクリル酸エステル共重合体ポリマーD:100重量部に対し、光開始剤として日本シイベルヘグナー社製の商品名「エザキュア TZT」(4-メチルベンゾフェノン):0.15重量部とを添加して紫外線硬化型の粘着剤組成物4を得た。
アクリル系接着剤(商品名SKダイン1882:綜研化学社製)1000重量部に対して、イソシアネート系硬化剤(商品名L-45:綜研化学社製)1.85重量部及びエポキシ系硬化剤(商品名E-5XM:綜研化学社製)0.5重量部を均一混合して粘着剤溶液を調製した。
アクリル酸エステル共重合体ポリマーD:100質量部に対して、架橋モノマーとして紫外線硬化樹脂ペンタエリスリトールアクリレート(ダイセルサイテック社製の商品名「PETIA」)20質量部と、光開始剤として4-メチルベンゾフェノン1.5質量部を混合して中間樹脂層用樹脂組成物を調製した。
前記ポリエチレンテレフタレートフィルム越しに、高圧水銀ランプにて積算光量2000mJ/cm2の紫外線を照射して前記中間層用樹脂組成物を架橋させ、中間樹脂層(A-1)を作製した。
また、塗工基材を、剥離処理した、厚み50μmのポリエチレンテレフタレートフィルムに変えた以外は、上記感圧粘着剤層(B-1)と同様に感圧粘着剤層(B-1’)を作製した。
2 折り曲げ試験後のサンプル
3 スクリーン
4 折れ痕
Claims (42)
- 屈曲又は湾曲可能な画像表示装置構成用フレキシブル部材と、基材レスの両面粘着シートとを有する積層体であって、
前記両面粘着シートは、(メタ)アクリル酸エステル(共)重合体(A)を含有する粘着剤組成物から形成され、厚みが10μm以上150μm以下であり、かつ、動的粘弾性のTanδピーク温度で定義される、ガラス転移温度(Tg)が-50℃~-20℃の範囲内にあり、かつ、周波数1Hz、温度100℃における貯蔵弾性率G’が、2.0×103~3.0×104Paの範囲内にあることを特徴とする、積層体。 - 前記両面粘着シートは、横軸に温度、縦軸にせん断貯蔵弾性率(G’)の対数をプロットした貯蔵弾性率-温度グラフにおいて、周波数1Hz、温度100℃における貯蔵弾性率G’(100)と、周波数1Hz、温度150℃における貯蔵弾性率G’(150)との2点間を通る指数曲線を作成したとき、該指数曲線の底の自然対数が-0.010以上となることを特徴とする、請求項1記載の積層体。
- 前記粘着剤組成物は、さらに、架橋剤(B)を含有する、請求項1又は2記載の積層体。
- 前記粘着剤組成物は、さらに、光開始剤(C)を含有する、請求項1~3の何れか一項記載の積層体。
- 前記(メタ)アクリル酸エステル(共)重合体(A)が、カルボキシル基含有モノマーを(共)重合成分として含まず、かつ、(共)重合成分として、少なくとも水酸基含有モノマー又はアミド基含有モノマーのいずれか若しくは両方を含む、請求項1~4の何れか一項記載の積層体。
- 前記(メタ)アクリル酸エステル(共)重合体(A)が、(共)重合成分として、(メタ)アクリロイル基と3級炭素原子が結合した(メタ)アクリル酸アルキルエステルを含む、請求項1~5の何れか一項記載の積層体。
- 前記光開始剤(C)が、水素引抜型の光開始剤である、請求項4~6の何れかに記載の積層体。
- 前記(メタ)アクリル酸エステル(共)重合体が、光を受光するとラジカル活性種を発生する単量体を含んでなる、請求項1~7の何れか一項記載の積層体。
- 前記両面粘着シートは、周波数1Hz、温度50℃における貯蔵弾性率G’が、3.0×102~4.0×104Paの範囲内にある、請求項1~8の何れか一項記載の積層体。
- 前記画像表示装置構成用部材は、表面保護パネル、タッチパネル、光学フィルム及び有機EL(Electronic Luminescent)ディスプレイパネルからなる群のうち2種類以上の組み合わせである、請求項1~9の何れか一項記載の積層体。
- 曲面形状を有している、請求項1~10の何れか一項記載の積層体。
- 請求項1~11の何れか一項記載の積層体を備えた、フレキシブルディスプレイ。
- 基材レスの両面粘着シートであって、
(メタ)アクリル酸エステル(共)重合体(A)を含有する粘着剤組成物から形成され、 動的粘弾性のTanδピーク温度で定義される、ガラス転移温度(Tg)が、-50℃~-20℃の範囲内にあり、かつ、周波数1Hz、温度100℃における貯蔵弾性率G’が、2.0×103~3.0×104Paの範囲内にあり、かつ、厚みが10μm以上150μm以下であることを特徴とする、両面粘着シート。 - 横軸に温度、縦軸にせん断貯蔵弾性率(G’)の対数をプロットした貯蔵弾性率-温度グラフにおいて、周波数1Hz、温度100℃における貯蔵弾性率G’(100)と、周波数1Hz、温度150℃における貯蔵弾性率G’(150)との2点間を通る指数曲線を作成したとき、該指数曲線の底の自然対数が-0.010以上となることを特徴とする、請求項13記載の両面粘着シート。
- 前記粘着剤組成物は、さらに、架橋剤(B)を含有する、請求項13又は14記載の両面粘着シート。
- 前記粘着剤組成物は、さらに、光開始剤(C)を含有する、請求項13~15の何れか一項記載の両面粘着シート。
- 前記(メタ)アクリル酸エステル(共)重合体(A)が、カルボキシル基含有モノマーを(共)重合成分として含まず、かつ、(共)重合成分として、少なくとも水酸基含有モノマー又はアミド基含有モノマーのいずれか若しくは両方を含む、請求項13~16の何れか一項記載の両面粘着シート。
- 前記(メタ)アクリル酸エステル(共)重合体(A)が、(共)重合成分として、(メタ)アクリロイル基と3級炭素原子が結合した(メタ)アクリル酸アルキルエステルを含む、請求項13~17の何れか一項記載の両面粘着シート。
- 前記光開始剤(C)が、水素引抜型の光開始剤である、請求項16~18の何れか一項記載の両面粘着シート。
- 前記(メタ)アクリル酸エステル(共)重合体が、光を受光するとラジカル活性種を発生する単量体を含んでなる、請求項13~19の何れか一項記載の両面粘着シート。
- 周波数1Hz、温度50℃における貯蔵弾性率G’が、3.0×102~4.0×104Paの範囲内にある、請求項13~20の何れか一項記載の両面粘着シート。
- フレキシブルディスプレイを構成する、画像表示装置構成用フレキシブル部材を貼合するために用いる両面粘着シートであって、
請求項13~21の何れか一項記載の両面粘着シートを用いてなる、フレキシブルディスプレイ用両面粘着シート。 - 請求項1~11の何れか一項記載の積層体を形成するための積層体形成キットであって、屈曲又は湾曲可能な画像表示装置構成用フレキシブル部材と、該フレキシブル部材に貼合するための両面粘着シートとを含み、
前記両面粘着シートは、(メタ)アクリル酸エステル(共)重合体(A)を含有する粘着剤組成物から形成され、厚みが10μm以上150μm以下であり、かつ、動的粘弾性のTanδピーク温度で定義される、ガラス転移温度(Tg)が-50℃~-20℃の範囲内にあり、かつ、周波数1Hz、温度100℃における貯蔵弾性率G’が、2.0×103~3.0×104Paの範囲内にあることを特徴とする、積層体形成キット。 - 前記両面粘着シートは、横軸に温度、縦軸にせん断貯蔵弾性率(G’)の対数をプロットした貯蔵弾性率-温度グラフにおいて、周波数1Hz、温度100℃における貯蔵弾性率G’(100)と、周波数1Hz、温度150℃における貯蔵弾性率G’(150)との2点間を通る指数曲線を作成したとき、該指数曲線の底の自然対数が-0.010以上となることを特徴とする、請求項23に記載の積層体形成キット。
- 前記粘着剤組成物は、さらに、架橋剤(B)を含有する、請求項23又は24記載の積層体形成キット。
- 前記粘着剤組成物は、さらに、光開始剤(C)を含有する、請求項23~25の何れか一項記載の積層体形成キット。
- 前記(メタ)アクリル酸エステル(共)重合体(A)が、カルボキシル基含有モノマーを(共)重合成分として含まず、かつ、(共)重合成分として、少なくとも水酸基含有モノマー又はアミド基含有モノマーのいずれか若しくは両方を含む、請求項23~26の何れか一項記載の積層体形成キット。
- 前記(メタ)アクリル酸エステル(共)重合体(A)が、(共)重合成分として、(メタ)アクリロイル基と3級炭素原子が結合した(メタ)アクリル酸アルキルエステルを含む、請求項23~27の何れか一項記載の積層体形成キット。
- 前記光開始剤(C)が、水素引抜型の光開始剤である、請求項26~28の何れか一項記載の積層体形成キット。
- 前記(メタ)アクリル酸エステル(共)重合体が、光を受光するとラジカル活性種を発生する単量体を含んでなる、請求項23~29の何れか一項記載の積層体形成キット。
- 前記両面粘着シートは、周波数1Hz、温度50℃における貯蔵弾性率G’が、3.0×102~4.0×104Paの範囲内にある、請求項23~30の何れか一項記載の積層体形成キット。
- 画像表示装置構成用フレキシブル部材の貼合方法としての両面粘着シートの使用であって、
前記両面粘着シートは、基材レスであって、(メタ)アクリル酸エステル(共)重合体(A)を含有する粘着剤組成物から形成され、厚みが10μm以上150μm以下であり、かつ、動的粘弾性のTanδピーク温度で定義される、ガラス転移温度(Tg)が-50℃~-20℃の範囲内にあり、かつ、周波数1Hz、温度100℃における貯蔵弾性率G’が2.0×103~3.0×104Paの範囲内にあることを特徴とする、画像表示装置構成用フレキシブル部材の貼合方法としての両面粘着シートの使用。 - 前記両面粘着シートは、横軸に温度、縦軸にせん断貯蔵弾性率(G’)の対数をプロットした貯蔵弾性率-温度グラフにおいて、周波数1Hz、温度100℃における貯蔵弾性率G’(100)と、周波数1Hz、温度150℃における貯蔵弾性率G’(150)との2点間を通る指数曲線を作成したとき、該指数曲線の底の自然対数が-0.01以上となる、画像表示装置構成用フレキシブル部材の貼合方法としての請求項32記載の両面粘着シートの使用。
- 前記粘着剤組成物は、さらに、架橋剤(B)を含有する、画像表示装置構成用フレキシブル部材の貼合方法としての請求項32又は33記載の両面粘着シートの使用。
- 前記粘着剤組成物は、さらに、光開始剤(C)を含有する、画像表示装置構成用フレキシブル部材の貼合方法としての請求項32~34の何れか一項記載の両面粘着シートの使用。
- 前記(メタ)アクリル酸エステル(共)重合体(A)が、カルボキシル基含有モノマーを(共)重合成分として含まず、かつ、少なくとも水酸基含有モノマー又はアミド基含有モノマーのいずれか若しくは両方を、共重合成分として含む、画像表示装置構成用フレキシブル部材の貼合方法としての請求項32~35の何れか一項記載の両面粘着シートの使用。
- 前記(メタ)アクリル酸エステル(共)重合体(A)が、(共)重合成分として、(メタ)アクリロイル基と3級炭素原子が結合した(メタ)アクリル酸アルキルエステルを含む、画像表示装置構成用フレキシブル部材の貼合方法としての請求項32~36の何れか一項記載の両面粘着シートの使用。
- 前記光開始剤(C)が、水素引抜型の光開始剤である、画像表示装置構成用フレキシブル部材の貼合方法としての請求項35~37の何れか一項記載の両面粘着シートの使用。
- 前記(メタ)アクリル酸エステル(共)重合体が、光を受光するとラジカル活性種を発生する単量体を含んでなる、請求項32~38の何れか一項記載の両面粘着シートの使用。
- 周波数1Hz、温度50℃における貯蔵弾性率G’が、3.0×102~4.0×104Paの範囲内にある、画像表示装置構成用フレキシブル部材の貼合方法としての請求項32~39の何れか一項記載の両面粘着シートの使用。
- 前記画像表示構成部材は、表面保護パネル、タッチパネル、光学フィルム及び有機ELディスプレイパネルからなる群のうち2種類以上の組み合わせである、画像表示装置構成用フレキシブル部材の貼合方法としての請求項32~40の何れか一項記載の両面粘着シートの使用。
- 請求項32~41の何れか一項記載の両面粘着シートの使用による、画像表示装置構成用フレキシブル部材の貼合方法。
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WO2022163281A1 (ja) * | 2021-01-27 | 2022-08-04 | 三菱ケミカル株式会社 | 活性エネルギー線硬化性粘着シート、離型フィルム付き粘着シート、積層体、積層体の製造方法、積層シート、画像表示装置用積層体、フレキシブル画像表示装置,フレキシブルディスプレイ用粘着シートおよび画像表示装置用積層体の製造方法 |
WO2023176606A1 (ja) * | 2022-03-14 | 2023-09-21 | 三菱ケミカル株式会社 | 粘着シート、及びフレキシブル画像表示装置 |
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TWI830400B (zh) | 2024-01-21 |
JP7243621B2 (ja) | 2023-03-22 |
JP2022130399A (ja) | 2022-09-06 |
CN110461972B (zh) | 2022-04-22 |
JP2022130400A (ja) | 2022-09-06 |
KR20190124797A (ko) | 2019-11-05 |
TWI830399B (zh) | 2024-01-21 |
CN110461972A (zh) | 2019-11-15 |
KR20240038118A (ko) | 2024-03-22 |
JP7491342B2 (ja) | 2024-05-28 |
TW202305081A (zh) | 2023-02-01 |
TW201842128A (zh) | 2018-12-01 |
KR102500174B1 (ko) | 2023-02-15 |
KR20230004969A (ko) | 2023-01-06 |
TWI781992B (zh) | 2022-11-01 |
US20200017722A1 (en) | 2020-01-16 |
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US11535777B2 (en) | 2022-12-27 |
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KR20240035646A (ko) | 2024-03-15 |
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