CN116761860A - Pressure-sensitive adhesive sheet for image display device, pressure-sensitive adhesive sheet with release film, laminate for image display device, and image display device - Google Patents
Pressure-sensitive adhesive sheet for image display device, pressure-sensitive adhesive sheet with release film, laminate for image display device, and image display device Download PDFInfo
- Publication number
- CN116761860A CN116761860A CN202180090779.9A CN202180090779A CN116761860A CN 116761860 A CN116761860 A CN 116761860A CN 202180090779 A CN202180090779 A CN 202180090779A CN 116761860 A CN116761860 A CN 116761860A
- Authority
- CN
- China
- Prior art keywords
- adhesive sheet
- image display
- display device
- meth
- pressure
- 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.)
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- 239000000853 adhesive Substances 0.000 claims abstract description 312
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
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- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 3
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- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
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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
- C09J7/30—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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
Abstract
Provided is an adhesive sheet for an image display device, which has excellent curved surface adhesiveness to a curved surface member having a curved portion and excellent durability after being adhered to the curved surface member, wherein the adhesive sheet has an adhesive force to soda lime glass at a temperature of 23 ℃ and a peeling speed of 300mm/min of 2N/cm or more, has a deflection length of 10mm or less as measured in a holding force test of an adhesive surface having a load of 0.5kg, a measurement time of 30 minutes, a width of 20mm x a length of 20mm based on JIS Z0237 and a temperature of 70 ℃ and a peeling speed of 300mm/min, and has a peeling distance of 20mm or less in a constant load peeling test.
Description
Technical Field
The invention relates to an adhesive sheet for an image display device, an adhesive sheet with a release film, a laminate for an image display device, and an image display device.
Background
The following operations are performed in order to improve the visibility of the image display apparatus: the gap between an image display panel such as a Liquid Crystal Display (LCD), a Plasma Display (PDP), or an electroluminescence display (ELD), and a protective panel or a touch panel member disposed on the front side (visible side) thereof is filled with a resin such as an adhesive or an adhesive, and reflection of incident light or emitted light from a display image at an air layer interface is suppressed.
For example, patent document 1 discloses a method for producing a constituent laminate for an image display device, which comprises a structure in which at least one side of a transparent double-sided adhesive sheet is laminated with constituent members of the image display device, the method comprising: after the adhesive sheet once crosslinked by ultraviolet rays is adhered to the image display device constituent member, the adhesive sheet is irradiated with ultraviolet rays through the image display device constituent member to be secondarily cured.
Further, patent document 2 discloses, as an adhesive sheet useful for display and touch panels, a pressure-sensitive adhesive sheet containing a (meth) acrylic copolymer having an ultraviolet-crosslinkable site.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 4971529
Patent document 2: japanese patent No. 6062740
Disclosure of Invention
Problems to be solved by the invention
In recent years, high design performance has been demanded for image display devices, and the shape of the protective panel on the front surface side has gradually changed from a flat shape to a shape in which the end surface or corner portion is curved, a design in which the display portion is curved as a whole, and the like.
However, when an image display device constituent member made of a resin film or the like is adhered to a curved portion using an adhesive sheet, an influence due to rebound of the resin film or the like is likely to occur, and it is difficult to make the adhesive sheet follow the curved portion. The adhesive sheets of patent documents 1 and 2 have been studied on the conventional laminated structure using the flat image display device constituent member, and the reliability of adhesion to the curved member having the curved portion has not been considered.
In addition, when the curved portion of the curved member has irregularities such as a print level difference, the adhesive sheet is more likely to float and peel off from the interface with the irregularities than a flat member. Therefore, a curved member having a curved portion is required to have higher adhesion reliability and level difference following property than conventional ones.
Accordingly, an object of the present invention is to provide an adhesive sheet having excellent curved surface adhesiveness to a curved surface member having a curved portion and excellent durability after the adhesive sheet is adhered to the curved surface member, and capable of adhering without any air bubbles.
Solution for solving the problem
The present inventors have conducted intensive studies to solve the above problems, and as a result, found that: the above problems can be solved by setting the adhesive force of the adhesive sheet, the offset length measured in the holding force test, and the peel distance in the constant load peel test to specific numerical ranges.
Specifically, the present invention uses the following [1] to [15] as its gist.
[1] An adhesive sheet for an image display device, which is used for adhering two image display device constituent members, has an adhesive force to soda-lime glass of 2N/cm or more at a peeling speed of 300mm/min at a temperature of 23 ℃, has a deflection length of 10mm or less as measured in a holding force test of an adhesive surface having a load of 0.5kg, a measurement time of 30 minutes, and a width of 20mm x a length of 20mm based on JIS Z0237 at a temperature of 70 ℃, and has a peeling distance of 20mm or less in a constant load peeling test below.
(measurement conditions)
1) An adhesive sheet of the size 10mm in width and 150mm in length was adhered to an adherend as an adhering region, and the adherend was fixed in the horizontal direction so that the non-adhering region of the adhesive sheet was hung down, with the region of the adhesive sheet other than the adhering region being a non-adhering region.
2) A load of 0.45N was applied to the longitudinal end of the non-adhesive region of the pressure-sensitive adhesive sheet for 30 minutes, and the distance of the adhesive region of the pressure-sensitive adhesive layer from the adherend during this period was measured as a constant load peeling distance.
[2] The adhesive sheet for an image display device according to [1], wherein the ball number in the oblique ball tack test (oblique angle: 30 ℃) is 5 to 25.
[3] The adhesive sheet for an image display device according to [1] or [2], wherein the adhesive sheet has a thickness of 0.6 to 0.8mm, and after a pressure of 1kPa for 180 seconds is applied at a temperature of 25 ℃, the residual creep strain after 180 seconds is 20% or less.
[4] The adhesive sheet for an image display device according to any one of [1] to [3], wherein a ratio (E '/G') of a tensile storage modulus (E ') to a shear storage modulus (G') is 5.0 or more.
[5] The adhesive sheet for an image display device according to any one of [1] to [4], wherein the loss tangent (Tan δ) measured by dynamic viscoelasticity measurement in a stretching mode at a frequency of 1Hz has two maxima (peak temperature) and the difference is 5 to 50 ℃.
[6] The pressure-sensitive adhesive sheet for an image display device according to any one of [1] to [5], wherein the pressure-sensitive adhesive sheet has at least 3 layers, wherein the outermost layer and the innermost layer are acrylic pressure-sensitive adhesive layers, and the ratio of the total thickness of the outermost layer and the innermost layer to the total thickness is 5 to 70%.
[7] The adhesive sheet for an image display device according to any one of [1] to [6], wherein the adhesive sheet comprises at least 3 layers of an outermost layer, an innermost layer and an intermediate layer, and the outermost layer, the innermost layer and the intermediate layer are formed from a resin composition containing a (meth) acrylic polymer having a different composition.
[8] The adhesive sheet for an image display device according to any one of [1] to [7], which has active energy ray curability.
[9]According to [8]]The adhesive sheet for an image display device, wherein the cumulative light amount of the adhesive sheet irradiated with light is 3000mJ/cm 2 After curing by active energy rays having a wavelength of 365nm, the thickness is set to 0.6 to 0.8mm, and the strain (creep strain) when a pressure of 1kPa is applied at a temperature of 25 ℃ for 10 seconds is 3% or less.
[10]According to [8 ]]Or [9 ]]The adhesive sheet for an image display device, wherein the cumulative light amount of the adhesive sheet irradiated with light is 3000mJ/cm 2 After curing by active energy rays having a wavelength of 365nm, the thickness is set to 0.6 to 0.8mm, and the maximum value (glass transition temperature) of the loss tangent obtained by dynamic viscoelasticity measurement in a shear mode having a frequency of 1Hz is 0 ℃ or lower.
[11] The adhesive sheet for an image display device according to any one of [1] to [10], wherein the adhesive sheet is formed of a resin composition comprising a (meth) acrylic resin, a crosslinking agent (B) and a photopolymerization initiator (C).
[12] The pressure-sensitive adhesive sheet for an image display device according to [11], wherein the crosslinking agent (B) is contained in an amount of 0.5 to 50 parts by mass based on 100 parts by mass of the (meth) acrylic polymer.
[13] An adhesive sheet with a release film comprising the adhesive sheet for an image display device according to any one of [1] to [12] and a release film laminated.
[14] A laminate for an image display device, comprising a laminate of two image display device constituent members each comprising a cover glass having a curved surface shape and one member selected from the group consisting of a touch sensor, an image display panel, a surface protective film, an antireflection film, a color filter, a polarizing film and a retardation film, or a member formed of a combination of two or more of the above two image display device constituent members, wherein the adhesive sheet for an image display device is described in any one of [1] to [12 ].
[15] An image display device using the laminate for an image display device described in [14 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present adhesive sheet, the adhesiveness to a curved surface and the durability after the adhesive sheet is adhered to the curved surface member are excellent, and therefore, the adhesive sheet can be suitably used as an adhesive sheet for an image display device having a curved surface.
Drawings
Fig. 1 is a diagram for explaining an evaluation method of the constant load peel test.
Fig. 2 is a diagram for explaining an evaluation method of the roll adhesiveness test.
Detailed Description
Hereinafter, an example of the embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
In the present specification, "(meth) acrylic acid" means a meaning including "acrylic acid" and "methacrylic acid", respectively, and "(meth) acrylic acid ester" means a meaning including "acrylic acid ester" and "methacrylic acid ester", respectively.
The pressure-sensitive adhesive sheet for an image display device of the present invention (referred to as "the present pressure-sensitive adhesive sheet") is generally a double-sided pressure-sensitive adhesive sheet having pressure-sensitive adhesive layers on both sides thereof, and is used for adhering two image display device constituent members. In particular, the adhesive sheet can be suitably used in the case where the image display device constituent member has a curved shape.
In addition, from the viewpoint of improving reliability, the present adhesive sheet preferably has active energy ray curability in which curing occurs by irradiation with active energy rays such as ultraviolet rays.
< adhesion force >
The adhesive sheet has an adhesive force to soda lime glass of 2N/cm or more at a temperature of 23 ℃ and a peeling speed of 300 mm/min. By setting the adhesive force to 2N/cm or more, peeling does not occur even when the adhesive is adhered to a curved member, and excellent curved surface adhesion can be exhibited. From this viewpoint, the adhesion force is preferably 3N/cm or more, more preferably 4N/cm or more, and still more preferably 5N/cm or more. The upper limit of the adhesion force is usually 50N/cm, preferably 30N/cm, from the viewpoint of suppressing the elastic modulus in order to balance the level difference absorbency and the roll adhesiveness.
In the case where the adhesive sheet has active energy ray curability, the adhesive strength of the cured adhesive sheet to soda lime glass is preferably 2N/cm or more at a temperature of 23℃and a peeling speed of 300 mm/min. When the adhesion is 2N/cm or more, excellent durability can be exhibited when a laminate for an image display device is produced. From this viewpoint, the adhesion after curing is preferably 3N/cm or more, more preferably 4N/cm or more, and still more preferably 5N/cm or more. The upper limit of the adhesive force is usually 50N/cm, preferably 30N/cm, depending on the range of the adhesive force before curing.
[ method for measuring adhesive force ]
The adhesion was measured by the following method.
A polyethylene terephthalate (PET) film (COSMESINE A4300, manufactured by Toyobo Co., ltd.) having a thickness of 100 μm was bonded to one surface of the adhesive sheet, and the other surface was roll-bonded to soda lime glass to prepare a bonded product. Thereafter, the above-mentioned adhesive article was subjected to autoclave treatment (temperature 60 ℃ C., gauge pressure 0.2MPa, 20 minutes) to finally adhere the adhesive article, and the thus-obtained sample was used as a sample for measuring adhesive force. Using this sample, peeling was performed under conditions of a peeling angle of 180 ° and a peeling speed of 300 mm/min at a temperature of 23 ℃ and a humidity of 50% rh, and the peeling force (N/cm) at this time was used as the adhesive force.
In addition, a high-pressure mercury lamp was used for the adhesion after curing so that the cumulative light amount became 3000mJ/cm 2 After 365nm ultraviolet rays were irradiated from the PET film surface of the above-mentioned sample for measuring adhesive force, the resulting sample was cured in an atmosphere of a temperature of 23℃and a humidity of 50% RH for 12 hours, and the peel force was measured by the same method as described above.
< holding force >
The adhesive sheet has a deflection length of 10mm or less measured in a holding force test of an adhesive surface having a temperature of 70 ℃ and a load of 0.5kg, a measurement time of 30 minutes, and a width of 20mm by a length of 20mm in accordance with JIS Z0237. By setting the offset length to 10mm or less, the pressure-sensitive adhesive sheet does not undergo cohesive failure with time even when adhered to a curved member, and excellent curved-surface adhesion can be exhibited. From this viewpoint, the offset length is more preferably 8mm or less, and still more preferably 5mm or less.
In the case where the adhesive sheet has active energy ray curability, the offset length of the adhesive sheet after curing is preferably 5mm or less as measured in a holding force test of an adhesive surface having a temperature of 70 ℃ and a load of 0.5kg, a measurement time of 30 minutes, and a width of 20mm×a length of 20mm in accordance with JIS Z0237. When the offset length is 5mm or less, excellent durability can be exhibited in the production of a laminate for an image display device. From this viewpoint, the offset length is more preferably 1mm or less, and still more preferably 0.5mm or less.
[ method of measuring holding force ]
The holding force was measured by the following method.
A polyethylene terephthalate (PET) film (DIAFOIL S100, manufactured by Mitsubishi chemical corporation) having a thickness of 38 μm was stuck to one surface of the adhesive sheet and cut into a width of 20mm, and the other surface was stuck to a polished stainless steel plate (SUS 304) so that the stuck area became 20 mm. Times.20 mm, to obtain a sample for measuring holding force. Using this sample, the offset length (mm) of the adhesive sheet was measured under a load of 0.5kg and a temperature of 70℃for 30 minutes.
In addition, regarding the holding power after curing, the cumulative light amount at a wavelength of 365nm was 3000mJ/cm by a high-pressure mercury lamp 2 The offset length of the adhesive sheet may be measured by irradiating the adhesive sheet with light to cure the adhesive sheet, and then producing a cured adhesive sheet and using the same method as described above.
< constant load stripping >
Further, the release distance of the adhesive sheet in the following constant load release test was 20mm or less. By setting the separation distance to 20mm or less, even when the adhesive is applied to a curved surface member, the occurrence of floating with time can be suppressed, and excellent curved surface adhesion can be exhibited. From this viewpoint, the peeling distance in the constant load peeling test is preferably 15mm or less, more preferably 12mm or less, and further preferably 8mm or less.
[ method for measuring constant load peeling ]
The constant load peel test was measured by the following method.
A polyethylene terephthalate (PET) film (COSMESINE A4300, manufactured by Toyobo Co., ltd.) having a thickness of 100 μm was adhered to one surface of the adhesive sheet. The resultant was cut into pieces of Cheng Kuandu mm and 150mm in length, and a region roll of 10mm in width and 100mm in length was pressed against soda lime glass to prepare an adhesive article. In this case, the region to be bonded to the soda lime glass is referred to as a bonding region, and the region other than the bonding region is referred to as a non-bonding region. The above-mentioned adhesive article was subjected to autoclave treatment (temperature: 50 ℃ C., gauge pressure: 0.2MPa, 20 minutes), and then cured at a temperature of 40 ℃ C. For 30 minutes to finally adhere, and the thus-obtained sample was used as a sample for a constant load peel test. Using this sample, soda lime glass was fixed in the horizontal direction in such a manner that the non-adhesive region of the adhesive sheet was hung down in the environment of a temperature of 23 ℃ and a humidity of 50% rh. Thereafter, a load of 0.45N was applied to the longitudinal end of the non-adhesive region of the adhesive sheet for 30 minutes, and the distance of the adhesive region of the adhesive sheet from the soda lime glass during this period was measured as a constant load peeling distance.
By providing the adhesive sheet with the adhesive force, the holding force and the constant load peeling property in the above-described ranges, an adhesive sheet excellent in curved surface adhesiveness and durability can be produced.
< ball tackiness >
The ball number of the adhesive sheet in the inclined ball tack test is preferably 5 to 25, more preferably 8 to 20. By setting the ball number in the inclined ball tack test to the above range, the adhesive sheet roll is not displaced when the adhesive sheet roll is attached to the image display device constituent member, and an adhesive sheet excellent in roll adhesiveness can be produced. The ball number was determined under the conditions of a temperature of 23℃and an inclination angle of 30℃according to the inclination type ball tackiness defined in JIS Z0237:2009.
< residual creep Strain >
The adhesive sheet is set to a thickness of 0.6 to 0.8mm, and after a pressure of 1kPa for 180 seconds is applied at a temperature of 25 ℃, the residual creep strain after the pressure is released and 180 seconds is preferably 20% or less. By setting the residual creep strain to 20% or less, it is possible to obtain a laminate for an image display device without causing paste collapse at the time of pasting and without paste overflow. From this viewpoint, the residual creep strain is preferably 10% or less, more preferably 7% or less, still more preferably 5% or less, particularly preferably 2% or less.
In the case where the adhesive sheet has active energy ray curability, the residual creep strain of the adhesive sheet after curing is preferably 5% or less.
In general, after two image display device constituent members are bonded to each other via an adhesive sheet to form a laminate for an image display device, the image display device is usedWhen an image display device is produced by laminating a plurality of layers, the image display device may be used in some casesThe laminate is locally stressed, and the pressure-sensitive adhesive sheet is provided with indentations, which impair the appearance and visibility of the image display device. By setting the residual creep strain of the cured adhesive sheet to 5% or less, a laminate for an image display device having excellent indentation resistance can be obtained. From this viewpoint, the residual creep change of the cured adhesive sheet is preferably 3% or less, more preferably 1% or less, and still more preferably 0.5% or less.
The residual creep strain of the adhesive sheet after curing was obtained by using the following samples: the cumulative light quantity at a wavelength of 365nm was 3000mJ/cm by means of a high-pressure mercury lamp 2 The present adhesive sheet was irradiated with light and cured to obtain a sample.
As described above, the residual creep strain is a value obtained when the thickness of the adhesive sheet is 0.6 to 0.8 mm. This is because: in order to accurately measure the residual creep strain of the adhesive sheet, it is necessary to avoid the occurrence of variations in the measurement result due to the influence of the measurement tool caused by the insufficient thickness of the adhesive sheet. Therefore, in order to measure the residual creep strain, the present adhesive sheet needs to be adjusted to a certain thickness range.
By measuring the residual creep strain by adjusting the thickness of the adhesive sheet in the above range in advance, the residual creep strain of the adhesive sheet can be accurately grasped without being affected by the measuring tool.
< creep Strain >
The adhesive sheet is set to have a thickness of 0.6 to 0.8mm, and preferably has a creep strain of 10% or less when a pressure of 1kPa is applied at a temperature of 25 ℃ for 10 seconds. By setting the creep strain to 10% or less, an adhesive sheet excellent in resistance to cement collapse can be obtained. From this viewpoint, the creep change is preferably 7% or less, more preferably 5% or less, and still more preferably 3% or less.
In the case where the adhesive sheet has active energy ray curability, the creep strain of the adhesive sheet after curing is preferably 7% or less. By setting the creep strain of the cured adhesive sheet to 7% or less, a laminate for an image display device having excellent indentation resistance can be obtained. From this viewpoint, the creep strain of the cured adhesive sheet is preferably 7% or less, more preferably 5% or less, and still more preferably 3% or less.
The creep strain of the cured adhesive sheet was obtained by using the following samples: the cumulative light quantity at a wavelength of 365nm was 3000mJ/cm by means of a high-pressure mercury lamp 2 The present adhesive sheet was irradiated with light and cured to obtain a sample.
As described above, creep strain is a value obtained when the thickness of the adhesive sheet is 0.6 to 0.8 mm. This is because: in order to accurately measure the creep strain of the adhesive sheet, it is necessary to avoid the influence of the measuring tool due to the insufficient thickness of the adhesive sheet, and the measurement result is changed. Therefore, in order to measure creep strain, the adhesive sheet needs to be adjusted to a certain thickness range.
By measuring the creep strain by adjusting the thickness of the adhesive sheet in the above range in advance, the creep strain of the adhesive sheet can be accurately grasped without being affected by the measuring tool.
< dynamic viscoelastic Properties >
The ratio (E '/G') of the tensile storage modulus (E ') to the shear storage modulus (G') obtained by the dynamic viscoelasticity measurement of the pressure-sensitive adhesive sheet is preferably 5.0 or more, more preferably 6.0 or more, still more preferably 7.0 or more, and particularly preferably 8.0 or more. The content is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less.
That is, the present adhesive sheet having a ratio of E '/G' of 5.0 or more can be judged as the present adhesive sheet "having at least 2 layers having different glass transition temperatures" or "having a layer having a glass transition temperature inclined in the thickness direction". The adhesive sheet has such a layer structure, and thus has high level of adhesion suitability and durability such as curved surface adhesion, roll adhesion, resistance to cement collapse, high level difference absorption, and resistance to tracking.
The tensile storage modulus (E ') and the shear storage modulus (G') were obtained by the following methods.
[ method for measuring tensile storage modulus (E') ]
The adhesive sheet was cut into pieces having a width of 4mm and a length of 15mm, and the adhesive sheet was subjected to a stretching mode using a dynamic viscoelasticity measuring apparatus (manufactured by IT Measurement Control Co., ltd., "itkVA-200"): vibration frequency 1Hz, heating rate: 3 ℃/min, temperature range: -measuring the dynamic viscoelasticity spectrum in the tensile mode at 120-80 ℃ and reading the tensile storage modulus (E') at 25 ℃ from the data obtained.
[ method for measuring shear storage modulus (G') ]
The pressure-sensitive adhesive sheet was laminated so that the thickness thereof was 0.6 to 0.8mm, and the thus obtained sample was die-cut into a round shape having a diameter of 8mm, to obtain a measurement sample. For this measurement sample, a dynamic viscoelasticity spectrum in the shear mode was measured using a rheometer (manufactured by TA Instruments corporation, "discovery hr 2") under the following measurement conditions, and the shear storage modulus (G') at 25 ℃ was read from the obtained data.
[ measurement conditions ]
Bonding tool: phi 8mm parallel plate
Strain: 0.1%
Frequency: 1Hz
Temperature: 120-200 DEG C
Heating rate: 5 ℃/min
As described above, the shear storage modulus (G') is a value obtained when the thickness of the adhesive sheet is 0.6 to 0.8 mm. This is because: in order to accurately measure the shear storage modulus (G') of the pressure-sensitive adhesive sheet, it is necessary to avoid variation in measurement results due to the influence of a measurement tool caused by insufficient thickness of the pressure-sensitive adhesive sheet. Therefore, in order to measure the shear storage modulus (G'), it is necessary to measure the pressure-sensitive adhesive sheet after adjusting the pressure-sensitive adhesive sheet to a certain thickness range.
By measuring the shear storage modulus (G ') by adjusting the thickness of the adhesive sheet in the above range in advance, the shear storage modulus (G') of the adhesive sheet can be accurately grasped without being affected by a measuring tool.
In the case where the adhesive sheet has active energy ray curability, the sample used for the measurement of the tensile storage modulus (E ') and the measurement of the shear storage modulus (G') may be either before or after curing. The cured adhesive sheet was brought to 3000mJ/cm by a high-pressure mercury lamp with an accumulated light quantity of 365nm in wavelength 2 The pressure-sensitive adhesive sheet is obtained by irradiating the pressure-sensitive adhesive sheet with light and curing the same.
The loss tangent (Tan δ) of the adhesive sheet obtained by dynamic viscoelasticity measurement in the stretching mode preferably has two maxima (peak temperatures (T1) and (T2)). The difference between the two peak temperatures (T1) and (T2) is preferably 5 to 50 ℃, more preferably 10 to 40 ℃, and particularly preferably 15 to 30 ℃. By setting the range as described above, it is possible to achieve both adhesion suitability and reliability such as curved surface adhesion, roll adhesion, resistance to cement collapse, level difference absorbability, and resistance to tracking.
The peak temperatures (T1) and (T2) of the loss tangent can be obtained by reading the peak temperature, which is the temperature at which the loss tangent (Tan δ) becomes maximum, from dynamic viscoelasticity spectrum data in the stretching mode obtained by the same method as the measurement of the above-mentioned tensile storage modulus (E').
The shear storage modulus (G') of the pressure-sensitive adhesive sheet is not particularly limited, but is preferably 50 to 400kPa, more preferably 60 to 300kPa, and even more preferably 100 to 200kPa at 25℃from the viewpoint of achieving both the level difference absorbency and the curved surface adhesiveness at a high level.
The shear storage modulus (G') at 65℃is preferably 5 to 60kPa, more preferably 10 to 50kPa, and even more preferably 20 to 45kPa.
Further, the shear storage modulus (G') at 85℃is preferably 1 to 40kPa, more preferably 5 to 35kPa, still more preferably 10 to 30kPa.
By setting the shear storage modulus (G') of the present adhesive sheet to such a range, an adhesive sheet having more excellent level difference absorbency can be produced.
In the case where the adhesive sheet has active energy ray curability, the shear storage modulus (G') of the adhesive sheet after curing is not particularly limited, but is preferably 50 to 500kPa, more preferably 60 to 400kPa, still more preferably 100 to 300kPa at 25 ℃.
The shear storage modulus (G') at 65℃is preferably 10 to 100kPa, more preferably 15 to 90kPa, and even more preferably 20 to 55kPa.
Further, the shear storage modulus (G') at 85℃is preferably 1 to 90kPa, more preferably 5 to 80kPa, still more preferably 10 to 50kPa.
By setting the shear storage modulus (G') of the cured adhesive sheet to such a range, an adhesive sheet excellent in indentation resistance and durability can be produced.
The shear storage modulus (G ') at 65 ℃ and 85 ℃ was obtained by reading the shear storage modulus (G ') at 65 ℃ and 85 ℃ from dynamic viscoelasticity spectrum data in the shear mode obtained by the same method as the measurement of the shear storage modulus (G ') described above.
The glass transition temperature, which is the maximum value (peak temperature) of the loss tangent (Tan δ) obtained by dynamic viscoelasticity measurement in the shear mode, of the pressure-sensitive adhesive sheet is not particularly limited, but is preferably 0 ℃ or less, more preferably-10 ℃ or less, further preferably-15 ℃ or less, and particularly preferably-20 ℃ or less. The lower limit is typically-100 ℃. By setting the range as described above, an adhesive sheet excellent in level difference absorbency can be produced.
In the case where the adhesive sheet has active energy ray curability, the glass transition temperature, which is the maximum value of the loss tangent (Tan δ) obtained by dynamic viscoelasticity measurement in the shear mode (peak temperature), of the adhesive sheet after curing is preferably 0 ℃ or less, more preferably-10 ℃ or less, still more preferably-15 ℃ or less, and particularly preferably-20 ℃ or less. The lower limit is typically-100 ℃. By setting the range as described above, an adhesive sheet having improved peel resistance at low temperature, low-temperature characteristics and excellent impact resistance can be produced.
The glass transition temperature (Tg) is obtained by reading a peak temperature, which is a temperature at which a loss tangent (Tan δ) becomes a maximum, from dynamic viscoelasticity spectrum data in the shear mode obtained by the same method as the measurement of the storage modulus (G') in the shear mode.
< gel fraction >
The adhesive sheet preferably has a gel fraction of 10% or more and 90% or less.
By setting the gel fraction to 10% or more, the adhesive sheet does not undergo cohesive failure with time even when adhered to a curved member, and excellent curved-surface adhesion can be exhibited. From this viewpoint, the gel fraction is preferably 20% or more, more preferably 40% or more, and still more preferably 60% or more.
On the other hand, from the viewpoint of the level difference following property at the time of curved surface pasting, the gel fraction is preferably 90% or less, more preferably 80% or less, and still more preferably 75% or less.
In addition, the adhesive sheet had active energy ray curability at 3000mJ/cm 2 When the polymer is cured by irradiation with active energy rays having a wavelength of 365nm, the gel fraction is preferably 70% to 95%, more preferably 73% to 90%, and even more preferably 78% to 85% as compared with the polymer before curing.
By setting the gel fraction after curing with active energy rays to the above range, the adhesive sheet can be provided with shape stability and durability when a laminate for an image display device is produced.
The gel fraction after curing is preferably increased by 2% or more, more preferably by 3% or more, and even more preferably by 5% or more, in terms of the difference between the gel fractions before curing. By setting the difference in gel fraction between before and after curing to the above range, the following performance of the height difference and durability when producing an image display device tend to be provided.
In order to adjust the gel fraction of the adhesive sheet to the above range, it is preferable to adjust the composition and molecular weight of the (meth) acrylic polymer to be described later, or to adjust the kind and addition amount of the crosslinking agent (B) and the photopolymerization initiator (C), or to adjust the intensity and cumulative light amount of the active energy rays irradiated. However, the method is not limited to this method.
The pressure-sensitive adhesive sheet may be a single layer or a plurality of layers, preferably at least 3 layers, more preferably at least 3 layers including a top layer, a bottom layer and an intermediate layer, and particularly preferably at least 3 layers including a top layer and a bottom layer as acrylic pressure-sensitive adhesive layers. By forming such a layer structure, an adhesive sheet excellent in adhesion suitability such as curved surface adhesion and level difference following property can be produced.
When the adhesive sheet is composed of at least 3 layers of the top layer, the innermost layer and the intermediate layer, the top layer, the innermost layer and the intermediate layer (layers sandwiched between the top layer and the innermost layer) are preferably formed of resin compositions containing (meth) acrylic polymers having different compositions, particularly resin compositions containing (meth) acrylic polymers having different compositions as main components. By forming such a layer structure, wet-heat whitening of the adhesive sheet can be effectively suppressed. The outermost layer and the innermost layer may be formed of resin compositions containing (meth) acrylic polymers having different compositions, particularly, resin compositions containing (meth) acrylic polymers having different compositions as a main component, and preferably, resin compositions containing (meth) acrylic polymers having the same composition.
When the pressure-sensitive adhesive sheet has at least 3 layers (outermost layer/intermediate layer/innermost layer) in which the outermost layer and the innermost layer are acrylic pressure-sensitive adhesive layers, the outermost and innermost layers (surfaces to be bonded to the image display device constituent members) are preferably low Tg layers. In addition, the intermediate layer sandwiched by the outermost surface and the innermost surface is preferably a high Tg layer. Further, the low Tg layers used for the top-most layer and the bottom-most layer may have glass transition temperatures (Tg) different from each other, and the top-most layer and the bottom-most layer preferably have the same glass transition temperature, and the top-most layer and the bottom-most layer are particularly preferably the same acrylic pressure-sensitive adhesive layer.
The aforementioned low Tg layer refers to: the maximum value (glass transition temperature) of the loss tangent (Tan δ) obtained by the dynamic viscoelasticity measurement in the shear mode is usually-10 ℃ or lower, preferably-100 to-15 ℃, and particularly preferably-50 to-20 ℃.
In addition, the high Tg layer refers to: the maximum value (glass transition temperature) of the loss tangent (Tan δ) obtained by the dynamic viscoelasticity measurement in the shear mode is usually higher than-10 ℃, preferably-5 to 20 ℃, particularly preferably 0 to 15 ℃.
In the case where the pressure-sensitive adhesive sheet has at least 3 layers, in which the outermost layer and the innermost layer are acrylic pressure-sensitive adhesive layers, the ratio of the total thickness of the outermost layer and the innermost layer to the total thickness is preferably 5 to 70%, more preferably 10 to 60%, and particularly preferably 20 to 45%. By setting the thickness of the outermost layer and the innermost layer to the above-described ranges, an adhesive sheet excellent in adhesion suitability such as curved surface adhesion and level difference absorption and durability can be produced.
The thickness of the pressure-sensitive adhesive sheet is preferably 50 to 1000. Mu.m, more preferably 60 to 500. Mu.m, particularly preferably 75 to 300. Mu.m.
The adhesive sheet is used for adhering two image display device constituent members, and specifically, can be used for adhering constituent members of image display devices such as personal computers, mobile terminals (PDA), game machines, televisions (TV), car navigation, touch panels, liquid Crystal Displays (LCD) such as stylus pads, plasma Displays (PDP), and electroluminescence displays (ELD).
As the image display device constituent member, more specifically, it is preferable that: of the two image display device constituent members, one is glass and the other is a film, and it is particularly preferable that: the glass is a reinforced glass, and the film is a laminate formed of any one or a combination of two or more selected from the group consisting of a touch sensor, an image display panel, a surface protection panel, a polarizing film, and a retardation film.
In recent years, in image display panels such as Liquid Crystal Displays (LCDs), plasma Displays (PDPs), and electroluminescence displays (ELDs), there are many cases where cover glass having a curved surface shape is used from the viewpoint of appearance, but the cover glass is expensive, and when it is intended to suppress a reduction in yield due to a sticking failure, the use of the present adhesive sheet is advantageous in terms of curved surface adhesion, and therefore, it is also effective for cover glass having a curved surface shape.
Examples of the film include resin films containing one or more resins selected from polyester resins, polyolefin resins, (meth) acrylic resins, polyurethane resins, polyethersulfone resins, polycarbonate resins, polysulfone resins, polyether ketone resins, (meth) acrylonitrile resins, cycloolefin resins, epoxy resins, polyimide resins, and cellulose resins as main component resins. At this time, the main component resin means the resin having the highest mass ratio among the resins constituting the resin film, and is the resin having 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, and 95 mass% or more (including 100 mass%) among the resins constituting the resin film.
When the image display device constituent member formed of the resin film or the like is adhered to the cover glass having the curved surface shape via the adhesive sheet, a bending stress conforming to the curved surface shape is continuously applied to the resin film so as to bend the resin film or the like along the curved surface shape of the cover glass. Therefore, since the resin film is continuously applied to the adhesive sheet to restore the flat force, that is, the elastic force, it is difficult to make the adhesive sheet follow the curved portion. Therefore, it is critical to improve the peeling resistance, i.e., the constant load peeling force, when high adhesive force, holding force and predetermined load are continuously applied to the adhesive sheet, to have curved surface adhesiveness and durability after adhesion.
As described above, the present adhesive sheet having the above-described characteristics preferably has an acrylic adhesive layer, and the acrylic adhesive layer is preferably formed of a resin composition containing an acrylic polymer. In the case where the pressure-sensitive adhesive sheet has 3 layers including the outermost layer and the innermost layer as the acrylic pressure-sensitive adhesive layers, the intermediate layer is preferably formed of a resin composition containing an acrylic polymer.
Hereinafter, a resin composition for forming the acrylic pressure-sensitive adhesive layer and the intermediate layer will be described.
The resin composition contains a (meth) acrylic polymer, preferably a (meth) acrylic polymer, as a main component, and may further contain a crosslinking agent (B), a photopolymerization initiator (C), a silane coupling agent (D), an anticorrosive agent (E), and other additives.
The above-mentioned "main component" means: the (meth) acrylic polymer is contained in an amount of 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more, based on the entire resin composition.
[ (meth) acrylic Polymer ]
Examples of the (meth) acrylic polymer include a polymer obtained by copolymerizing an alkyl (meth) acrylate monomer having an alkyl group with 4 to 18 carbon atoms with a monomer component copolymerizable therewith.
Examples of the alkyl (meth) acrylate monomer having 4 to 18 carbon atoms in the alkyl group include linear alkyl (meth) acrylates such as n-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and the like; branched alkyl (meth) acrylates such as isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, and the like; alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 3, 5-trimethylcyclohexane (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate. They may be used in 1 kind or in combination of more than 2 kinds.
Examples of the monomer component copolymerizable with the alkyl (meth) acrylate monomer having 4 to 18 carbon atoms in the alkyl group include hydroxyl group-containing monomers, nitrogen atom-containing monomers, carboxyl group-containing monomers, epoxy group-containing monomers, vinyl monomers, alkyl (meth) acrylate monomers having 1 to 3 carbon atoms in the alkyl group, and other copolymerizable monomers.
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-1-methylethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (meth) acrylate, polypropylene glycol polytetramethylene glycol mono (meth) acrylate, and hydroxyphenyl (meth) acrylate. They may be 1 or 2 or more in combination.
Examples of the nitrogen atom-containing monomer include aminoalkyl (meth) acrylates such as aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, and aminopropyl (meth) acrylate; amino group-containing (meth) acrylate monomers such as N-alkylaminoalkyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate; amide group-containing (meth) acrylate monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hydroxymethyl propane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, maleic amide, and maleimide. They may be 1 or 2 or more in combination.
Examples of the carboxyl group-containing monomer include (meth) acrylic acid, and (meth) acrylic acid dimer. They may be 1 or 2 or more in combination.
Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and 4-hydroxybutyl glycidyl (meth) acrylate. They may be 1 or 2 or more in combination.
Examples of the vinyl monomer include alkyl (meth) acrylates having an alkyl group with 1 to 12 carbon atoms; and functional monomers having functional groups such as hydroxyl groups, amide groups, and alkoxyalkyl groups in the molecule; polyalkylene glycol di (meth) acrylates; vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl laurate; aromatic vinyl monomers such as styrene, chlorostyrene, chloromethylstyrene, alpha-methylstyrene and other substituted styrenes. They may be 1 or 2 or more in combination.
Examples of the alkyl (meth) acrylate monomer having 1 to 3 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. They may be 1 or 2 or more in combination.
Examples of the other copolymerizable monomer include an acid anhydride group-containing monomer such as maleic anhydride and itaconic anhydride; heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole; macromers, and the like. They may be 1 or 2 or more in combination.
In the present invention, in order to have specific physical properties when producing the pressure-sensitive adhesive sheet, a (meth) acrylic polymer obtained by copolymerizing the above-mentioned various monomer components may be used, and the copolymerization method may be carried out according to a conventionally known method, for example, solution radical polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, or the like.
When the pressure-sensitive adhesive sheet has at least 3 layers, in which the outermost layer and the innermost layer are acrylic pressure-sensitive adhesive layers, the outermost layer and the innermost layer are preferably formed of a resin composition containing a (meth) acrylic polymer (a) having a glass transition temperature of-10 ℃ or less, and more preferably the (meth) acrylic polymer contained in the resin composition is composed of only the (meth) acrylic polymer (a).
[ (meth) acrylic Polymer (A) ]
The (meth) acrylic polymer (a) having a glass transition temperature of-10 ℃ or lower preferably contains substantially no structural unit derived from a carboxyl group-containing monomer, and contains, as monomer components constituting the (meth) acrylic polymer (a), a polar group-containing monomer (a 2) and a (meth) acrylic ester monomer (a 1), wherein the polar group-containing monomer (a 2) is at least 1 selected from the group consisting of a hydroxyl group-containing monomer and a nitrogen atom-containing monomer, the (meth) acrylic ester monomer (a 1) is a monomer other than the (a 2), and the glass transition temperature (Tg) when a homopolymer is formed from the monomer components is-30 ℃ or lower.
The term "substantially free of structural units derived from a carboxyl group-containing monomer" means that: not only the case of being completely absent but also the case of containing not more than 0.5 mass% of a carboxyl group-containing monomer, preferably not more than 0.1 mass% of a carboxyl group-containing monomer, in the (meth) acrylic polymer.
Examples of the (meth) acrylate monomer (a 1) having a glass transition temperature (Tg) of-30℃or lower (preferably-40℃or lower, particularly preferably-50℃or lower) when a homopolymer is formed from the above monomer components include: among the alkyl (meth) acrylate monomers having 4 to 18 carbon atoms in the alkyl group, a monomer having a glass transition temperature of-30 ℃ or lower. Specifically, examples thereof include linear alkyl (meth) acrylate monomers such as n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-heptyl acrylate, n-hexyl acrylate, n-octyl acrylate, nonyl acrylate, lauryl methacrylate, stearyl methacrylate, and the like; and branched alkyl (meth) acrylate monomers such as 2-ethylhexyl acrylate, isononyl acrylate, and isodecyl acrylate. They may be 1 or 2 or more in combination. Among them, branched alkyl (meth) acrylates are preferable, and 2-ethylhexyl acrylate is particularly preferable.
The polar group-containing monomer (a 2) includes the hydroxyl group-containing monomer and the nitrogen atom-containing monomer, and among them, hydroxyl group-containing monomers are preferable, and 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly preferable.
Further, as the copolymerization component of the (meth) acrylic polymer (a), monomers other than the above monomers (a 1) and (a 2) may be used. As the monomer other than the above-mentioned monomers (a 1) and (a 2), the above-mentioned various monomers can be used, and among them, alkyl (meth) acrylate having 1 to 3 carbon atoms of the alkyl group is preferably used, and methyl (meth) acrylate is particularly preferably used.
The glass transition temperature of the (meth) acrylic polymer (A) obtained by copolymerizing these is preferably-10℃or less, more preferably-100 to-15℃and particularly preferably-50 to-20℃from the viewpoints of the level difference absorbability and adhesion reliability.
In the present invention, the glass transition temperature (Tg) of the acrylic polymer (a) is obtained by reading the temperature at which the loss tangent (loss elastic modulus G "/storage modulus G' =tan δ) reaches the maximum when the dynamic viscoelasticity is measured in the shear mode at a frequency of 1Hz using a dynamic viscoelasticity measuring device.
The weight average molecular weight of the (meth) acrylic polymer (a) is preferably 5 to 150 ten thousand, more preferably 10 to 70 ten thousand, particularly preferably 15 to 60 ten thousand.
In the present specification, the weight average molecular weight is measured by the following method.
A sample obtained by dissolving 4mg of a (meth) acrylic polymer in 12mL of THF was used as a measurement sample, and a molecular weight distribution curve was measured using a gel permeation chromatography (Gel Permeation Chromatography: GPC) analyzer (HLC-8320 GPC, manufactured by Tosoh Corp.) under the following conditions to determine a weight average molecular weight (Mw).
Protection column: TSKguardcolumnHXL
Separation column: TSKgelGMHXL (4 root)
Temperature: 40 DEG C
Injection amount: 100 mu L
Polystyrene conversion
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0mL/min
The hydroxyl value of the (meth) acrylic polymer (A) is usually 20 to 150mgKOH/g, preferably 30 to 100mgKOH/g, more preferably 40 to 80mgKOH/g.
As described above, when the pressure-sensitive adhesive sheet has at least 3 layers including the outermost layer and the innermost layer as the acrylic pressure-sensitive adhesive layers, the outermost layer and the innermost layer and the intermediate layer (the layers sandwiched between the outermost layer and the innermost layer) are preferably formed of a resin composition containing a (meth) acrylic polymer having a different composition, and preferably a resin composition containing a (meth) acrylic polymer as a main component. By forming such a layer structure, wet-heat whitening of the adhesive sheet can be effectively suppressed.
Among them, the intermediate layer is preferably formed of a resin composition containing an acrylic polymer (A ') having a glass transition temperature higher than-10 ℃, and more preferably the (meth) acrylic polymer contained in the resin composition is composed of only the (meth) acrylic polymer (A').
[ (meth) acrylic Polymer (A') ]
The (meth) acrylic polymer (A ') having a glass transition temperature of higher than-10 ℃ preferably contains at least 1 or more polar group-containing monomers (a 2) selected from the group consisting of hydroxyl group-containing monomers and nitrogen atom-containing monomers, and an alkyl (meth) acrylate monomer (a 3) having an alkyl group with 1 to 18 carbon atoms, as the monomer component constituting the (meth) acrylic polymer (A').
The polar group-containing monomer (a 2) includes the hydroxyl group-containing monomer and the nitrogen atom-containing monomer, and among them, the nitrogen atom-containing monomer is preferable, the amide group-containing monomer is more preferable, and (meth) acrylamide is particularly preferable.
The alkyl (meth) acrylate monomer (a 3) having 1 to 18 carbon atoms in the alkyl group includes an alkyl (meth) acrylate monomer having 4 to 18 carbon atoms in the alkyl group and an alkyl (meth) acrylate monomer having 1 to 3 carbon atoms in the alkyl group, and among these, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and isobornyl (meth) acrylate are particularly preferable. Further, from the viewpoint of versatility of the monomer and Tg of the (meth) acrylic polymer (A') being at least-10 ℃, methyl (meth) acrylate, ethyl methacrylate, t-butyl (meth) acrylate, isobutyl methacrylate, and isobornyl (meth) acrylate are more preferable.
Further, as the copolymerization component of the (meth) acrylic acid ester-based polymer (a'), monomers other than the above-mentioned monomers (a 2) and (a 3) may be used. As the monomer other than the above-mentioned monomers (a 2) and (a 3), the above-mentioned various monomers can be used.
The glass transition temperature of the (meth) acrylic polymer (A') obtained by copolymerizing them is preferably higher than-10 ℃, more preferably from-5 to 20 ℃, particularly preferably from 0 to 15 ℃ from the viewpoint of reworkability.
The weight average molecular weight of the (meth) acrylic polymer (a') is 5 to 100 ten thousand, preferably 7 to 70 ten thousand, particularly preferably 10 to 50 ten thousand.
[ Cross-linking agent (B) ]
The resin composition for forming each layer may contain a crosslinking agent (B) in addition to the (meth) acrylic polymer. It is particularly preferable to compound the crosslinking agent (B) to the resin composition forming the adhesive sheet intermediate layer.
The crosslinking agent (B) is preferably a crosslinking agent having at least a double bond. Examples of the crosslinking agent include a crosslinking agent having at least 1 crosslinkable functional group selected from the group consisting of a (meth) acryloyl group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, a carbodiimide group, an oxazoline group, an aziridine group, a vinyl group, an amino group, an imino group, and an amide group, and 1 or 2 or more crosslinking agents may be used in combination. Further, the present invention also includes a method of chemically bonding the crosslinking agent (B) to the (meth) acrylic polymer.
Among them, a crosslinking agent having a (meth) acryloyl group is preferable, and from the viewpoint of obtaining adhesion suitability and reliability, a polyfunctional (meth) acrylate is particularly preferable. The term "polyfunctional" as used herein means a functional group having two or more crosslinking properties. The crosslinkable functional group may be 3 or more and 4 or more as needed. The crosslinkable functional group may be protected with a protecting group capable of deprotection.
As the above-mentioned polyfunctional (meth) acrylate, for example, 1, 4-butanediol di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol glycidyl ether di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol propane trioxyethyl (meth) acrylate, epsilon-caprolactone modified tri (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 tetra (meth) acrylate, di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate, examples of the ultraviolet curable polyfunctional (meth) acrylic monomers include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, and the like, as well as ultraviolet curable polyfunctional (meth) acrylic monomers such as tris (acryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, and epsilon-caprolactone adduct of hydroxypivalate neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. They may be 1 or 2 or more in combination. Among them, propoxylated pentaerythritol tri (meth) acrylate and polypropylene glycol di (meth) acrylate are preferable.
The content of the crosslinking agent (B) is usually 0.5 to 50 parts by mass, preferably 1 to 40 parts by mass, particularly preferably 5 to 30 parts by mass, relative to 100 parts by mass of the (meth) acrylic polymer. If the content is within the above range, adhesion suitability and reliability can be easily obtained, and thus it is preferable.
[ photopolymerization initiator (C) ]
The resin composition preferably contains a photopolymerization initiator (C). As the photopolymerization initiator (C), conventionally known ones can be suitably used, and among them, a photopolymerization initiator that induces ultraviolet rays having a wavelength of 380nm or less is preferable from the viewpoint of easiness of control of the crosslinking reaction.
Photopolymerization initiators (C) are roughly classified into two types according to a radical generation mechanism: a cleavage type photopolymerization initiator capable of cleaving and decomposing a single bond of the photopolymerization initiator itself to generate a radical; and a hydrogen abstraction type photopolymerization initiator capable of transferring hydrogen of a hydrogen donor by forming an excitation complex with the hydrogen donor in the system by the photopolymerization initiator excited by light.
When the cleavage type photopolymerization initiator generates radicals by irradiation with light, it is decomposed to form other compounds, and once excited, it no longer functions as a reaction initiator. Therefore, it is preferable that the cured product such as the adhesive after the completion of the crosslinking reaction does not remain as an active species, and unexpected photodegradation or the like is not likely to occur in the cured product.
On the other hand, the hydrogen abstraction type photopolymerization initiator is useful in that it does not generate decomposition products such as a cleavage type photopolymerization initiator when it generates a reaction of radicals by irradiation with active energy rays such as ultraviolet rays, and therefore is less likely to become volatile after the completion of the reaction, and damage to an adherend can be reduced.
Examples of the cleavage type photopolymerization initiator include 2, 2-dimethoxy-1, 2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propane-1-one, 2-)Hydroxy group-1- [4- {4- (2-hydroxy-2-methyl-propionyl) benzyl } phenyl]-2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglyoxylic acid methyl ester, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl]-2-morpholinopropan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl]-1- [4- (4-morpholinyl) phenyl ]]-1-butanone, bis (2, 4, 6-trimethylbenzoyl) benzenePhosphine oxides, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxides, derivatives thereof, and the like. Among them, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone is preferable.
Examples of the hydrogen abstraction photopolymerization initiator include benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, 4-phenylbenzophenone, 3' -dimethyl-4-methoxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis (2-phenyl-2-oxoacetic acid) oxydivinyl, 4- (1, 3-acryl-1, 4,7,10, 13-pentaoxo-tridecyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2, 4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, derivatives thereof, and the like. Among them, 4-methylbenzophenone and 2,4, 6-trimethylbenzophenone are preferable.
The photopolymerization initiator (C) is not limited to the above-listed ones. The photopolymerization initiator (C) may be either a cleavage type photopolymerization initiator or a hydrogen abstraction type photopolymerization initiator, or may be used in combination.
The content of the photopolymerization initiator (C) is not particularly limited, but is usually 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, and particularly preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the (meth) acrylic polymer.
By setting the content of the photopolymerization initiator (C) to the above range, appropriate reaction sensitivity with respect to active energy rays can be obtained.
[ silane coupling agent (D) ]
In order to improve the adhesion to the image display device constituent member, particularly to glass, it is preferable to blend the silane coupling agent (D) into the resin composition. Among them, the resin composition forming the acrylic pressure-sensitive adhesive layer of the double-sided pressure-sensitive adhesive sheet in contact with the image display device constituent member preferably contains a silane coupling agent (D).
Examples of the silane coupling agent (D) include compounds having an unsaturated group such as a vinyl group, an acryloxy group, or a methacryloxy group, an amino group, an epoxy group, or the like, and having a hydrolyzable functional group such as an alkoxy group.
Examples of the silane coupling agent (D) include N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyl dimethoxy silane, 3-aminopropyl triethoxy silane, 3-glycidoxypropyl trimethoxysilane, and 3-methacryloxypropyl trimethoxysilane. They may be used singly or in combination of 2 or more. Among them, 3-glycidoxypropyl trimethoxysilane is preferable from the viewpoints of good adhesion to the constituent members of the image display device, less discoloration such as yellowing, and the like.
The content of the silane coupling agent (D) is preferably 0.01 to 5 parts by mass, particularly preferably 0.2 to 3 parts by mass, relative to 100 parts by mass of the (meth) acrylic polymer.
In addition, as in the case of the silane coupling agent (D), a coupling agent such as an organic titanate compound can be effectively used.
[ Metal Corrosion inhibitor (E) ]
The resin composition further preferably contains a metal corrosion inhibitor (E). Among them, the metal corrosion inhibitor (E) is preferably contained in the resin composition of the acrylic adhesive layer in contact with the image display device constituent member forming the double-sided adhesive sheet.
Examples of the metal corrosion inhibitor (E) include benzotriazole compounds, benzimidazole compounds, benzothiazole compounds, and other triazole derivatives.
The metal corrosion inhibitor (E) is preferably at least one selected from the group consisting of benzotriazole-based compounds, 1,2, 3-triazoles and 1,2, 4-triazoles. Among them, triazole derivatives such as 1,2, 3-triazole and 1,2, 4-triazole are preferable, and 1,2, 3-triazole is particularly preferable, because it is excellent in reliability as a double-sided adhesive sheet in addition to metal corrosion resistance.
The content of the metal corrosion inhibitor (E) is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 1 part by mass, particularly preferably 0.05 to 0.5 part by mass, based on 100 parts by mass of the (meth) acrylic polymer, from the viewpoints of the bleeding of the metal corrosion inhibitor, the metal corrosion inhibiting effect, and the like.
[ other additives ]
In addition to the above components, other additives may be contained in the resin composition. Examples of the other additives include various additives such as a light stabilizer, an ultraviolet absorber, a metal deactivator, an antioxidant, an antistatic agent, a hygroscopic agent, a foaming agent, a defoaming agent, inorganic particles, a viscosity modifier, a tackifying resin, a photosensitizer, and a fluorescent agent; a reaction catalyst (tertiary amine compound, quaternary ammonium compound, tin laurate compound, etc.), and the like. They may be used singly or in combination of 2 or more.
In addition, other known components which are generally blended into the binder-forming resin composition may be appropriately contained.
The resin composition is obtained by mixing a predetermined amount of a (meth) acrylic polymer, a crosslinking agent (B), a photopolymerization initiator (C), a silane coupling agent (D), a metal corrosion inhibitor (E), and other additives, as required. The method of mixing the above components is not particularly limited, and the order of mixing the components is not particularly limited. In addition, the heat treatment step may be added at the time of producing the resin composition, and in this case, it is preferable to mix the components of the resin composition in advance and then perform the heat treatment. In the above mixing, a substance in which various mixed components are concentrated to prepare a master batch can be used.
The mixing method is not particularly limited, and for example, a universal mixer, a planetary mixer, a Banbury mixer, a kneader, a gate valve mixer, a pressure kneader, a three-roll mill, a two-roll mill, or the like can be used. When mixing the components of the resin composition, a solvent may be used for mixing as needed. In addition, the resin composition may also be used in the form of a solvent-free system containing no solvent. The use of the solvent-free system provides the advantages of no residual solvent, improved heat resistance and light resistance.
[ method for producing adhesive sheet ]
Hereinafter, the method for producing the pressure-sensitive adhesive sheet is described, but the method is not limited thereto. The pressure-sensitive adhesive sheet may be a single layer or a plurality of layers, and preferably has a multilayer structure, and more preferably has at least 3 layers in which the outermost layer and the innermost layer are acrylic pressure-sensitive adhesive layers. Typically, the present adhesive sheet is preferably manufactured in the form of an adhesive sheet with a release film having a structure in which the present adhesive sheet and the release film are laminated by the following steps. The pre-curing in the following steps may be omitted.
The release film may be laminated on only one side of the pressure-sensitive adhesive sheet, or may be laminated on both sides.
As a material of the release film, a known release film can be suitably used.
As the material of the release film, for example, a film obtained by coating a silicone resin on a film such as a polyester film, a polyolefin film, a polycarbonate film, a polystyrene film, an acrylic film, a cellulose triacetate film, a fluororesin film, a release paper, or the like can be suitably selected and used.
The release film may have other layers such as an antistatic layer, a hard coat layer, an anchor layer, and the like as required.
In the case where the release films are laminated on both sides of the adhesive sheet, one release film and the other release film may have the same laminated structure and/or material, or may have different laminated structures and/or materials. In addition, the thickness may be the same or different.
In addition, release films having different peeling forces and release films having different thicknesses may be laminated on both sides of the adhesive sheet.
The thickness of the release film is not particularly limited. Among them, from the viewpoints of, for example, workability and handling properties, 10 to 250 μm is preferable, 25 to 200 μm is more preferable, and 35 to 190 μm is even more preferable.
In the case where the adhesive sheet is a single layer, for example, the release film is coated with a substance obtained by heating and melting (hot-melting) the resin composition, and the release film is sandwiched between other release films and heated, thereby obtaining an adhesive sheet with a release film. In the case where the present adhesive sheet is a multilayer, the adhesive sheet having a multilayer structure can be obtained by preparing the number of adhesive sheets with release films corresponding to the layers required for the adhesive sheet by the above method, peeling off the release films, and laminating the adhesive sheets.
In the case where the pressure-sensitive adhesive sheet has a multilayer structure, the pressure-sensitive adhesive sheet having a multilayer structure can be produced by repeating the operations of forming a pressure-sensitive adhesive layer by applying the resin composition to a release sheet, forming a resin layer by further applying another resin composition to the pressure-sensitive adhesive layer, and the like. In addition, instead of the release sheet, an adhesive sheet may be formed by applying a resin composition to an adherend. Further, the adhesive sheet can be produced by a method of simultaneously forming the resin composition into a plurality of layers by multilayer coating and coextrusion molding.
The pressure-sensitive adhesive sheet may be formed by, for example, injecting a resin composition into a mold, instead of using a release film or an adherend as described above.
Further, the adhesive sheet can be produced by directly filling the resin composition between the image display device constituent members as the adherend.
The obtained adhesive sheet is preferably pre-cured by active energy ray crosslinking in such a manner as to have a latent active energy ray reactivity, in other words, in such a manner as to remain active energy ray reactivity. In the case of pre-curing, the active energy rays may be irradiated through the release film to crosslink the layers by the active energy rays. In this case, the degree of crosslinking of the active energy rays (gel fraction) can be adjusted by controlling the irradiation amount of the active energy rays, but as described above, the degree of crosslinking of the active energy rays (gel fraction) can also be adjusted by blocking a part of the active energy rays by irradiating ultraviolet rays through the release film.
The adhesive sheet thus obtained was an optically transparent adhesive sheet. The term "optically transparent" as used herein means that the total light transmittance is 80% or more, preferably 85% or more, and more preferably 90% or more.
The haze value of the pressure-sensitive adhesive sheet is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less.
The pressure-sensitive adhesive sheet is generally in a state of a pressure-sensitive adhesive sheet with a release film in which acrylic pressure-sensitive adhesive layers on both sides are sandwiched between release films. When the double-sided pressure-sensitive adhesive sheet is used, the release film may be peeled off from the acrylic pressure-sensitive adhesive layer, and the acrylic pressure-sensitive adhesive layer may be adhered to the image display constituent member.
[ laminate for image display device ]
A laminate for an image display device (referred to as a "laminate for an image display device") as an example of an embodiment of the present invention has a structure in which two image display device constituent members are laminated with the adhesive sheet interposed therebetween.
Of the two image display device constituent members, it is preferable that: one is a cover glass having a curved shape, and the other is any one member selected from the group consisting of a touch sensor, an image display panel, a surface protective film, an antireflection film, a color filter, a polarizing film, and a phase difference film, or a member formed of a combination of 2 or more. The above configuration can particularly enjoy the effects of the present invention.
[ image display device ]
An image display device according to an example of the embodiment of the present invention is an image display device obtained using the laminate for an image display device.
As an example of the image display device, an image display device having a structure in which the laminate for the image display device is combined with other image display device constituent members is given.
In this case, examples of the "other image display device constituent members" include FPC cables, reflective sheets, light guide plates and light sources, diffusion films, prism sheets, liquid crystal panels, organic EL panels, antireflection films, color filters, polarizing plates, retardation plates, glass substrates, surface protection films, and members obtained by integrating these members in a composite manner.
Specific examples of the present image display device include a liquid crystal display, an organic EL display, an inorganic EL display, an electronic paper, a plasma display, and a microelectromechanical system (MEMS) display used in, for example, a personal computer, a mobile terminal (PDA), a game machine, a Television (TV), a car navigation system, a touch panel, a stylus panel, and the like.
(description of sentence, etc.)
In general, "patch" means: in the definition of JIS, an article which is thin and whose thickness is small and flat with respect to length and width; in general, "film" refers to: thin and flat articles having a minimum thickness and a maximum thickness, which are arbitrarily defined, are generally supplied in the form of rolls (japanese industrial standard JISK 6900). However, the boundaries between the sheets and the films are not defined, and the distinction between the two is not required in terms of language in the present invention, and therefore, in the present invention, the term "sheet" is also considered to include the term "sheet" in the case of being referred to as "sheet" and the term "film" is also considered to include the term "film" in the case of being referred to as "sheet".
In addition, when expressed as a "panel" such as an image display panel, a protective panel, or the like, the panel includes a plate body, a sheet, and a film.
In the present specification, the term "x to y" (x and y are arbitrary numbers) includes the meaning of "x or more and y or less" and the meaning of "preferably greater than x" and "preferably less than y" unless otherwise specified.
Note that unless otherwise specified, "x" or "x" (x being an arbitrary number) includes the meaning of "x or" x "and the meaning of" preferably greater than x ", and unless otherwise specified," y "or" y "(y being an arbitrary number), includes the meaning of" y or "y" and the meaning of "preferably less than y".
Examples
Hereinafter, examples and comparative examples will be described in more detail. However, the present invention is not limited to these examples.
First, details of raw materials of the resin compositions prepared in examples are described.
(meth) acrylic Polymer
(meth) acrylic Polymer (A-1): acrylic Polymer (weight average molecular weight: 43 ten thousand, tg: -25 ℃ C., hydroxyl value: 67 mgKOH/g) formed from 2-ethylhexyl acrylate/methyl acrylate/2-hydroxyethyl acrylate
(meth) acrylic polymer (A' -1): (meth) acrylic Polymer (weight average molecular weight: 25 ten thousand, tg:4 ℃ C.) formed from 2-ethylhexyl acrylate/methyl acrylate/acrylamide/methyl methacrylate/isobornyl methacrylate
(meth) acrylic polymer (A' -2): acrylic Polymer (weight average molecular weight: 54 ten thousand, tg:1 ℃ C., hydroxyl value: 62 mgKOH/g) formed from methyl acrylate/ethyl acrylate/2-ethylhexyl acrylate/2-hydroxyethyl acrylate
The weight average molecular weight, glass transition temperature (Tg) and hydroxyl value of the (meth) acrylic polymer were measured by the following methods.
[ weight average molecular weight ]
The weight average molecular weight of the (meth) acrylic polymer was measured using a gel permeation chromatography (Gel Permeation Chromatography: GPC) analyzer (HLC-8320 GPC, manufactured by Tosoh Corp.). Specifically, after dissolution of 4mg of a (meth) acrylic polymer in 12mL of THF was used as a measurement sample, a molecular weight distribution curve was measured under the following conditions to determine a weight average molecular weight (Mw).
Protection column: TSKguardcolumnHXL
Separation column: TSKgelGMHXL (4 root)
Temperature: 40 DEG C
Injection amount: 100 mu L
Polystyrene conversion
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0mL/min
[ glass transition temperature (Tg) ]
The glass transition temperature (Tg) of the (meth) acrylic polymer was measured using a rheometer (manufactured by TA Instruments, discovery HR 2). Specifically, the (meth) acrylic polymer having a thickness of 0.6 to 0.8mm is produced by: phi 8mm parallel plate, strain: 0.1%, frequency: 1Hz, temperature: -120-200 ℃, and the temperature rising speed is as follows: the glass transition temperature (Tg) was obtained by measuring a dynamic viscoelasticity spectrum at a temperature ranging from-120 to 200℃under a condition of 5℃per minute and reading from the obtained data a temperature at which the loss tangent (Tan. Delta.) reaches a maximum.
[ hydroxyl value ]
The hydroxyl value of the (meth) acrylic polymer was measured by a neutralization titration method.
To the Erlenmeyer flask, 2g of a sample was collected, 10mL of a mixed solution of acetic anhydride and pyridine=1:13 was added by a quantitative pipette, and 10mL of toluene was further added. An air-cooled tube was attached to the upper part of the Erlenmeyer flask, and the flask was heated at 95℃for 90 minutes. After heating, 10mL of toluene and 10mL of pure water were added thereto, and the mixture was cooled to room temperature (23 ℃ C.) while stirring. Thereafter, a few drops of phenolphthalein solution were added and titration was performed with 0.1mol/L potassium hydroxide (KOH) solution. In addition, as a blank test, the same procedure as described above was performed without collecting a sample in the Erlenmeyer flask. The hydroxyl value is calculated according to the following calculation formula (1).
(computing type)
Hydroxyl value= 5.611 × (amount of potassium hydroxide solution (mL) used in blank test) -amount of potassium hydroxide solution (mL) used in titration ×f/amount of sample collected (g) +acid value … (1)
F: factor of 0.1mol/L Potassium hydroxide solution
[ acid value ]
The acid value was measured by the following method. Acrylic copolymer Yg was collected in a beaker and dissolved in a mixed solvent of toluene: methanol=7:3. After that, an appropriate amount of phenolphthalein was added after dissolution, and the solution was titrated with 0.1mol/L KOH solution while stirring with a stirrer, and the amount of KOH solution XmL at which the solution turns pale pink was read as an end point, and the acid value was calculated according to the following equation (2).
(computing type)
Acid value (mgKOH/g) =x× (f×m×56.1)/Y … (2)
F: factor of KOH solution
M: molar concentration (mol/L)
X: KOH solution quantity (mL)
Y: sample size (g)
In the case where the acid value is low, 0.01mol/L KOH solution is used to improve the accuracy.
< crosslinker (B) >
Crosslinking agent (B-1): propoxylated pentaerythritol triacrylate
Crosslinking agent (B-2): polypropylene glycol #400 diacrylate
< photopolymerization initiator (C) >)
Photopolymerization initiator (C-1): mixtures of 2,4, 6-trimethylbenzophenone and 4-methylbenzophenone (manufactured by IGM Co., ltd. "Esacure TZT")
< silane coupling agent (D) >)
Silane coupling agent (D-1): 3-epoxypropoxypropyl trimethoxysilane
Example 1 ]
1kg of (meth) acrylic polymer (A' -1), 100g of crosslinking agent (B-1) and 5g of photopolymerization initiator (C-1) were uniformly melt-kneaded to prepare a resin composition 1.
The resin composition 1 was formed into a sheet at 80℃so that the thickness of the sheet became 67 μm by sandwiching the two release films, which were two polyethylene terephthalate films (DIAFOIL MRF (thickness: 75 μm) manufactured by Mitsubishi chemical corporation) and DIAFOIL MRT (thickness: 38 μm) manufactured by Mitsubishi chemical corporation) after the release treatment, to prepare an intermediate layer sheet (1-1).
1kg of (meth) acrylic polymer (A-1), 15g of photopolymerization initiator (C-1) and 2g of silane coupling agent (D-1) were uniformly melt-kneaded to prepare a resin composition 2.
The resin composition 2 was formed into a sheet at 80℃by sandwiching two release films (namely, two polyethylene terephthalate films (DIAFOIL MRF (thickness: 75 μm) manufactured by Mitsubishi chemical corporation) and DIAFOIL MRT (thickness: 38 μm) manufactured by Mitsubishi chemical corporation) between each other so that the thickness of the release films became 16.5 μm, and two pressure-sensitive adhesive sheets (2-1) for the outermost layer and the innermost layer (outermost layer) were produced.
A laminate comprising layers of (2-1)/(1-1)/(2-1) was produced by adhering the intermediate layer sheet (1-1) from which the release films on both sides were peeled to the adhesive surface of the outermost layer adhesive sheet (2-1) from which the release films on one side were peeled.
The cumulative light quantity at a wavelength of 365nm is 1000mJ/cm via a release film remaining on the surface of the pressure-sensitive adhesive sheet (2-1) for the outermost and the inner layers 2 In the above method, the adhesive sheet with a release film (pre-cured product) of example 1 was produced by pre-curing the sheet by irradiation with light from a high-pressure mercury lamp.
The adhesive sheet of example 1 was a sheet having active energy ray curability, with room for light curing by light irradiation.
< example 2, 3>
Adhesive sheets (pre-cured products) with release films of examples 2 and 3 were produced in the same manner as in example 1, except that the proportions, thickness configurations and pre-curing conditions shown in table 1 were set.
The adhesive sheets of examples 2 and 3 have room for photocuring by light irradiation, and are active energy ray-curable sheets.
Example 4 ]
1kg of a (meth) acrylic polymer (A' -2), 80g of a crosslinking agent (B-2), 10g of a photopolymerization initiator (C-1) and 1g of a silane coupling agent (D-1) were uniformly melt-kneaded to prepare a resin composition 5.
The resin composition 5 was formed into a sheet at 80℃by sandwiching two release films (namely, two polyethylene terephthalate films (DIAFOIL MRF (thickness: 75 μm) manufactured by Mitsubishi chemical corporation) and DIAFOIL MRT (thickness: 38 μm) manufactured by Mitsubishi chemical corporation) each having been subjected to release treatment, so that the thickness became 100 μm.
A cumulative light quantity of 365nm wavelength of 1000mJ/cm with a release film on the surface 2 In (3), the release film-attached adhesive sheet of example 4 was produced by pre-curing the sheet by irradiation with light from a high-pressure mercury lamp(precured product).
The adhesive sheet of example 4 was a sheet having active energy ray curability, with room for light curing by light irradiation.
Comparative examples 1 to 3 ]
Adhesive sheets with release films of comparative examples 1 to 3 were produced in the same manner as in example 1, except that the proportions shown in table 1 were used.
The adhesive sheets of comparative examples 1 to 3 have room for photocuring by light irradiation, and are active energy ray-curable sheets.
< evaluation of physical Properties of adhesive sheet >
Physical properties of the adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 obtained by the above-described operations were measured as follows.
[ adhesive force ]
One release film of the release film-attached adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 was peeled off, and a polyethylene terephthalate film (cosmosfine a4300, manufactured by eastern spinning corporation) having a thickness of 100 μm as a lining film was adhered to prepare a laminate.
After cutting the laminate into pieces having a length of 150mm and a width of 10mm, the remaining release film was peeled off to expose the adhesive surface, and the adhesive sheet was rolled onto soda lime glass by 1 round trip of a manual roller, and finally attached by autoclave treatment (temperature 60 ℃ C., gauge pressure 0.2MPa, 20 minutes).
The peel force (N/cm) was measured for the glass when the adhesive force measurement sample was peeled off under conditions of a peel angle of 180℃and a peel speed of 300 mm/min at a temperature of 23℃and a humidity of 50% RH.
[ adhesion after curing ]
One release film of the release film-attached adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 was peeled off, and a polyethylene terephthalate film (cosmosfine a4300, manufactured by eastern spinning corporation) having a thickness of 100 μm as a lining film was adhered to prepare a laminate.
Cutting the laminated product into pieces with a length of 150mm,After the width of 10mm, the adhesive sheet was rolled onto soda lime glass by reciprocating a manual roller 1 time against the adhesive surface exposed by peeling the remaining release film, and the resultant was subjected to autoclave treatment (temperature: 60 ℃ C., gauge pressure: 0.2MPa, 20 minutes) to finally apply the adhesive sheet, and a high-pressure mercury lamp was used to set the cumulative light amount to 3000mJ/cm 2 After 365nm ultraviolet light was irradiated from the liner film surface, the cured sample was cured at a temperature of 23℃and a humidity of 50% RH for 12 hours.
The peel force (N/cm) was measured for the glass when the cured adhesive force measurement sample was peeled off under conditions of a peel angle of 180℃and a peel speed of 300 mm/min at a temperature of 23℃and a humidity of 50% RH.
[ holding force ]
One release film of the release film-attached adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 was peeled off, and a polyethylene terephthalate (PET) film (diafil S100, manufactured by mitsubishi chemical company) having a thickness of 38 μm was adhered as a lining film, to prepare a laminate.
The laminate was cut into pieces having a length of 150mm and a width of 20mm, and then the remaining release film was peeled off to expose an adhesive surface, and the adhesive surface was adhered to a polished stainless steel plate (SUS 304) so that the adhesion area became 20 mm. Times.20 mm, to obtain a sample for measuring holding power.
After preheating the retention force measurement sample at a temperature of 70℃for 15 minutes, a weight of 0.5kg was applied thereto, and the sample was kept at a temperature of 70℃for 30 minutes, whereby the offset length (mm) of the adhesive sheet was measured.
[ holding force after curing ]
The pressure-sensitive adhesive sheets with release films of examples 1 to 4 and comparative examples 1 to 3 were subjected to a high-pressure mercury lamp so that the cumulative light amount at a wavelength of 365nm became 3000mJ/cm 2 In (2) irradiating the pressure-sensitive adhesive sheet with light through the release film to thereby be photo-cured, thereby preparing a cured pressure-sensitive adhesive sheet.
One of the obtained cured adhesive sheets was peeled off, and a polyethylene terephthalate (PET) film (diaface S100, manufactured by mitsubishi chemical company) having a thickness of 38 μm was adhered as a lining film to prepare a laminate.
After the laminate was cut into pieces having a length of 150mm and a width of 20mm, the remaining release film was peeled off, and the exposed adhesive surface was adhered to a polished stainless steel plate (SUS 304) so that the adhering area became 20mm×20mm, to obtain a sample for measuring holding force after curing.
After preheating the cured holding power measurement sample at a temperature of 70℃for 15 minutes, a weight of 0.5kg was applied thereto, and the sample was held at a temperature of 70℃for 30 minutes, whereby the offset length (mm) of the adhesive sheet was measured.
[ constant load stripping ]
One release film of the release film-attached adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 was peeled off, and a polyethylene terephthalate film (cosmosfine a4300, manufactured by eastern spinning corporation) having a thickness of 100 μm as a lining film was adhered to prepare a laminate.
After the laminate was cut into pieces of 150mm in length and 10mm in width, a manual roller was reciprocated 1 time, and a 10mm wide and 100mm long region roller was pressed against soda lime glass as an adhesive region, and a region of the adhesive sheet other than the adhesive region was defined as a non-adhesive region, among the adhesive surfaces exposed by peeling off the remaining release film. Thereafter, autoclave treatment (temperature: 50 ℃ C., gauge pressure: 0.2MPa, 20 minutes) was performed, and the resultant was cured at a temperature of 40 ℃ C. For 30 minutes to carry out final adhesion, whereby the obtained sample was used as a sample for a constant load peel test.
Using this sample, soda lime glass was fixed in the horizontal direction so that the non-adhering region of the adhesive sheet was hung down in the environment of a temperature of 23 ℃ and a humidity of 50% rh, a load of 0.45N was applied to the longitudinal end of the non-adhering region of the adhesive sheet for 30 minutes, and the distance at which the adhering region of the adhesive sheet was peeled from the soda lime glass during this period was measured as a constant load peeling distance (see fig. 1).
[ ball tackiness ]
The measurement was performed under the conditions of a temperature of 23℃and an inclination angle of 30℃according to the inclination type ball tackiness defined in JIS Z0237:2009.
Specifically, the adhesive sheets with release films of examples 1 to 4 and comparative examples 1 to 3 were cut into a length of 10cm and a width of 2.5cm, and then one release film was peeled off, and a polyethylene terephthalate film (DIAFOIL S100, manufactured by Mitsubishi chemical corporation) having a thickness of 25 μm was adhered as a lining film to prepare a laminate. The ball tack measurement sample was set in a test machine with an inclination angle of 30 ° at a position of 10cm from the start point of ball rolling to the sample, and after the other release film of the adhesive sheet was peeled off, the ball was rolled onto the adhesive surface (length 10 cm) while changing the ball size (ball number), and the ball number of the ball stopped on the adhesive surface was set as the ball tack value.
[ tensile storage modulus (E') and peak temperatures (T1), (T2) ]
The release film-carrying adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 were cut into pieces having a width of 4 mm. Times.15 mm in length, and the pieces were subjected to a dynamic viscoelasticity test (manufactured by IT Measurement Control Co., ltd., itkVA-200) in a stretching mode: vibration frequency 1Hz, heating rate: speed and temperature range of 3 ℃/min: -measuring the dynamic viscoelasticity spectrum in the tensile mode at a temperature of 120-80 ℃ and reading the tensile storage modulus (E') at 25 ℃ from the obtained data.
Peak temperatures (T1) and (T2) which are maximum values of loss tangent (Tan δ) are read from the dynamic viscoelasticity spectrum data.
[ tensile storage modulus (E') after curing and peak temperatures (T1), (T2) ]
The adhesive sheets with release films produced in examples and comparative examples were set to 3000mJ/cm in cumulative light quantity at 365nm wavelength 2 In the above method, the pressure-sensitive adhesive sheet is cured by irradiation of light through a release film by a high-pressure mercury lamp, thereby preparing a cured pressure-sensitive adhesive sheet.
The dynamic viscoelasticity spectrum in the stretching mode was measured for the adhesive sheet after curing under the same measurement conditions as for the adhesive sheet before curing (pre-cured product), and the tensile storage modulus (E') of the adhesive sheet after curing at a temperature of 25 ℃ was determined from the obtained data.
Peak temperatures (T1) and (T2) which are maximum values of loss tangent (Tan δ) are read from the dynamic viscoelasticity spectrum data.
[ shear storage modulus (G') and glass transition temperature (Tg) ]
The pressure-sensitive adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 were laminated so that the thickness thereof became 0.6 to 0.8mm, and the samples thus obtained were die-cut into round shapes having a diameter of 8mm, to obtain measurement samples. Dynamic viscoelasticity spectra were measured on the measurement samples using a rheometer (discoveryHR 2, manufactured by TA Instruments Co.) under the following measurement conditions. The shear storage modulus (G') at 25 ℃, 65 ℃ and 85 ℃ was read from the data obtained by the measurement.
The glass transition temperature (Tg) which is the maximum value of the loss tangent (Tan δ) is read from the dynamic viscoelasticity spectrum data.
(measurement conditions)
Bonding tool: phi 8mm parallel plate
Strain: 0.1%
Frequency: 1Hz
Temperature: 120-200 DEG C
Heating rate: 5 ℃/min
[ shear storage modulus (G') and glass transition temperature (Tg) after curing ]
The adhesive sheets with release films of examples 1 to 4 and comparative examples 1 to 3 were each provided with a cumulative light amount of 3000mJ/cm at a wavelength of 365nm 2 In the above method, the pressure-sensitive adhesive sheet is cured by irradiation of light through a release film by a high-pressure mercury lamp, thereby preparing a cured pressure-sensitive adhesive sheet.
The cured adhesive sheet was laminated so as to have a thickness of 0.6 to 0.8mm, the thus obtained sample was die-cut into a round shape having a diameter of 8mm, and the dynamic viscoelasticity spectrum was measured by a shear method under the same measurement conditions as those of the adhesive sheet before curing (pre-cured product) as a measurement sample, and the storage modulus (G') of the cured adhesive sheet at 25 ℃, 65 ℃ and 85 ℃ was obtained from the obtained data.
The glass transition temperature (Tg) which is the maximum value of the loss tangent (Tan δ) is read from the dynamic viscoelasticity spectrum data.
[ residual creep Strain ]
The pressure-sensitive adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 were laminated so that the thickness thereof became 0.6 to 0.8mm, and the samples thus obtained were die-cut into round shapes having a diameter of 8mm, to obtain measurement samples. The measurement sample was subjected to a pressure of 1kPa at a temperature of 25 ℃ for 180 seconds using a rheometer (manufactured by TA Instruments, discover hr 2), and then the pressure was released and the strain (%) at that time, that is, residual creep strain (%) was read after 180 seconds.
In addition, the adhesive sheets with release films of examples 1 to 4 and comparative examples 1 to 3 were set to 3000mJ/cm in cumulative light amount at 365nm wavelength 2 In the above method, the pressure-sensitive adhesive sheet is prepared by irradiating the pressure-sensitive adhesive sheet with light through a release film by means of a high-pressure mercury lamp to thereby photo-cure the pressure-sensitive adhesive sheet, the cured pressure-sensitive adhesive sheet is laminated so that the thickness thereof is 0.6 to 0.8mm, and the sample obtained by the lamination is die-cut into a round shape having a diameter of 8mm to obtain a measurement sample. The measurement sample was subjected to a pressure of 1kPa at a temperature of 25 ℃ for 180 seconds using a rheometer (manufactured by TA Instruments, discover hr 2), and then the pressure was released and the strain amount at that time, that is, residual creep strain (%), was read out after 180 seconds.
[ creep Strain ]
The pressure-sensitive adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 were laminated so that the thickness thereof became 0.6 to 0.8mm, and the samples thus obtained were die-cut into round shapes having a diameter of 8mm, to obtain measurement samples. The creep strain (%) at this time was read by applying a pressure of 1kPa for 10 seconds to the measurement sample at a temperature of 25℃using a rheometer (manufactured by TA Instruments Co., ltd., discover HR 2).
In addition, the adhesive sheets with release films of examples 1 to 4 and comparative examples 1 to 3 were set to 3000mJ/cm in cumulative light amount at 365nm wavelength 2 In the above method, the pressure-sensitive adhesive sheet is cured by irradiation of light through a release film by a high-pressure mercury lamp, thereby preparing a cured pressure-sensitive adhesive sheet.
The cured adhesive sheet was laminated so that the thickness thereof was 0.6 to 0.8mm, and the thus obtained sample was die-cut into a round shape having a diameter of 8mm, to obtain a measurement sample. The creep strain (%) at this time was read by applying a pressure of 1kPa for 10 seconds to the measurement sample at a temperature of 25℃using a rheometer (manufactured by TA Instruments Co., ltd., discover HR 2).
[ gel fraction ]
The release films were peeled from the adhesive sheets with release films of examples 1 to 4 and comparative examples 1 to 3, and about 0.1g of adhesive sheet pieces were collected.
The collected pressure-sensitive adhesive sheet small pieces were wrapped with SUS mesh (# 150) of a previously-prepared bag-like mass (X), and a sample was produced by closing the bag mouth, and the mass (Y) of the sample was measured. After the sample was stored in the dark at a temperature of 23℃for 24 hours while being immersed in ethyl acetate, the sample was taken out and heated at a temperature of 70℃for 4.5 hours, whereby ethyl acetate was evaporated, and the mass (Z) of the dried sample was measured. Based on the measured respective masses, gel fractions were calculated using the following formulas.
Gel fraction (%) = [ (Z-X)/(Y-X) ]×100
In addition, the adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 were each provided with a cumulative light quantity of 3000mJ/cm at 365nm by using a high-pressure mercury lamp 2 In the above method, the adhesive sheet is cured by irradiating the adhesive sheet with light through the release film, thereby preparing the cured adhesive sheet. The gel fraction of the cured adhesive sheet was obtained in the same manner as in the evaluation step of the gel fraction.
< adhesion adaptability >
The adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 were evaluated for adhesion suitability in the following manner.
[ curved surface adhesion ]
As an image display device constituent member, a glass plate (cover glass having a curved surface shape) having 156mm×73mm×0.5mm thickness and a long side end portion bent with a radius of curvature of 3mm was prepared. The member was printed along the periphery of the inner curved surface with a width of 2mm and a thickness of 10. Mu.m.
One release film of the release film-attached adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 was peeled off, and a polyethylene terephthalate film (cosmosfine a4100, manufactured by eastern corporation) having a thickness of 125 μm was stuck to the exposed adhesive surface to prepare a laminate.
After the release film remaining in the laminate was peeled off and the exposed adhesive surface was placed so as to face the inner curved surface of the cover glass, the laminate was bonded using a diaphragm vacuum bonding apparatus at a temperature of 30 ℃ under a pressure of 0.1MPa and a pressing time of 60 seconds, to produce a laminate for an image display device.
After the laminate for an image display device was stored at a temperature of 23℃and a humidity of 50% for 200 hours, visual observation was performed, and when peeling and cohesive failure of the adhesive sheet were observed in the curved surface portion of the cover glass, it was judged as "X (bad)", and when the adhesive sheet was kept in a good appearance without peeling and cohesive failure, it was judged as "O (good)". The failure mode when "x (bad)" was presented is shown in table 1.
[ level Difference absorbency ]
The release film-attached pressure-sensitive adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 were cut into 52mm×80mm using a thomson die-cutting machine in a state where the release films were laminated.
The adhesive surface exposed by peeling the release film on one side was press-bonded to a printed surface (temperature 25 ℃ C. And pressing pressure 0.1 MPa) of soda lime glass (82 mm. Times.54 mm. Times.0.5 mm in thickness, printing thickness: 8 to 40 μm) on which printing was performed at 5mm of the edge portion in a thickness different from each other so that the 4 sides of the adhesive sheet exhibited a difference in printing height, using a vacuum press machine.
Then, the remaining release film was peeled off and pressure-bonded to soda lime glass (82 mm. Times.54 mm. Times.0.5 mm in thickness) having no print level difference, and then autoclave-treated (60 ℃ C. At a gauge pressure of 0.2MPa for 20 minutes) to finally bond the glass/double-sided adhesive sheet/glass laminate having level difference.
The produced laminate was visually observed to confirm the print thickness at which no bubbles were present near the print level difference and the laminate was able to be attached with good appearance. The case where the height difference thickness (μm)/the pressure-sensitive adhesive sheet thickness (μm) which can be adhered with good appearance was 20% or more was judged as "verygood", the case where 10% or more was judged as "good", and the case where less than 10% was judged as "× (bad)".
[ resistance to cement collapse ]
One release film was peeled off and half-cut into 10mm×10mm for the release film-attached adhesive sheets of examples 1 to 4 and comparative examples 1 to 3. The exposed adhesive surface was opposed to soda lime glass having a thickness of 0.6mm, and the adhesive sheet was pressure-bonded to the glass using a vacuum laminator at a temperature of 23℃under a gauge pressure of 0.4MPa for a pressure time of 60 seconds.
The distance by which the adhesive was overflowed from the half cut mark was measured for the center portion of each side of the adhesive sheet, and the average value of 4 sides was taken as the adhesive overflow distance (μm). The cement overflow distance was determined to be "verygood" when it was 300 μm or less, "good" when it was 500 μm or less, and "× (bad)" when it was more than 500 μm.
[ roll adhesion ]
For the adhesive sheets with release films of examples 1 to 4 and comparative examples 1 to 3, a roll sticking operation was performed using a roll sticking apparatus using two plate-like suction bases, and positional displacement at the time of the roll sticking operation was evaluated.
Specifically, the release film-attached adhesive sheets produced in examples and comparative examples were cut into 70mm×100mm pieces and fixed to the first suction base of the roll-attaching apparatus. The adhesive surface exposed by peeling one release film was opposed to a base film (polyethylene terephthalate film (cosmosfine a4300, manufactured by eastern spinning corporation) fixed to a second adsorption base (see fig. 2).
The pressure-sensitive adhesive sheet and the base film were roll-bonded by means of an adsorption base under the following conditions to prepare a laminate for evaluating roll-adhesiveness.
(roll sticking apparatus conditions)
Roll diameter: 12mm
Feed speed: 25 mm/sec
Roll pressure: 0.2MPa
Roller rubber hardness: 70 (ASKER A)
Base station adsorption pressure: 0.05MPa
Temperature: 23 DEG C
30 sheets of the laminate were produced and visually observed for appearance. Of all 30 sheets, the sheet was judged to be "verygood" (perfect) when the end on the roll attachment start point side was attached without positional displacement, and if the laminate having a positional displacement of 1mm or more was 1 to 3 sheets (the yield was 90% or more) among the 30 sheets, the sheet was judged to be "good", and if the sheet was 4 sheets or more, the sheet was judged to be "× (bad)".
[ indentation resistance ]
The release films on one side of the adhesive sheets with release films of examples 1 to 4 and comparative examples 1 to 3 were peeled off, and copper foil having a thickness of 50 μm was attached. The remaining release film was peeled off to expose the adhesive surface, and a manual roller was reciprocated 1 time, and the adhesive sheet was rolled on the entire surface of soda lime glass (82 mm. Times.54 mm. Times.0.5 mm in thickness) and subjected to autoclave treatment (temperature: 60 ℃ C., gauge pressure: 0.2MPa, 20 minutes) to carry out final adhesion. Using a high-pressure mercury lamp to accumulate the light quantity to 3000mJ/cm 2 After 365nm ultraviolet rays were irradiated from the soda lime glass surface, the glass was cured at a temperature of 23℃and a humidity of 50% RH for 12 hours, to thereby prepare a sample for evaluating indentation resistance.
A polyimide film (UPILEX-S, manufactured by Yu Xin Co., ltd.) having a width of 20mm, a length of 30mm and a thickness of 125 μm was placed on the copper foil surface of the sample, and the sample was pressed using a press under conditions of a temperature of 25℃and a pressing pressure of 0.3MPa and a treatment time of 10 seconds. The pressurized sample was allowed to stand at room temperature (23 ℃) for 12 hours.
The pressed sample was visually observed, and the case where no indentation was visually observed was judged as "verygood", the case where the uneven shape was slightly observed at a part due to transfer of the edge portion of the polyimide film was judged as "good", and the case where the uneven shape was clearly confirmed was judged as "× (bad)".
Reliability
The adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 were evaluated for reliability after adhesion as follows.
[ Low temperature Properties ]
One release film of the release film-attached adhesive sheets of examples 1 to 4 and comparative examples 1 to 3 was peeled off, and a polyethylene terephthalate film (cosmosfine a4300, manufactured by eastern spinning corporation) having a thickness of 100 μm as a lining film was adhered to prepare a laminate.
After the laminate was cut into pieces of 150mm in length and 10mm in width, the remaining release film was peeled off to expose the adhesive surface, the adhesive sheet was rolled onto soda lime glass by returning a manual roller 1 time, and the resultant was subjected to autoclave treatment (temperature: 60 ℃ C., gauge pressure: 0.2MPa, 20 minutes) to carry out final attachment, and a high-pressure mercury lamp was used to set the cumulative light quantity to 3000mJ/cm 2 After 365nm ultraviolet light was irradiated from the liner film surface, the cured sample was cured at a temperature of 23℃and a humidity of 50% RH for 12 hours.
The peel force (N/cm) was measured for the glass when the cured adhesive force measurement sample was peeled off at a temperature of 0℃under the conditions of a peel angle of 180℃and a peel speed of 300 mm/min.
[ haze due to damp Heat ]
For the release film-attached adhesive sheets of examples 1 to 4 and comparative examples 1 to 3, one release film was peeled off, and a manual roller was reciprocated once to roll-attach soda lime glass (82 mm. Times.54 mm. Times.0.5 mm in thickness). The remaining release film was peeled off by once reciprocating a manual roller, and the adhesive surface roller exposed by peeling was adhered to another piece of soda lime glass (82 mm. Times.54 mm. Times.0.5 mm in thickness), and subjected to autoclave treatment (60 ℃ C., gauge pressure: 0.2MPa, 20 minutes) to carry out final adhesion. Using a high-pressure mercury lamp to accumulate the light quantity to 3000mJ/cm 2 After 365nm ultraviolet light was irradiated from one glass surface, the glass was cured at a temperature of 23℃and 50% RH for 12 hours, to thereby prepare a sample for wet heat haze evaluation.
The above samples were stored for 500 hours in an environmental tester having a temperature of 85℃and a humidity of 85% RH, and haze values were obtained according to JIS K7136 using a haze meter (NDH 5000, manufactured by Nippon electric color industry Co., ltd.) for the stored samples.
[ durability ]
Using the pressure-sensitive adhesive sheets of examples 1 to 4 and comparative examples 1 to 3, laminates for image display devices were produced by the above-described method. Using a high-pressure mercury lamp to become 3000mJ/cm 2 From (a)The laminate was irradiated with a cover glass surface light having a curved shape with an accumulated light quantity of 365nm, and then cured at a temperature of 23℃and a humidity of 50% RH for 12 hours, thereby producing a sample for durability evaluation.
After the above-mentioned samples were stored for 1000 hours in an environmental test at a temperature of 85℃and a humidity of 85% RH, the samples were visually observed, and the cases where foaming and peeling were observed in the adhesive sheet were judged as "X (bad)", and the cases where foaming and peeling were not observed were judged as "O (good)".
TABLE 1
The adhesive sheets of examples 1 to 4 had an adhesive force of 2N/cm or more to soda lime glass, a displacement length of 10mm or less as measured in the retention test, and a peel distance of 20mm or less in the constant load peel test, and therefore were excellent in foaming resistance and peeling resistance in the curved surface adhesion and durability test.
The adhesive sheets of examples 1 and 2 have a ratio of tensile storage modulus (E ') to shear storage modulus (G') of 5.0 or more, and are satisfactory in terms of high quality in terms of adhesion suitability. The adhesive sheets of examples 1 to 3 were excellent in low-temperature characteristics in that the glass transition temperature of the adhesive sheet after curing was 0 ℃ or lower.
Further, the adhesive sheets of examples 1 and 2 were adhesive sheets formed of 3 layers of the outermost layer, the innermost layer and the intermediate layer, and the outermost layer and the innermost layer and the intermediate layer were formed of resin compositions containing a (meth) acrylic polymer as a main component resin having different compositions, and therefore were particularly excellent in wet heat whitening resistance in reliability evaluation.
In contrast, the pressure-sensitive adhesive sheet of comparative example 1 has a displacement length of 10mm or more in the holding force test, and therefore, when used for adhering a curved member, the pressure-sensitive adhesive sheet suffers cohesive failure and has poor curved adhesion. The pressure-sensitive adhesive sheets of comparative example 2 and 3 had a peel length of 20mm or more or an adhesive force of 2N/cm or less in a constant load peel test, and thus, peeling occurred when adhered to a curved member, and the curved surface adhesiveness was poor.
The above-described embodiments are merely illustrative examples and are not to be construed as limiting the invention. Various modifications apparent to those skilled in the art should be considered to be within the scope of the invention.
Industrial applicability
The adhesive sheet for an image display device of the present invention is excellent in adhesiveness to a curved surface member having a curved portion, and durability after being adhered to the curved surface member, and therefore, can be used for adhering an image display device constituent member, and is particularly suitable for adhering an image display constituent member having a curved surface shape.
Claims (15)
1. An adhesive sheet for an image display device, which is an adhesive sheet for adhering two image display device constituent members,
the adhesive force to the soda-lime glass is more than 2N/cm at the temperature of 23 ℃ and the peeling speed of 300mm/min,
an offset length of 10mm or less as measured in a holding force test of an adhesive surface having a temperature of 70 ℃ and a load of 0.5kg, a measurement time of 30 minutes, a width of 20mm by a length of 20mm in accordance with JIS Z0237, and
in the following constant load peel test, the peel distance was 20mm or less,
measurement conditions:
1) An adhesive sheet of a size of 10mm in width and 150mm in length was adhered to an adherend as an adhering region, and the adherend was fixed in the horizontal direction so that the non-adhering region of the adhesive sheet was hung down, with the region of the adhesive sheet other than the adhering region being a non-adhering region,
2) A load of 0.45N was applied to the longitudinal end of the non-adhesive region of the pressure-sensitive adhesive sheet for 30 minutes, and the distance of the adhesive region of the pressure-sensitive adhesive layer from the adherend during this period was measured as a constant load peeling distance.
2. The adhesive sheet for an image display device according to claim 1, wherein the ball number in the inclined ball tack test at an inclination angle of 30 ° is 5 to 25.
3. The adhesive sheet for an image display device according to claim 1 or 2, wherein the adhesive sheet is set to a thickness of 0.6 to 0.8mm, and after a pressure of 1kPa is applied for 180 seconds at a temperature of 25 ℃, the residual creep strain after the pressure is released and 180 seconds passes is 20% or less.
4. The adhesive sheet for an image display device according to any one of claims 1 to 3, wherein a ratio E '/G' of a tensile storage modulus E 'to a shear storage modulus G' is 5.0 or more.
5. The adhesive sheet for an image display device according to any one of claims 1 to 4, wherein the loss tangent Tan δ measured by dynamic viscoelasticity measurement in a stretching mode at a frequency of 1Hz has two maxima, namely, peak temperatures, and the difference is 5 to 50 ℃.
6. The pressure-sensitive adhesive sheet for an image display device according to any one of claims 1 to 5, wherein the outermost layer and the innermost layer are acrylic pressure-sensitive adhesive layers and have at least 3 layers, and the ratio of the total thickness of the outermost layer and the innermost layer to the total thickness is 5 to 70%.
7. The adhesive sheet for an image display device according to any one of claims 1 to 6, which is an adhesive sheet composed of at least 3 layers of an outermost layer, an innermost layer and an intermediate layer, the outermost layer and the innermost layer being formed of a resin composition containing a (meth) acrylic polymer having a composition different from that of the intermediate layer.
8. The adhesive sheet for an image display device according to any one of claims 1 to 7, which has active energy ray curability.
9. Root of Chinese characterThe adhesive sheet for an image display device according to claim 8, wherein an accumulated light amount is 3000mJ/cm when the adhesive sheet is irradiated with 2 After curing by active energy rays having a wavelength of 365nm, the thickness is set to 0.6 to 0.8mm, and the creep strain, which is a strain when a pressure of 1kPa is applied for 10 seconds at a temperature of 25 ℃, is 3% or less.
10. The adhesive sheet for an image display device according to claim 8 or 9, wherein an accumulated light amount upon irradiation of the adhesive sheet is 3000mJ/cm 2 After curing by active energy rays having a wavelength of 365nm, the thickness is set to 0.6 to 0.8mm, and the glass transition temperature, which is the maximum value of the loss tangent obtained by dynamic viscoelasticity measurement in a shear mode at a frequency of 1Hz, is 0 ℃ or lower.
11. The adhesive sheet for an image display device according to any one of claims 1 to 10, wherein the adhesive sheet is formed of a resin composition comprising a (meth) acrylic polymer, a crosslinking agent (B), and a photopolymerization initiator (C).
12. The pressure-sensitive adhesive sheet for an image display device according to claim 11, wherein the crosslinking agent (B) is contained in an amount of 0.5 to 50 parts by mass based on 100 parts by mass of the (meth) acrylic polymer.
13. An adhesive sheet with a release film, comprising the adhesive sheet for an image display device according to any one of claims 1 to 12 and a release film laminated together.
14. A laminate for an image display device, comprising a laminate of two image display device constituent members, one of which is a cover glass having a curved surface shape and the other of which is any one member selected from the group consisting of a touch sensor, an image display panel, a surface protective film, an antireflection film, a color filter, a polarizing film and a retardation film, or a member formed by a combination of two or more members, wherein the adhesive sheet for an image display device according to any one of claims 1 to 12 is sandwiched between the two image display device constituent members.
15. An image display device using the laminate for an image display device according to claim 14.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-012500 | 2021-01-28 | ||
| JP2021012500 | 2021-01-28 | ||
| PCT/JP2021/047566 WO2022163232A1 (en) | 2021-01-28 | 2021-12-22 | Adhesive sheet for image display devices, adhesive sheet with mold-release film, laminate for image display devices, and image display device |
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| CN116761860A true CN116761860A (en) | 2023-09-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202180090779.9A Pending CN116761860A (en) | 2021-01-28 | 2021-12-22 | Pressure-sensitive adhesive sheet for image display device, pressure-sensitive adhesive sheet with release film, laminate for image display device, and image display device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2022163232A1 (en) |
| KR (1) | KR20230133296A (en) |
| CN (1) | CN116761860A (en) |
| TW (1) | TW202231463A (en) |
| WO (1) | WO2022163232A1 (en) |
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| JP7173384B1 (en) | 2022-02-18 | 2022-11-16 | 王子ホールディングス株式会社 | Double-sided pressure-sensitive adhesive sheet, laminate, and method for producing laminate |
| JP7173383B1 (en) | 2022-02-18 | 2022-11-16 | 王子ホールディングス株式会社 | Double-sided pressure-sensitive adhesive sheet, laminate, and method for producing laminate |
| CN115420678A (en) * | 2022-08-31 | 2022-12-02 | 中国路桥工程有限责任公司 | Quantitative test device for hard asphalt interface adhesion |
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| JPS5138898Y2 (en) | 1972-10-11 | 1976-09-24 | ||
| JPS6062740U (en) | 1983-10-06 | 1985-05-02 | ホシデン株式会社 | slide switch |
| CN105745293A (en) * | 2013-11-26 | 2016-07-06 | 琳得科株式会社 | Double-sided adhesive sheet and method for producing double-sided adhesive sheet |
| JP6067895B1 (en) * | 2015-08-18 | 2017-01-25 | 住友化学株式会社 | Polarizing plate for curved image display panel |
| KR102144950B1 (en) * | 2017-09-29 | 2020-08-14 | 주식회사 엘지화학 | Adhesive composition and adhesive film |
| JP2019104804A (en) * | 2017-12-12 | 2019-06-27 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition and adhesive sheet |
| JP6947665B2 (en) * | 2018-03-13 | 2021-10-13 | アイカ工業株式会社 | Photocurable adhesive resin composition |
| JP7080144B2 (en) * | 2018-09-19 | 2022-06-03 | アイカ工業株式会社 | Photocurable adhesive resin composition |
| JP7151518B2 (en) * | 2019-02-01 | 2022-10-12 | 三菱ケミカル株式会社 | Photo-curing adhesive sheet, photo-curing adhesive sheet with release sheet, optical film with photo-curing adhesive sheet, laminate for constituting image display device, and image display device |
| JP7151589B2 (en) * | 2019-03-28 | 2022-10-12 | 三菱ケミカル株式会社 | Double-sided pressure-sensitive adhesive sheet, laminate with release film, and laminate for image display device |
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2021
- 2021-12-22 JP JP2022578161A patent/JPWO2022163232A1/ja active Pending
- 2021-12-22 KR KR1020237024267A patent/KR20230133296A/en unknown
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| WO2022163232A1 (en) | 2022-08-04 |
| JPWO2022163232A1 (en) | 2022-08-04 |
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