WO2024157790A1 - 粘着シート、離型フィルム付き粘着シート、画像表示装置用積層体、及びフレキシブル画像表示装置 - Google Patents
粘着シート、離型フィルム付き粘着シート、画像表示装置用積層体、及びフレキシブル画像表示装置 Download PDFInfo
- Publication number
- WO2024157790A1 WO2024157790A1 PCT/JP2024/000537 JP2024000537W WO2024157790A1 WO 2024157790 A1 WO2024157790 A1 WO 2024157790A1 JP 2024000537 W JP2024000537 W JP 2024000537W WO 2024157790 A1 WO2024157790 A1 WO 2024157790A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- adhesive sheet
- acrylate
- pressure
- sensitive adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J7/387—Block-copolymers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—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
- C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—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
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to a pressure-sensitive adhesive sheet, a pressure-sensitive adhesive sheet with a release film, a laminate for an image display device, and a flexible image display device.
- the image display device has a laminated structure in which multiple components, such as a surface protection film, a cover lens, a circular polarizing plate, a touch film sensor, and a light-emitting element, are bonded together with a transparent adhesive sheet.
- Each laminated structure in the image display device can be considered as a laminated sheet in which a component and an adhesive sheet are laminated together.
- Flexible image display devices using organic light-emitting diodes (OLEDs) and quantum dots (QDs) have been developed and are becoming widely commercialized.
- Flexible image display devices include bendable types with curved image display surfaces, foldable types that can be repeatedly folded, rollable types that can be rolled up, and stretchable types that can be stretched and contracted.
- the laminated sheet for a flexible image display device is required to have not only optical properties but also flexibility, and particularly high durability against bending.
- foldable flexible display devices have various issues caused by interlayer stress when folded. For example, when the screen is opened from a folded state, the laminated sheet of a flexible display device is required to quickly restore to a flat state without any residual effects from being in a bent state. Furthermore, repeated folding operations may cause the adhesive sheet to peel off, or the adherend member may be subjected to stress, causing cracks in the member and ultimately causing the member to break. There is also a demand for the laminated sheet to be durable, especially when folded repeatedly under harsh conditions at low temperatures.
- Patent Document 1 discloses a laminated film with an adhesive layer that is free from the risk of causing distortion of an image displayed at the folded portion after repeated folding.
- Patent Literature 2 discloses a laminate that does not break or peel even in a bending test similar to an actual use environment.
- the laminate includes a double-sided pressure-sensitive adhesive sheet having a glass transition temperature and storage modulus within a predetermined range, and a flexible member for constituting an image display device.
- Laminated sheets for image display devices have problems such as light scattering at the interface between the adhesive sheet and the component due to the difference in refractive index between the adhesive sheet and the component, resulting in reduced light transmittance of the laminated sheet and unevenness in the displayed image. Such problems become more pronounced when the surface of the component is uneven, or in the curved parts of a flexible image display device. For this reason, there is a growing demand for adhesive sheets with a high refractive index to reduce the difference in refractive index between the adhesive sheet and the component.
- Patent Document 3 discloses an adhesive layer for bonding various optical components, which contains a base polymer with a glass transition temperature of 5°C or less and has a refractive index of 1.54 or more.
- Patent Documents 1 and 2 take into consideration durability when folded, they do not take into consideration the refractive index of the pressure-sensitive adhesive sheet.
- the adhesive layer disclosed in Patent Document 3 has a high refractive index, but contains a large amount of high refractive index monomers for increasing the refractive index, and the adhesive has a high glass transition temperature, so it cannot be said to be flexible, and flexibility was not taken into consideration. Further improvement is required to achieve both flexibility and a high refractive index.
- the present invention aims to provide an adhesive sheet that has a high refractive index and is soft and highly flexible, an adhesive sheet with a release film that uses the same, a laminate for an image display device, and a flexible image display device.
- a pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition contains a (meth)acrylic copolymer (A), A pressure-sensitive adhesive sheet that satisfies the following requirements (1) and (2): Requirement (1)
- the refractive index of the pressure-sensitive adhesive sheet is 1.480 or more and less than 1.550.
- Requirement (2) A PSA sheet having a shear storage modulus (G'(-20°C)) at -20°C, as measured by dynamic viscoelasticity measurement in a shear mode at a frequency of 1 Hz, of 10 kPa or more and 1,000 kPa or less.
- the (meth)acrylic copolymer (A) further has a structural unit derived from an aromatic (meth)acrylate (a1) having a refractive index of 1.500 or more,
- the pressure-sensitive adhesive sheet according to [14] or [15] wherein the content ratio (a10/a1) of the structural units derived from the macromonomer (a10) to the structural units derived from the aromatic (meth)acrylate (a1) in the (meth)acrylic copolymer (A) is 0.1 to 10 by weight.
- a pressure-sensitive adhesive sheet with a release film comprising: the pressure-sensitive adhesive sheet according to any one of [1] to [17] above; and a release film laminated on at least one surface of the pressure-sensitive adhesive sheet.
- a pressure-sensitive adhesive sheet according to any one of [1] to [17] above which is for use as a component of a flexible image display device.
- a laminate for an image display device comprising two image display device components and an adhesive sheet according to any one of [1] to [17], wherein the two image display device components are laminated via the adhesive sheet, and at least one of the two image display device components has a step with a height difference of 2 ⁇ m or more on a contact surface with the adhesive sheet.
- a flexible image display device comprising the laminate for an image display device according to [20] above.
- the present invention provides an adhesive sheet that has a high refractive index and is soft and highly flexible, an adhesive sheet with a release film that uses the same, a laminate for an image display device, and a flexible image display device.
- (Meth)acrylate is a general term for acrylate and methacrylate.
- the term "(meth)acrylic copolymer” refers to a copolymer having a structural unit derived from a (meth)acrylic monomer.
- the (meth)acrylic copolymer may further have a structural unit derived from a monomer other than the (meth)acrylic monomer (e.g., styrene, etc.).
- (meth)acrylic monomer refers to a monomer having a (meth)acryloyl group.
- Vinyl monomer means a compound having an ethylenically unsaturated bond (a polymerizable carbon-carbon double bond).
- An embodiment of the present invention relates to a pressure-sensitive adhesive sheet.
- the pressure-sensitive adhesive sheet according to the embodiment is formed from a pressure-sensitive adhesive composition containing the (meth)acrylic copolymer (A).
- the pressure-sensitive adhesive composition preferably further contains a photoinitiator (B).
- the pressure-sensitive adhesive composition preferably further contains a photocurable compound (C).
- the pressure-sensitive adhesive composition may further contain other components in addition to the (meth)acrylic copolymer (A), the photoinitiator (B) and the photocurable compound (C).
- the adhesive sheet according to the embodiment is typically a cured adhesive composition containing the (meth)acrylic copolymer (A).
- the adhesive sheet is in a state after the active energy ray curable adhesive composition has been cured.
- the pressure-sensitive adhesive sheet according to the embodiment satisfies the following requirement (1).
- the refractive index of the pressure-sensitive adhesive sheet is 1.480 or more and less than 1.550.
- a pressure-sensitive adhesive sheet satisfying the requirement (1) can reduce the difference in refractive index between the image display device constituent members and the pressure-sensitive adhesive sheet, and can suppress diffuse reflection and optical unevenness caused by the difference in refractive index.
- the refractive index of requirement (1) is preferably 1.482 or more, more preferably 1.485 or more, and even more preferably 1.490 or more.
- the refractive index of requirement (1) is preferably 1.570 or less, more preferably 1.560 or less, even more preferably 1.550 or less, and particularly preferably 1.520 or less.
- the lower limit and the upper limit of the refractive index of requirement (1) can be combined arbitrarily.
- the refractive index in requirement (1) is a value at the surface of the pressure-sensitive adhesive sheet.
- the refractive index of requirement (1) is measured using an Abbe refractometer at a wavelength of 589 nm and at 23°C.
- Methods for adjusting the refractive index of requirement (1) include, for example, a method for adjusting the composition or molecular weight of the (meth)acrylic copolymer, the type or amount of the photocurable compound, and a method for incorporating a refractive index adjuster.
- the refractive index of requirement (1) can be made 1.480 or more by incorporating a structural unit derived from an aromatic (meth)acrylate (a1) having a refractive index of 1.500 or more into the (meth)acrylic copolymer (A).
- the method is not limited to these.
- refractive index adjusters examples include high refractive index nanoparticles such as zirconium oxide particles, niobium oxide particles, tin oxide particles (including phosphorus-doped tin oxide particles and fluorine-doped tin oxide particles), diamond particles, and titanium oxide particles, as well as monomers, resins, and polymers having substituted or unsubstituted aromatic groups.
- high refractive index nanoparticles such as zirconium oxide particles, niobium oxide particles, tin oxide particles (including phosphorus-doped tin oxide particles and fluorine-doped tin oxide particles), diamond particles, and titanium oxide particles, as well as monomers, resins, and polymers having substituted or unsubstituted aromatic groups.
- refractive index adjusters can be appropriately selected depending on not only the refractive index but also other properties required of the adhesive sheet.
- the pressure-sensitive adhesive sheet according to the embodiment further satisfies the following requirement (2).
- the shear storage modulus (G'(-20°C)) at -20°C, as determined by dynamic viscoelastic measurement in a shear mode at a frequency of 1 Hz, is 10 kPa or more and 1,000 kPa or less.
- a PSA sheet satisfying the requirement (2) is soft even at low temperatures and has excellent flexibility. For example, even when repeatedly folded at a low temperature of ⁇ 20° C., the member to which the PSA sheet is adhered is unlikely to crack or break.
- G'(-20°C) in requirement (2) is preferably 30 kPa or more, more preferably 50 kPa or more, and even more preferably 100 kPa or more.
- G'(-20°C) in requirement (2) is preferably 800 kPa or less, more preferably 600 kPa or less, even more preferably 400 kPa or less, and particularly preferably 300 kPa or less.
- the lower limit and upper limit of G'(-20°C) in requirement (2) can be combined in any combination.
- Requirement (2) is a value measured after adjusting the thickness to the range of 0.7 to 1.0 mm, which allows the shear storage modulus G' to be accurately measured without being influenced by the measuring tool.
- Adjusting the thickness to the range of 0.7 to 1.0 mm means that if the thickness of the PSA sheet as the measurement sample does not fall within this range, the thickness of the measurement sample is adjusted to within this range by stacking several sheets, etc. The same applies when the thickness of the measurement sample is specified in other tests.
- the measurement of G'(-20°C) in the requirement (2) is carried out, for example, as follows.
- the pressure-sensitive adhesive sheet is repeatedly laminated to adjust the thickness to 0.7 to 1.0 mm, and then a circular sample having a diameter of 8 mm is punched out.
- the obtained sample is subjected to dynamic viscoelasticity measurement using a rheometer under the conditions of a measuring tool: a parallel plate having a diameter of 8 mm, a frequency of 1 Hz, a measuring temperature of -50 to 150°C, and a heating rate of 5°C/min, and the shear storage modulus (G') at -20°C is read.
- Examples of methods for adjusting G' (-20°C) of requirement (2) in the pressure-sensitive adhesive sheet to the above range include methods for adjusting the composition and molecular weight of the (meth)acrylic copolymer (A) and the type and amount of the photocurable compound (C). However, the methods are not limited to these.
- the pressure-sensitive adhesive sheet according to the embodiment further satisfies the following requirement (3).
- the glass transition temperature (Tg) defined as the maximum value of Tan ⁇ obtained by dynamic viscoelasticity measurement in a shear mode at a frequency of 1 Hz is ⁇ 20° C. or lower.
- a PSA sheet satisfying the requirement (3) has excellent flexibility.
- the Tg of the requirement (3) is preferably ⁇ 25° C. or lower, more preferably ⁇ 28° C. or lower, further preferably ⁇ 30° C. or lower, and particularly preferably ⁇ 35° C. or lower.
- the lower limit is usually ⁇ 80° C.
- Examples of the method for adjusting the Tg of requirement (3) to the above range include a method for adjusting the composition or molecular weight of the (meth)acrylic copolymer (A) or the type or amount of the photocurable compound (C) added, as well as a method for adjusting the amount of active energy ray irradiation.
- the method is not limited to these methods.
- the pressure-sensitive adhesive sheet according to the embodiment further satisfies the following requirement (4).
- the ratio of the shear storage modulus G'(-20°C) at -20°C to the shear storage modulus G'(60°C) at 60°C (G'(-20°C)/G'(60°C)) obtained by dynamic viscoelastic measurement in a shear mode at a frequency of 1 Hz is 150 or less.
- a pressure-sensitive adhesive sheet satisfying the requirement (4) has an excellent balance between flexibility and adhesive strength in a low-temperature environment.
- G'(-20°C)/G'(60°C) in requirement (4) is preferably 100 or less, more preferably 80 or less, even more preferably 50 or less, particularly preferably 40 or less, and most preferably 30 or less.
- G'(-20°C)/G'(60°C) in requirement (4) is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more.
- the upper and lower limits of G'(-20°C)/G'(60°C) in requirement (4) can be combined in any desired manner.
- the measurement of G'(-20°C) in requirement (4) is the same as the measurement of G'(-20°C) in requirement (2).
- the measurement of G'(60°C) in requirement (4) is the same as the measurement of G'(-20°C) in requirement (2), except that the shear storage modulus (G') value at 60°C is read.
- Examples of a method for adjusting G'(-20°C)/G'(60°C) in the above range in requirement (4) include a method for adjusting the composition or molecular weight of the (meth)acrylic copolymer (A) or the type or amount of the photocurable compound, as well as a method for adjusting the amount of active energy ray irradiation.
- the method is not limited to these methods.
- the pressure-sensitive adhesive sheet according to the embodiment further satisfies the following requirement (5).
- the recovery rate calculated from the maximum strain value ( ⁇ max ) when a stress of 2 kPa is applied to the pressure-sensitive adhesive sheet at 60° C. for 600 seconds and the residual strain value ( ⁇ min ) 600 seconds after the stress is removed, using the following formula, is 60% or more.
- Recovery rate (%) [( ⁇ max ⁇ min )/ ⁇ max ] ⁇ 100
- a pressure-sensitive adhesive sheet satisfying the requirement (5) has excellent restoring properties when folded.
- the restoring ratio of requirement (5) is preferably 65% or more, more preferably 70% or more, even more preferably 75% or more, particularly preferably 80% or more, and most preferably 85% or more.
- the restoring ratio of requirement (5) is preferably 99% or less, more preferably 98% or less, and even more preferably 97% or less.
- the lower limit and upper limit of the restoring ratio of requirement (5) can be arbitrarily combined.
- the measurement of the restoration rate in accordance with requirement (5) is carried out, for example, as follows.
- the pressure-sensitive adhesive sheet is repeatedly laminated to adjust the thickness to 0.7 to 1.0 mm, and then a circular sample with a diameter of 8 mm is punched out.
- a rheometer is used to measure the strain ( ⁇ max ) after a pressure of 2 kPa is applied for 600 seconds at 60°C, and the strain ( ⁇ min ) after 600 seconds have passed since the stress was removed.
- the obtained values are substituted into the following formula to calculate the recovery rate.
- Recovery rate (%) [( ⁇ max ⁇ min )/ ⁇ max ] ⁇ 100
- Examples of a method for adjusting the recovery rate of requirement (5) to fall within the above range include a method for adjusting the composition or molecular weight of the (meth)acrylic copolymer (A), the type or amount of the photocurable compound, and a method for adjusting the amount of active energy ray irradiation.
- the present invention is not limited to these methods.
- the pressure-sensitive adhesive sheet according to the embodiment further satisfies the following requirement (6).
- the pressure-sensitive adhesive sheet has a gel fraction of 30% or more.
- a pressure-sensitive adhesive sheet satisfying the requirement (6) has excellent cohesive strength.
- the gel fraction of requirement (6) is preferably 35% or more, more preferably 40% or more, and even more preferably 45% or more.
- the gel fraction of requirement (6) is preferably 90% or less, more preferably 87% or less, and even more preferably 85% or less.
- the lower and upper limits of the gel fraction of requirement (6) can be combined in any combination.
- the measurement of the gel fraction in the requirement (6) is carried out, for example, as follows.
- the pre-weighed adhesive sheet is wrapped in a 150 mesh SUS wire net and immersed in ethyl acetate for 24 hours at 23° C. Then, it is dried at 70° C. for 4.5 hours, and the mass of the adhesive is measured before and after immersion in ethyl acetate, and the difference between the two masses is the mass of the insoluble adhesive remaining in the wire net (mass after immersion).
- the percentage of the mass of the insoluble adhesive remaining in the wire net (mass after immersion) relative to the mass of the adhesive before immersion in ethyl acetate (mass before immersion) is calculated as the gel fraction (%) of requirement (6).
- Examples of the method of adjusting the gel fraction of requirement (6) to fall within the above range include a method of adjusting the composition or molecular weight of the (meth)acrylic copolymer (A), the type or amount of the photocurable compound, and a method of adjusting the amount of active energy radiation irradiation.
- the method is not limited to these methods.
- the pressure-sensitive adhesive sheet according to the embodiment further satisfies the following requirement (7).
- the adhesive strength to the polyester film surface is 0.5 N/cm or more at 23° C., 50% RH, a peel angle of 180°, and a peel speed of 300 mm/min.
- a pressure-sensitive adhesive sheet satisfying the requirement (7) has excellent adhesion and is unlikely to undergo delamination even when a laminate attached to an adherend such as a component of an image display device is folded, and therefore has excellent durability.
- the adhesive strength of requirement (7) is preferably 1 N/cm or more, more preferably 2 N/cm or more, and even more preferably 3 N/cm or more.
- the upper limit of the adhesive strength of requirement (7) is not particularly limited, and may be, for example, 20 N/cm or less.
- the measurement of the adhesive strength in requirement (7) is carried out, for example, as follows.
- a polyester film is attached to one side of the adhesive sheet as a backing film, and the test piece is cut into a strip of 10 mm wide x 150 mm long.
- the test piece is attached to a polyester film previously attached to soda lime glass, and autoclaved (60°C, gauge pressure 0.2 MPa, 20 minutes) to obtain an adhesive strength measurement sample.
- the adhesive strength measurement sample obtained is peeled off from the polyester film attached to the soda lime glass together with the backing film under conditions of 23°C, 50% RH, peel angle 180°, and peel speed 300 mm/min, and the tensile strength (N/cm) is measured with a load cell to obtain the adhesive strength.
- Examples of the method for adjusting the adhesive strength of requirement (7) include a method for adjusting the composition or molecular weight of the (meth)acrylic copolymer (A), the type or amount of the photocurable compound, or a method for adjusting the amount of active energy radiation irradiation.
- the method is not limited to these methods.
- the pressure-sensitive adhesive sheet according to the embodiment further satisfies the following requirement (8).
- the total light transmittance is 80% or more.
- a PSA sheet satisfying the requirement (8) has excellent transparency and is useful for applications requiring transparency, such as image display devices.
- the total light transmittance of the requirement (8) is preferably 85% or more, and more preferably 90% or more. The higher the total light transmittance of the requirement (8), the more preferable it is, and there is no particular upper limit.
- the measurement of the total light transmittance in requirement (8) is carried out in accordance with the standard JIS-K7361-1 (ISO-13468-1).
- the pressure-sensitive adhesive sheet according to the embodiment further satisfies the following requirement (9).
- (9) Haze is 5% or less.
- a PSA sheet satisfying the requirement (9) has excellent transparency and is useful for applications requiring transparency, such as image display devices.
- the haze of the requirement (9) is preferably 4% or less, more preferably 2% or less, and even more preferably 1% or less. The lower the haze of the requirement (9), the better, and there is no particular lower limit.
- the measurement of haze in the requirement (9) is carried out in accordance with the standard JIS-K7136 (ISO-14782).
- Methods for adjusting the total light transmittance of requirement (8) and the haze of requirement (9) include, for example, adjusting the composition of the (meth)acrylic acid ester copolymer, using a colorless photoinitiator, or not containing a colorant. Also, coloring due to heating or deterioration over time may be suppressed by using an antioxidant. However, the methods are not limited to these.
- the pressure-sensitive adhesive sheet according to the embodiment may have a single layer structure or a multi-layer structure.
- each of the multiple layers is formed from a pressure-sensitive adhesive composition containing the (meth)acrylic copolymer (A).
- the thickness of the adhesive sheet according to the embodiment is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, even more preferably 15 ⁇ m or more, and particularly preferably 20 ⁇ m or more, because it has good handleability and is easy to obtain excellent conformability to uneven surfaces.
- the thickness of the adhesive sheet according to the embodiment is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, even more preferably 70 ⁇ m or less, and particularly preferably 60 ⁇ m or less, because it is easy to reduce stress when bending or curving and to make a flexible image display device to which the adhesive sheet is applied thin.
- the lower and upper limits of the thickness of the adhesive sheet can be arbitrarily combined.
- ((Meth)acrylic copolymer (A)) In the pressure-sensitive adhesive sheet according to the embodiment, one method for adjusting the requirements (1) to (9) is to adjust the composition of the (meth)acrylic copolymer (A).
- An example of the (meth)acrylic copolymer (A) (hereinafter also simply referred to as "copolymer (A)") that can be preferably used in the pressure-sensitive adhesive sheet according to the embodiment will be described below.
- the copolymer (A) preferably has a structural unit derived from an aromatic (meth)acrylate (a1) (hereinafter also simply referred to as "aromatic (meth)acrylate (a1)”) having a refractive index of 1.500 or more, since this makes it easier to obtain a pressure-sensitive adhesive sheet that satisfies requirement (1).
- aromatic (meth)acrylate (a1) hereinafter also simply referred to as "aromatic (meth)acrylate (a1)
- refractive index of 1.500 or more
- the aromatic (meth)acrylate (a1) is a (meth)acrylate having one or more aromatic groups in one molecule.
- Aromatic groups include, for example, phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, pyrenyl, and the like.
- the aromatic ring may have one or more substituents.
- an aromatic ring has a substituent means that a substituent is bonded to an atom (such as a carbon atom) constituting the ring skeleton of the aromatic ring.
- the substituent examples include halogens such as F, Cl, Br, and I, alkyls having 1 to 10 carbon atoms, alkoxys having 1 to 10 carbon atoms, and acyloxys having 2 to 11 carbon atoms.
- the number of aromatic rings contained in the aromatic (meth)acrylate (a1) is preferably 2 or more from the viewpoint of increasing the refractive index, and is preferably 4 or less from the viewpoint of compatibility.
- the aromatic ring may be bonded directly to the (meth)acryloyl group of the aromatic (meth)acrylate (a1) or via a linking group such as alkylene, (poly)alkylene glycol, ether, ester, urethane, carbonate, amide, or urea.
- the refractive index of the aromatic (meth)acrylate (a1) is preferably 1.500 or more, more preferably 1.510 or more, and even more preferably 1.520 or more.
- the refractive index of the aromatic (meth)acrylate (a1) is preferably 1.700 or less, more preferably 1.690 or less, even more preferably 1.600 or less, and particularly preferably 1.550 or less.
- the lower limit and upper limit of the refractive index can be combined arbitrarily.
- the refractive index of the aromatic (meth)acrylate (a1) is determined in accordance with the standard JIS-K7142. As the refractive index of the aromatic (meth)acrylate (a1), a value listed in a catalog or the like may be adopted.
- Aromatic (meth)acrylates (a1) include, for example, m-phenoxybenzyl acrylate (refractive index: 1.566, polymer Tg: -35°C), o-phenylphenoxyethyl acrylate (refractive index: 1.577, polymer Tg: 33°C), 2-phenylbenzyl acrylate (refractive index: 1.600, polymer Tg: 6°C), o-phenylphenol acrylate (refractive index: 1.575, polymer Tg: 82°C), phenoxyethyl acrylate (refractive index: 1.519, polymer Tg: -22°C), benzyl acrylate (refractive index: 1.519, polymer Tg: -22°C), Tg: 6°C), phenoxyethyl methacrylate (refractive index: 1.511, polymer Tg: 54°C), phenyl diethylene glycol acrylate (refractive index: 1.514, polymer Tg:
- the aromatic (meth)acrylate (a1) is preferably m-phenoxybenzyl acrylate, o-phenylphenoxyethyl acrylate, 2-phenylbenzyl acrylate, o-phenylphenol acrylate, phenoxyethyl acrylate, benzyl acrylate, phenyldiethylene glycol acrylate, phenyltetraethylene glycol acrylate, or (1-naphthyl)methyl acrylate, more preferably m-phenoxybenzyl acrylate, o-phenylphenoxyethyl acrylate, or phenoxyethyl acrylate, and even more preferably m-phenoxybenzyl acrylate.
- the glass transition temperature (hereinafter also referred to as "polymer Tg") of the homopolymer of the aromatic (meth)acrylate (a1) is preferably 60°C or less, more preferably 50°C or less, 40°C or less, 30°C or less, and 20°C or less, and further more preferably 0°C or less, -10°C or less, and -20°C or less.
- the lower limit is usually -70°C or higher, but from the viewpoint of imparting an appropriate cohesive strength to the pressure-sensitive adhesive sheet, -40°C or higher is preferable, -20°C or higher is more preferable, 0°C or higher is more preferable, and 10°C or higher is even more preferable.
- the lower and upper limits of the polymer Tg can be combined in any desired manner.
- the polymer Tg of the aromatic (meth)acrylate (a1) a literature value, for example, a value described in the Polymer Handbook [Polymer Handbook, J. Brandrup, Interscience, 1989] or a monomer catalog, can be used.
- the ratio of the aromatic (meth)acrylate (a1)-derived structural units to all structural units of copolymer (A) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, particularly preferably 10% by mass or more, and especially preferably 15% by mass, from the viewpoint of increasing the refractive index.
- the ratio of the aromatic (meth)acrylate (a1)-derived structural units to all structural units of copolymer (A) is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, particularly preferably 30% by mass or less, especially preferably 25% by mass or less, and most preferably 20% by mass or less, from the viewpoint of maintaining the flexibility of the adhesive sheet and obtaining bendability.
- the lower limit and upper limit of the ratio can be arbitrarily combined.
- the copolymer (A) preferably has a structural unit derived from an alkyl (meth)acrylate (a2) having an alkyl group of 4 to 30 carbon atoms in addition to a structural unit derived from an aromatic (meth)acrylate (a1).
- the structural units derived from aromatic (meth)acrylate (a1) and the structural units derived from alkyl (meth)acrylate (a2) having an alkyl group with 4 to 30 carbon atoms it is preferable to have one or more structural units derived from copolymerizable monomers selected from the group consisting of carboxy group-containing monomers (a3), hydroxyl group-containing monomers (a4), nitrogen-containing monomers (a5), epoxy group-containing monomers (a6), vinyl monomers (a7), alkyl (meth)acrylate monomers (a8) having an alkyl group with 1 to 3 carbon atoms, alicyclic monomers (a9), macromonomers (a10), and other copolymerizable monomers (a11).
- copolymerizable monomers selected from the group consisting of carboxy group-containing monomers (a3), hydroxyl group-containing monomers (a4), nitrogen-containing monomers (a5), epoxy group-containing monomers (a6), vinyl monomers (a7),
- the copolymerizable monomers (a3) to (a11) at least one selected from the group consisting of a carboxyl group-containing monomer (a3), a hydroxyl group-containing monomer (a4), and a nitrogen-containing monomer (a5) is preferred.
- the copolymer (A) does not contain a carboxyl group-containing monomer (a3) and is any one or more selected from the group consisting of a hydroxyl group-containing monomer (a4) and a nitrogen-containing monomer (a5).
- a copolymer (A) having a structural unit derived from any one or more selected from the group consisting of a hydroxyl group-containing monomer (a4) and a nitrogen-containing monomer (a5) it is possible to provide both corrosion resistance, adhesion, and resistance to wet heat whitening when the adherend contains a corrosive component such as a metal.
- the nitrogen-containing monomers (a5) those having a tertiary nitrogen atom are preferred, since they have a sensitizing effect on the hydrogen abstraction reaction described below, and as a result, can efficiently form crosslinks.
- the alkyl (meth)acrylate (a2) is a linear or branched alkyl (meth)acrylate having an alkyl group with 4 to 30 carbon atoms, and is represented by the following formula (1).
- CH 2 CH(R 1 )-COO(R 2 ) (1)
- R1 represents a hydrogen atom or a methyl group
- R2 represents a linear or branched alkyl group having 4 to 30 carbon atoms.
- the alkyl (meth)acrylate represented by formula (1) may, for example, be straight-chain alkyl (meth)acrylates such as n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, henicosyl (meth)acrylate, and behenyl (meth)acrylate; sec-butyl (meth)acrylate, iso
- the alkyl group has 4 to 20 carbon atoms, more preferably 5 or more, even more preferably 6 or more, particularly preferably 9 or more, and especially preferably 10 or more, while it is preferable that the alkyl group has 18 or less, even more preferably 16 or less, particularly preferably 15 or less, and especially preferably 14 or less.
- the alkyl group preferably has 4 to 20 carbon atoms, more preferably 5 or more, even more preferably 6 or more, particularly preferably 9 or more, and especially preferably 10 or more, while the alkyl group preferably has 18 or less, even more preferably 16 or less, particularly preferably 15 or less, and especially preferably 14 or less.
- Examples include n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, and tridecyl (meth)acrylate.
- a branched alkyl (meth)acrylate since a hydrogen abstraction reaction described below is likely to occur upon light irradiation, and as a result, a crosslinking reaction can be efficiently formed.
- a branched alkyl (meth)acrylate having an alkyl group with 4 to 20 carbon atoms, further 5 to 18 carbon atoms, particularly 6 to 16 carbon atoms, and especially 7 to 14 carbon atoms is preferable.
- sec-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, and isodecyl (meth)acrylate are preferable.
- alkyl (meth)acrylates (a2) alkyl (meth)acrylates having a tertiary carbon atom in the alkyl group are preferred.
- the ratio of the alkyl (meth) acrylate (a2) derived structural unit to the total structural units of the copolymer (A) is preferably 5% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 90% by mass or less, even more preferably 15% by mass or more and 85% by mass or less, and particularly preferably 20% by mass or more and 80% by mass or less. If the ratio of the alkyl (meth) acrylate derived structural unit is above the lower limit, the flexibility tends to be excellent, and the conformability to unevenness tends to be excellent when the adherend has unevenness. If it is below the upper limit, the effect of the copolymerizable monomer described later is easily obtained, and the adhesive strength and cohesive strength tend to be excellent.
- the lower limit and the upper limit of the content of the structural unit derived from the alkyl (meth)acrylate (a2) can be combined in any desired manner.
- carboxyl group-containing monomer (a3) examples include (meth)acrylic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, and itaconic acid. These may be used alone or in combination of two or more.
- hydroxyl group-containing monomer (a4) examples include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; caprolactone-modified hydroxy (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate; oxyalkylene-modified (meth)acrylates such as diethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate;
- the hydroxyl group-containing (meth)acrylate examples include primary hydroxyl group-containing (meth)acrylates such as 2-acryloyloxyethyl-2-hydroxyethyl phthalate, secondary hydroxyl group-containing (meth)acrylates such as 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (
- hydroxyl group-containing monomers (a4) hydroxyl group-containing monomers having a hydroxyalkyl group with 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and especially 2 to 4 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether, are preferred, and primary hydroxyl group-containing (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, are particularly preferred.
- the content of the structural units derived from the hydroxyl group-containing monomer (a4) in the copolymer (A) is preferably 0.1 to 15 mass%, more preferably 0.5 to 13 mass%, even more preferably 1 to 10 mass%, and particularly preferably 2 to 7 mass%, based on the total structural units of the copolymer (A), from the viewpoint of imparting adhesive strength and resistance to wet heat whitening.
- Examples of the nitrogen-containing monomer (a5) include amino group-containing monomers, amide group-containing monomers, isocyanate group-containing monomers, and (meth)acrylonitrile.
- the nitrogen-containing monomer (a5) improves the cohesive strength of the adhesive sheet and can suppress whitening due to moist heat. These monomers may be used alone or in combination of two or more.
- the nitrogen-containing monomer (a5) also has the effect of promoting the hydrogen abstraction reaction described below.
- amino group-containing monomers include primary amino group-containing (meth)acrylates such as aminomethyl (meth)acrylate and aminoethyl (meth)acrylate; secondary amino group-containing (meth)acrylates such as t-butylaminoethyl (meth)acrylate and t-butylaminopropyl (meth)acrylate; tertiary amino group-containing (meth)acrylates such as ethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and dimethylaminopropylacrylamide; N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole
- amide group-containing monomers include (meth)acrylamide; N-alkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-n-butyl (meth)acrylamide, diacetone (meth)acrylamide, and N,N'-methylene bis (meth)acrylamide; N,N-dialkyl (meth)acrylamides such as N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, N,N-ethylmethyl acrylamide, and N,N-diallyl (meth)acrylamide; hydroxyalkyl (meth)acrylamides such as N-hydroxymethyl (meth)acrylamide and N-hydroxyethyl (meth)acrylamide; alkoxyalkyl (meth)acrylamides such as N-methoxymethyl
- isocyanate group-containing monomers examples include 2-(meth)acryloyloxyethyl isocyanate and their alkylene oxide adducts.
- the isocyanate group may be protected with a blocking agent such as methyl ethyl ketone oxime, 3,5-dimethylpyrazole, 1,2,4-triazole, or diethyl malonate.
- those having a tertiary nitrogen atom are preferred because they have a sensitizing effect on the hydrogen abstraction reaction described below, and as a result, crosslinks can be formed efficiently.
- tertiary amino group-containing (meth)acrylates, N,N-dialkyl (meth)acrylamides, N-vinylpyrrolidone, acryloylmorpholine, etc. are particularly preferred.
- the content of the structural units derived from the nitrogen-containing monomer (a5) in the copolymer (A) is preferably 0.1 to 15 mass%, more preferably 0.5 to 13 mass%, even more preferably 1 to 10 mass%, and particularly preferably 2 to 7 mass%, based on the total structural units of the copolymer (A), from the viewpoint of imparting cohesive strength and resistance to wet heat whitening.
- Examples of the epoxy group-containing monomer (a6) 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 vinyl monomer (a7) include compounds having a vinyl group in the molecule.
- Examples of such compounds include vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl laurate, and vinyl stearate, as well as aromatic vinyl monomers such as styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, and other substituted styrenes. These may be used alone or in combination of two or more.
- alkyl (meth)acrylate monomer (a8) having an alkyl group with 1 to 3 carbon atoms examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, etc. These may be used alone or in combination of two or more.
- the content of the structural units derived from the alkyl (meth)acrylate monomer (a8) in the copolymer (A) is preferably 0.1 to 15 mass%, more preferably 0.5 to 13 mass%, even more preferably 1 to 10 mass%, and particularly preferably 2 to 7 mass%, based on all structural units of the copolymer (A).
- Examples of the alicyclic monomer (a9) include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, adamantyl (meth)acrylate, etc. These may be used alone or in combination of two or more.
- the content of the structural units derived from the copolymerizable monomer (a9) in the copolymer (A) is preferably from 0.1 to 15 mass%, more preferably from 0.5 to 13 mass%, even more preferably from 1 to 10 mass%, and particularly preferably from 2 to 7 mass%, based on all structural units of the copolymer (A).
- the macromonomer (a10) is a monomer that can easily increase the number of carbon atoms in the side chain, for example, to 20 or more, when it becomes a (meth)acrylic (co)polymer by polymerization.
- the (meth)acrylic (co)polymer can be made into a graft copolymer having a segment having a structural unit derived from the macromonomer (a10).
- the cohesive force of the copolymer (A) is improved, which is preferable in that the cohesive force of the pressure-sensitive adhesive sheet can be easily increased.
- the properties of the main chain and side chains of the graft copolymer can be changed by selecting the macromonomer (a10) and other monomers and adjusting the blending ratio.
- the macromonomer (a10) preferably has a skeleton component composed of an acrylic copolymer or a vinyl polymer.
- the skeleton component of the macromonomer include alkyl(meth)acrylate (a2) having an alkyl group with 4 to 30 carbon atoms, vinyl monomer (a7), alkyl(meth)acrylate monomer (a8) having an alkyl group with 1 to 3 carbon atoms, and alicyclic monomer (a9).
- alkyl (meth)acrylates having an alkyl group with 1 to 8 carbon atoms, alicyclic monomers, and aromatic monomers such as styrene, since this allows the production of a pressure-sensitive adhesive sheet with excellent cohesive strength.
- an alkyl (meth)acrylate having an alkyl group with 9 to 30 carbon atoms, preferably 10 to 20 carbon atoms is preferred since it allows the production of a pressure-sensitive adhesive sheet having suitable cohesive strength and excellent flexibility.
- alkyl (meth)acrylate having an alkyl group with 9 to 30 carbon atoms, preferably 10 to 20 carbon atoms is preferred since it allows the production of a pressure-sensitive adhesive sheet having suitable cohesive strength and excellent flexibility.
- the macromonomer has a radical polymerizable functional group or a functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxy group, an amino group, an amide group, or a thiol group.
- a radical polymerizable functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxy group, an amino group, an amide group, or a thiol group.
- the macromonomer may have one or more radical polymerizable functional groups, and among them, one having one is particularly preferable.
- the functional group may also have one or more functional groups, and among them, one having one is particularly preferable.
- the compound may contain either a radically polymerizable functional group or a functional group, or may contain both.
- the weight average molecular weight of the macromonomer (a10) is preferably from 1,000 to 40,000, more preferably from 1,500 to 20,000, and even more preferably from 2,000 to 15,000.
- the weight average molecular weight of the macromonomer (a10) is a value calculated in terms of standard polystyrene as measured by gel permeation chromatography (GPC).
- macromonomers such as macromonomers manufactured by Toagosei Co., Ltd.
- Toagosei Co., Ltd. can be used as appropriate.
- the content of the structural units derived from macromonomer (a10) in copolymer (A) is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and even more preferably 5% by mass or more and 15% by mass or less, based on the total structural units of copolymer (A). If it is equal to or more than the lower limit, the phase separation force between the segments having the structural units derived from macromonomer (a10) and the segments formed by the other structural units becomes stronger, and the pressure-sensitive adhesive sheet tends to have better shape retention when not laminated. If it is equal to or less than the upper limit, the phase separation structure tends to collapse easily when laminated, and the unevenness-following ability tends to be better.
- the lower limit and upper limit of the content can be combined arbitrarily.
- copolymerizable monomers (a11) include, for example, (meth)acrylates having an alkoxyalkylene glycol skeleton such as methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, butoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, butoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, butoxypolytetramethylene glycol (meth)acrylate, methoxypolyoxyethylene polyoxypropylene glycol (meth)acrylate, and butoxypolyoxyethylene polyoxypropylene glycol (meth)acrylate, as well as heterocyclic ring-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate. These can be used alone or in combination of two or more.
- the content ratio (a10/a1) of the structural units derived from the macromonomer (a10) to the structural units derived from the aromatic (meth)acrylate (a1) in the (meth)acrylic copolymer (A) is 0.1 to 10 (weight ratio).
- a content ratio (a10/a1) is more preferably 0.11 to 5, even more preferably 0.12 to 3, and particularly preferably 0.15 to 2.
- the weight average molecular weight (Mw) of the copolymer (A) is preferably 50,000 or more and 2,000,000 or less, more preferably 100,000 or more and 1,500,000 or less, and even more preferably 300,000 or more and 1,000,000 or less. If the weight average molecular weight of the copolymer (A) is the lower limit or more, the durability of the adhesive sheet after lamination tends to be good. If the weight average molecular weight of the copolymer (A) is the upper limit or less, the moldability during the production of the adhesive sheet tends to be good. The lower limit and the upper limit of the weight average molecular weight can be combined arbitrarily.
- the weight average molecular weight of the copolymer (A) is a value calculated in terms of standard polystyrene as measured by gel permeation chromatography (GPC).
- the melt viscosity of the copolymer (A) at 130°C is preferably 20 Pa ⁇ s or more and 800 Pa ⁇ s or less, more preferably 50 Pa ⁇ s or more and 600 Pa ⁇ s or less, and even more preferably 100 Pa ⁇ s or more and 500 Pa ⁇ s or less. If the melt viscosity of the copolymer (A) at 130°C is within the above range, the adhesive composition containing the copolymer (A) can be directly heated and applied by the hot melt method. The lower limit and the upper limit of the melt viscosity can be arbitrarily combined. The melt viscosity can be measured, for example, using a viscoelasticity measuring device Rheosol-G5000 manufactured by UBM Corporation.
- the method for producing the copolymer (A) is not particularly limited, and any known polymerization method can be used.
- the polymerization method may be a known polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization, etc. Since the adhesive sheet is to be used as such, the solution polymerization method is preferred.
- the content of copolymer (A) in the adhesive composition forming the adhesive sheet according to the embodiment is preferably 50% by mass or more and 99.5% by mass or less, more preferably 75% by mass or more and 99% by mass or less, and even more preferably 90% by mass or more and 98% by mass or less, based on the total amount of the adhesive composition.
- the lower limit and upper limit of the content of copolymer (A) can be arbitrarily combined.
- the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive sheet preferably further contains a photoinitiator (B) in addition to the copolymer (A).
- a photoinitiator (B) is a compound that generates active radical species when irradiated with light such as ultraviolet light or visible light, more specifically, with light having a wavelength of 200 nm to 780 nm.
- the photoinitiator (B) can be appropriately selected from known photoinitiators, such as cleavage-type photoinitiators and hydrogen abstraction-type photoinitiators.
- cleavage-type photoinitiators examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 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), 2-benzyl-2-dimethylamino-1-(4-morpholino-1-methylamino)propanone, and 2-benzyl-2-dimethylamino-1-(4-morpholino-1-methylamino)propanone.
- hydrogen abstraction type photoinitiators examples include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(meth)acryloyloxybenzophenone, 2-methylbenzoylbenzoate, 4-[(4-methylphenyl)thio]benzophenone, 4-acryloyloxybenzophenone, 4-acryloyloxyethoxybenzophenone, 4-acryloyloxy-4'-methoxybenzophenone, 4-acryloyloxyethoxy-4'-methoxybenzophenone, 4-acryloyloxy-4'-bromobenzophenone, 4-acryloyloxyethoxy Intermolecular hydrogen abstraction type photoinitiators such as 4'-bromobenzophenone, 4-methacryloyloxybenzophenone, 4-methacryloyloxyethoxybenzophenone, 4-methacryloyloxye
- the cleavage type photoinitiator and the hydrogen abstraction type photoinitiator may be used either alone or in combination. Furthermore, the cleavage type photoinitiator and the hydrogen abstraction type photoinitiator may each be used alone or in combination of two or more.
- the photoinitiator (B) preferably contains a hydrogen abstraction type photoinitiator. When the photoinitiator (B) contains a hydrogen abstraction type photoinitiator, a hydrogen abstraction reaction occurs from the copolymer (A), and not only the photocurable compound (C) but also the copolymer (A) is incorporated into the crosslinked structure, forming a crosslinked structure with many crosslinking points.
- intramolecular hydrogen abstraction type photoinitiators are preferred in that they can be the starting point for radical generation, not only as a hydrogen donor in the system, but also themselves.
- the content of the photoinitiator (B) in the adhesive composition forming the adhesive sheet is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more, relative to 100 parts by mass of copolymer (A).
- the content of the photoinitiator (B) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less, relative to 100 parts by mass of copolymer (A).
- the lower limit and upper limit of the content of the photoinitiator (B) can be arbitrarily combined.
- the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive sheet further contains a photocurable compound (C) in addition to the copolymer (A) or in addition to the copolymer (A) and the photoinitiator (B). It is preferred.
- the pressure-sensitive adhesive composition can increase the curing efficiency with active energy rays and can also increase the cohesive strength after curing with active energy rays.
- the copolymer (A) undergoes a hydrogen abstraction reaction due to the action of the photoinitiator (B) or the like, and a sufficient crosslinking structure can be formed within and/or between the copolymers.
- the pressure-sensitive adhesive composition does not necessarily need to contain the photocurable compound (C).
- the photocurable compound (C) is a compound having one or more radically polymerizable groups, preferably a (meth)acryloyl group.
- examples of the photocurable compound (C) include monofunctional (meth)acrylic monomers, polyfunctional (meth)acrylic monomers, and (meth)acrylic oligomers.
- the monofunctional (meth)acrylic monomer has one (meth)acryloyl group.
- the monofunctional (meth)acrylic monomer those mentioned as the monomers forming the copolymer (A) can be exemplified.
- polyfunctional (meth)acrylic monomers include those having two (meth)acryloyl groups and those having three or more (meth)acryloyl groups.
- polyfunctional (meth)acrylic monomers having two (meth)acryloyl groups 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 polyethoxy di(meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, bisphenol B polyethoxy di(meth)acrylate, bisphenol C polyethoxy di(meth)acrylate, bisphenol D polyethoxy di(meth)acrylate, bisphenol E polyethoxy di(meth)acrylate, bisphenol F polyeth
- examples include phenol A polypropoxy di(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, and di(meth)acrylate of hydroxypivalic acid neopentyl glycol adduct with ⁇ -caprolactone.
- polyfunctional (meth)acrylic monomers having three or more (meth)acryloyl groups include trimethylolpropane trioxyethyl (meth)acrylate, ⁇ -caprolactone modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra ...
- acrylates examples include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (tris(acryloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.
- polyfunctional (meth)acrylic monomers having an alkylene glycol skeleton such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate, are more preferred.
- the molecular weight of the polyfunctional (meth)acrylic monomer is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, and particularly preferably 500 or more, from the viewpoint of imparting appropriate flexibility to the cured product.
- the upper limit of the molecular weight of the polyfunctional (meth)acrylic monomer is usually 3000 or less, and preferably 2000 or less.
- the (meth)acrylic oligomer either monofunctional or polyfunctional can be used, and examples thereof include polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyether (meth)acrylate, etc.
- polyfunctional urethane (meth)acrylates are preferred from the viewpoint of imparting appropriate toughness to the cured product.
- the molecular weight of the (meth)acrylic oligomer is preferably 3,000 or more, more preferably 5,000 or more, even more preferably 8,000 or more, and particularly preferably 10,000 or more.
- the upper limit of the molecular weight of the (meth)acrylic oligomer is usually 100,000 or less, and preferably 50,000 or less.
- the content of the photocurable compound (C) in the adhesive composition forming the adhesive sheet is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, and particularly preferably 1.2 parts by mass or more, relative to 100 parts by mass of copolymer (A).
- the content of the photocurable compound (C) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less, relative to 100 parts by mass of copolymer (A).
- the lower limit and upper limit of the content of the photocurable compound (C) can be arbitrarily combined.
- the adhesive composition forming the adhesive sheet may contain various additives, such as a silane coupling agent, a tackifier resin, a plasticizer, an antioxidant, a light stabilizer, a metal deactivator, an antiaging agent, a moisture absorber, a polymerization inhibitor, an ultraviolet absorber, an antirust agent, inorganic particles, a sensitizer, a pigment, etc.
- additives such as a silane coupling agent, a tackifier resin, a plasticizer, an antioxidant, a light stabilizer, a metal deactivator, an antiaging agent, a moisture absorber, a polymerization inhibitor, an ultraviolet absorber, an antirust agent, inorganic particles, a sensitizer, a pigment, etc.
- the amount of these additives is preferably set so as not to adversely affect the curing of the adhesive sheet or to adversely affect the physical properties of the adhesive sheet.
- the manufacturing method of the pressure-sensitive adhesive sheet according to the embodiment is not particularly limited.
- the copolymer (A), preferably the photoinitiator (B), more preferably the photocurable compound (C), additives, etc. are mixed in a predetermined amount to prepare a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is formed into a sheet, crosslinked, i.e., polymerized, and cured, and then processed appropriately as necessary to obtain the pressure-sensitive adhesive sheet according to the embodiment.
- the pressure-sensitive adhesive composition may be prepared as described above, coated on a component of an image display device, and the pressure-sensitive adhesive composition may be cured to form the pressure-sensitive adhesive sheet according to the embodiment.
- Examples of the method for mixing the components include methods using a single screw extruder, a twin screw extruder, a planetary mixer, a twin screw mixer, a pressure kneader, and the like.
- Methods for forming the pressure-sensitive adhesive composition into a sheet include, for example, wet lamination, dry lamination, extrusion casting using a T-die, extrusion lamination, calendaring, inflation, injection molding, and pouring and curing.
- the adhesive sheet according to the embodiment may be formed by dissolving the adhesive composition in an appropriate solvent and coating it using various coating methods.
- the adhesive composition can be cured by irradiating it with active energy rays.
- the adhesive sheet according to the embodiment can be produced by irradiating a molded product of the adhesive composition, for example, a sheet product of the adhesive composition, with active energy rays.
- the adhesive composition can also be heated to further cure it.
- irradiation energy, irradiation time, irradiation method, etc. of the active energy rays there are no particular limitations on the irradiation energy, irradiation time, irradiation method, etc. of the active energy rays, as long as they can activate the photoinitiator and polymerize the monomer components.
- Examples of the active energy rays to be irradiated include ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, and electron beams, ultraviolet rays, and visible light.
- ultraviolet rays are preferred from the viewpoints of suppressing damage to components of the image display device and controlling reactions.
- Examples of light sources for irradiating the active energy rays include high-pressure mercury lamps, metal halide lamps, xenon lamps, halogen lamps, LED lamps, and fluorescent lamps.
- the amount of irradiation of the active energy ray is preferably 1000 mJ/cm 2 or more, preferably 2000 mJ/cm 2 or more, more preferably 3000 mJ/cm 2 or more, and even more preferably 3500 mJ/cm 2 or more.
- the amount of irradiation of the active energy ray is preferably 10000 mJ/cm 2 or less, more preferably 7000 mJ/cm 2 or less, and even more preferably 5000 mJ/cm 2 or less.
- the lower limit and the upper limit of the amount of irradiation of the active energy ray can be arbitrarily combined.
- the adhesive sheet according to the embodiment described above satisfies requirements (1) and (2), and therefore has a high refractive index and is soft and highly flexible. Therefore, the adhesive sheet according to the embodiment is suitable as a component of a flexible image display device. It is also suitable for bonding a component having an uneven surface to a component having an organic light-emitting diode.
- the pressure-sensitive adhesive sheet according to the embodiment preferably has a release film laminated on at least one surface thereof, and more preferably has release films laminated on both surfaces thereof, prior to lamination.
- the release film is provided on both sides of the present pressure-sensitive adhesive sheet, it is preferable to use a laminate structure in which a light release film with a relatively low release force and a heavy release film with a relatively high release force are laminated.
- one release film (light release film) is peeled off to expose one side of the pressure-sensitive adhesive sheet, and the image display device component (first member) is bonded to the other side of the pressure-sensitive adhesive sheet exposed by peeling off the other release film (heavy release film), and the image display device component (second member) is bonded to the other side of the pressure-sensitive adhesive sheet.
- the release film examples include polyester film, polyolefin film, polycarbonate film, polystyrene film, acrylic film, triacetyl cellulose film, and fluororesin film.
- polyester film and polyolefin film are preferred, and polyester film is more preferred.
- the release film since the release film is easily peeled off from the pressure-sensitive adhesive sheet after irradiation with active energy rays, it is preferable that the release film be a film having a peel strength of 0.1 N/cm or less when measured under conditions of a peel angle of 180° and a peel speed of 300 mm/min.
- the thickness of the release film is preferably 25 ⁇ m or more and 500 ⁇ m or less, more preferably 38 ⁇ m or more and 250 ⁇ m or less, and even more preferably 50 ⁇ m or more and 200 ⁇ m or less.
- the lower limit and upper limit of the thickness of the release film can be combined arbitrarily.
- the laminate for an image display device Another embodiment of the present invention relates to a laminate for an image display device.
- the laminate for an image display device according to the embodiment has two image display device components laminated together via the pressure-sensitive adhesive sheet of the present invention.
- the pressure-sensitive adhesive sheet of the present invention has excellent conformability to unevenness, and therefore even if the surface of a component of an image display device has steps, it can conform and deform, absorbing the steps while bonding two components of an image display device together.
- the pressure-sensitive adhesive sheet has a high refractive index and is soft and flexible, the difference in refractive index between the pressure-sensitive adhesive sheet and the components is small, and therefore light scattering is unlikely to occur at the interface between the pressure-sensitive adhesive sheet and the components, and a laminate for an image display device with excellent visibility can be obtained.
- Examples of image display device components constituting the present laminate for image display devices include flat panel image display device components and flexible image display device components.
- image display device components include flexible displays such as liquid crystal displays and organic electroluminescence (EL) displays, cover lenses (cover films), polarizing plates, polarizers, retardation films, barrier films, viewing angle compensation films, brightness improvement films, contrast improvement films, diffusion films, semi-transmissive reflective films, electrode films, transparent conductive films, metal mesh films, touch sensor films, light-emitting elements, PSA, color filters, and flexible printed circuit boards. Any one of these or two of these can be used in combination. Examples of combinations include a combination of a flexible display and other image display device components, and a combination of a cover lens and other image display device components.
- the material of the image display device constituent member is not particularly limited.
- a resin sheet mainly composed of a resin such as a urethane resin, a cycloolefin resin, a triacetyl cellulose resin, a (meth)acrylate resin, an epoxy resin, or a polyimide resin, a thin film glass, or a metal can be mentioned.
- the "main component” means a component having the largest mass ratio among the components constituting the image display device constituent member, and is preferably 50 mass% or more, more preferably 55 mass% or more, and even more preferably 60 mass% or more.
- a flexible image display device component is a bendable component, meaning a component used in an image display device having a curved surface shape or a component that can be repeatedly bent.
- the component it is preferable for the component to be capable of being fixed into a curved shape with a radius of curvature of 25 mm or more, and more preferably, a component that can withstand bending action with a radius of curvature of less than 25 mm, and more preferably, less than 3 mm.
- the image display device member may have steps on its surface. For example, various irregularities may be present on the contact surface of the image display device member with the pressure-sensitive adhesive sheet due to wiring, printing, pattern development, surface treatment, embossing, etc.
- the height difference of the step of the image display device constituent member is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 4 ⁇ m or more, while it is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, still more preferably 7 ⁇ m or less, and particularly preferably 6 ⁇ m or less.
- the lower limit and upper limit of the height difference of the step can be combined arbitrarily.
- the step that the image display device component has on the surface that comes into contact with the adhesive sheet can be, for example, unevenness with a height difference of 2 to 10 ⁇ m and spaced at intervals of 10 mm or less.
- the thickness of the laminate for an image display device according to the embodiment is preferably 0.02 mm or more, more preferably 0.03 mm or more, and even more preferably 0.05 mm or more. Since the laminate can be made thinner, the thickness of the laminate for an image display device according to the embodiment is preferably 1.0 mm or less, more preferably 0.7 mm or less, and even more preferably 0.5 mm or less. The lower and upper thickness limits of the laminate for an image display device can be combined in any desired manner.
- the method for producing the laminate for an image display device according to the embodiment is not particularly limited.
- the pressure-sensitive adhesive composition may be applied onto a component of an image display device to form a pressure-sensitive adhesive sheet, or a pressure-sensitive adhesive sheet with a release film may be formed in advance and then attached to the component of an image display device.
- the method of laminating the adhesive sheet to the stepped surface of the image display device component is not particularly limited, and known methods such as roll lamination, press lamination using parallel plates, and diaphragm lamination can be used.
- the lamination environment may be either an atmospheric lamination method in which lamination is performed at normal pressure, or a vacuum lamination method in which lamination is performed under reduced pressure.
- the heating temperature during the heat treatment is preferably from 40°C to 100°C, more preferably from 50°C to 90°C, and even more preferably from 55°C to 85°C.
- a press pressure may be applied to the laminate in addition to the heat treatment.
- pressure treatment using an autoclave may be carried out in addition to the heat treatment.
- Flexible image display device refers to an image display device that leaves no traces of bending even when repeatedly bent, curved, or wound, and quickly recovers to its original state when released from the bent, curved, or wound state, and can display images without distortion.
- a flexible image display device includes the laminate for an image display device of the present invention.
- the laminate for an image display device is disposed on the side opposite to the viewing side of the image display panel, i.e., on the light source side.
- other members may be further laminated between the image display panel and the laminate for an image display device of the present invention, or on the opposite side of the laminate for an image display device of the present invention to the image display panel. Examples of the other members include the same image display device constituent members exemplified in the description of the laminate for an image display device of the embodiment.
- the adhesive sheet conforms to and absorbs the step, suppressing the generation of air bubbles, and also suppresses delamination and cracking even when the device is bent, curved, or wound in a low-temperature environment.
- Parts in the examples means “parts by mass.”
- TKgel SuperHZM-M (4.6mm ID x 15cmL) x 2
- TKgel SuperHZ2000 (4.6mmID x 15cmL) x 1
- Eluent Tetrahydrofuran (stabilizer BHT)
- Flow rate 0.35 mL/min Column temperature: 40° C.
- Non-volatile content volatile content
- Volatile content (%) 100 - non-volatile content (%)
- the release film on one side was removed from the pressure-sensitive adhesive sheet with release film prepared in each example, and the refractive index was measured using an Abbe refractometer (manufactured by ATAGO, model DR-A1-Plus) at a wavelength of 589 nm and at 23°C.
- Abbe refractometer manufactured by ATAGO, model DR-A1-Plus
- the release film was removed from the pressure-sensitive adhesive sheet with release film prepared in each example, and this was used as a sample.
- a pre-weighed sample was wrapped in a 150 mesh SUS wire net and immersed in ethyl acetate at 23° C. for 24 hours. The sample was then dried at 70° C. for 4.5 hours, and the mass of the insoluble sample remaining in the wire net after immersion in ethyl acetate was measured. The mass percentage of the insoluble sample remaining in the wire net relative to the mass of the sample before immersion in ethyl acetate was calculated as the gel fraction (%).
- the release film on one side was removed from the pressure-sensitive adhesive sheet with release film prepared in each example, and a PET film (thickness 50 ⁇ m) was attached as a backing film with a hand roller. This was cut into a strip of width 10 mm ⁇ length 150 mm, and the remaining release film was peeled off to expose the adhesive surface, which was then attached with a hand roller to a PET film (manufactured by Mitsubishi Chemical Corporation, Diafoil S-100, thickness 50 ⁇ m) that had been previously attached to soda-lime glass. The obtained laminate was subjected to autoclave treatment (60 ° C, gauge pressure 0.2 MPa, 20 minutes) for finish attachment to prepare a sample for measuring adhesive strength.
- autoclave treatment 60 ° C, gauge pressure 0.2 MPa, 20 minutes
- the obtained adhesive strength measurement sample was pulled at an angle of 180° at a peeling rate of 300 mm/min under conditions of 23°C and 50% RH, and the adhesive sheet together with the backing film was peeled off from the PET film attached to the soda-lime glass, and the tensile strength (N/cm) was measured with a load cell to obtain the adhesive strength.
- Total light transmittance The release film on one side was removed from the pressure-sensitive adhesive sheet with release film prepared in each example, and the exposed adhesive surface was roll-pressed to soda lime glass (82 mm x 53 mm x 0.55 mm thick). Next, the remaining release film was removed, and the sheet was roll-pressed to soda lime glass (82 mm x 53 mm x 0.5 mm thick). After that, the sheet was autoclaved (60°C, gauge pressure 0.2 MPa, 20 minutes) for finish-pasting to prepare a sample for measuring optical properties. The total light transmittance of the sample for measuring optical properties was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH5000) in accordance with ISO-13468-1.
- a haze meter manufactured by Nippon Denshoku Industries Co., Ltd., NDH5000
- SLMA a mixture of an alkyl methacrylate having an alkyl group with 12 carbon atoms and an alkyl methacrylate having an alkyl group with 13 carbon atoms, manufactured by Mitsubishi Chemical Corporation, trade name: Acryester SL.
- POB-A m-phenoxybenzyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. (refractive index: 1.566).
- OPPEA o-phenylphenoxyethyl acrylate, manufactured by MIWON Corporation, trade name: Miramer M1142 (refractive index: 1.577).
- PO-A Phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.
- AA acrylic acid, manufactured by Mitsubishi Chemical Corporation. 4HBA: 4-hydroxybutyl acrylate, manufactured by Mitsubishi Chemical Corporation. nBA: n-butyl acrylate, manufactured by Mitsubishi Chemical Corporation. 2EHA: 2-ethylhexyl acrylate, manufactured by Mitsubishi Chemical Corporation. nOA: n-octyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. MMA: methyl methacrylate, manufactured by Mitsubishi Chemical Corporation. AMBN: 2,2'-azobis(2-methylbutyronitrile), manufactured by Otsuka Chemical Co., Ltd.
- the reaction solution was kept at 60 ° C. for 6 hours, and then cooled to room temperature to obtain a dispersant 1 having a solid content of 10 mass % as a transparent aqueous solution.
- a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.1 parts of sodium sulfate, and 0.25 parts of dispersant 1 (solid content 10% by mass) were added and stirred to obtain a uniform aqueous solution.
- MMA-MM macromonomer having MMA as a constituent unit.
- the weight average molecular weight of the macromonomer (MMA-MM) was 5,800.
- Example 1 (Production of (meth)acrylic copolymer) A four-neck flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet was charged with 25 parts of ethyl acetate, 2 parts of isopropyl alcohol (IPA), and 15 parts of a macromonomer (SLMA-MM) solution (concentration: 50% by mass) as a charging solvent, and the external temperature was raised to 85 ° C. in a water bath under nitrogen gas aeration.
- IPA isopropyl alcohol
- SLMA-MM macromonomer
- a solvent-containing adhesive composition was prepared by blending 100 parts (solids) of a (meth)acrylic copolymer, 1.5 parts of a (meth)acrylic oligomer (Mitsubishi Chemical Corporation, Shikoh UV-3700B) as a photocurable compound, 1.5 parts of a photoinitiator (IGM, Esacure TZT), and 154.5 parts of ethyl acetate.
- the adhesive composition was spread in a sheet shape on a 100 ⁇ m-thick release film (Mitsubishi Chemical Corporation, silicone release-treated PET film) so that the thickness after drying would be 50 ⁇ m.
- the sheet-shaped adhesive composition together with the release film was placed in a dryer heated to 90° C. and held for 10 minutes to volatilize the solvent contained in the adhesive composition. Furthermore, a release film (manufactured by Mitsubishi Chemical Corporation, silicone release-treated PET film) having a thickness of 75 ⁇ m was laminated on the sheet-shaped adhesive composition from which the solvent had been dried, and active energy rays were irradiated to the adhesive composition through the release film using a high-pressure mercury lamp so that the integrated light amount at a wavelength of 365 nm was 4000 mJ/cm 2 , thereby obtaining an adhesive sheet with a release film in which release films were laminated on both the front and back sides of a 50 ⁇ m-thick adhesive sheet.
- a release film manufactured by Mitsubishi Chemical Corporation, silicone release-treated PET film
- Examples 2 to 11, Comparative Examples 1 and 2 Except for changing the copolymerization composition of the (meth)acrylic copolymer as shown in Table 1, a pressure-sensitive adhesive sheet with a release film was produced in the same manner as in Example 1. The results of the measurements and evaluations of the pressure-sensitive adhesive sheets of each example are shown in Table 1.
- the pressure-sensitive adhesive sheets of Examples 1 to 11 had a high refractive index of 1.480 or more.
- G' (-20°C) was 10 kPa or more and 1000 kPa or less, indicating that the sheets had excellent flexibility in a low-temperature environment.
- the adhesive strength was also good.
- the pressure-sensitive adhesive sheets of Examples 3 to 8 had a high recovery rate of 90% or more, indicating that the sheets had excellent recovery when folded.
- the pressure-sensitive adhesive sheet of Comparative Example 1 had a lower refractive index than the pressure-sensitive adhesive sheets of the Examples.
- the pressure-sensitive adhesive sheet of Comparative Example 2 had a storage modulus at -20°C (G'(-20°C)) of more than 1000 kPa, and was poor in flexibility in a low-temperature environment.
- the present invention provides an adhesive sheet that has a high refractive index and is soft and highly flexible, an adhesive sheet with a release film that uses the same, a laminate for an image display device, and a flexible image display device.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本願は、2023年1月23日に日本国特許庁に出願された、特願2023-8193号に基づき優先権を主張し、その内容をここに援用する。
フレキシブル画像表示装置の積層シートには、光学特性は勿論のこと、フレキシブル性、特に折り曲げに対する高度な耐久性が必要となる。
特許文献2には、実使用環境下に近い屈曲試験によっても、折れや剥がれが発生することのない、積層体が開示されている。この積層体は、所定範囲のガラス転移温度及び貯蔵弾性率を有する両面粘着シートと、画像表示装置構成用フレキシブル部材とを有する。
特許文献3に開示の粘着剤層は、高屈折率ではあるものの、屈折率を高めるための高屈折率モノマーを多く含み粘着剤のガラス転移温度が高いため柔軟とはいえず、フレキシブル性は考慮されていないものであった。フレキシブル性と高屈折率の両立において更なる改良が求められる。
[1]粘着剤組成物から形成された粘着シートであって、
前記粘着剤組成物は、(メタ)アクリル系共重合体(A)を含有し、
下記の要件(1)及び要件(2)を満たす、粘着シート。
要件(1)前記粘着シートの屈折率が、1.480以上1.550未満である。
要件(2)周波数1Hzの剪断モードでの動的粘弾性測定により得られる、-20℃の剪断貯蔵弾性率(G’(-20℃))が10kPa以上1000kPa以下である、粘着シート。
[2]前記(メタ)アクリル系共重合体(A)が、屈折率が1.500以上の芳香族(メタ)アクリレート(a1)由来の構成単位を有する、前記[1]に記載の粘着シート。
[3]前記芳香族(メタ)アクリレート(a1)のホモポリマーのガラス転移温度(Tg)が、60℃以下である、[2]に記載の粘着シート。
[4]前記(メタ)アクリル系共重合体(A)の全構成単位に対する、前記芳香族(メタ)アクリレート(a1)由来の構成単位の割合が、1~50質量%である、前記[2]又は[3]に記載の粘着シート。
[5]周波数1Hzの剪断モードでの動的粘弾性測定により得られる、Tanδの極大値で定義されるガラス転移温度(Tg)が、-20℃以下である、前記[1]~[4]のいずれかに記載の粘着シート。
[6]前記粘着剤組成物が、光開始剤(B)をさらに含有する、前記[1]~[5]のいずれかに記載の粘着シート。
[7]前記粘着剤組成物が、光硬化性化合物(C)をさらに含有する、前記[1]~[5]のいずれかに記載の粘着シート。
[8]前記粘着剤組成物が、光開始剤(B)及び光硬化性化合物(C)をさらに含有する、前記[1]~[5]のいずれかに記載の粘着シート。
[9]周波数1Hzの剪断モードでの動的粘弾性測定により得られる、60℃の剪断貯蔵弾性率G’(60℃)に対する-20℃の剪断貯蔵弾性率G’(-20℃)の比(G’(-20℃)/G’(60℃))が150以下である、前記[1]~[8]のいずれかに記載の粘着シート。
[10]前記粘着シートに60℃にて2kPaの応力を600秒印加した時の最大歪み値(γmax)と、その後、前記応力を除いた600秒後の残留歪み値(γmin)とから下記式により算出される復元率が60%以上である、前記[1]~[9]のいずれかに記載の粘着シート。
復元率(%)=〔(γmax-γmin)/γmax〕×100
[11]ゲル分率が、30%以上である、前記[1]~[10]のいずれかに記載の粘着シート。
[12]前記(メタ)アクリル系共重合体(A)が、アルキル基の炭素数が9~30のアルキル(メタ)アクリレート由来の構成単位を有する、前記[1]~[11]のいずれかに記載の粘着シート。
[13]前記(メタ)アクリル系共重合体(A)が、ブロック共重合体又はグラフト共重合体である、前記[1]~[12]のいずれかに記載の粘着シート。
[14]前記(メタ)アクリル系共重合体(A)は、マクロモノマー(a10)由来の構成単位を有する、前記[1]~[13]のいずれかに記載の粘着シート。
[15]前記マクロモノマー(a10)が、アルキル基の炭素数が9~30のアルキル(メタ)アクリレート由来の構成単位を有する、[14]に記載の粘着シート。
[16]前記(メタ)アクリル系共重合体(A)は、屈折率が1.500以上の芳香族(メタ)アクリレート(a1)由来の構成単位をさらに有し、
前記(メタ)アクリル系共重合体(A)中における前記芳香族(メタ)アクリレート(a1)由来の構成単位に対する前記マクロモノマー(a10)由来の構成単位の含有割合(a10/a1)が、重量比で0.1~10である、[14]又は[15]に記載の粘着シート。
[17]表面に凹凸を有する部材と有機発光ダイオードを有する部材との貼合用である、前記[1]~[16]のいずれかに記載の粘着シート。
[18]前記[1]~[17]のいずれかに記載の粘着シートと、前記粘着シートの少なくとも一方の表面に積層された離型フィルムと、を備えた、離型フィルム付き粘着シート。
[19]フレキシブル画像表示装置構成部材用である、前記[1]~[17]のいずれかに記載の粘着シート。
[20]2つの画像表示装置構成部材と、前記[1]~[17]のいずれかに記載の粘着シートと、を備え、前記2つの画像表示装置構成部材が、前記粘着シートを介して積層され、前記2つの画像表示装置構成部材の少なくとも一方が、前記粘着シートとの接触面に、高低差2μm以上の段差を有する、画像表示装置用積層体。
[21]前記[20]に記載の画像表示装置用積層体を備えた、フレキシブル画像表示装置。
「(メタ)アクリレート」は、アクリレート及びメタクリレートの総称である。「(メタ)アクリロイル基」、「(メタ)アクリル酸」、「(メタ)アクリロニトリル」、「(メタ)アクリルアミド」も同様である。
「(メタ)アクリル系共重合体」は、(メタ)アクリル系単量体由来の構成単位を有する共重合体を意味する。(メタ)アクリル系共重合体は、(メタ)アクリル系単量体以外の単量体(例えば、スチレン等)由来の構成単位をさらに有していてもよい。
「(メタ)アクリル系単量体」は、(メタ)アクリロイル基を有する単量体を意味する。
「ビニル単量体」は、エチレン性不飽和結合(重合性炭素-炭素二重結合)を有する化合物を意味する。
数値範囲を示す「~」は、その前後に記載された数値を下限値及び上限値として含むことを意味すると共に、「好ましくは下限値より大きい」あるいは「好ましくは上限値より小さい」の意も包含するものである。
また、「x以上」(xは任意の数字)と記載した場合、特にことわらない限り「好ましくはxより大きい」の意を包含し、「y以下」(yは任意の数字)と記載した場合、特にことわらない限り「好ましくはyより小さい」の意も包含するものである。
さらに、「x及び/又はy(x,yは任意の構成)」とは、x及びyの少なくとも一方を意味するものであって、xのみ、yのみ、x及びy、の3通りを意味するものである。
本発明の一実施形態は、粘着シートに関する。
実施形態に係る粘着シートは、(メタ)アクリル系共重合体(A)を含有する粘着剤組成物から形成されたものである。
粘着剤組成物は、光開始剤(B)をさらに含有することが好ましい。
粘着剤組成物は、光硬化性化合物(C)をさらに含有することが好ましい。
粘着剤組成物は、(メタ)アクリル系共重合体(A)、光開始剤(B)及び光硬化性化合物(C)以外の他の成分をさらに含有してもよい。
(1)粘着シートの屈折率が1.480以上1.550未満である。
屈折率差のさらなる低減の観点から、要件(1)の屈折率は、1.482以上が好ましく、1.485以上がより好ましく、1.490以上がさらに好ましい。同様の観点から、要件(1)の屈折率は、1.570以下が好ましく、1.560以下がより好ましく、1.550以下がさらに好ましく、1.520以下が殊に好ましい。要件(1)の屈折率の下限と上限は任意に組み合わせることができる。
要件(1)の屈折率の測定は、アッベ屈折率計を使用し、波長589nm及び23℃の条件で測定される。
(2)周波数1Hzの剪断モードでの動的粘弾性測定により得られる、-20℃の剪断貯蔵弾性率(G’(-20℃))が10kPa以上1000kPa以下である。
粘着シートの非貼合時の形状保持力の観点から、要件(2)のG’(-20℃)は、30kPa以上が好ましく、50kPa以上がより好ましく、100kPa以上がさらに好ましい。一方、粘着シートの低温環境下での柔軟性の観点から、要件(2)のG’(-20℃)は、800kPa以下が好ましく、600kPa以下がより好ましく、400kPa以下がさらに好ましく、300kPa以下が特に好ましい。要件(2)のG’(-20℃)の下限と上限は任意に組み合わせることができる。
「厚さを0.7~1.0mmの範囲に調整」とは、測定サンプルとしての粘着シートの厚さがこの範囲に満たない場合には、何枚か重ねるなどして、測定サンプルの厚さをこの範囲に調整することを意味する。他の試験において、測定サンプルの厚さを規定している場合も同様である。
粘着シートを繰り返し積層して厚さを0.7~1.0mmに調整した後、直径8mmの円状のサンプルを打ち抜く。得られたサンプルについて、レオメータを用い、測定治具:直径8mmパラレルプレート、周波数:1Hz、測定温度:-50~150℃、昇温速度:5℃/分の条件で動的粘弾性測定を行い、-20℃における剪断貯蔵弾性率(G’)の値を読み取る。
(3)周波数1Hzの剪断モードでの動的粘弾性測定により得られる、Tanδの極大値で定義されるガラス転移温度(Tg)が-20℃以下である。
優れたフレキシブル性を得る観点から、要件(3)のTgは、-25℃以下が好ましく、-28℃以下がより好ましく、-30℃以下がさらに好ましく、-35℃以下が特に好ましい。一方、下限は、通常-80℃である。
(4)周波数1Hzの剪断モードでの動的粘弾性測定により得られる、60℃の剪断貯蔵弾性率G’(60℃)に対する-20℃の剪断貯蔵弾性率G’(-20℃)の比(G’(-20℃)/G’(60℃))が150以下である。
低温環境下での柔軟性向上の観点から、要件(4)のG’(-20℃)/G’(60℃)は、100以下が好ましく、80以下がより好ましく、50以下がさらに好ましく、40以下が特に好ましく、30以下が最も好ましい。一方、粘着力向上の観点から、要件(4)のG’(-20℃)/G’(60℃)は、3以上が好ましく、5以上がより好ましく、10以上がさらに好ましい。要件(4)のG’(-20℃)/G’(60℃)の上限と下限は任意に組み合わせることができる。
(5)粘着シートに60℃にて2kPaの応力を600秒印加した時の最大歪み値(γmax)と、その後、前記応力を除いた600秒後の残留歪み値(γmin)とから下記式により算出される復元率が60%以上である。
復元率(%)=〔(γmax-γmin)/γmax〕×100
折り曲げ時の復元性に優れた粘着シートを得る観点から、要件(5)の復元率は、65%以上が好ましく、70%以上がより好ましく、75%以上がさらに好ましく、80%以上が特に好ましく、85%以上が最も好ましい。一方、粘着力向上の観点から、要件(5)の復元率は、99%以下が好ましく、98%以下がより好ましく、97%以下がさらに好ましい。要件(5)の復元率の下限と上限は任意に組み合わせることができる。
粘着シートを繰り返し積層して厚さを0.7~1.0mmに調整した後、直径8mmの円状のサンプルを打ち抜く。得られたサンプルについて、レオメータを用いて、60℃で2kPaの圧力を600秒印加した後のひずみ(γmax)と、その後応力を除荷し600秒経過後のひずみ(γmin)を測定する。得られた値を下記式に代入し、復元率を算出する。
復元率(%)=〔(γmax-γmin)/γmax〕×100
(6)粘着シートのゲル分率が30%以上である。
凝集力向上の観点から、要件(6)のゲル分率は、35%以上が好ましく、40%以上がより好ましく、45%以上がさらに好ましい。一方、粘着力を得る観点から、要件(6)のゲル分率は、90%以下が好ましく、87%以下がより好ましく、85%以下がさらに好ましい。要件(6)のゲル分率の下限と上限は任意に組み合わせることができる。
予め秤量した粘着シートを150メッシュのSUS製金網で包み、23℃で、酢酸エチル中に24時間浸漬する。その後70℃で4.5時間乾燥させ、酢酸エチル浸漬の前後における粘着剤の質量をそれぞれ測定し、両質量の差を金網中に残存した不溶解の粘着剤の質量(浸漬後質量)とする。酢酸エチル浸漬前における粘着剤の質量(浸漬前質量)に対する、金網中に残存した不溶解の粘着剤の質量(浸漬後質量)の百分率を要件(6)のゲル分率(%)として算出する。
(7)粘着シートをポリエステルフィルムに貼合した時の、23℃、50%RH、剥離角180°、剥離速度300mm/分におけるポリエステルフィルム表面に対する粘着力が0.5N/cm以上である。
粘着シートの粘着性の観点から、要件(7)の粘着力は、1N/cm以上が好ましく、2N/cm以上がより好ましく、3N/cm以上がさらに好ましい。要件(7)の粘着力の上限は、特に限定されず、例えば、20N/cm以下であり得る。
粘着シートの片面に裏打ちフィルムとしてポリエステルフィルムを背貼りし、幅10mm×長さ150mmの短冊状に裁断して試験片とする。予めソーダライムガラスに貼り合わせたポリエステルフィルムに試験片を貼着し、オートクレーブ処理(60℃、ゲージ圧0.2MPa、20分)を施して粘着力測定サンプルとする。得られた粘着力測定サンプルについて、23℃、50%RHの環境下、剥離角180°、剥離速度300mm/分の条件で、ソーダライムガラスに貼り合わせたポリエステルフィルムから裏打ちフィルムとともに粘着シートを剥離し、ロードセルで引張強度(N/cm)を測定して粘着力とする。
(8)全光線透過率が80%以上である。
要件(8)を満たす粘着シートは透明性に優れ、画像表示装置等、透明性が求められる用途に有用である。
要件(8)の全光線透過率は、85%以上が好ましく、90%以上がより好ましい。要件(8)の全光線透過率は高いほど好ましく、上限は特に限定されない。
要件(8)の全光線透過率の測定は、JIS-K7361-1(ISO-13468-1)の規格に準じて行われる。
(9)ヘイズが5%以下である。
要件(9)を満たす粘着シートは透明性に優れ、画像表示装置等、透明性が求められる用途に有用である。
要件(9)のヘイズは、4%以下が好ましく、2%以下がより好ましく、1%以下がさらに好ましい。要件(9)のヘイズは低いほど好ましく、下限は特に限定されない。
要件(9)のヘイズの測定は、JIS-K7136(ISO-14782)の規格に準じて行われる。
実施形態に係る粘着シートにおいて、要件(1)~(9)を調整する方法の1つは、(メタ)アクリル系共重合体(A)の組成を調整することである。
以下、実施形態に係る粘着シートに好ましく用い得る(メタ)アクリル系共重合体(A)(以下、単に「共重合体(A)」とも記す。)の一例について説明する。
芳香族基としては、例えば、フェニル、ビフェニル、ナフチル、フェナントレニル、アントラセニル、ピレニル等が挙げられる。
芳香環は1以上の置換基を有していてもよい。芳香環が置換基を有するとは、芳香環の環骨格を構成する原子(炭素原子等)に置換基が結合していることを意味する。置換基としては、例えば、F、Cl、Br、I等のハロゲンや、炭素数1~10のアルキル、炭素数1~10のアルコキシ、炭素数2~11のアシロキシ等が挙げられる。
芳香族(メタ)アクリレート(a1)が有する芳香環の数は、屈折率を高める観点から、2以上が好ましく、相溶性の観点から、4以下が好ましい。
芳香環は、芳香族(メタ)アクリレート(a1)の(メタ)アクリロイル基に直接結合していてもよく、連結基を介して結合していてもよい。連結基としては、例えば、アルキレン、(ポリ)アルキレングリコール、エーテル、エステル、ウレタン、カーボネート、アミド、ウレア等が挙げられる。
芳香族(メタ)アクリレート(a1)の屈折率は、JIS-K7142の規格に準じて求められる。
芳香族(メタ)アクリレート(a1)の屈折率として、カタログ等に記載された値を採用してもよい。
一方、下限は通常-70℃以上であるが、粘着シートに適度な凝集力を付与する観点からは-40℃以上が好ましく、-20℃以上がより好ましく、0℃以上が好ましく、10℃以上がさらに好ましい。
ポリマーTgの下限と上限は任意に組み合わせることができる。
芳香族(メタ)アクリレート(a1)のポリマーTgは、文献値、例えば、ポリマーハンドブック〔Polymer HandBook,J.Brandrup,Interscience,1989〕や単量体のカタログに記載されている値を用いることができる。
また、優れた粘着物性を得る観点から、芳香族(メタ)アクリレート(a1)由来の構成単位及びアルキル基の炭素数が4~30のアルキル(メタ)アクリレート(a2)由来の構成単位以外に、カルボキシ基含有モノマー(a3)、水酸基含有モノマー(a4)、窒素含有モノマー(a5)、エポキシ基含有モノマー(a6)、ビニルモノマー(a7)、アルキル基の炭素数が1~3であるアルキル(メタ)アクリレートモノマー(a8)、脂環式モノマー(a9)、マクロモノマー(a10)、及びその他の共重合性モノマー(a11)からなる群から選択される何れか一つ以上の共重合性モノマー由来の構成単位を有することが好ましい。
また、カルボキシ基含有モノマー(a3)を含まず、水酸基含有モノマー(a4)、及び窒素含有モノマー(a5)からなる群から選択される何れか一つ以上が特に好ましい。水酸基含有モノマー(a4)、及び窒素含有モノマー(a5)からなる群から選択される何れか一つ以上に由来する構成単位を有する共重合体(A)の場合、被着体が金属などの腐食性を有する成分を含有する場合の耐腐食特性、接着性及び耐湿熱白化特性の兼備が可能となる。
さらに、窒素含有モノマー(a5)の中でも、後述する水素引抜反応の増感作用を有し、その結果、効率的に架橋を形成できる点からは、3級窒素原子を有するものが好ましい。
CH2=CH(R1)-COO(R2) (1)
(式中、R1は水素原子又はメチル基を表し、R2は炭素原子数4~30の直鎖又は分岐状のアルキル基を表す。)
アルキル(メタ)アクリレート(a2)の中でも、アルキル基中に3級炭素原子を有するアルキル(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、光照射時に、水素引抜反応が起こりやすく、その結果、効率的に架橋を形成しやすくなる。
アルキル(メタ)アクリレート(a2)由来の構成単位の含有量の下限と上限は任意に組み合わせることができる。
水酸基含有モノマー(a4)により、粘着シートの粘着力が向上するとともに、湿熱白化を抑止することができる。
共重合体(A)中のアルキル(メタ)アクリレートモノマー(a8)由来の構成単位の含有量は、粘着シートに凝集力を付与する観点から、共重合体(A)の全構成単位に対して、0.1~15質量%が好ましく、0.5~13質量%がより好ましく、1~10質量%がさらに好ましく、2~7質量%が特に好ましい。
共重合体(A)中の共重合性モノマー(a9)由来の構成単位の含有量は、粘着シートに凝集力を付与する観点から、共重合体(A)の全構成単位に対して、0.1~15質量%が好ましく、0.5~13質量%がより好ましく、1~10質量%がさらに好ましく、2~7質量%が特に好ましい。
マクロモノマー(a10)と、それ以外のモノマーの選択や配合比率によって、グラフト共重合体の主鎖と側鎖の特性を変化させることができる。
中でも、アルキル基の炭素数が1~8のアルキル(メタ)アクリレートや脂環式モノマー、スチレン等の芳香族モノマーを用いることが、凝集力に優れた粘着シートとすることができる点で好ましい。
一方、アルキル基の炭素数が9~30、好ましくは10~20のアルキル(メタ)アクリレートを用いることが、適度な凝集力を有しながらフレキシブル性に優れた粘着シートとすることができる点で好ましい。
これらは単独で又は2種類以上を組み合わせて使用することができる。
また、ラジカル重合性官能基と官能基はどちらか一方でも、両方含有していてもよい。
マクロモノマー(a10)の重量平均分子量は、ゲル透過クロマトグラフィー(GPC)により測定される標準ポリスチレン換算の値である。
共重合体(A)の重量平均分子量は、ゲル透過クロマトグラフィー(GPC)により測定される標準ポリスチレン換算の値である。
溶融粘度は、例えば、株式会社ユービーエム製の粘弾性測定装置Rheosol-G5000を用いて測定することができる。
重合方法としては、溶液重合法、懸濁重合法及び乳化重合法等、公知の重合方法によって製造することが可能である。粘着シートとして用いるため、溶液重合法が好ましい。
粘着シートを形成する粘着剤組成物は、共重合体(A)に加えて、光開始剤(B)をさらに含有することが好ましい。粘着剤組成物が光開始剤(B)を含有することで、活性エネルギー線による硬化性を有し得る。
光開始剤(B)は、紫外線や可視光線等の光、より具体的には、波長200nm~780nmの光を照射することによって活性なラジカル種を発生する化合物である。
光開始剤(B)としては、公知の光開始剤のなかから適宜選択できる。例えば、開裂型光開始剤、水素引抜型光開始剤が挙げられる。
光開始剤(B)は、水素引抜型光開始剤を含むことが好ましい。光開始剤(B)が水素引抜型光開始剤を含むと、共重合体(A)からも水素引抜反応を起こし、光硬化性化合物(C)のみならず共重合体(A)も架橋構造に取り込まれ、架橋点が多い架橋構造を形成することができる。また、水素引抜型光開始剤の中でも、分子内水素引抜型光開始剤は、系中の水素供与体のみならず、自身もラジカル発生の起点となりうる点で好ましい。
粘着シートを形成する粘着剤組成物は、共重合体(A)に加えて、又は共重合体(A)及び光開始剤(B)に加えて、光硬化性化合物(C)をさらに含有することが好ましい。
粘着剤組成物が光硬化性化合物(C)をさらに含有することにより活性エネルギー線による硬化効率を高めることができるとともに、活性エネルギー線硬化後の凝集力を高めることができる。
ただし、共重合体(A)が光開始剤(B)等の作用によって水素引抜反応を起こして、本共重合体内及び/又は本共重合体間で十分な架橋構造を形成することができる場合は、粘着剤組成物は必ずしも光硬化性化合物(C)を含有する必要はない。
光硬化性化合物(C)としては、例えば、単官能(メタ)アクリル系単量体、多官能(メタ)アクリル系単量体、(メタ)アクリル系オリゴマーが挙げられる。
単官能(メタ)アクリル系単量体は、(メタ)アクリロイル基を1つ有する。
単官能(メタ)アクリル系単量体としては、共重合体(A)を形成する単量体として挙げたものを例示できる。
中でも、硬化物に適度な靭性を付与する観点から、多官能ウレタン(メタ)アクリレートが好ましい。
粘着シートを形成する粘着剤組成物には、必要に応じて、シランカップリング剤、粘着付与樹脂、可塑剤、酸化防止剤、光安定化剤、金属不活性化剤、老化防止剤、吸湿剤、重合禁止剤、紫外線吸収剤、防錆剤、無機粒子、増感剤、顔料等の各種の添加剤を添加してもよい。これら添加剤の量は、典型的には、粘着シートの硬化に悪影響を与えないように、又は、粘着シートの物理的特性に悪影響を与えないように設定することが好ましい。
実施形態に係る粘着シートの製造方法は、特に限定されない。例えば、共重合体(A)と、好ましくは光開始剤(B)、さらに好ましくは光硬化性化合物(C)、添加剤等をそれぞれ所定量混合して粘着剤組成物を調製し、当該粘着剤組成物をシート状に成形し、架橋すなわち重合反応させて硬化させ、必要に応じて適宜加工を施すことにより、実施形態に係る粘着シートを得ることができる。又は、上記のようにして粘着剤組成物を調製し、これを画像表示装置構成部材上にコーティングし、当該粘着剤組成物を硬化させることにより、実施形態に係る粘着シートを形成してもよい。
粘着剤組成物をシート状に成形する方法としては、例えば、ウェットラミネーション法、ドライラミネート法、Tダイを用いる押出キャスト法、押出ラミネート法、カレンダー法やインフレーション法、射出成形法、注液硬化法が挙げられる。
活性エネルギー線を照射する際の光源については、例えば、高圧水銀ランプ、メタルハライドランプ、キセノンランプ、ハロゲンランプ、LEDランプ、蛍光ランプが挙げられる。
本発明の他の実施形態は、離型フィルム付き粘着シートに関する。
実施形態に係る粘着シートは、貼合前にはその少なくとも一方の表面に離型フィルムが積層されていることが好ましく、両方の表面に離型フィルムが積層されていることがより好ましい。
本粘着シートの両面に離型フィルムを設ける場合は、剥離力の相対的に低い軽剥離フィルムと、剥離力の相対的に高い重剥離フィルムが積層された積層体構成とするのが好ましい。両面に離型フィルムを設けた離型フィルム付き粘着シートの使用時には、まず、一方の離型フィルム(軽剥離フィルム)を剥離して粘着シートの一方の面を露出させて、画像表示装置構成部材(第1部材とする)との貼り合わせを行い、他方の離型フィルム(重剥離フィルム)を剥離して露出した粘着シートの他方の面に、画像表示装置構成部材(第2部材とする)を貼り合わせればよい。
また、活性エネルギー線を照射した後の粘着シートからも剥離しやすいことから、離型フィルムは、剥離角180°、剥離速度300mm/分の条件で測定される剥離力が0.1N/cm以下であるフィルムが好ましい。
本発明の他の実施形態は画像表示装置用積層体に関する。
実施形態に係る画像表示装置用積層体は、2つの画像表示装置構成部材が本発明の粘着シートを介して積層されている。
本発明の粘着シートは、凹凸追従性に優れるため、画像表示装置構成部材表面が段差を有していても追随して変形し、段差を吸収しつつ2つの画像表示装置構成部材を貼合することができる。また、高屈折率であるとともに、柔軟でフレキシブル性に優れていることから、粘着シートと部材との屈折率の差が小さいことに起因して、粘着シートと部材との界面において光散乱等が発生しにくく、視認性に優れた画像表示装置用積層体を得ることができる。
画像表示装置構成部材の材質は、特に限定されない。例えば、ウレタン樹脂、シクロオレフィン樹脂、トリアセチルセルロース樹脂、(メタ)アクリレート樹脂、エポキシ樹脂、ポリイミド樹脂等の樹脂を主成分とする樹脂シート、薄膜ガラス、金属等が挙げられる。ここで「主成分」とは、画像表示装置構成部材を構成する成分のうち質量比率が最も多い成分であることを意味し、50質量%以上が好ましく、55質量%以上がより好ましく、60質量%以上がさらに好ましい。
画像表示装置構成部材が有する段差の高低差は、2μm以上が好ましく、3μm以上がより好ましく、4μm以上がさらに好ましく、一方10μm以下が好ましく、8μm以下がより好ましく、7μm以下がさらに好ましく、6μm以下が特に好ましい。段差の高低差の下限と上限は任意に組み合わせることができる。
画像表示装置構成部材が粘着シートとの接触面に有する段差は、例えば、高低差2~10μmで、かつ10mm以下の間隔で設けられた凹凸であり得る。
例えば、粘着剤組成物を画像表示装置構成部材上に塗布して粘着シートを形成してもよいし、予め離型フィルム付き粘着シートを形成した後に、画像表示装置構成部材と貼合してもよい。
また、粘着シートを貼合する際には、加熱処理と併せてオートクレーブによる加圧処理を施してもよい。
本発明のさらに別の実施形態は、フレキシブル画像表示装置に関する。
「フレキシブル画像表示装置」とは、繰り返し折り曲げや湾曲操作、巻き取り操作をしても曲げ跡を残さず、折り曲げ状態や湾曲状態、巻き取り状態を解放した際には操作前の状態まで素早く回復し、歪みなく画像を表示できる画像表示装置を意味する。
実施形態に係るフレキシブル画像表示装置では、画像表示パネルと本発明の画像表示装置用積層体との間や、本発明の画像表示装置用積層体の画像表示パネルとは反対側に他の部材がさらに積層されていてもよい。他の部材としては、実施形態の画像表示装置用積層体の説明において例示した画像表示装置構成部材と同じものを例示できる。
実施例中の測定及び評価は、以下に示す方法で行った。
マクロモノマーの0.2質量%テトラヒドロフラン溶液を調製し、下記の条件にて、標準ポリスチレン換算による重量平均分子量(Mw)を求めた。
・GPC装置:東ソー社製「HLC-8320」
・カラム:東ソー社製の下記のカラムを直列に接続して使用した。ガードカラムは東ソー社製「TSKguardcolumn SuperHZ-L」(4.6mmID×2.0cmL)を用いた。
「TSKgel SuperHZM-M」(4.6mmID×15cmL)×2本
「TSKgel SuperHZ2000」(4.6mmID×15cmL)×1本
・注入量:10μL
・溶離液:テトラヒドロフラン(安定剤BHT)
・流速:0.35mL/分
・カラム温度:40℃
(メタ)アクリル系共重合体の0.27質量%テトラヒドロフラン溶液を調製し、下記の条件にて、標準ポリスチレン換算による重量平均分子量(Mw)を求めた。
・GPC装置:東ソー社製「HLC-8320」
・カラム:東ソー社製のカラム「TSKgel SuperHZM-H」(6.0mmID×15cmL)を2本直列に接続して使用した。ガードカラムは東ソー社製「TSKguardcolumn SuperHZ-H」(4.6mmID×3.5cmL)を用いた。
・注入量:10μL
・溶離液:テトラヒドロフラン(安定剤BHT)
・流速:0.5mL/分
・カラム温度:40℃
試料をアルミ皿の上に約1g載せ、105℃の送風機付きオーブンで2時間乾燥させ、乾燥前後の質量を電子天秤で測定し、下記式により不揮発分濃度を求めた。
不揮発分濃度(%)=(乾燥後の試料の質量(g)/乾燥前の試料の質量(g))×100
求めた不揮発分濃度から、下記式により揮発分濃度を求めた。
揮発分濃度(%)=100-不揮発分濃度(%)
各例で作製した離型フィルム付き粘着シートから片面側の離型フィルムを取り除き、アッベ屈折率計(ATAGO社製、型式DR-A1-Plus)を使用し、波長589nm及び23℃の測定条件で屈折率を測定した。
各例で作製した離型フィルム付き粘着シートから片面側の離型フィルムを取り除き、ハンドローラーで積層することを繰り返して厚さ約0.8mmに調整し、直径8mmの円状に打ち抜いたものをサンプルとした。得られたサンプルをレオメータ(T.A.Instruments社製「DHR-2」)に設置し、測定治具:直径8mmパラレルプレート、周波数:1Hz、測定温度:-50~150℃、昇温速度:5℃/分の条件で動的粘弾性測定を行い、-20℃、25℃、60℃及び80℃の剪断貯蔵弾性率G’の値を読み取った。測定結果から、G’(-20℃)/G’(60℃)の値を算出した。また、損失正接(tanδ)の極大点が現れる温度を粘着シートのガラス転移温度(Tg)として読み取った。
各例で作製した離型フィルム付き粘着シートから片面側の離型フィルムを取り除き、ハンドローラーで積層することを繰り返して厚さ約0.8mmに調整し、直径8mmの円状に打ち抜いたものをサンプルとした。得られたサンプルをレオメータ(T.A.Instruments社製「DHR-2」)に設置し、測定治具:直径8mmパラレルプレート、温度:60℃、圧力:2kPaの条件で600秒後の歪み(%)を測定し、その値をクリープ歪(最大値)とした。
離型フィルム付き粘着シートから片面側の離型フィルムを取り除き、ハンドローラーで積層することを繰り返して厚さ約0.8mmに調整し、直径8mmの円状に打ち抜いたもの(直径8mm、高さ約0.8mmの円柱体)をサンプルとした。得られたサンプルについて、粘弾性測定装置(T.A.Instruments社製 「DHR-2」)を用いて、60℃にて2kPaの応力を600秒間印加した時の最大歪み値(γmax)と、その後、前記応力を除いた600秒後の残留歪み値(γmin)を読み取り、下記式から復元率を算出した。
復元率(%)=〔(γmax-γmin)/γmax〕×100
各例で作製した離型フィルム付き粘着シートから離型フィルムを取り除き、これをサンプルとした。
150メッシュのSUS製金網で、予め秤量したサンプルを包み、23℃で酢酸エチル中に24時間浸漬した。その後70℃で4.5時間乾燥させ、酢酸エチル浸漬の後の金網中に残存した不溶解のサンプルの質量を測定した。酢酸エチル浸漬前におけるサンプルの質量に対する、金網中に残存した不溶解のサンプルの質量百分率をゲル分率(%)として算出した。
各例で作製した離型フィルム付き粘着シートから片面側の離型フィルムを取り除き、裏打ちフィルムとしてPETフィルム(厚さ50μm)をハンドローラーで貼着した。これを幅10mm×長さ150mmの短冊状に裁断し、残る離型フィルムを剥がして露出した粘着面を、予めソーダライムガラスに貼り合わせたPETフィルム(三菱ケミカル社製、ダイアホイルS-100、厚さ50μm)にハンドローラーで貼着した。得られた積層体にオートクレーブ処理(60℃、ゲージ圧0.2MPa、20分)を施して仕上げ貼着し、粘着力測定サンプルを作製した。
得られた粘着力測定サンプルについて、23℃、50%RHの条件にて、180°をなす角度に剥離速度300mm/分にて引っ張りながら、ソーダライムガラスに貼り合わせたPETフィルムから裏打ちフィルムとともに粘着シートを剥離し、ロードセルで引張強度(N/cm)を測定して粘着力とした。
各例で作製した離型フィルム付き粘着シートから片面側の離型フィルムを取り除き、露出した粘着面を、ソーダライムガラス(82mm×53mm×厚さ0.55mm)にロール圧着した。次いで、残る離型フィルムを取り除き、ソーダライムガラス(82mm×53mm×厚さ0.5mm)にロール圧着した。その後、オートクレーブ処理(60℃、ゲージ圧0.2MPa、20分)を施して仕上げ貼着し、光学特性測定用サンプルを作製した。
光学特性測定用サンプルについて、ヘイズメーター(日本電色工業社製、NDH5000)を用い、ISO-13468-1に準じて全光線透過率の測定を行った。
SLMA:アルキル基の炭素数が12であるアルキルメタクリレートと、アルキル基の炭素数が13であるアルキルメタクリレートとの混合物、三菱ケミカル社製、商品名:アクリエステルSL。
POB-A:m-フェノキシベンジルアクリレート、共栄社化学社製(屈折率:1.566)。
OPPEA:o-フェニルフェノキシエチルアクリレート、MIWON社製、商品名:Miramer M1142(屈折率:1.577)。
PO-A:フェノキシエチルアクリレート 共栄社化学社製(屈折率:1.519)。
AA:アクリル酸、三菱ケミカル社製。
4HBA:4-ヒドロキシブチルアクリレート、三菱ケミカル社製。
nBA:n-ブチルアクリレート、三菱ケミカル社製。
2EHA:2-エチルヘキシルアクリレート、三菱ケミカル社製。
nOA:n-オクチルアクリレート、大阪有機化学工業社製。
MMA:メタクリル酸メチル、三菱ケミカル社製。
AMBN:2,2’-アゾビス(2-メチルブチロニトリル)、大塚化学社製。
撹拌装置、温度計、冷却管、窒素ガス導入口を備えた四つ口フラスコに、SLMA100部、連鎖移動剤としてビス[(ジフルオロボリル)ジフェニルグリオキシメイト]コバルト(II)0.00075部、及び酢酸エチル58部を仕込み、窒素バブリングによって酸素を置換した。次に、重合開始剤としてAMBN0.4部、及び酢酸エチル2部を加えた。次に、ウォーターバスで外温を90℃まで昇温し、還流状態で2時間反応させた。次に、AMBN0.2部、酢酸エチル20部を1時間かけて滴下し、その後さらに還流状態で2時間保持した。その後、反応液を40℃に冷却してマクロモノマー(SLMA-MM)を含有する溶液を得た。この溶液に酢酸エチルを加えることで、不揮発分濃度を50質量%に調整した。マクロモノマー(SLMA-MM)の重量平均分子量は9420であった。
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水900部、メタクリル酸2-スルホエチルナトリウム60部、メタクリル酸カリウム10部、及びMMA12部を入れて撹拌し、重合装置内を窒素置換しながら、50℃に昇温した。その中に、重合開始剤として2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩0.08部を添加し、さらに60℃に昇温した。昇温後、滴下ポンプを使用して、MMAを0.24部/分の速度で75分間連続的に滴下した。反応溶液を60℃で6時間保持した後、室温に冷却して、透明な水溶液である固形分10質量%の分散剤1を得た。
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水145部、硫酸ナトリウム0.1部及び分散剤1(固形分10質量%)0.25部を入れて撹拌し、均一な水溶液とした。次に、MMAを100部、連鎖移動剤としてビス[(ジフルオロボリル)ジフェニルグリオキシメイト]コバルト(II)を0.0035部及び重合開始剤としてパーオクタO(日本油脂社製)0.35部を加え、水性懸濁液とした。次に、重合装置内を窒素置換し、80℃に昇温して1時間反応し、さらに重合率を上げるため、90℃に昇温して1時間保持した。その後、反応液を40℃に冷却して、マクロモノマーを含有する水性懸濁液を得た。この水性懸濁液を濾過し、濾過物を脱イオン水で洗浄し、脱水し、40℃で16時間乾燥して、MMAを構成単位とするマクロモノマー(MMA-MM)を得た。
マクロモノマー(MMA-MM)の重量平均分子量は5800であった。
((メタ)アクリル系共重合体の製造)
撹拌装置、温度計、冷却管、窒素ガス導入口を備えた四つ口フラスコに、仕込み溶媒として酢酸エチル25部、イソプロピルアルコール(IPA)2部、マクロモノマー(SLMA-MM)溶液(濃度50質量%)15部を仕込み、窒素ガス通気下、ウォーターバスで外温を85℃に昇温した。還流状態が安定した後、酢酸エチル20部、POB-A10部、nBA75部、ナイパーBK40 MT(日本油脂社製)0.13部からなる混合物を4時間かけて滴下した。滴下終了後1時間保持した後、パーオクタO(日本油脂社製)0.3部と酢酸エチル15部からなる混合物を1時間かけて添加した。その後、2時間保持した後、酸化防止剤として「イルガノックス1010」(BASF社製商品名)0.5部、酢酸エチル23部を添加し、室温まで冷却して、(メタ)アクリル系共重合体(SLMA-MM/POB-A/nBA(質量比)=15/10/75、重量平均分子量:51万)を得た。
(メタ)アクリル系共重合体100部(固形分)、光硬化性化合物としての(メタ)アクリル系オリゴマー(三菱ケミカル社製、紫光UV-3700B)1.5部、光開始剤(IGM社製、Esacure TZT)1.5部、酢酸エチル154.5部を配合して、溶剤を含有した粘着剤組成物を調製した。厚さ100μmの離型フィルム(三菱ケミカル社製、シリコーン離型処理されたPETフィルム)上に、粘着剤組成物を乾燥後の厚みが50μmとなるようにシート状に展開した。
(メタ)アクリル系共重合体の共重合組成を表1に示すように変更したこと以外は、実施例1と同様にして離型フィルム付き粘着シートを作製した。
各例の粘着シートの測定、評価を行った結果を表1に示す。
一方、比較例1の粘着シートは、実施例の粘着シートに比べ、低屈折率であった。
比較例2の粘着シートは、-20℃における貯蔵弾性率が-20℃の剪断貯蔵弾性率(G’(-20℃))が1000kPaを超えており、低温環境下での柔軟性に乏しいものであった。
Claims (21)
- 粘着剤組成物から形成された粘着シートであって、
前記粘着剤組成物は、(メタ)アクリル系共重合体(A)を含有し、
下記の要件(1)及び要件(2)を満たす、粘着シート。
要件(1)前記粘着シートの屈折率が、1.480以上1.550未満である。
要件(2)周波数1Hzの剪断モードでの動的粘弾性測定により得られる、-20℃の剪断貯蔵弾性率(G’(-20℃))が、10kPa以上1000kPa以下である。 - 前記(メタ)アクリル系共重合体(A)が、屈折率が1.500以上の芳香族(メタ)アクリレート(a1)由来の構成単位を有する、請求項1に記載の粘着シート。
- 前記芳香族(メタ)アクリレート(a1)のホモポリマーのガラス転移温度(Tg)が、60℃以下である、請求項2に記載の粘着シート。
- 前記(メタ)アクリル系共重合体(A)の全構成単位に対する、前記芳香族(メタ)アクリレート(a1)由来の構成単位の割合が、1~50質量%である、請求項2に記載の粘着シート。
- 周波数1Hzの剪断モードでの動的粘弾性測定により得られる、Tanδの極大値で定義されるガラス転移温度(Tg)が、-20℃以下である、請求項1に記載の粘着シート。
- 前記粘着剤組成物が、光開始剤(B)をさらに含有する、請求項1に記載の粘着シート。
- 前記粘着剤組成物が、光硬化性化合物(C)をさらに含有する、請求項1に記載の粘着シート。
- 前記粘着剤組成物が、光開始剤(B)及び光硬化性化合物(C)をさらに含有する、請求項1に記載の粘着シート。
- 周波数1Hzの剪断モードでの動的粘弾性測定により得られる、60℃の剪断貯蔵弾性率G’(60℃)に対する-20℃の剪断貯蔵弾性率G’(-20℃)の比(G’(-20℃)/G’(60℃))が、150以下である、請求項1に記載の粘着シート。
- 前記粘着シートに60℃にて2kPaの応力を600秒印加した時の最大歪み値(γmax)と、その後、前記応力を除いた600秒後の残留歪み値(γmin)とから下記式により算出される復元率が、60%以上である、請求項1に記載の粘着シート。
復元率(%)=〔(γmax-γmin)/γmax〕×100 - ゲル分率が、30%以上である、請求項1に記載の粘着シート。
- 前記(メタ)アクリル系共重合体(A)が、アルキル基の炭素数が9~30のアルキル(メタ)アクリレート由来の構成単位を有する、請求項1に記載の粘着シート。
- 前記(メタ)アクリル系共重合体(A)が、ブロック共重合体又はグラフト共重合体である、請求項1に記載の粘着シート。
- 前記(メタ)アクリル系共重合体(A)は、マクロモノマー(a10)由来の構成単位を有する、請求項1に記載の粘着シート。
- 前記マクロモノマー(a10)が、アルキル基の炭素数が9~30のアルキル(メタ)アクリレート由来の構成単位を有する、請求項14に記載の粘着シート。
- 前記(メタ)アクリル系共重合体(A)は、屈折率が1.500以上の芳香族(メタ)アクリレート(a1)由来の構成単位をさらに有し、
前記(メタ)アクリル系共重合体(A)中における前記芳香族(メタ)アクリレート(a1)由来の構成単位に対する前記マクロモノマー(a10)由来の構成単位の含有割合(a10/a1)が、重量比で0.1~10である、請求項14に記載の粘着シート。 - 表面に凹凸を有する部材と有機発光ダイオードを有する部材との貼合用である、請求項1に記載の粘着シート。
- 請求項1~17のいずれか一項に記載の粘着シートと、
前記粘着シートの少なくとも一方の表面に積層された離型フィルムと、
を備えた、離型フィルム付き粘着シート。 - フレキシブル画像表示装置構成部材用である、請求項1~17のいずれか一項に記載の粘着シート。
- 2つの画像表示装置構成部材と、
請求項1~17のいずれか一項に記載の粘着シートと、
を備え、
前記2つの画像表示装置構成部材が、前記粘着シートを介して積層され、
前記2つの画像表示装置構成部材の少なくとも一方が、前記粘着シートとの接触面に、高低差2μm以上の段差を有する、画像表示装置用積層体。 - 請求項20に記載の画像表示装置用積層体を備えた、フレキシブル画像表示装置。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2024572958A JPWO2024157790A1 (ja) | 2023-01-23 | 2024-01-12 | |
| CN202480004676.XA CN120202271A (zh) | 2023-01-23 | 2024-01-12 | 粘合片、带有脱模薄膜的粘合片、图像显示装置用层叠体及挠性图像显示装置 |
| KR1020257017175A KR20250139809A (ko) | 2023-01-23 | 2024-01-12 | 점착 시트, 이형 필름 부착 점착 시트, 화상 표시 장치용 적층체, 및 플렉시블 화상 표시 장치 |
| US19/271,726 US20250340757A1 (en) | 2023-01-23 | 2025-07-16 | Adhesive sheet, adhesive sheet equipped with mold release film, laminate for image display devices, and flexible image display device |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2023008193 | 2023-01-23 | ||
| JP2023-008193 | 2023-01-23 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US19/271,726 Continuation US20250340757A1 (en) | 2023-01-23 | 2025-07-16 | Adhesive sheet, adhesive sheet equipped with mold release film, laminate for image display devices, and flexible image display device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024157790A1 true WO2024157790A1 (ja) | 2024-08-02 |
Family
ID=91970420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2024/000537 Ceased WO2024157790A1 (ja) | 2023-01-23 | 2024-01-12 | 粘着シート、離型フィルム付き粘着シート、画像表示装置用積層体、及びフレキシブル画像表示装置 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20250340757A1 (ja) |
| JP (1) | JPWO2024157790A1 (ja) |
| KR (1) | KR20250139809A (ja) |
| CN (1) | CN120202271A (ja) |
| TW (1) | TW202432774A (ja) |
| WO (1) | WO2024157790A1 (ja) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011215601A (ja) * | 2010-03-16 | 2011-10-27 | Nitto Denko Corp | 粘接着剤層付光学シート、粘接着剤層付光学シートの製造方法、粘接着剤層付光学シートを用いた光源、粘接着剤層付光学シートを用いた画像表示装置 |
| JP2018524425A (ja) * | 2015-06-03 | 2018-08-30 | スリーエム イノベイティブ プロパティズ カンパニー | フレキシブルディスプレイ用のアクリルブロックコポリマー系アセンブリ層 |
| JP2021143339A (ja) * | 2019-11-22 | 2021-09-24 | 三菱ケミカル株式会社 | 粘着シート、積層シート、フレキシブル画像表示装置部材及びフレキシブル画像表示装置 |
| JP2021161377A (ja) * | 2020-03-31 | 2021-10-11 | 三菱ケミカル株式会社 | 粘着シート、粘着部品、フレキシブル画像表示装置部材、積層体、画像表示装置 |
| WO2023013399A1 (ja) * | 2021-08-03 | 2023-02-09 | 日東電工株式会社 | 粘着剤組成物および粘着シート |
| WO2023042686A1 (ja) * | 2021-09-14 | 2023-03-23 | 日東電工株式会社 | 粘着剤組成物および粘着シート |
| JP2024008704A (ja) * | 2022-07-08 | 2024-01-19 | 日東電工株式会社 | 粘着剤および粘着シート |
| JP2024008705A (ja) * | 2022-07-08 | 2024-01-19 | 日東電工株式会社 | 粘着剤および粘着シート |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110461972B (zh) | 2017-03-23 | 2022-04-22 | 三菱化学株式会社 | 层叠体、双面粘合片及其应用 |
| JP7485515B2 (ja) | 2019-02-15 | 2024-05-16 | 日東電工株式会社 | 粘着剤層および粘着シート |
| JP7574546B2 (ja) | 2019-05-28 | 2024-10-29 | 東洋紡株式会社 | ポリエステルフィルムとその用途 |
-
2024
- 2024-01-12 WO PCT/JP2024/000537 patent/WO2024157790A1/ja not_active Ceased
- 2024-01-12 TW TW113101320A patent/TW202432774A/zh unknown
- 2024-01-12 CN CN202480004676.XA patent/CN120202271A/zh active Pending
- 2024-01-12 JP JP2024572958A patent/JPWO2024157790A1/ja active Pending
- 2024-01-12 KR KR1020257017175A patent/KR20250139809A/ko active Pending
-
2025
- 2025-07-16 US US19/271,726 patent/US20250340757A1/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011215601A (ja) * | 2010-03-16 | 2011-10-27 | Nitto Denko Corp | 粘接着剤層付光学シート、粘接着剤層付光学シートの製造方法、粘接着剤層付光学シートを用いた光源、粘接着剤層付光学シートを用いた画像表示装置 |
| JP2018524425A (ja) * | 2015-06-03 | 2018-08-30 | スリーエム イノベイティブ プロパティズ カンパニー | フレキシブルディスプレイ用のアクリルブロックコポリマー系アセンブリ層 |
| JP2021143339A (ja) * | 2019-11-22 | 2021-09-24 | 三菱ケミカル株式会社 | 粘着シート、積層シート、フレキシブル画像表示装置部材及びフレキシブル画像表示装置 |
| JP2021161377A (ja) * | 2020-03-31 | 2021-10-11 | 三菱ケミカル株式会社 | 粘着シート、粘着部品、フレキシブル画像表示装置部材、積層体、画像表示装置 |
| WO2023013399A1 (ja) * | 2021-08-03 | 2023-02-09 | 日東電工株式会社 | 粘着剤組成物および粘着シート |
| WO2023042686A1 (ja) * | 2021-09-14 | 2023-03-23 | 日東電工株式会社 | 粘着剤組成物および粘着シート |
| JP2024008704A (ja) * | 2022-07-08 | 2024-01-19 | 日東電工株式会社 | 粘着剤および粘着シート |
| JP2024008705A (ja) * | 2022-07-08 | 2024-01-19 | 日東電工株式会社 | 粘着剤および粘着シート |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20250139809A (ko) | 2025-09-23 |
| TW202432774A (zh) | 2024-08-16 |
| CN120202271A (zh) | 2025-06-24 |
| JPWO2024157790A1 (ja) | 2024-08-02 |
| US20250340757A1 (en) | 2025-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102482550B (zh) | 用于光学部件的放射线固化型压敏粘合剂组合物及压敏粘合型光学部件 | |
| JP7243621B2 (ja) | 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 | |
| CN102015950B (zh) | 压敏粘合剂组合物,以及包括该压敏粘合剂组合物的偏振片和液晶显示器 | |
| TW202039754A (zh) | 附黏著劑層之抗反射膜、自發光型顯示裝置及其製造方法 | |
| JP7767784B2 (ja) | 粘着シート、積層シート及びフレキシブル画像表示装置 | |
| CN102076804A (zh) | 粘合剂组合物、偏振片和液晶显示器 | |
| TWI570203B (zh) | Adhesive compositions, adhesives, and adhesive sheets | |
| US20220274376A1 (en) | Adhesive sheet, flexible image display device member, optical member, and image display device | |
| CN113383052A (zh) | 光学膜粘合剂、粘合层、光学元件和图像显示装置 | |
| WO2021172017A1 (ja) | 粘着材、粘着シートおよび屈曲性積層部材 | |
| WO2021066037A1 (ja) | 粘着シート及び粘着シートの製造方法 | |
| JP7151589B2 (ja) | 両面粘着シート、離型フィルム付積層体及び画像表示装置用積層体 | |
| JP2024139738A (ja) | 粘着シート、離型フィルム付き粘着シート、画像表示装置用積層体、画像表示装置及び、画像表示装置構成部材用粘着シート | |
| JP2024139739A (ja) | 粘着シート、離型フィルム付き粘着シート、画像表示装置用積層体、画像表示装置、画像表示装置構成部材用粘着シート | |
| WO2024157790A1 (ja) | 粘着シート、離型フィルム付き粘着シート、画像表示装置用積層体、及びフレキシブル画像表示装置 | |
| WO2024157791A1 (ja) | 光硬化性粘着シート、離型フィルム付き光硬化性粘着シート、画像表示装置用積層体、及びフレキシブル画像表示装置 | |
| CN118591602A (zh) | 粘合片材及可挠性图像显示装置 | |
| WO2024195441A1 (ja) | 粘着シート、離型フィルム付き粘着シート、フレキシブル画像表示装置構成部材用粘着シート、画像表示装置用積層体、フレキシブル画像表示装置、光硬化性粘着シート、及び粘着剤組成物 | |
| WO2024111438A1 (ja) | 透明粘着シート、離型フィルム付き透明粘着シート、フレキシブル画像表示装置構成部材用透明粘着シート、画像表示装置用積層体及びフレキシブル画像表示装置 | |
| WO2024106096A1 (ja) | 粘着シート、これを用いた離型フィルム付き粘着シート、画像表示装置用積層体、フレキシブル画像表示装置、フレキシブル画像表示装置構成部材用粘着シート、及び粘着剤組成物 | |
| WO2025022825A1 (ja) | 粘着シート、離型フィルム付き粘着シート、画像表示装置用積層体、フレキシブル画像表示装置、及びフレキシブル画像表示装置構成部材用粘着シート | |
| WO2024203790A1 (ja) | 粘着シート、離型フィルム付き粘着シート、画像表示装置用積層体、画像表示装置及び、画像表示装置構成部材用粘着シート | |
| WO2024185314A1 (ja) | 粘着シート、離型フィルム付き粘着シート、画像表示装置用積層体、フレキシブル画像表示装置、及びフレキシブル画像表示装置構成部材用粘着シート | |
| JP2025138386A (ja) | 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、画像表示装置用積層体、画像表示装置、画像表示装置構成部材用活性エネルギー線硬化性粘着シート、及び活性エネルギー線硬化性粘着シートの製造方法 | |
| WO2024203789A1 (ja) | 粘着シート、離型フィルム付き粘着シート、画像表示装置用積層体、画像表示装置及び、画像表示装置構成部材用粘着シート |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 24747121 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2024572958 Country of ref document: JP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: CN202480004676X Country of ref document: CN Ref document number: 202480004676.X Country of ref document: CN |
|
| WWP | Wipo information: published in national office |
Ref document number: 202480004676.X Country of ref document: CN |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |