WO2023120136A1 - Adhesive sheet with release film, laminate for flexible image display device, flexible image display device, and adhesive sheet - Google Patents
Adhesive sheet with release film, laminate for flexible image display device, flexible image display device, and adhesive sheet Download PDFInfo
- Publication number
- WO2023120136A1 WO2023120136A1 PCT/JP2022/044730 JP2022044730W WO2023120136A1 WO 2023120136 A1 WO2023120136 A1 WO 2023120136A1 JP 2022044730 W JP2022044730 W JP 2022044730W WO 2023120136 A1 WO2023120136 A1 WO 2023120136A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- adhesive sheet
- pressure
- sensitive adhesive
- release film
- image display
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 168
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 168
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 310
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- 238000000926 separation method Methods 0.000 abstract description 2
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- 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
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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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
Definitions
- the present invention relates to a pressure-sensitive adhesive sheet with a release film, and more particularly to a pressure-sensitive adhesive sheet with a release film that is used for bonding a constituent member for a flexible image display device to another adherend member. More particularly, the present invention relates to a pressure-sensitive adhesive sheet with a release film, which is useful for rollable or stretchable laminates for image display devices because of its excellent flexibility. The present invention also relates to a laminate for a flexible image display device and a flexible image display device having the adhesive sheet.
- an image display panel such as a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), and the front side (viewing side) thereof
- LCD liquid crystal display
- PDP plasma display
- ELD electroluminescence display
- a gap between a protective panel and a touch panel member to be placed is filled with an adhesive sheet or the like to suppress reflection of incident light or emitted light from a display image at the air layer interface.
- flexible image display devices using organic light emitting diodes (OLED) and quantum dots (QD) have been developed and are being widely commercialized.
- the flexible image display device include a bendable device having a curved image display surface, a foldable device that can be repeatedly bent, a rollable device that can be wound up, and a stretchable device that can be expanded and contracted.
- a rollable image display device also referred to as a “rollable image display device” that can be rolled up has attracted particular attention because it can realize a compact and large-area display.
- a stretchable image display device also referred to as a “stretchable image display device” is attracting attention because it is possible to realize a large-area display from a compact display.
- Patent Document 1 As a pressure-sensitive adhesive sheet that can be used for a rollable image display device, for example, in Patent Document 1, a separate film with a pressure-sensitive adhesive layer used for bonding two optical members constituting a flexible display is used as a separate film. It is disclosed that a concave portion is provided on the adhesive layer surface on the side.
- the adhesive sheet 10 and the component 20 (30) for a flexible image display device are partially peeled off from each other when the pressure-sensitive adhesive sheet 10 is wound around the core 50 and then unwound and unfolded, the adhesive sheet 10 and the flexible image display device component 20 (30) may be partially peeled off to cause "floating". I was having some issues. Further, even when the adhesive sheet 10 is stretched in the laminated state, the adhesive sheet 10 and the component 20 (30) for a flexible image display device may be partially peeled off.
- an object of the present invention is to laminate a component for a flexible image display device on one or both sides of a pressure-sensitive adhesive sheet, roll it up in the laminated state, and then unwind and unfold it, so that the pressure-sensitive adhesive sheet and the flexible
- a pressure-sensitive adhesive sheet with a release film capable of preventing the occurrence of "floating" due to partial separation from constituent members for an image display device is laminated.
- another object of the present invention is to laminate a constituent member for a flexible image display device on one or both sides of an adhesive sheet, and when the adhesive sheet and the constituent member for a flexible image display device are stretched in the laminated state, the adhesive sheet and the constituent member for a flexible image display device are laminated.
- the pressure-sensitive adhesive sheet with a release film, the laminate for a flexible image display device, and the flexible image display device proposed by the present invention have the following configurations in order to solve the above problems.
- a first aspect of the present invention is a pressure-sensitive adhesive sheet with a release film comprising a release film and a pressure-sensitive adhesive sheet, wherein a space is provided between the release film and the pressure-sensitive adhesive sheet, and the space is A pressure-sensitive adhesive sheet with a release film having a porosity (X) of 3 to 70%.
- a second aspect of the present invention is, in the first aspect, provided with an uneven pattern in which at least one uneven unit having a convex portion is provided on at least one of the front and back adhesive surfaces of the adhesive sheet. , is a pressure-sensitive adhesive sheet with a release film.
- a third aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the second aspect, wherein the height ( ⁇ ) of the protrusions in the uneven unit is 7 to 100 ⁇ m.
- a fourth aspect of the present invention is a pressure-sensitive adhesive sheet with a release film according to the second or third aspect, wherein the maximum width (w1) of the convex portion constituting the concave-convex unit is 1 to 1000 ⁇ m. be.
- a fifth aspect of the present invention is the ratio ( ⁇ /b ) is 0.01 or more and less than 1. It is a pressure-sensitive adhesive sheet with a release film.
- a sixth aspect of the present invention is, in any one of the second to fifth aspects, provided with an uneven pattern in which the uneven unit is repeated, and the repeating pitch (w2) of the uneven unit is A pressure-sensitive adhesive sheet with a release film having a thickness of 2 to 1000 ⁇ m.
- a seventh aspect of the present invention is any one of the second to sixth aspects, wherein the interval (w3) between the convex portion constituting the uneven unit and the adjacent convex portion is 1 to 1000 ⁇ m. It is a pressure-sensitive adhesive sheet with a release film.
- the top surface of the protrusion in the uneven unit is a flat surface, and the top surface width (w4) of the protrusion is is 1 to 1000 ⁇ m, the pressure-sensitive adhesive sheet with a release film.
- the height ( ⁇ ) of the convex portion with respect to the maximum width (w1) of the convex portion constituting the concave-convex unit A pressure-sensitive adhesive sheet with a release film having a ratio ( ⁇ /w1) of 0.03 to 0.3.
- the adhesive strength (peeling speed: 300 mm/min) to the polyethylene terephthalate sheet when peeled at 90° C. is 0.5 to 30 N/min. It is a pressure-sensitive adhesive sheet with a release film of 20 mm.
- An eleventh aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to any one of the first to tenth aspects, wherein the thickness (b) of the pressure-sensitive adhesive sheet is 10 to 100 ⁇ m.
- a twelfth aspect of the present invention is any one of the first to eleventh aspects, wherein the pressure-sensitive adhesive sheet contains a (meth)acrylic polymer (A) and a photopolymerization initiator (B). It is a pressure-sensitive adhesive sheet with a release film, which is a pressure-sensitive adhesive sheet formed from the photocurable pressure-sensitive adhesive composition contained.
- a thirteenth aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the twelfth aspect, wherein the photocurable pressure-sensitive adhesive composition contains a cross-linking agent (C).
- a fourteenth aspect of the present invention is, in any one of the first to thirteenth aspects, a pressure-sensitive adhesive sheet with a release film, which is used for bonding constituent members for a flexible image display device.
- a fifteenth aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the fourteenth aspect, wherein the constituent member for a flexible image display device is a rollable member.
- a sixteenth aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the fourteenth aspect, wherein the constituent member for a flexible image display device is a stretchable member.
- a seventeenth aspect of the present invention is a configuration in which the pressure-sensitive adhesive sheet of the pressure-sensitive adhesive sheet with a release film according to any one of the first to sixteenth aspects and a component for a flexible image display device are laminated. It is a laminate for a flexible image display device.
- An eighteenth aspect of the present invention is a cured adhesive sheet obtained by curing the adhesive sheet of the adhesive sheet with a release film according to any one of the first to sixteenth aspects, and a flexible image display device. It is a laminate for a flexible image display device having a configuration in which the constituent members are laminated.
- a nineteenth aspect of the present invention is a laminate for a flexible image display device comprising a configuration in which a constituent member for a flexible image display device and an adhesive sheet are laminated,
- the laminate for a flexible image display device has a porosity (X) of 3 to 70% in the space formed between the component for the flexible image display device and the adhesive sheet.
- a twentieth aspect of the present invention is a flexible image, wherein the adhesive sheet in the nineteenth aspect is the adhesive sheet of the adhesive sheet with a release film in any one of the first to sixteenth aspects. This is a laminate for a display device.
- a twenty-first aspect of the present invention is a flexible image display device comprising the laminate for a flexible image display device according to any one of the seventeenth to twentieth aspects.
- a twenty-second aspect of the present invention is a pressure-sensitive adhesive sheet used for bonding constituent members for a flexible image display device, wherein the pressure-sensitive adhesive surface on at least one of the front and back sides of the pressure-sensitive adhesive sheet has projections and depressions.
- the concave-convex pattern is provided with at least one unit, the height ( ⁇ ) of the convex portion in the concave-convex unit is 7 to 100 ⁇ m, and the maximum width (w1) of the convex portion constituting the concave-convex unit is 1 to 1 It is an adhesive sheet with a thickness of 1000 ⁇ m.
- a space is formed between the release film and the pressure-sensitive adhesive sheet, and the space has a porosity (X) within a predetermined range. Therefore, even when the pressure-sensitive adhesive sheet from which the release film has been peeled off is adhered to and laminated on a component for a flexible image display device having a flat surface, the same gap is formed between the pressure-sensitive adhesive sheet and the component for a flexible image display device.
- a void having a modulus (X) can be formed.
- the pressure-sensitive adhesive sheet of the pressure-sensitive adhesive sheet with a release film proposed by the present invention can have excellent flexibility, particularly rollability.
- the present invention by further adjusting the porosity of the space portion, even when the pressure-sensitive adhesive sheet from which the release film has been peeled off is adhered to a constituent member for a flexible image display device and stretched in a laminated state.
- the stress can be dispersed and the stress can be relieved, and the space between the pressure-sensitive adhesive sheet and the flexible image display device component can be reduced. It is possible to prevent "peeling" from occurring. Therefore, the pressure-sensitive adhesive sheet with a release film proposed by the present invention can have particularly excellent stretchability.
- FIG. 2 is a cross-sectional view showing a general example of a state in which constituent members for a flexible image display device are laminated on both front and back sides of an adhesive sheet and wound up in the laminated state.
- FIG. 2 is a cross-sectional view showing a general example of a laminated state in which constituent members for a flexible image display device are laminated on both front and back sides of an adhesive sheet.
- FIG. 2 is a cross-sectional view for explaining that a winding length difference (L2 ⁇ L1) occurs between the inner circumference and the outer circumference of the adhesive sheet in the state of being wound as shown in FIG. 1, depending on the thickness of the adhesive sheet.
- L2 ⁇ L1 winding length difference
- FIG. 4(a) to 4(d) are top views each showing an example of a top view shape of an uneven pattern formed on an adhesive sheet according to an example of the present invention.
- FIG. 4A to 4D are cross-sectional views showing examples of cross-sectional shapes of uneven patterns formed on the pressure-sensitive adhesive sheet according to one example of the present invention.
- FIG. 3 is a cross-sectional view for explaining a cross-sectional state of a mold manufactured in Examples.
- FIG. 4 is a cross-sectional view for explaining a method of forming a concavo-convex pattern on a pressure-sensitive adhesive sheet carried out in Examples.
- FIG. 2 is a cross-sectional view for explaining a cross-sectional state of a pressure-sensitive adhesive sheet produced in Examples.
- FIG. 2 is a cross-sectional view for explaining a cross-sectional state in which the pressure-sensitive adhesive sheet produced in Example is sandwiched between release films.
- FIG. 2 is a cross-sectional view for explaining a cross-sectional state in which a PET film base material and a release film are laminated on the adhesive sheet produced in Examples.
- a pressure-sensitive adhesive sheet with a release film (referred to as “the pressure-sensitive adhesive sheet with the release film of the present invention") which is an example of an embodiment of the present invention is a pressure-sensitive adhesive sheet according to an example of the embodiment of the present invention (hereinafter referred to as “the pressure-sensitive adhesive sheet of the present invention”). ”) and a release film according to an example of the embodiment of the present invention (hereinafter also referred to as “the release film of the present invention”). It has a configuration in which the release film of the present invention is laminated on both sides.
- the pressure-sensitive adhesive sheet of the present invention in the pressure-sensitive adhesive sheet with the release film of the present invention is in a state before curing, a state after curing, and a state in the middle of curing, that is, a state in which there is still room for curing. contain.
- the pressure-sensitive adhesive sheet with a release film of the present invention can be suitably used for bonding constituent members for a flexible image display device, as described later.
- the space formed when sandwiched between the release films of the present invention that is, the space formed between the release film of the present invention and the pressure-sensitive adhesive sheet of the present invention.
- a pressure-sensitive adhesive sheet having a porosity (X) of 3 to 70% is preferred.
- the void ratio (X) of the space is 3 to 70%, the pressure-sensitive adhesive sheet of the present invention from which the release film of the present invention has been peeled off is adhered and laminated on a component for a flexible image display device having a flat surface.
- a space portion having the same porosity (X) can be formed between the pressure-sensitive adhesive sheet of the present invention and the constituent member for a flexible image display device.
- the pressure-sensitive adhesive sheet of the present invention from which the release film of the present invention has been peeled off in this way is adhered to a constituent member for a flexible image display device and laminated. It is possible to relieve the stress caused by the strain due to the difference in winding length of the adhesive sheet, and to prevent the occurrence of "floating" between the adhesive sheet of the present invention and the constituent member for a flexible image display device. Furthermore, even when the laminated state is expanded and contracted as described above, by further adjusting and providing the space portion, stress can be dispersed and the stress can be alleviated. It is possible to prevent "peeling" from occurring between the constituent members.
- the porosity (X) of the space is preferably 3% or more, especially 4% or more, 4.5% or more, 5% or more, 6% or more, particularly 8% or more, and among them 10% or more is more preferable. On the other hand, it is more preferably 70% or less, more preferably 60% or less, 50% or less, or 48% or less, especially 45% or less, and even more preferably 40% or less.
- the porosity (X) of the space is preferably 4% or more, especially 4.5% or more, 5% or more, 6% or more, especially 8% or more, among which 10% or more, on the other hand, it is more preferably 70% or less, among which 60% or less, 50% or less, 48% or less, among them 45% or less, among which 40% or less is more preferred.
- a concavo-convex pattern having a predetermined height of protrusions is formed on the surface of the pressure-sensitive adhesive sheet of the present invention, as described above. should be formed.
- the height ( ⁇ ) of the convex portion In order to adjust the porosity of the space portion to the above range, the height ( ⁇ ) of the convex portion, the maximum width (w1) ( ⁇ m) of the convex portion, the repetition pitch (w2) ( ⁇ m), the adjacent convex portion spacing (w3) ( ⁇ m), the ratio of the height ( ⁇ ) of the protrusion to the spacing (w3) between the adjacent protrusions ( ⁇ /w3), the top surface width of the protrusion (w4) ( ⁇ m), the adhesion It can be obtained by appropriately adjusting the sheet thickness (b) ( ⁇ m), the ratio ( ⁇ /b) of the height ( ⁇ ) of the convex portion to the thickness (b) of the adhesive sheet, the aspect ratio ( ⁇ /w1), etc. .
- the porosity (%) can be measured by the following method.
- the surface of the pressure-sensitive adhesive sheet with a release film is examined with an optical microscope to determine the uneven area per unit area, and then the cross section of the pressure-sensitive adhesive sheet with a release film having an uneven structure is examined with an optical microscope to determine the height of the unevenness. Seek to be The porosity (%) is measured from the product of the uneven area and the uneven height.
- an optical microscope eg, manufactured by Keyence Corporation, Microscope VH
- the pressure-sensitive adhesive sheet of the present invention has a concave-convex pattern 4 in which at least one concave-convex unit 3 having convex portions 3A is provided on one or both sides of the pressure-sensitive adhesive surface 2 of the pressure-sensitive adhesive sheet 1. It is an adhesive sheet with The convex portion 3A is a projected portion, and the concave portion 3B is a recessed portion. Therefore, if the concave portions 3B are formed on the adhesive surface of the adhesive sheet, the convex portions 3A are also formed at the same time.
- the pressure-sensitive adhesive sheet of the present invention includes all of the state before curing, the state after curing, and the state in the middle of curing, that is, the state in which there is still room for curing.
- the pressure-sensitive adhesive sheet of the present invention may have an uneven pattern 4 on the adhesive surface 2 on one of the front and back sides of the adhesive sheet 1 , or may have uneven patterns 4 on both the front and back adhesive surfaces 2 , 2 of the adhesive sheet 1 .
- the shape of the uneven pattern 4 is such that the uneven units 3 having a predetermined plan view shape such as stripes, circles, and rectangles are arranged in a certain direction, preferably in the winding circumferential direction. Any shape may be used as long as it is formed in the direction of .
- the concave-convex pattern 4 may be formed such that the concave-convex units 3 are regularly repeated, or may be formed so as to be irregularly repeated.
- the uneven pattern 4 also includes the case of being composed of one uneven unit 3 .
- the uneven pattern 4 is locally formed. Even when 4 consists of one uneven unit 3, the effect of the present invention can be enjoyed.
- the concave-convex unit 3 constituting the concave-convex pattern 4 is preferably a convex portion or concave groove extending in the width direction of the adhesive sheet, that is, in a direction perpendicular to the winding direction, or a combination thereof.
- the cross-sectional shape of the uneven unit 3 constituting the uneven pattern 4 is, for example, triangular, square, or trapezoidal. , a semicircular shape, a semielliptical shape, or any other shape in which concave portions 3B or convex portions 3A of any predetermined shape are repeated (see FIG. 5).
- the height ( ⁇ ) of the convex portion 3A in the concave-convex unit 3 is 7 to 100 ⁇ m.
- the height ( ⁇ ) of the convex portion 3A in the uneven unit 3 is the topmost portion of the uneven unit 3 when viewed in a longitudinal section cut in the thickness direction along the winding circumferential direction of the pressure-sensitive adhesive sheet of the present invention. and vertical length based on the lowest part. If the height ( ⁇ ) of the convex portion 3A in the concave-convex unit 3 is 7 ⁇ m or more, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2.
- the stress caused by the strain caused by the winding length difference during unwinding can be alleviated, and the occurrence of floating can be prevented.
- stress during expansion and contraction can be relaxed, and peeling can be further prevented.
- the thickness is 100 ⁇ m or less, it is possible to obtain uniform uneven units 3 with excellent moldability.
- the height ( ⁇ ) of the convex portion 3A in the concave-convex unit 3 is more preferably 7.5 ⁇ m or more, still more preferably 8 ⁇ m or more, and particularly preferably 8.5 ⁇ m or more.
- it is more preferably 100 ⁇ m or less, further preferably 95 ⁇ m or less, particularly preferably 90 ⁇ m or less, particularly preferably 80 ⁇ m or less, particularly preferably 75 ⁇ m or less, most preferably 70 ⁇ m or less. preferable.
- the ratio ( ⁇ /b) of the height ( ⁇ ) of the projections 3A to the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is preferably 0.01 or more and less than 1. If the ratio ( ⁇ /b) is 0.01 or more, the stress derived from the strain caused by the winding length difference during winding and unwinding can be further alleviated, and the occurrence of floating can be further prevented. can. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if it is less than 1, it is possible to obtain uniform uneven units 3 with excellent moldability.
- the ratio ( ⁇ /b) of the height ( ⁇ ) of the projections 3A to the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is preferably 0.015 or more, and more preferably 0.017 or more. is more preferable, and 0.02 or more, 0.03 or more, 0.05 or more, 0.1 or more, or 0.15 or more is particularly preferable. On the other hand, it is preferably less than 1, more preferably 0.998 or less, particularly preferably 0.995 or less, 0.99 or less, 0.95 or less, or 0.90 or less.
- the maximum width (w1) of the convex portion 3A constituting the concave-convex unit 3 is 1 to 1000 ⁇ m.
- the maximum width (w1) of the convex portion 3A constituting the concave-convex unit 3 is the width (w1) of the convex portion 3A when viewed in a longitudinal section cut in the thickness direction along the winding circumferential direction of the pressure-sensitive adhesive sheet of the present invention. It means the width of the longest portion in the winding circumferential direction. For example, when the convex portion 3A is trapezoidal, the length of the base portion is the maximum width (w1).
- the maximum width (w1) of the convex portion 3A is 1 ⁇ m or more, a sufficient space can be provided between the component 20 (30) for the flexible image display device and the adhesive surface 2.
- the stress resulting from the strain caused by the winding length difference can be further alleviated, and the occurrence of floating can be further prevented.
- stress during expansion and contraction can be relaxed, and peeling can be further prevented.
- the thickness is 1000 ⁇ m or less, strain and stress generated during winding or expansion and contraction can be alleviated.
- the maximum width (w1) of the convex portion 3A constituting the concave-convex unit 3 is more preferably 2 ⁇ m or more, more preferably 5 ⁇ m or more, and is 10 ⁇ m or more, 50 ⁇ m or more, or 100 ⁇ m or more. is particularly preferred. On the other hand, it is more preferably 900 ⁇ m or less, even more preferably 800 ⁇ m or less, and particularly preferably 700 ⁇ m or less.
- the repeating pitch (w2) of the concave-convex unit 3 is preferably 2 to 1000 ⁇ m.
- the repetition pitch (w2) of the uneven unit 3 is the same shape portion of the adjacent uneven unit 3 when viewed in a longitudinal section cut in the thickness direction along the winding circumferential direction of the pressure-sensitive adhesive sheet of the present invention. is the meaning of the distance between If the repetition pitch (w2) is 2 ⁇ m or more, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2, so that the difference in winding length during winding and unwinding can be reduced. The stress resulting from the strain caused by this can be further alleviated, and the occurrence of floating can be further prevented.
- the repeating pitch (w2) of the uneven units 3 is more preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and particularly preferably 10 ⁇ m or more, 50 ⁇ m or more, or 100 ⁇ m or more. On the other hand, it is more preferably 900 ⁇ m or less, even more preferably 800 ⁇ m or less, and particularly preferably 700 ⁇ m or less. Note that the repetition pitch (w2) does not necessarily have to be constant.
- the interval (w3) between the convex portion 3A forming the concave-convex unit 3 and the adjacent convex portion 3A is preferably 1 to 1000 ⁇ m.
- the interval (w3) between the convex portion 3A and the adjacent convex portion 3A is the distance between the convex portion 3A and the adjacent convex portion 3A when viewed in a longitudinal section cut in the thickness direction along the winding circumferential direction of the pressure-sensitive adhesive sheet of the present invention. It means the length in the winding circumferential direction of the plane portion between the adjacent convex portions 3A.
- the interval (w3) is 1 ⁇ m or more, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2.
- the stress resulting from the generated distortion can be further relieved, and the occurrence of floating can be further prevented.
- stress during expansion and contraction can be relaxed, and peeling can be further prevented.
- the thickness is 1000 ⁇ m or less, sufficient adhesiveness can be ensured between the component 20 (30) for the flexible image display device and the adhesive surface 2, which is preferable.
- the distance (w3) between the convex portion 3A constituting the concave-convex unit 3 and the adjacent convex portion 3A is more preferably 2 ⁇ m or more, further preferably 5 ⁇ m or more, 10 ⁇ m or more, and 30 ⁇ m or more. is particularly preferred. On the other hand, it is more preferably 900 ⁇ m or less, even more preferably 800 ⁇ m or less, and particularly preferably 700 ⁇ m or less, 500 ⁇ m or less, or 200 ⁇ m or less. In addition, as shown in FIG. 5(D), the interval (w3) between adjacent convex portions 3A may be zero.
- the top surface width (w4) of the convex portion 3A constituting the concave-convex unit 3 is 1 to 1000 ⁇ m.
- the top surface width (w4) of the convex portion 3A is the winding width of the flat portion of the top portion of the convex portion when viewed in a longitudinal section cut in the thickness direction along the winding circumferential direction of the pressure-sensitive adhesive sheet of the present invention. It means circumferential length. If the top surface width (w4) of the convex portion 3A is 1 ⁇ m or more, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2, so that the winding and unwinding can be performed.
- the top surface width (w4) of the projection 3A is more preferably 2 ⁇ m or more, even more preferably 5 ⁇ m or more, and particularly preferably 10 ⁇ m or more. On the other hand, it is more preferably 900 ⁇ m or less, even more preferably 800 ⁇ m or less, and particularly preferably 700 ⁇ m or less. Note that, as shown in FIG. 5C, the top surface width (w4) of the convex portion 3A may be zero.
- the thickness (b) of the adhesive sheet of the present invention is preferably 10 ⁇ m to 100 ⁇ m.
- the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is the thickness including the thickness of the uneven pattern 4 . If the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is 10 ⁇ m or more, the desired adhesive strength can be expressed, and if it is 100 ⁇ m or less, the winding length difference ( ⁇ L/b) becomes small, and the resulting distortion is reduced. can be suppressed further. From this point of view, the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is more preferably 15 ⁇ m or more, still more preferably 20 ⁇ m or more, and particularly preferably 25 ⁇ m or more. On the other hand, it is more preferably 90 ⁇ m or less, even more preferably 85 ⁇ m or less, and particularly preferably 80 ⁇ m or less.
- the ratio ( ⁇ /b) of the height ( ⁇ ) of the projections to the thickness (b) of the pressure-sensitive adhesive sheet is preferably 0.01 or more and less than 1. If the ratio ( ⁇ /b) is equal to or higher than the above lower limit, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2. The stress resulting from the strain caused by the length difference can be further alleviated, and the occurrence of floating can be further prevented. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if it is less than the above upper limit, strain and stress generated during winding or expansion and contraction can be alleviated.
- the ratio ( ⁇ /b) is more preferably 0.015 or more, still more preferably 0.017 or more, 0.03 or more, 0.05 or more, 0.1 or more, 0.01 or more. 15 or more is particularly preferred. On the other hand, it is more preferably 0.998 or less, particularly preferably 0.995 or less, 0.99 or less, 0.95 or less, or 0.90 or less.
- the aspect ratio of the protrusions in the uneven pattern that is, the ratio ( ⁇ /w1) of the height ( ⁇ ) of the protrusions to the maximum width (w1) of the protrusions constituting the uneven unit is 0.03 to 0.03. 3 is preferred. If the aspect ratio ( ⁇ /w1) of the convex portion is 0.03 or more, it is possible to maintain the space, and if it is 0.3 or less, the stress during expansion and contraction can be relaxed, and peeling can be further prevented. It is preferable because it can Therefore, the aspect ratio ( ⁇ /w1) of the projections is more preferably 0.032 or more, more preferably 0.034 or more, and most preferably 0.035 or more. On the other hand, it is more preferably 0.29 or less, more preferably 0.28 or less, and even more preferably 0.26 or less.
- the concave-convex pattern 4 can be formed evenly over the entire adhesive surface of the adhesive sheet, or can be formed only on the portion where the curvature is applied.
- the pressure-sensitive adhesive sheet of the present invention is a photocurable pressure-sensitive adhesive composition containing a (meth)acrylic polymer (A) and a photopolymerization initiator (B), optionally a cross-linking agent (C), and other components. (also referred to as "the adhesive composition of the present invention”).
- the pressure-sensitive adhesive composition of the present invention contains a (meth)acrylic polymer (A), especially as a main component resin. That is, the (meth)acrylic polymer (A) is the component having the highest mass ratio among the non-volatile components constituting the pressure-sensitive adhesive composition of the present invention. At this time, among the non-volatile components constituting the pressure-sensitive adhesive composition of the present invention, the (meth)acrylic polymer (A) has a mass ratio of 50% by mass or more, especially 70% by mass or more, especially 80% by mass or more. Above all, it may be 90% by mass or more.
- the (meth)acrylic polymer (A) As the (meth)acrylic polymer (A), the following formula 1 (wherein R 1 represents a hydrogen atom or a methyl group and R 2 represents a linear or branched alkyl having 4 to 18 carbon atoms group or an alicyclic hydrocarbon), and is preferably obtained by polymerizing a polymer component containing 50% by mass or more of the monomer component.
- the (meth)acrylic polymer (A) is more preferably polymerized to contain 55% by mass or more of the monomer component as a polymerization component, and particularly preferably polymerized to contain 60% by mass or more.
- (meth)acrylic means acrylic and methacrylic
- (meth)acryloyl means acryloyl and methacryloyl
- (meth)acrylate means acrylate and methacrylate, respectively.
- (co)polymer is meant to include polymers and copolymers.
- Examples of the monomer represented by Formula 1 include n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl ( meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, unde
- butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate and lauryl (meth)acrylate is particularly preferable.
- the (meth)acrylic polymer (A) is preferably a copolymer having "another copolymerizable monomer" other than the monomer component as a copolymerization component.
- the above-mentioned "other copolymerizable monomer” is preferably contained in the (meth)acrylic polymer (A) in an amount of 1 to 30% by mass, and is contained in a proportion of 2% by mass or more or 25% by mass or less. is more preferred.
- Examples of the “other copolymerizable monomer” include (a) a carboxyl group-containing monomer (hereinafter also referred to as “copolymerizable monomer a1”), (b) a hydroxyl group-containing monomer (hereinafter also referred to as “copolymerizable monomer a2").
- Examples of the copolymerizable monomer a1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypropyl (meth)acrylate, carboxybutyl (meth)acrylate, ⁇ -carboxypolycaprolactone mono(meth)acrylate, 2- (Meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxypropyl hexahydrophthalate, 2-(meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxypropyl phthalate, 2-(meth) ) ) acryloyloxyethyl maleate, 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxypropyl succinate, crotonic acid, fumaric acid, maleic acid, itacon Men
- Examples of the copolymerizable monomer a2 include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol Hydroxyalkyl (meth)acrylates such as polybutylene glycol mono(meth)acrylate, polypropylene glycol polybutylene glycol mono(meth)acrylate and hydroxyphenyl(meth)acrylate can be mentioned. These may be used alone or in combination of two or more.
- the macromonomer as the copolymerizable monomer a8 is a macromonomer having a terminal functional group and a high-molecular-weight skeleton component.
- the "other copolymerizable monomer” is the copolymerizable monomer a8
- the (meth)acrylic polymer (A) is a copolymer containing a macromonomer-derived structural unit.
- the macromonomer is a macromonomer obtained by copolymerizing a (meth)acrylate having a linear or branched alkyl group having 1 to 3 carbon atoms. It is good because it can improve the properties.
- the number average molecular weight of such a macromonomer is preferably 1,000 to 10,000, particularly preferably 1,500 or more or 5,000 or less, and still more preferably 2,000 or more or 4,000 or less.
- the copolymerization ratio of the macromonomer in the (meth)acrylic polymer (A) is preferably 30% by mass or less in terms of imparting fluidity during hot-melt, more preferably 2 % by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less, particularly preferably 4% by mass or more and 7% by mass or less.
- the (meth)acrylic polymer (A) preferably does not contain or substantially does not contain the "copolymerizable monomer a1" from the viewpoint of metal corrosion resistance and wet heat whitening resistance. .
- "does not contain or substantially does not contain copolymerizable monomer a1” means not only the case where it does not contain completely, but also the case where copolymerizable monomer a1 is contained in the (meth)acrylic acid ester (co)polymer. It is intended to allow a content of less than 0.5% by mass, preferably less than 0.1% by mass.
- the (meth)acrylic polymer (A) preferably has a glass transition temperature of -70 to 0°C.
- the glass transition temperature of the copolymer component means a value calculated by the Fox formula from the glass transition temperature of the polymer obtained from the homopolymer of each component of the copolymer and the composition ratio.
- the glass transition temperature of at least one of the (meth)acrylic acid ester-derived repeating units of the (meth)acrylic polymer (A) is preferably -70 to 0°C.
- the glass transition temperature of at least one of the repeating units derived from the (meth)acrylic acid ester of the (meth)acrylic polymer (A) is 20 to 120° C.
- excellent processing is achieved. It is preferable because it can maintain the properties and storage stability.
- the glass transition temperature (Tg) is preferably 30° C. to 120° C., especially 40° C. or higher or 110° C. or lower, especially 50° C., because it affects the hot-melt temperature of the pressure-sensitive adhesive sheet of the present invention. It is more preferable that the temperature is 100° C. or higher or 100° C. or lower. If there is a repeating unit having such a glass transition temperature (Tg), it is possible to maintain excellent workability and storage stability by adjusting the molecular weight, and to adjust it so that it hot melts at 50 ° C. or higher. can.
- the polymerization initiator (B) imparts active energy ray curability to the pressure-sensitive adhesive sheet of the present invention, and may be any compound that generates radicals by means of active energy rays.
- the polymerization initiator (B) is roughly classified into two groups according to the mechanism of radical generation: a cleavage-type photoinitiator capable of cleaving and decomposing a single bond of the polymerization initiator itself to generate radicals, and an excited initiator. and a hydrogen abstraction type photoinitiator capable of forming an exciplex with a hydrogen donor in the system and transferring hydrogen of the hydrogen donor.
- the (meth)acrylic polymer (A) has a structure, such as a benzophenone structure, which is excited by active energy ray irradiation and can extract hydrogen radicals in the system in the excited state.
- a structure such as a benzophenone structure
- the polymerization initiator (B) is not necessarily included.
- the polymerization initiator (B) may be either a cleavage photoinitiator or a hydrogen abstraction photoinitiator, each of which may be used alone or a mixture of both may be used. may be used alone or in combination of two or more.
- a hydrogen abstraction type photoinitiator is used as a photoinitiator, a hydrogen abstraction reaction also occurs from the (meth)acrylic polymer, and not only the active energy ray-curable compound but also the (meth)acrylic polymer has a crosslinked structure. It is preferable in terms of being able to form a crosslinked structure with many crosslinked points.
- cleavage type photoinitiator when used as the polymerization initiator (B), it is decomposed and deactivated once radicals are generated, which is preferable in that there is no risk of unexpected reaction or deterioration after curing.
- cleavage-type photoinitiators examples include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one. , 1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4- ⁇ 4-(2-hydroxy-2- Methyl-propionyl)benzyl ⁇ phenyl]-2-methyl-propan-1-one, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone), phenylglyoxylic acid methyl, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one , 2-(dimethylamino)-2-[(4-methylpheny
- Hydrogen abstraction photoinitiators include, for example, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(meth)acryloyl Oxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis(2-phenyl-2-oxoacetic acid)oxybisethylene, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxo tridecyl)benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone and derivatives thereof, etc. can be mentioned.
- the content of the polymerization initiator (B) is not particularly limited.
- the cross-linking agent (C) is a compound or composition that forms a cross-linked structure in the pressure-sensitive adhesive composition of the present invention, and is a compound having two or more cross-linkable functional groups.
- the cross-linking agent (C) in the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive composition of the present invention forms a crosslinked structure, and durability can be imparted to the pressure-sensitive adhesive sheet of the present invention.
- the (meth)acrylic polymer (A) causes a hydrogen abstraction reaction by the action of the polymerization initiator (B) or the like, and the (meth)acrylic polymer (A) and/or the (meth)acrylic polymer If a sufficient crosslinked structure can be formed between coalescence (A), the crosslinker (C) does not necessarily need to be included.
- crosslinkable functional groups examples include isocyanate groups, epoxy groups, (meth)acryloyl groups, thioisocyanate groups, primary or secondary amino groups, and thiol groups. These may be protected with a suitable protecting group.
- crosslinkable functional groups contained in the crosslinker include only epoxy groups, only isocyanate groups, only (meth)acryloyl groups, only thioisocyanate groups, only thiol groups, only primary or secondary amino groups, epoxy
- a combination of a group and a (meth)acryloyl group, and an isocyanate group and a (meth)acryloyl group can be mentioned.
- a polyfunctional (meth)acrylate (c1 ) is preferred.
- the content of the polyfunctional (meth)acrylate (c1) is preferably 0.5 parts by mass or more, preferably 1 part by mass or more, based on 100 parts by mass of the (meth)acrylic polymer (A). Among them, 1.5 parts by mass or more is more preferable. Regarding the upper limit, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, from the viewpoint of maintaining appropriate flexibility and ensuring followability to the adherend when bent. It is more preferably 10 parts by mass or less, more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less.
- Polyfunctional (meth)acrylates (c1) include, for example, 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin glycidyl ether di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethacrylate, tricyclodecanedimethanol di(meth)acrylate, bisphenol A polyethoxydi(meth)acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ⁇ -
- the pressure-sensitive adhesive composition of the present invention may further contain a monofunctional (meth)acrylate component (D) having one (meth)acryloyl group.
- a monofunctional (meth)acrylate component By including a monofunctional (meth)acrylate component, the molecular weight between cross-linking points of the cured product can be increased, so that the degree of freedom of movement of the molecular chains is increased, and the components constituting the image display device can be pasted via the pressure-sensitive adhesive sheet of the present invention.
- the pressure-sensitive adhesive sheet of the present invention made of the pressure-sensitive adhesive composition of the present invention can be deformed accordingly.
- Examples of the monofunctional (meth)acrylate component (D) include ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, Acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate Acrylate, dodecyl (meth)acrylate, isododecyl (meth)acrylate, tetradecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate
- the content ratio by mass of the polyfunctional (meth)acrylate (c1) and the monofunctional (meth)acrylate component (D) is the polyfunctional (meth)acrylate (c1):
- Monofunctional (meth)acrylate (D) is preferably 1:0.1 to 1:9, more preferably 1:1 to 1:9, and preferably 1:2 to 1:9. More preferred. Within this range, the amount of the monofunctional (meth)acrylate component is not too large, and there is no concern that the sensitivity to light will decrease and the productivity will decrease.
- “Other components” other than those described above contained in the pressure-sensitive adhesive composition of the present invention include, for example, silane coupling agents, tackifier resins, plasticizers, antioxidants, light stabilizers, metal inerts, if necessary.
- Various additives such as activators, antioxidants, hygroscopic agents, polymerization inhibitors, ultraviolet absorbers, rust preventives, inorganic particles, sensitizers and pigments can be incorporated as appropriate.
- the amounts of these additives are typically preferably selected so as not to adversely affect the curing of the adhesive sheet or adversely affect the physical properties of the adhesive sheet.
- a reaction catalyst such as a tertiary amine compound, a quaternary ammonium compound, a tin laurate compound, or the like may be appropriately contained.
- the pressure-sensitive adhesive composition of the present invention in addition to the (meth)acrylic polymer (A), preferably a photopolymerization initiator (B), more preferably a cross-linking agent (C), and optionally other components
- the pressure-sensitive adhesive composition of the present invention is prepared, the pressure-sensitive adhesive composition is formed into a sheet, and if necessary, the curable compound is crosslinked, that is, polymerized to be cured to form unevenness.
- a pattern may be formed to produce the pressure-sensitive adhesive sheet of the present invention. However, it is not limited to this method.
- the pressure-sensitive adhesive composition of the present invention can be formed into a sheet, formed with an uneven pattern, and then cured.
- the raw materials are kneaded using a temperature-controllable kneader (e.g., single-screw extruder, twin-screw extruder, planetary mixer, twin-screw mixer, pressure kneader, etc.). do it.
- a temperature-controllable kneader e.g., single-screw extruder, twin-screw extruder, planetary mixer, twin-screw mixer, pressure kneader, etc.
- various additives such as silane coupling agents and antioxidants may be blended in advance with the resin and then supplied to the kneader, or all the materials may be melted and mixed in advance.
- a masterbatch in which only the additive is concentrated in the resin in advance may be prepared and supplied.
- Methods for forming the pressure-sensitive adhesive composition of the present invention into a sheet include known methods such as wet lamination, dry lamination, extrusion casting using a T-die, extrusion lamination, calendering, inflation, injection molding, An injection curing method or the like can be employed. Among them, the wet lamination method, the extrusion casting method, and the extrusion lamination method are suitable for producing a sheet.
- the curing method include a method of curing by irradiation with heat and/or active energy rays to obtain a cured product.
- the pressure-sensitive adhesive composition or pressure-sensitive adhesive sheet of the present invention molded into a sheet can be cured by irradiating heat and/or active energy rays.
- the active energy rays to be irradiated include ⁇ rays, ⁇ rays, ⁇ rays, ionizing radiation such as neutron rays and electron beams, ultraviolet rays, visible rays, and the like. Ultraviolet rays are preferable from the viewpoint of suppression and reaction control.
- the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as the initiator can be activated to polymerize the (meth)acrylate component.
- the pressure-sensitive adhesive composition of the present invention can be dissolved in a suitable solvent, and various coating techniques can be used.
- the pressure-sensitive adhesive sheet can also be obtained by thermal curing in addition to the active energy ray irradiation curing described above.
- the thickness of the adhesive sheet can be adjusted by the coating thickness and the solid content concentration of the coating liquid.
- the uneven pattern 4 can be formed by pressing the uneven surface of a mold against the adhesive surface of the adhesive sheet to transfer the uneven structure of the mold to the adhesive surface of the adhesive sheet. Then, the pressure-sensitive adhesive sheet of the present invention on which an uneven pattern is formed is obtained.
- the mold may be flat, columnar, or cylindrical.
- the material of the mold is arbitrary, such as metal, resin, and glass.
- the pressure is preferably 0.00001 to 1 MPa, especially 0.00005 MPa or more or 0.9 MPa or less, among which 0.0001 MPa or more or 0.001 MPa or more. 8 MPa or less is more preferable.
- the mold When pressing the uneven surface of the mold against the adhesive surface of the adhesive sheet, the mold may be heated as necessary. At this time, the heating temperature is preferably 20 to 100° C., more preferably 30° C. or higher or 90° C. or lower, and more preferably 40° C. or higher or 80° C. or lower.
- the pressure-sensitive adhesive sheet of the present invention may have a single-layer structure composed of a pressure-sensitive adhesive layer (also referred to as "the pressure-sensitive adhesive layer of the present invention") made of the pressure-sensitive adhesive composition of the present invention, or two or more layers comprising the pressure-sensitive adhesive layer of the present invention.
- a multilayer structure may be used.
- the composition of layers other than the pressure-sensitive adhesive layer of the present invention is arbitrary.
- the pressure-sensitive adhesive composition that forms the layer other than the pressure-sensitive adhesive layer of the present invention from the viewpoint of further increasing the interlayer adhesion is preferably formed from a pressure-sensitive adhesive composition containing a (meth)acrylic polymer, more preferably containing the same (meth)acrylic polymer (A) as the pressure-sensitive adhesive layer of the present invention.
- layers other than the pressure-sensitive adhesive layer of the present invention also contain a photopolymerization initiator (B) and/or a cross-linking agent (C).
- the pressure-sensitive adhesive sheet of the present invention has a multilayer structure of two or more layers, it is preferable that at least the outermost layer, the backmost layer, or both layers correspond to the pressure-sensitive adhesive layer of the present invention. All layers may be layers corresponding to the pressure-sensitive adhesive layer of the present invention.
- the thickness of the layer corresponding to the pressure-sensitive adhesive layer of the present invention preferably accounts for 10% or more and 100% or less of the total thickness of the pressure-sensitive adhesive sheet of the present invention. , above all, 14% or more or 70% or less, more preferably 20% or more or 50% or less.
- the pressure-sensitive adhesive sheet of the present invention preferably has a storage elastic modulus of 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa at a frequency of 1 Hz and a temperature of 23° C., especially 1 ⁇ 10 3 Pa or more, or 0.5 ⁇ 10 6 Pa or less, preferably 1 ⁇ 10 4 Pa or more or 1 ⁇ 10 5 Pa or less.
- the storage elastic modulus can be measured, for example, by a shear method using a viscoelasticity measuring device "Dynamic Analyzer RDAII" manufactured by Rheometrics Co., Ltd. under the following conditions. However, it is not limited to this measuring method.
- ⁇ Jig ⁇ 25mm parallel plate
- ⁇ Distortion 0.5%
- ⁇ Frequency 1Hz
- ⁇ Temperature -70 to 200°C (measured at a temperature increase rate of 3°C/min from -70°C)
- Sample thickness 500 ⁇ m
- the thickness can be adjusted by laminating pressure-sensitive adhesive layers until each thickness reaches 500 ⁇ m.
- the pressure-sensitive adhesive sheet of the present invention can have an adhesive strength of 0.5 to 30 N/20 mm when peeled at 90° C. (peeling speed: 300 mm/min) to a polyethylene terephthalate sheet as a substitute member for flexible image display devices.
- Such adhesive strength is preferably 0.5 N/20 mm or more, further 1.0 N/20 mm or more, particularly 1.5 N/20 mm or more, particularly 2.0 N/20 mm or more, from the viewpoint of resistance to peeling during stretching.
- it is preferably 30 N/20 mm or less, more preferably 28 N/20 mm or less, and particularly preferably 25 N/20 mm or less from the viewpoint of shape retention.
- the polyethylene terephthalate sheet as a substitute member for the flexible image display device is preferably a biaxially oriented sheet.
- the thickness is preferably 50 to 300 ⁇ m.
- ⁇ Release film of the present invention examples include polyester films, polyolefin films, polycarbonate films, polystyrene films, acrylic films, triacetylcellulose films, and fluororesin films. Among these, polyester films and polyolefin films are particularly preferred.
- the surface of the release film of the present invention is preferably flat.
- the thickness of the release film of the present invention is not particularly limited. Among them, for example, from the viewpoint of workability and handleability, the thickness is preferably 25 ⁇ m to 500 ⁇ m, more preferably 38 ⁇ m or more or 250 ⁇ m or less, and more preferably 50 ⁇ m or more or 200 ⁇ m or less.
- the release film of the present invention is preferably a polyester-based film, and from the standpoint of releasability, it is preferable that the release film is easy to peel even after irradiation with active energy rays. .
- the peel force for the pressure-sensitive adhesive sheet of the present invention when irradiated with an active energy ray having a wavelength of 365 nm with an accumulated light amount of 2000 to 4000 mJ/cm 2 is 0.1 N/cm or less at a peel angle of 180 ° and a peel speed of 300 mm / min. It is preferable that
- a laminate for a flexible image display device (referred to as "the flexible laminate of the present invention"), which is an example of an embodiment of the present invention, has a configuration in which the pressure-sensitive adhesive sheet of the present invention and a constituent member for a flexible image display device are laminated. It is prepared.
- the pressure-sensitive adhesive sheet of the present invention in the flexible laminate of the present invention includes all of a state before curing, a state after curing, and a state in the middle of curing, that is, a state in which there is still room for curing.
- the release film of the present invention can be used. Even when the flexible laminate of the present invention is formed by sticking the pressure-sensitive adhesive sheet of the present invention from which the mold film has been peeled off to a structural member for a flexible image display device having a flat surface, the pressure-sensitive adhesive sheet of the present invention and the structural member for a flexible image display device are formed.
- a space having the same porosity (X) can be formed between and, when the flexible laminate of the present invention is wound up, unwound and spread, the pressure-sensitive adhesive sheet of the present invention and a component for a flexible image display device It is possible to prevent “floating” from occurring between In addition, even when the flexible laminate of the present invention is stretched, it is possible to prevent “peeling” between the adhesive sheet of the present invention and the constituent members for a flexible image display device. Therefore, in the flexible laminate of the present invention, the porosity (X) of the space formed between the component for a flexible image display device and the pressure-sensitive adhesive sheet of the present invention is preferably 3% or more, more preferably 4% or more.
- the porosity (X) of the space is preferably 4% or more, especially 4.5% or more, 5% or more, 6% or more, especially 8% or more, among which 10% or more, on the other hand, it is more preferably 70% or less, among which 60% or less, 50% or less, 48% or less, among them 45% or less, among which 40% or less is more preferred.
- a laminate for a flexible image display device having a configuration in which two constituent members for a flexible image display device are laminated via a curable adhesive layer made of the adhesive sheet of the present invention. can be mentioned.
- a laminate for a flexible image display device having a configuration in which two constituent members for a flexible image display device are laminated via an adhesive layer formed by curing the adhesive sheet of the present invention. can be mentioned.
- the flexible laminate includes a first flexible image display device constituent member (hereinafter sometimes referred to as "first member”), the pressure-sensitive adhesive sheet of the present invention, and a second flexible image display
- first member a first flexible image display device constituent member
- second member a laminate having a configuration in which the members are laminated in this order.
- first member, the second member, and the third member for constituting a flexible image display device are placed in this order via the pressure-sensitive adhesive sheet of the present invention.
- It may be a laminate having a laminated structure. Two or more members to be laminated may be the same or different.
- the thickness of the flexible laminate of the present invention is not particularly limited.
- the flexible laminate of the present invention when used in an image display device, is in the form of a sheet. If it is 0 mm or less, it can contribute to thinning of the laminate. Therefore, the thickness of the flexible laminate of the present invention is preferably 0.02 mm or more, more preferably 0.03 mm or more, particularly 0.05 mm or more.
- the upper limit is preferably 1.0 mm or less, more preferably 0.7 mm or less, particularly 0.5 mm or less.
- the flexible laminate of the present invention By attaching the adhesive sheet of the present invention to the first member, the second member and/or the third member, the flexible laminate of the present invention can be produced. However, it is not limited to such a manufacturing method.
- the first member, the second member and the third member include: Examples thereof include cover lenses, polarizing plates, retardation films, barrier films, touch sensor films, light-emitting elements, PSA, and the like.
- Examples of flexible image display device constituent members include a rollable member, that is, a member that can be wound up and rewound, and a stretchable member, that is, a member that can be expanded and contracted.
- Examples include glass, cover plastic, or a composite and integrated product of two or more of these members, a surface protective film, and the like.
- other layers such as an antistatic layer, a hard coat layer, an anchor layer, a release layer, an easy adhesion layer, a protective layer, an anti-bleeding layer and a flattening layer are interposed as necessary. may
- the first member preferably has a touch input function.
- the second member to the third member may have a touch input function.
- at least one of the members may have various irregularities formed by wiring, printing, pattern development, surface treatment, embossing, etc. on the contact surface with the pressure-sensitive adhesive sheet of the present invention.
- At least one of the flexible image display device constituent members (including the first member, the second member, and the third member) to be laminated is made of urethane resin, cycloolefin resin, triacetylcellulose resin, (meta ) It may be a resin sheet or a thin film glass mainly composed of one or more resins selected from the group consisting of acrylate resins, epoxy resins and polyimide resins.
- the "main component” refers to a component occupying the largest mass ratio among the components constituting the flexible image display device constituent member, specifically, 50 mass of the flexible image display device constituent member. % or more, especially 55 mass % or more, especially 60 mass % or more.
- the adhesive sheet of the present invention can be hot-melted after being cured by active energy rays. With such a hot melt, even if the adherend surface of the adherend has unevenness, it can be laminated so as to follow the unevenness and absorb the unevenness, and the surface can be smoothed. . Therefore, when two members for constituting a flexible image display device are laminated via the pressure-sensitive adhesive sheet of the present invention, even if one or both of the members for constituting a flexible image display device do not transmit light, the unevenness can be eliminated. It is possible to bond two members for constituting a flexible image display device while absorbing.
- one side of the pressure-sensitive adhesive sheet of the present invention which is cured by irradiating an active energy ray at the time of forming an uneven pattern, is attached to the member 1 for constituting a flexible image display device, and then the adhesive sheet of the present invention is laminated.
- the flexible image display device-constituting member 2 is attached to the other surface of the pressure-sensitive adhesive sheet to form a laminate.
- the flexible laminate of the present invention can be obtained, for example, by bonding one surface of the pressure-sensitive adhesive sheet of the present invention to the flexible image display device constituent member 1, and curing the pressure-sensitive adhesive sheet of the present invention by irradiating an active energy ray.
- the member 2 for constituting a flexible image display device can be adhered to the other surface of the cured pressure-sensitive adhesive sheet of the present invention to form a laminate.
- the flexible laminate of the present invention can be obtained, for example, by laminating one surface of the pressure-sensitive adhesive sheet of the present invention to the flexible image display device constituent member 1, and attaching the flexible image display device constituent member to the other surface of the pressure-sensitive adhesive sheet of the present invention.
- the pressure-sensitive adhesive sheet of the present invention can be cured by irradiating active energy rays through one of the members for constituting a flexible image display device.
- a method for laminating the pressure-sensitive adhesive sheet of the present invention known methods such as roll lamination, press lamination using a parallel plate, and diaphragm lamination can be used.
- the lamination environment there are an air lamination method in which lamination is performed under normal pressure and a vacuum lamination method in which lamination is performed under reduced pressure. From the viewpoint of preventing air bubbles during lamination, a method of laminating with a parallel plate under a reduced pressure environment is preferable. Moreover, you may adjust bonding temperature suitably.
- the pressure-sensitive adhesive sheet of the present invention When laminating the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive sheet of the present invention, the image display device-constituting member 1, or the image display device-constituting member 2 may be heated, if necessary.
- the image display device laminate composed of image display device constituent member 1/the pressure-sensitive adhesive sheet of the present invention/image display device constituent member 2 is heated from both sides with a press plate heated to a predetermined temperature. A method of pressurizing can be mentioned.
- the heating temperature at this time is preferably 50° C. or higher and 80° C. or lower. That is, the image display device constituent member 1 and/or the image display device constituent member 2 are heated to 50° C. or more and 80° C.
- the press pressure when pressing with the press plate is preferably 0.01 MPa or more or 0.4 MPa or less, more preferably 0.02 MPa or more or 0.35 MPa or less.
- the pressure-sensitive adhesive sheet of the present invention is produced by irradiating an active energy ray
- ultraviolet rays and visible rays are suitable as the active energy ray.
- the light source when irradiating the active energy ray it is possible to use properly according to the wavelength and irradiation amount of the light to be irradiated from, for example, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a halogen lamp, an LED lamp, a fluorescent lamp, etc. can.
- the irradiation time and irradiation means are not particularly limited.
- the integrated light amount at a wavelength of 365 nm is 1000 mJ/cm 2 or more, further 2000 mJ/cm 2 or more, particularly 3000 mJ/cm 2 or more. is preferred.
- the upper limit of the integrated amount of light is usually 10000 mJ/cm 2 .
- the flexible laminate of the present invention is wound around a winding core or the like, and then unwound and unrolled to relax the stress derived from the strain due to the difference in winding length of the pressure-sensitive adhesive sheet of the present invention. It is possible to prevent "floating" between the pressure-sensitive adhesive sheet and the component for a flexible image display device. Therefore, the flexible laminate of the present invention is excellent in flexibility and also in rollability.
- the pressure-sensitive adhesive sheet of the present invention in the case where uneven convex portions are formed on one side, the same effect can be obtained whether the convex portions are wound outward or inward.
- the winding diameter c of the flexible laminate of the present invention is preferably 5 to 500 mm. If the winding diameter c is 5 mm or more, the strain generated during winding can be further alleviated, and if it is 500 mm or less, the handleability is excellent. From this point of view, the winding diameter c of the flexible laminate of the present invention is more preferably 6 mm or more, still more preferably 7 mm or more, and particularly preferably 10 mm or more. On the other hand, it is more preferably 450 mm or less, even more preferably 400 mm or less, and particularly preferably 350 mm or less.
- this flexible image display device By incorporating the flexible laminate of the present invention, for example, by laminating the flexible laminate of the present invention to other constituent members of an image display device, a flexible image display device equipped with the flexible laminate of the present invention (“this flexible image display device”) ) can be formed.
- a flexible image display device leaves no trace of bending even after repeated bending, bending, or winding operations, and can be bent, bent, or wound up when the bending, bending, or winding state is released. It is an image display device that can quickly recover to the state before the display and can display an image without distortion.
- a flexible image display device suitable for rollable can be obtained.
- it is possible to obtain a flexible image display device suitable for stretchable use, in which even when expansion and contraction operations such as stretching and contracting are repeatedly performed, peeling of the constituent members of the image display device does not occur. can be done.
- the pressure-sensitive adhesive sheet of the present invention can be placed on the viewing side of an image display panel such as a liquid crystal panel, or can be placed on the side opposite to the viewing side of the image display panel, that is, on the light source side. can also
- the term “film” includes the “sheet”
- the term “sheet” includes the “film”.
- the expression “panel” such as an image display panel, a protective panel, etc. includes a plate, a sheet and a film.
- (meth)acrylic means “acrylic” and “methacrylic
- (meth)acrylate means “acrylate” and “methacrylate”
- (meth)acryloyl means " It is a meaning that encompasses “acryloyl” and “methacryloyl” respectively.
- acrylic polymer means one containing a (meth)acrylate-derived monomer unit, and includes (meth)acrylic copolymers.
- a pressure-sensitive adhesive sheet was produced using the following raw materials.
- Photoinitiator (B) - Initiator (B-1): a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone ("Esacure TZT" manufactured by IGM)
- the adhesive sheet 1 was an active energy ray-curing adhesive sheet that was cured by irradiation with light.
- Example 1 As shown in FIG. 7, the uneven side of the mold X is laminated on the sticking surface from which one of the release films 12 of the pressure-sensitive adhesive sheet 1 with a release film has been peeled off, and the release film on the side opposite to the mold X is laminated. After laminating the surface of 12 with a roller, a glass plate was placed on the surface of the release film 12 and allowed to stand for 30 minutes while applying a load (P) at a mold temperature of 23° C. and a pressure of 0.001 MPa.
- P load
- the pressure-sensitive adhesive sheet 10 is exposed to light with a wavelength of 200 to 500 nm through the release film 12 from the opposite side of the mold X with an integrated light amount of 4000 mJ/cm 2 . to cure the adhesive sheet 10.
- the mold X was released, and a release film 13 was further laminated to obtain a release film-attached pressure-sensitive adhesive sheet 1 (the pressure-sensitive adhesive sheet of the present invention) having an uneven pattern.
- a concave-convex pattern formed repeatedly at appropriate intervals was formed.
- the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
- Example 2 unevenness was formed in the same manner as in Example 1, except that the pressure-sensitive adhesive sheet 2 with a release film was used and the mold temperature was 23 ° C. and the load was applied at a pressure of 0.001 MPa for 30 minutes. A release film-attached pressure-sensitive adhesive sheet 2 (the pressure-sensitive adhesive sheet of the present invention) in which a pattern was formed was obtained.
- the uneven unit consisting of the convex portion having a trapezoidal cross section extending in the film width direction, that is, the TD direction, extends along the length of the film.
- a concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the MD direction.
- the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
- Example 3 the pressure-sensitive adhesive sheet with a release film having an uneven pattern was formed in the same manner as in Example 2, except that the mold temperature was 60 ° C. and the load was applied at a pressure of 0.001 MPa for 30 minutes. 3 (the pressure-sensitive adhesive sheet of the present invention) was obtained.
- the unevenness unit consisting of a convex portion having a trapezoidal cross section extending in the film width direction, that is, the TD direction, extends over the length of the film.
- a concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the longitudinal direction, that is, the MD direction.
- the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
- Example 4 the pressure-sensitive adhesive sheet with a release film having an uneven pattern was formed in the same manner as in Example 2, except that the mold temperature was 23 ° C. and the pressure was 0.001 MPa and the pressure was applied for 30 minutes. 4 (the pressure-sensitive adhesive sheet of the present invention) was obtained.
- the uneven unit consisting of the convex portion having a trapezoidal cross section extending in the film width direction, that is, the TD direction, extends along the length of the film.
- a concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the MD direction.
- the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
- Example 5 the pressure-sensitive adhesive sheet with a release film having an uneven pattern was formed in the same manner as in Example 2, except that the mold temperature was 23 ° C. and the load was applied at a pressure of 0.005 MPa for 30 minutes. 5 (the pressure-sensitive adhesive sheet of the present invention) was obtained.
- the uneven unit consisting of the convex portion having a trapezoidal cross section extending in the film width direction, that is, in the TD direction, extends along the length of the film.
- a concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the MD direction.
- the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
- Example 2 A concavo-convex pattern was formed in the same manner as in Example 1, except that the pressure-sensitive adhesive sheet 1 with a release film was used and allowed to stand for 30 minutes with a mold temperature of 23 ° C. and a pressure of 0.00001 MPa. A release film-attached pressure-sensitive adhesive sheet 2' (comparative pressure-sensitive adhesive sheet) was obtained.
- the concave-convex unit consisting of a convex portion having a trapezoidal cross section extending in the film width direction, that is, the TD direction, extends over the length of the film.
- a concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the MD direction.
- the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
- the void ratio of the space of the pressure-sensitive adhesive sheet with release film is as follows. measured to The measurement results are shown in Table 1.
- the surface of the pressure-sensitive adhesive sheet with the release film of the present invention having an uneven structure is examined through the release film using an optical microscope (Microscope VHX-600, manufactured by Keyence Corporation) to determine the width of the protrusions (w2, w3, w4). was measured.
- the pressure-sensitive adhesive sheet with the release film of the present invention was cut in the thickness direction, and the height (h) of unevenness in the cross section and the thickness (H) of the pressure-sensitive adhesive sheet were measured using an optical microscope. From the obtained results, the porosity (%) was measured from ((w3+(w2-w4)) ⁇ h ⁇ 2)/(w2 ⁇ H).
- pressure-sensitive adhesive sheets 1 to 5 of Examples (the pressure-sensitive adhesive sheets of the present invention) and pressure-sensitive adhesive sheets 1' to 2' of Comparative Examples (comparative pressure-sensitive adhesive sheets) were cut into a width of 20 mm and a length of 100 mm.
- the adhesive surface is applied to the PET film base material 11 (Diafoil, manufactured by Mitsubishi Chemical Co., Ltd., "T913E125C" thickness 125 ⁇ m), which is a biaxially stretched film.
- a laminate having a layer structure of release film 12/adhesive sheet 10/PET film substrate 11 was formed by sticking with a roller.
- the pressure-sensitive adhesive sheets 1 to 5 of the examples (the pressure-sensitive adhesive sheets of the present invention) and the pressure-sensitive adhesive sheets 1′ to 2′ of the comparative examples (comparative pressure-sensitive adhesive sheets) were separated from the pressure-sensitive adhesive surface side on which the uneven pattern was formed.
- the surface of the pressure-sensitive adhesive was pasted on a PET film substrate 11 (Diafoil, manufactured by Mitsubishi Chemical Corporation, “T913E125C” thickness 125 ⁇ m), which is a biaxially stretched film, with a roller.
- a laminate having a layer configuration of /adhesive sheet 10/PET film substrate 11 was obtained.
- the ratio of the winding length difference ( ⁇ L) between the inner unit circumference length (inner winding length) L1 and the outer unit circumference length (outer winding length) L2 of the pressure-sensitive adhesive sheet 10 when wound with respect to the thickness b of the winding This is believed to be due to the distortion due to the length ( ⁇ L/b). Therefore, as a result of forming a concavo-convex pattern having a predetermined convex portion height on the adhesive surface on which the constituent members for a flexible image display device are laminated, it is possible to relax the distortion due to the winding length generated when the adhesive is wound. It is presumed that it was possible to prevent the occurrence of floating.
- Example 6> As shown in FIG. 7, the uneven side of the mold Y is laminated on the adhesion surface from which one of the release films 12 of the adhesive sheet 2 with a release film (before forming the uneven pattern) is peeled off. After bonding the surface of the release film 12 on the opposite side with a roller, a glass plate was placed on the surface of the release film 12, and a load (P) was applied at a mold temperature of 23 ° C. and a pressure of 0.01 MPa. Let stand for a minute.
- the pressure-sensitive adhesive sheet 10 is exposed to light with a wavelength of 200 to 500 nm through the release film 12 from the opposite side of the mold Y with an integrated light amount of 4000 mJ/cm 2 . to cure the adhesive sheet 10.
- the mold Y was released, and a release film 13 was further laminated to obtain a release film-attached pressure-sensitive adhesive sheet 6 (the pressure-sensitive adhesive sheet of the present invention) on which an uneven pattern was formed.
- the uneven unit consisting of the convex portions extending in the film width direction, that is, the TD direction, extends in the film length direction, that is, the MD direction.
- a concave-convex pattern formed repeatedly at appropriate intervals was formed.
- the uneven pattern has a shape as shown in Table 2 in a longitudinal section obtained by cutting the adhesive sheet of the present invention in the MD direction, that is, in the direction of the winding circumference in the thickness direction. It was something.
- ⁇ Reference example 1> As shown in FIG. 7, the uneven side of the mold Y is laminated on the adhesion surface from which one of the release films 12 of the adhesive sheet 2 with a release film (before forming the uneven pattern) is peeled off. After bonding the surface of the release film 12 on the opposite side with a roller, a glass plate was placed on the surface of the release film 12, and a load (P) was applied at a mold temperature of 23 ° C. and a pressure of 0.01 MPa. Let stand for a minute.
- the pressure-sensitive adhesive sheet 10 is exposed to light with a wavelength of 200 to 500 nm through the release film 12 from the opposite side of the mold Y with an integrated light amount of 4000 mJ/cm 2 . to cure the adhesive sheet 10.
- the mold Y was released, and a release film 13 was further laminated to obtain a release film-attached pressure-sensitive adhesive sheet 3′ (comparative pressure-sensitive adhesive sheet) on which an uneven pattern was formed.
- the uneven pattern On the adhesive surface of the obtained pressure-sensitive adhesive sheet 3′ with a release film (comparative pressure-sensitive adhesive sheet) having an uneven pattern formed thereon, uneven units composed of convex portions extending in the film width direction, that is, the TD direction, are formed in the film length direction, that is, A concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the MD direction.
- the uneven pattern has a shape as shown in Table 2 in a longitudinal section obtained by cutting the adhesive sheet of the present invention in the MD direction, that is, in the direction of the winding circumference in the thickness direction. It was something.
- Adhesion (N/20 mm) was measured by the same method as above. The measurement results are shown in Table 2.
- the release film 13 on the pressure-sensitive adhesive surface side on which the concave-convex pattern is formed of the pressure-sensitive adhesive sheet 6 of the example (the pressure-sensitive adhesive sheet of the present invention) and the pressure-sensitive adhesive sheet 3' of the reference example (comparative pressure-sensitive adhesive sheet) is peeled off.
- the adhesive surface is pasted with a roller to a PET film base material 11 (Diafoil, manufactured by Mitsubishi Chemical Corporation, "T913E125C" thickness 125 ⁇ m), which is a biaxially stretched film, to form a release film 12 / adhesive sheet 10 / A laminate having a layer structure of the PET film substrate 13 was formed.
- the pressure-sensitive adhesive sheet formed when it was sandwiched with a release film on at least one of the front and back sides of the pressure-sensitive adhesive sheet. If the porosity of the space portion of the adhesive sheet is within a predetermined range, when the flexible image display device component is laminated on the adhesive surface of the adhesive sheet and stretched or contracted, the adhesive sheet and the flexible image display device configuration It was found that it is possible to prevent "peeling" from occurring between the material and the member.
- the pressure-sensitive adhesive sheet and the constituent members for a flexible image display device are partially peeled off when the adhesive sheet is stretched in a laminated state, the stress cannot be dispersed when the tensile stress is generated, and the film ends It is considered that the peeling of the film occurred more. Therefore, it is presumed that by adjusting the porosity of the predetermined space portion, the pressure-sensitive adhesive sheet can be prevented from being peeled off even when it is stretched.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having excellent flexibility, particularly rollability and stretchability, and is useful, for example, for flexible image display devices using organic light-emitting diodes (OLEDs) and quantum dots (QDs). be.
- OLEDs organic light-emitting diodes
- QDs quantum dots
- Adhesive sheet 2 Adhesive surface 3 Concave and convex unit 3A Convex part 3B Concave part 4 Concave and convex pattern 10
- Adhesive sheet 11 PET film substrate 12 Release film 13 Release film 20
- Component for flexible image display device 30 Component for flexible image display device 50 Core X, Y Mold P Load
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Abstract
An adhesive sheet with a release film having a space part between the release film and the adhesive sheet and having a porosity (X) of 3 to 70% in the space part is proposed as an adhesive sheet with a release film including an adhesive sheet that can prevent the occurrence of "separation" where the adhesive sheet and a constituting member for a flexible image display device are partially separated from each other when the constituting member for the flexible image display device is laminated on one or both sides of the adhesive sheet and expanded/contracted in a laminated state.
Description
本発明は、離型フィルム付き粘着シートに関し、とりわけフレキシブル画像表示装置用構成部材を他の被着部材に貼り合わせるために用いられる離型フィルム付き粘着シートに関する。更に詳しくは、フレキシブル性に優れることから、ローラブル用やストレッチャブル用の画像表示装置用積層体に用いるのに有用な粘着シートを備えた離型フィルム付き粘着シートに関する。また、当該粘着シートを備えたフレキシブル画像表示装置用積層体及びフレキシブル画像表示装置に関する。
The present invention relates to a pressure-sensitive adhesive sheet with a release film, and more particularly to a pressure-sensitive adhesive sheet with a release film that is used for bonding a constituent member for a flexible image display device to another adherend member. More particularly, the present invention relates to a pressure-sensitive adhesive sheet with a release film, which is useful for rollable or stretchable laminates for image display devices because of its excellent flexibility. The present invention also relates to a laminate for a flexible image display device and a flexible image display device having the adhesive sheet.
近年、画像表示装置においては、その視認性を向上させるために、液晶ディスプレイ（ＬＣＤ）、プラズマディスプレイ（ＰＤＰ）、エレクトロルミネッセンスディスプレイ（ＥＬＤ）等の画像表示パネルと、その前面側（視認側）に配置する保護パネルやタッチパネル部材との間の空隙を、粘着シート等で充填し、入射光や表示画像からの出射光の空気層界面での反射を抑えることが行われている。
In recent years, in an image display device, in order to improve the visibility, an image display panel such as a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), and the front side (viewing side) thereof A gap between a protective panel and a touch panel member to be placed is filled with an adhesive sheet or the like to suppress reflection of incident light or emitted light from a display image at the air layer interface.
一方、有機発光ダイオード（ＯＬＥＤ）や量子ドット（ＱＤ）を用いた、フレキシブル画像表示装置が開発され、広く商用化されつつある。
フレキシブル画像表示装置としては、画像表示面が曲面形状を有するベンダブル、繰り返し折り曲げが可能なフォルダブル、巻き取ることができるローラブル、伸縮されるストレッチャブル等を挙げることができる。中でも、コンパクトで大面積なディスプレイの実現が可能な点から、巻き取ることができるローラブル用の画像表示装置（「ローラブル画像表示装置」とも称する）は特に注目されている。また、同様にコンパクトなディスプレイから大面積なディスプレイの実現が可能な点からストレッチャブル用の画像表示装置（「ストレッチャブル画像表示装置」とも称する）が注目されている。 On the other hand, flexible image display devices using organic light emitting diodes (OLED) and quantum dots (QD) have been developed and are being widely commercialized.
Examples of the flexible image display device include a bendable device having a curved image display surface, a foldable device that can be repeatedly bent, a rollable device that can be wound up, and a stretchable device that can be expanded and contracted. Among them, a rollable image display device (also referred to as a “rollable image display device”) that can be rolled up has attracted particular attention because it can realize a compact and large-area display. In addition, a stretchable image display device (also referred to as a “stretchable image display device”) is attracting attention because it is possible to realize a large-area display from a compact display.
フレキシブル画像表示装置としては、画像表示面が曲面形状を有するベンダブル、繰り返し折り曲げが可能なフォルダブル、巻き取ることができるローラブル、伸縮されるストレッチャブル等を挙げることができる。中でも、コンパクトで大面積なディスプレイの実現が可能な点から、巻き取ることができるローラブル用の画像表示装置（「ローラブル画像表示装置」とも称する）は特に注目されている。また、同様にコンパクトなディスプレイから大面積なディスプレイの実現が可能な点からストレッチャブル用の画像表示装置（「ストレッチャブル画像表示装置」とも称する）が注目されている。 On the other hand, flexible image display devices using organic light emitting diodes (OLED) and quantum dots (QD) have been developed and are being widely commercialized.
Examples of the flexible image display device include a bendable device having a curved image display surface, a foldable device that can be repeatedly bent, a rollable device that can be wound up, and a stretchable device that can be expanded and contracted. Among them, a rollable image display device (also referred to as a “rollable image display device”) that can be rolled up has attracted particular attention because it can realize a compact and large-area display. In addition, a stretchable image display device (also referred to as a “stretchable image display device”) is attracting attention because it is possible to realize a large-area display from a compact display.
ローラブル画像表示装置に用いることが可能な粘着シートとしては、例えば特許文献１において、フレキシブルディスプレイを構成する二つの光学部材を貼合するために用いられる粘着剤層付セパレートフィルムとして、セパレートフィルムと反対側の粘着層表面に凹部を設けたものが開示されている。
As a pressure-sensitive adhesive sheet that can be used for a rollable image display device, for example, in Patent Document 1, a separate film with a pressure-sensitive adhesive layer used for bonding two optical members constituting a flexible display is used as a separate film. It is disclosed that a concave portion is provided on the adhesive layer surface on the side.
従来開示されていた粘着シートに関しては、例えば図１及び図２に示すように、粘着シート１０の表裏一側又は両側にフレキシブル画像表示装置用構成部材２０（３０）を積層し、積層状態のまま、巻芯５０に巻き付けて巻き取り、その後、巻き戻して展開したときに、粘着シート１０とフレキシブル画像表示装置用構成部材２０（３０）とが一部剥離して“浮き”が発生する場合があるなどの課題を抱えていた。
また、前記積層状態のまま伸縮させたときにも、粘着シート１０とフレキシブル画像表示装置用構成部材２０（３０）とが一部剥離する場合があった。 Regarding the conventionally disclosed pressure-sensitive adhesive sheet, for example, as shown in FIGS. When the pressure-sensitiveadhesive sheet 10 and the component 20 (30) for a flexible image display device are partially peeled off from each other when the pressure-sensitive adhesive sheet 10 is wound around the core 50 and then unwound and unfolded, the adhesive sheet 10 and the flexible image display device component 20 (30) may be partially peeled off to cause "floating". I was having some issues.
Further, even when theadhesive sheet 10 is stretched in the laminated state, the adhesive sheet 10 and the component 20 (30) for a flexible image display device may be partially peeled off.
また、前記積層状態のまま伸縮させたときにも、粘着シート１０とフレキシブル画像表示装置用構成部材２０（３０）とが一部剥離する場合があった。 Regarding the conventionally disclosed pressure-sensitive adhesive sheet, for example, as shown in FIGS. When the pressure-sensitive
Further, even when the
そこで、本発明の目的は、粘着シートの表裏一側又は両側にフレキシブル画像表示装置用構成部材を積層し、積層状態のまま、巻き取り、その後、巻き戻して展開したときに、粘着シートとフレキシブル画像表示装置用構成部材とが一部剥離して“浮き”が生じるのを防ぐことができる粘着シートを備えた離型フィルム付き粘着シートを提供することにある。
更に、本発明の他の目的は、粘着シートの表裏一側又は両側にフレキシブル画像表示装置用構成部材を積層し、積層状態のまま伸縮させたときに、粘着シートとフレキシブル画像表示装置用構成部材とが一部剥離して“剥がれ”が生じるのを防ぐことができる粘着シートを備えた離型フィルム付き粘着シートを提供することにある。 Therefore, an object of the present invention is to laminate a component for a flexible image display device on one or both sides of a pressure-sensitive adhesive sheet, roll it up in the laminated state, and then unwind and unfold it, so that the pressure-sensitive adhesive sheet and the flexible To provide a pressure-sensitive adhesive sheet with a release film capable of preventing the occurrence of "floating" due to partial separation from constituent members for an image display device.
Further, another object of the present invention is to laminate a constituent member for a flexible image display device on one or both sides of an adhesive sheet, and when the adhesive sheet and the constituent member for a flexible image display device are stretched in the laminated state, the adhesive sheet and the constituent member for a flexible image display device are laminated. To provide a pressure-sensitive adhesive sheet with a release film capable of preventing the occurrence of "peeling" due to partial peeling of the adhesive sheet.
更に、本発明の他の目的は、粘着シートの表裏一側又は両側にフレキシブル画像表示装置用構成部材を積層し、積層状態のまま伸縮させたときに、粘着シートとフレキシブル画像表示装置用構成部材とが一部剥離して“剥がれ”が生じるのを防ぐことができる粘着シートを備えた離型フィルム付き粘着シートを提供することにある。 Therefore, an object of the present invention is to laminate a component for a flexible image display device on one or both sides of a pressure-sensitive adhesive sheet, roll it up in the laminated state, and then unwind and unfold it, so that the pressure-sensitive adhesive sheet and the flexible To provide a pressure-sensitive adhesive sheet with a release film capable of preventing the occurrence of "floating" due to partial separation from constituent members for an image display device.
Further, another object of the present invention is to laminate a constituent member for a flexible image display device on one or both sides of an adhesive sheet, and when the adhesive sheet and the constituent member for a flexible image display device are stretched in the laminated state, the adhesive sheet and the constituent member for a flexible image display device are laminated. To provide a pressure-sensitive adhesive sheet with a release film capable of preventing the occurrence of "peeling" due to partial peeling of the adhesive sheet.
本発明が提案する離型フィルム付き粘着シート、フレキシブル画像表示装置用積層体及びフレキシブル画像表示装置は、上記課題を解決するために、次の構成を有する。
The pressure-sensitive adhesive sheet with a release film, the laminate for a flexible image display device, and the flexible image display device proposed by the present invention have the following configurations in order to solve the above problems.
[１] 本発明の第１の態様は、離型フィルムと粘着シートを備えた離型フィルム付き粘着シートであって、離型フィルムと粘着シートとの間に空間部を有し、当該空間部の空隙率（Ｘ）が３～７０％である離型フィルム付き粘着シートである。
[1] A first aspect of the present invention is a pressure-sensitive adhesive sheet with a release film comprising a release film and a pressure-sensitive adhesive sheet, wherein a space is provided between the release film and the pressure-sensitive adhesive sheet, and the space is A pressure-sensitive adhesive sheet with a release film having a porosity (X) of 3 to 70%.
[２] 本発明の第２の態様は、前記第１の態様において、前記粘着シートの少なくとも表裏一側の粘着面に、凸部を有する凹凸単位が少なくとも１つ設けられてなる凹凸パターンを備える、離型フィルム付き粘着シートである。
[３] 本発明の第３の態様は、前記第２の態様において、前記凹凸単位における凸部の高さ（α）が７～１００μｍである、離型フィルム付き粘着シートである。
[４] 本発明の第４の態様は、前記第２又は第３の態様において、前記凹凸単位を構成する凸部の最大幅（ｗ１）が１～１０００μｍである、離型フィルム付き粘着シートである。
[５] 本発明の第５の態様は、前記第２～第４の何れか一の態様において、粘着シートの厚み（ｂ）に対する、前記凸部の高さ（α）の比率（α／ｂ）が０．０１以上１未満である、離型フィルム付き粘着シートである。
[６] 本発明の第６の態様は、前記第２～第５の何れか一の態様において、前記凹凸単位が繰り返される凹凸パターンを備えるものであり、前記凹凸単位の繰り返しピッチ（ｗ２）が２～１０００μｍである、離型フィルム付き粘着シートである。
[７] 本発明の第７の態様は、前記第２～第６の何れか一の態様において、前記凹凸単位を構成する凸部と隣接する凸部との間隔（ｗ３）が１～１０００μｍである、離型フィルム付き粘着シートである。
[８] 本発明の第８の態様は、前記第２～第７の何れか一の態様において、前記凹凸単位における凸部の頂面は平坦面であり、前記凸部頂面幅（ｗ４）が１～１０００μｍである、離型フィルム付き粘着シートである。
[９] 本発明の第９の態様は、前記第２～第８の何れか一の態様において、前記凹凸単位を構成する凸部の最大幅（ｗ１）に対する、凸部の高さ（α）に比率（α／ｗ１）が０．０３～０．３である、離型フィルム付き粘着シートである。 [2] A second aspect of the present invention is, in the first aspect, provided with an uneven pattern in which at least one uneven unit having a convex portion is provided on at least one of the front and back adhesive surfaces of the adhesive sheet. , is a pressure-sensitive adhesive sheet with a release film.
[3] A third aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the second aspect, wherein the height (α) of the protrusions in the uneven unit is 7 to 100 μm.
[4] A fourth aspect of the present invention is a pressure-sensitive adhesive sheet with a release film according to the second or third aspect, wherein the maximum width (w1) of the convex portion constituting the concave-convex unit is 1 to 1000 μm. be.
[5] A fifth aspect of the present invention is the ratio (α/b ) is 0.01 or more and less than 1. It is a pressure-sensitive adhesive sheet with a release film.
[6] A sixth aspect of the present invention is, in any one of the second to fifth aspects, provided with an uneven pattern in which the uneven unit is repeated, and the repeating pitch (w2) of the uneven unit is A pressure-sensitive adhesive sheet with a release film having a thickness of 2 to 1000 μm.
[7] A seventh aspect of the present invention is any one of the second to sixth aspects, wherein the interval (w3) between the convex portion constituting the uneven unit and the adjacent convex portion is 1 to 1000 μm. It is a pressure-sensitive adhesive sheet with a release film.
[8] According to an eighth aspect of the present invention, in any one of the second to seventh aspects, the top surface of the protrusion in the uneven unit is a flat surface, and the top surface width (w4) of the protrusion is is 1 to 1000 μm, the pressure-sensitive adhesive sheet with a release film.
[9] In a ninth aspect of the present invention, in any one of the second to eighth aspects, the height (α) of the convex portion with respect to the maximum width (w1) of the convex portion constituting the concave-convex unit A pressure-sensitive adhesive sheet with a release film having a ratio (α/w1) of 0.03 to 0.3.
[３] 本発明の第３の態様は、前記第２の態様において、前記凹凸単位における凸部の高さ（α）が７～１００μｍである、離型フィルム付き粘着シートである。
[４] 本発明の第４の態様は、前記第２又は第３の態様において、前記凹凸単位を構成する凸部の最大幅（ｗ１）が１～１０００μｍである、離型フィルム付き粘着シートである。
[５] 本発明の第５の態様は、前記第２～第４の何れか一の態様において、粘着シートの厚み（ｂ）に対する、前記凸部の高さ（α）の比率（α／ｂ）が０．０１以上１未満である、離型フィルム付き粘着シートである。
[６] 本発明の第６の態様は、前記第２～第５の何れか一の態様において、前記凹凸単位が繰り返される凹凸パターンを備えるものであり、前記凹凸単位の繰り返しピッチ（ｗ２）が２～１０００μｍである、離型フィルム付き粘着シートである。
[７] 本発明の第７の態様は、前記第２～第６の何れか一の態様において、前記凹凸単位を構成する凸部と隣接する凸部との間隔（ｗ３）が１～１０００μｍである、離型フィルム付き粘着シートである。
[８] 本発明の第８の態様は、前記第２～第７の何れか一の態様において、前記凹凸単位における凸部の頂面は平坦面であり、前記凸部頂面幅（ｗ４）が１～１０００μｍである、離型フィルム付き粘着シートである。
[９] 本発明の第９の態様は、前記第２～第８の何れか一の態様において、前記凹凸単位を構成する凸部の最大幅（ｗ１）に対する、凸部の高さ（α）に比率（α／ｗ１）が０．０３～０．３である、離型フィルム付き粘着シートである。 [2] A second aspect of the present invention is, in the first aspect, provided with an uneven pattern in which at least one uneven unit having a convex portion is provided on at least one of the front and back adhesive surfaces of the adhesive sheet. , is a pressure-sensitive adhesive sheet with a release film.
[3] A third aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the second aspect, wherein the height (α) of the protrusions in the uneven unit is 7 to 100 μm.
[4] A fourth aspect of the present invention is a pressure-sensitive adhesive sheet with a release film according to the second or third aspect, wherein the maximum width (w1) of the convex portion constituting the concave-convex unit is 1 to 1000 μm. be.
[5] A fifth aspect of the present invention is the ratio (α/b ) is 0.01 or more and less than 1. It is a pressure-sensitive adhesive sheet with a release film.
[6] A sixth aspect of the present invention is, in any one of the second to fifth aspects, provided with an uneven pattern in which the uneven unit is repeated, and the repeating pitch (w2) of the uneven unit is A pressure-sensitive adhesive sheet with a release film having a thickness of 2 to 1000 μm.
[7] A seventh aspect of the present invention is any one of the second to sixth aspects, wherein the interval (w3) between the convex portion constituting the uneven unit and the adjacent convex portion is 1 to 1000 μm. It is a pressure-sensitive adhesive sheet with a release film.
[8] According to an eighth aspect of the present invention, in any one of the second to seventh aspects, the top surface of the protrusion in the uneven unit is a flat surface, and the top surface width (w4) of the protrusion is is 1 to 1000 μm, the pressure-sensitive adhesive sheet with a release film.
[9] In a ninth aspect of the present invention, in any one of the second to eighth aspects, the height (α) of the convex portion with respect to the maximum width (w1) of the convex portion constituting the concave-convex unit A pressure-sensitive adhesive sheet with a release film having a ratio (α/w1) of 0.03 to 0.3.
[１０] 本発明の第１０の態様は、前記第１～第９の何れか一の態様において、ポリエチレンテレフタレートシートに対する９０℃剥離による粘着力（剥離速度３００ｍｍ／ｍｉｎ）が０．５～３０Ｎ／２０ｍｍである、離型フィルム付き粘着シートである。
[１１] 本発明の第１１の態様は、前記第１～第１０の何れか一の態様において、粘着シートの厚み（ｂ）が１０～１００μｍである、離型フィルム付き粘着シートである。 [10] In a tenth aspect of the present invention, in any one of the first to ninth aspects, the adhesive strength (peeling speed: 300 mm/min) to the polyethylene terephthalate sheet when peeled at 90° C. is 0.5 to 30 N/min. It is a pressure-sensitive adhesive sheet with a release film of 20 mm.
[11] An eleventh aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to any one of the first to tenth aspects, wherein the thickness (b) of the pressure-sensitive adhesive sheet is 10 to 100 μm.
[１１] 本発明の第１１の態様は、前記第１～第１０の何れか一の態様において、粘着シートの厚み（ｂ）が１０～１００μｍである、離型フィルム付き粘着シートである。 [10] In a tenth aspect of the present invention, in any one of the first to ninth aspects, the adhesive strength (peeling speed: 300 mm/min) to the polyethylene terephthalate sheet when peeled at 90° C. is 0.5 to 30 N/min. It is a pressure-sensitive adhesive sheet with a release film of 20 mm.
[11] An eleventh aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to any one of the first to tenth aspects, wherein the thickness (b) of the pressure-sensitive adhesive sheet is 10 to 100 μm.
[１２] 本発明の第１２の態様は、前記第１～第１１の何れか一の態様において、前記粘着シートが、（メタ）アクリル系重合体（Ａ）及び光重合開始剤（Ｂ）を含有する光硬化性粘着剤組成物から形成される粘着シートである、離型フィルム付き粘着シートである。
[１３] 本発明の第１３の態様は、前記第１２の態様において、光硬化性粘着剤組成物が架橋剤（Ｃ）を含有する、離型フィルム付き粘着シートである。 [12] A twelfth aspect of the present invention is any one of the first to eleventh aspects, wherein the pressure-sensitive adhesive sheet contains a (meth)acrylic polymer (A) and a photopolymerization initiator (B). It is a pressure-sensitive adhesive sheet with a release film, which is a pressure-sensitive adhesive sheet formed from the photocurable pressure-sensitive adhesive composition contained.
[13] A thirteenth aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the twelfth aspect, wherein the photocurable pressure-sensitive adhesive composition contains a cross-linking agent (C).
[１３] 本発明の第１３の態様は、前記第１２の態様において、光硬化性粘着剤組成物が架橋剤（Ｃ）を含有する、離型フィルム付き粘着シートである。 [12] A twelfth aspect of the present invention is any one of the first to eleventh aspects, wherein the pressure-sensitive adhesive sheet contains a (meth)acrylic polymer (A) and a photopolymerization initiator (B). It is a pressure-sensitive adhesive sheet with a release film, which is a pressure-sensitive adhesive sheet formed from the photocurable pressure-sensitive adhesive composition contained.
[13] A thirteenth aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the twelfth aspect, wherein the photocurable pressure-sensitive adhesive composition contains a cross-linking agent (C).
[１４] 本発明の第１４の態様は、前記第１～第１３の何れか一の態様において、フレキシブル画像表示装置用構成部材を貼り合わせるために用いられる、離型フィルム付き粘着シートである。
[１５] 本発明の第１５の態様は、前記第１４の態様において、前記フレキシブル画像表示装置用構成部材がローラブル部材である、離型フィルム付き粘着シートである。
[１６] 本発明の第１６の態様は、前記第１４の態様において、前記フレキシブル画像表示装置用構成部材がストレッチャブル部材である、離型フィルム付き粘着シートである。 [14] A fourteenth aspect of the present invention is, in any one of the first to thirteenth aspects, a pressure-sensitive adhesive sheet with a release film, which is used for bonding constituent members for a flexible image display device.
[15] A fifteenth aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the fourteenth aspect, wherein the constituent member for a flexible image display device is a rollable member.
[16] A sixteenth aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the fourteenth aspect, wherein the constituent member for a flexible image display device is a stretchable member.
[１５] 本発明の第１５の態様は、前記第１４の態様において、前記フレキシブル画像表示装置用構成部材がローラブル部材である、離型フィルム付き粘着シートである。
[１６] 本発明の第１６の態様は、前記第１４の態様において、前記フレキシブル画像表示装置用構成部材がストレッチャブル部材である、離型フィルム付き粘着シートである。 [14] A fourteenth aspect of the present invention is, in any one of the first to thirteenth aspects, a pressure-sensitive adhesive sheet with a release film, which is used for bonding constituent members for a flexible image display device.
[15] A fifteenth aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the fourteenth aspect, wherein the constituent member for a flexible image display device is a rollable member.
[16] A sixteenth aspect of the present invention is the pressure-sensitive adhesive sheet with a release film according to the fourteenth aspect, wherein the constituent member for a flexible image display device is a stretchable member.
[１７] 本発明の第１７の態様は、前記第１～第１６の何れか一の態様における離型フィルム付き粘着シートの粘着シートと、フレキシブル画像表示装置用構成部材とが積層してなる構成を備えたフレキシブル画像表示装置用積層体である。
[１８] 本発明の第１８の態様は、前記第１～第１６の何れか一の態様における離型フィルム付き粘着シートの粘着シートが硬化してなる硬化後粘着シートと、フレキシブル画像表示装置用構成部材とが積層してなる構成を備えたフレキシブル画像表示装置用積層体である。 [17] A seventeenth aspect of the present invention is a configuration in which the pressure-sensitive adhesive sheet of the pressure-sensitive adhesive sheet with a release film according to any one of the first to sixteenth aspects and a component for a flexible image display device are laminated. It is a laminate for a flexible image display device.
[18] An eighteenth aspect of the present invention is a cured adhesive sheet obtained by curing the adhesive sheet of the adhesive sheet with a release film according to any one of the first to sixteenth aspects, and a flexible image display device. It is a laminate for a flexible image display device having a configuration in which the constituent members are laminated.
[１８] 本発明の第１８の態様は、前記第１～第１６の何れか一の態様における離型フィルム付き粘着シートの粘着シートが硬化してなる硬化後粘着シートと、フレキシブル画像表示装置用構成部材とが積層してなる構成を備えたフレキシブル画像表示装置用積層体である。 [17] A seventeenth aspect of the present invention is a configuration in which the pressure-sensitive adhesive sheet of the pressure-sensitive adhesive sheet with a release film according to any one of the first to sixteenth aspects and a component for a flexible image display device are laminated. It is a laminate for a flexible image display device.
[18] An eighteenth aspect of the present invention is a cured adhesive sheet obtained by curing the adhesive sheet of the adhesive sheet with a release film according to any one of the first to sixteenth aspects, and a flexible image display device. It is a laminate for a flexible image display device having a configuration in which the constituent members are laminated.
[１９] 本発明の第１９の態様は、フレキシブル画像表示装置用構成部材と粘着シートとが積層してなる構成を備えたフレキシブル画像表示装置用積層体であって、
フレキシブル画像表示装置用構成部材と粘着シートとの間に形成された空間部の空隙率（Ｘ）が３～７０％であるフレキシブル画像表示装置用積層体である。
[２０] 本発明の第２０の態様は、前記第１９の態様における前記粘着シートは、前記第１～第１６の何れか一の態様における離型フィルム付き粘着シートの粘着シートである、フレキシブル画像表示装置用積層体である。 [19] A nineteenth aspect of the present invention is a laminate for a flexible image display device comprising a configuration in which a constituent member for a flexible image display device and an adhesive sheet are laminated,
The laminate for a flexible image display device has a porosity (X) of 3 to 70% in the space formed between the component for the flexible image display device and the adhesive sheet.
[20] A twentieth aspect of the present invention is a flexible image, wherein the adhesive sheet in the nineteenth aspect is the adhesive sheet of the adhesive sheet with a release film in any one of the first to sixteenth aspects. This is a laminate for a display device.
フレキシブル画像表示装置用構成部材と粘着シートとの間に形成された空間部の空隙率（Ｘ）が３～７０％であるフレキシブル画像表示装置用積層体である。
[２０] 本発明の第２０の態様は、前記第１９の態様における前記粘着シートは、前記第１～第１６の何れか一の態様における離型フィルム付き粘着シートの粘着シートである、フレキシブル画像表示装置用積層体である。 [19] A nineteenth aspect of the present invention is a laminate for a flexible image display device comprising a configuration in which a constituent member for a flexible image display device and an adhesive sheet are laminated,
The laminate for a flexible image display device has a porosity (X) of 3 to 70% in the space formed between the component for the flexible image display device and the adhesive sheet.
[20] A twentieth aspect of the present invention is a flexible image, wherein the adhesive sheet in the nineteenth aspect is the adhesive sheet of the adhesive sheet with a release film in any one of the first to sixteenth aspects. This is a laminate for a display device.
[２１] 本発明の第２１の態様は、前記第１７～第２０の何れか一の態様におけるフレキシブル画像表示装置用積層体を備えたフレキシブル画像表示装置である。
[21] A twenty-first aspect of the present invention is a flexible image display device comprising the laminate for a flexible image display device according to any one of the seventeenth to twentieth aspects.
[２２] 本発明の第２２の態様は、フレキシブル画像表示装置用構成部材を貼り合わせるために使用する粘着シートであって、前記粘着シートの少なくとも表裏一側の粘着面に、凸部を有する凹凸単位が少なくとも１つ設けられてなる凹凸パターンを備え、前記凹凸単位における凸部の高さ（α）が７～１００μｍであり、前記凹凸単位を構成する凸部の最大幅（ｗ１）が１～１０００μｍである粘着シートである。
[22] A twenty-second aspect of the present invention is a pressure-sensitive adhesive sheet used for bonding constituent members for a flexible image display device, wherein the pressure-sensitive adhesive surface on at least one of the front and back sides of the pressure-sensitive adhesive sheet has projections and depressions. The concave-convex pattern is provided with at least one unit, the height (α) of the convex portion in the concave-convex unit is 7 to 100 μm, and the maximum width (w1) of the convex portion constituting the concave-convex unit is 1 to 1 It is an adhesive sheet with a thickness of 1000 μm.
本発明が提案する離型フィルム付き粘着シートは、離型フィルムと粘着シートとの間に空間部が形成されており、当該空間部は所定範囲の空隙率（Ｘ）を有している。そのため、離型フィルムを剥離した粘着シートを、表面平坦なフレキシブル画像表示装置用構成部材に貼着して積層した場合にも、粘着シートとフレキシブル画像表示装置用構成部材との間に同様の空隙率（Ｘ）を有する空間部を形成することができる。そのように離型フィルムを剥離した粘着シートを、フレキシブル画像表示装置用構成部材に貼着して積層した状態で巻き取り、巻き戻して広げた場合、前記空間部によって、粘着シートの巻き長差分による歪みに由来する応力を緩和することができ、粘着シートとフレキシブル画像表示装置用構成部材との間に“浮き”が生じるのを防ぐことができる。よって、本発明が提案する離型フィルム付き粘着シートの粘着シートは、フレキシブル性、特にローラブル性に優れた効果を有することができる。
In the pressure-sensitive adhesive sheet with a release film proposed by the present invention, a space is formed between the release film and the pressure-sensitive adhesive sheet, and the space has a porosity (X) within a predetermined range. Therefore, even when the pressure-sensitive adhesive sheet from which the release film has been peeled off is adhered to and laminated on a component for a flexible image display device having a flat surface, the same gap is formed between the pressure-sensitive adhesive sheet and the component for a flexible image display device. A void having a modulus (X) can be formed. When the pressure-sensitive adhesive sheet from which the release film has been peeled off in this way is adhered to and laminated on the constituent member for a flexible image display device, is wound up, and then unwound and spread, the difference in the winding length of the pressure-sensitive adhesive sheet is caused by the space. It is possible to relax the stress resulting from the strain caused by the stress, and prevent the occurrence of "floating" between the pressure-sensitive adhesive sheet and the constituent member for a flexible image display device. Therefore, the pressure-sensitive adhesive sheet of the pressure-sensitive adhesive sheet with a release film proposed by the present invention can have excellent flexibility, particularly rollability.
また、本発明では、前記空間部の空隙率を更に調整することにより、離型フィルムを剥離した粘着シートを、フレキシブル画像表示装置用構成部材に貼着して積層した状態で伸縮させた場合も、粘着シートとフレキシブル画像表示装置用構成部材との間に形成された空間を設けることで応力分散が可能となり応力を緩和することができ、粘着シートとフレキシブル画像表示装置用構成部材との間の“剥がれ”が生じるのを防ぐことができる。よって、本発明が提案する離型フィルム付き粘着シートは、特にストレッチャブル性にも優れた効果をも有することができる。
Further, in the present invention, by further adjusting the porosity of the space portion, even when the pressure-sensitive adhesive sheet from which the release film has been peeled off is adhered to a constituent member for a flexible image display device and stretched in a laminated state. By providing a space formed between the pressure-sensitive adhesive sheet and the flexible image display device component, the stress can be dispersed and the stress can be relieved, and the space between the pressure-sensitive adhesive sheet and the flexible image display device component can be reduced. It is possible to prevent "peeling" from occurring. Therefore, the pressure-sensitive adhesive sheet with a release film proposed by the present invention can have particularly excellent stretchability.
次に、実施の形態例に基づいて本発明を説明する。但し、本発明が次に説明する実施形態に限定されるものではない。
Next, the present invention will be described based on an embodiment. However, the present invention is not limited to the embodiments described below.
前述したように、粘着シート１０の表裏一側又は両側にフレキシブル画像表示装置用構成部材２０（３０）を積層し、積層状態のまま、巻き取り、その後、巻き戻して展開したときに、粘着シート１０とフレキシブル画像表示装置用構成部材２０（３０）とが一部剥離して“浮き”が発生する原因は、巻き取った際に生じる粘着シート１０の内側単位円周長（内側巻き長）Ｌ１と外側単位円周長（外側巻き長）Ｌ２との巻き長差（ΔＬ＝Ｌ２－Ｌ１）の、粘着シート１０の厚みｂに対する比率（ΔＬ／ｂ、「巻き長差分」とも称する。）による歪のためであると考えられる（図３参照）。そこで、フレキシブル画像表示装置用構成部材を積層する側の粘着シート表面に、所定の凸部の高さを有する凹凸パターンを形成したところ、巻き取った際に生じる歪を緩和することができ、巻き戻して展開したときに、粘着シートとフレキシブル画像表示装置用構成部材との間に浮きが生じるのを防ぐことができた。また、前記のように積層した状態で伸縮させた場合も、より好ましい空隙率を有する空間部を設けることで応力分散が可能となり、引張応力を緩和することができ、粘着シートとフレキシブル画像表示装置用構成部材との間の“剥がれ”が生じるのを防ぐことができた。
As described above, the constituent members 20 (30) for a flexible image display device are laminated on one or both sides of the pressure-sensitive adhesive sheet 10, wound up in the laminated state, and then unwound and unfolded. 10 and the component 20 (30) for a flexible image display device are partly peeled off and "floating" occurs because the inner unit circumferential length (inner winding length) L1 of the adhesive sheet 10 that occurs when the adhesive sheet 10 is wound and the outer unit circumference length (outer winding length) L2, the ratio of the winding length difference (ΔL = L2 - L1) to the thickness b of the adhesive sheet 10 (ΔL / b, also referred to as “winding length difference”) Distortion due to (See FIG. 3). Therefore, when a concavo-convex pattern having a predetermined convex height was formed on the surface of the pressure-sensitive adhesive sheet on which the constituent members for a flexible image display device were to be laminated, the strain generated during winding could be alleviated. When the adhesive sheet was put back and unfolded, it was possible to prevent the occurrence of floating between the pressure-sensitive adhesive sheet and the component for a flexible image display device. Further, even when the adhesive sheet and the flexible image display device are expanded and contracted in a laminated state as described above, stress can be dispersed by providing a space portion having a more preferable porosity, and tensile stress can be alleviated. It was possible to prevent "peeling" from occurring between the components.
＜＜本発明離型フィルム付き粘着シート＞＞
本発明の実施形態の一例である離型フィルム付き粘着シート（「本発明離型フィルム付き粘着シート」と称する）は、本発明の実施形態の一例に係る粘着シート（以下、「本発明粘着シート」とも称する。）と、本発明の実施形態の一例に係る離型フィルム（以下、「本発明離型フィルム」とも称する。）とを備えたものであり、本発明粘着シートの表裏一側又は両側に本発明離型フィルムが積層された構成を備えたものである。
なお、本発明離型フィルム付き粘着シートにおける本発明粘着シートは、硬化前の状態、硬化後の状態、及び、硬化途中の状態すなわち未だ硬化される余地のある状態に硬化された状態のいずれも包含する。 <<Adhesive sheet with release film of the present invention>>
A pressure-sensitive adhesive sheet with a release film (referred to as "the pressure-sensitive adhesive sheet with the release film of the present invention") which is an example of an embodiment of the present invention is a pressure-sensitive adhesive sheet according to an example of the embodiment of the present invention (hereinafter referred to as "the pressure-sensitive adhesive sheet of the present invention"). ”) and a release film according to an example of the embodiment of the present invention (hereinafter also referred to as “the release film of the present invention”). It has a configuration in which the release film of the present invention is laminated on both sides.
In addition, the pressure-sensitive adhesive sheet of the present invention in the pressure-sensitive adhesive sheet with the release film of the present invention is in a state before curing, a state after curing, and a state in the middle of curing, that is, a state in which there is still room for curing. contain.
本発明の実施形態の一例である離型フィルム付き粘着シート（「本発明離型フィルム付き粘着シート」と称する）は、本発明の実施形態の一例に係る粘着シート（以下、「本発明粘着シート」とも称する。）と、本発明の実施形態の一例に係る離型フィルム（以下、「本発明離型フィルム」とも称する。）とを備えたものであり、本発明粘着シートの表裏一側又は両側に本発明離型フィルムが積層された構成を備えたものである。
なお、本発明離型フィルム付き粘着シートにおける本発明粘着シートは、硬化前の状態、硬化後の状態、及び、硬化途中の状態すなわち未だ硬化される余地のある状態に硬化された状態のいずれも包含する。 <<Adhesive sheet with release film of the present invention>>
A pressure-sensitive adhesive sheet with a release film (referred to as "the pressure-sensitive adhesive sheet with the release film of the present invention") which is an example of an embodiment of the present invention is a pressure-sensitive adhesive sheet according to an example of the embodiment of the present invention (hereinafter referred to as "the pressure-sensitive adhesive sheet of the present invention"). ”) and a release film according to an example of the embodiment of the present invention (hereinafter also referred to as “the release film of the present invention”). It has a configuration in which the release film of the present invention is laminated on both sides.
In addition, the pressure-sensitive adhesive sheet of the present invention in the pressure-sensitive adhesive sheet with the release film of the present invention is in a state before curing, a state after curing, and a state in the middle of curing, that is, a state in which there is still room for curing. contain.
本発明離型フィルム付き粘着シートは、後述するように、フレキシブル画像表示装置用構成部材を貼り合わせるために好適に使用することができる。
The pressure-sensitive adhesive sheet with a release film of the present invention can be suitably used for bonding constituent members for a flexible image display device, as described later.
＜空間部＞
本発明離型フィルム付き粘着シートにおいては、本発明離型フィルムで挟持された際に形成される空間部、すなわち、本発明離型フィルムと本発明粘着シートとの間に形成された空間部の空隙率（Ｘ）が３～７０％である粘着シートであるのが好ましい。
当該空間部の空隙率（Ｘ）が３～７０％であれば、本発明離型フィルムを剥離した本発明粘着シートを、表面平坦なフレキシブル画像表示装置用構成部材に貼着して積層した場合にも、本発明粘着シートとフレキシブル画像表示装置用構成部材との間に同様の空隙率（Ｘ）を有する空間部を形成することができる。そのように本発明離型フィルムを剥離した本発明粘着シートを、フレキシブル画像表示装置用構成部材に貼着して積層した状態で巻き取り、巻き戻して広げた時に、前記空間部によって、本発明粘着シートの巻き長差分による歪みに由来する応力を緩和することができ、本発明粘着シートとフレキシブル画像表示装置用構成部材との間に“浮き”が生じるのを防ぐことができる。更に、前記のように積層した状態で伸縮させた場合も、前記空間部を更に調整して設けることで応力分散が可能となり応力を緩和することができ、本発明粘着シートとフレキシブル画像表示装置用構成部材との間の“剥がれ”が生じるのを防ぐことができる。
よって、空間部の空隙率（Ｘ）は３％以上であるのが好ましく、中でも４％以上、４．５％以上、５％以上、６％以上、特には８％以上、その中でも１０％以上であるのがさらに好ましい。他方、７０％以下であるのがより好ましく、中でも６０％以下、５０％以下、４８％以下、中でも４５％以下、その中でも４０％以下であるのがさらに好ましい。
特に、伸縮させた場合（ストレッチャブル性を目的とする場合）は、空間部の空隙率（Ｘ）は４％以上が好ましく、中でも４．５％以上、５％以上、６％以上、特には８％以上、その中でも１０％以上であり、他方、７０％以下であるのがより好ましく、中でも６０％以下、５０％以下、４８％以下、中でも４５％以下、その中でも４０％以下であるのがさらに好ましい。 <Space part>
In the pressure-sensitive adhesive sheet with a release film of the present invention, the space formed when sandwiched between the release films of the present invention, that is, the space formed between the release film of the present invention and the pressure-sensitive adhesive sheet of the present invention. A pressure-sensitive adhesive sheet having a porosity (X) of 3 to 70% is preferred.
When the void ratio (X) of the space is 3 to 70%, the pressure-sensitive adhesive sheet of the present invention from which the release film of the present invention has been peeled off is adhered and laminated on a component for a flexible image display device having a flat surface. Also, a space portion having the same porosity (X) can be formed between the pressure-sensitive adhesive sheet of the present invention and the constituent member for a flexible image display device. The pressure-sensitive adhesive sheet of the present invention from which the release film of the present invention has been peeled off in this way is adhered to a constituent member for a flexible image display device and laminated. It is possible to relieve the stress caused by the strain due to the difference in winding length of the adhesive sheet, and to prevent the occurrence of "floating" between the adhesive sheet of the present invention and the constituent member for a flexible image display device. Furthermore, even when the laminated state is expanded and contracted as described above, by further adjusting and providing the space portion, stress can be dispersed and the stress can be alleviated. It is possible to prevent "peeling" from occurring between the constituent members.
Therefore, the porosity (X) of the space is preferably 3% or more, especially 4% or more, 4.5% or more, 5% or more, 6% or more, particularly 8% or more, and among them 10% or more is more preferable. On the other hand, it is more preferably 70% or less, more preferably 60% or less, 50% or less, or 48% or less, especially 45% or less, and even more preferably 40% or less.
In particular, when stretched (for the purpose of stretchability), the porosity (X) of the space is preferably 4% or more, especially 4.5% or more, 5% or more, 6% or more, especially 8% or more, among which 10% or more, on the other hand, it is more preferably 70% or less, among which 60% or less, 50% or less, 48% or less, among them 45% or less, among which 40% or less is more preferred.
本発明離型フィルム付き粘着シートにおいては、本発明離型フィルムで挟持された際に形成される空間部、すなわち、本発明離型フィルムと本発明粘着シートとの間に形成された空間部の空隙率（Ｘ）が３～７０％である粘着シートであるのが好ましい。
当該空間部の空隙率（Ｘ）が３～７０％であれば、本発明離型フィルムを剥離した本発明粘着シートを、表面平坦なフレキシブル画像表示装置用構成部材に貼着して積層した場合にも、本発明粘着シートとフレキシブル画像表示装置用構成部材との間に同様の空隙率（Ｘ）を有する空間部を形成することができる。そのように本発明離型フィルムを剥離した本発明粘着シートを、フレキシブル画像表示装置用構成部材に貼着して積層した状態で巻き取り、巻き戻して広げた時に、前記空間部によって、本発明粘着シートの巻き長差分による歪みに由来する応力を緩和することができ、本発明粘着シートとフレキシブル画像表示装置用構成部材との間に“浮き”が生じるのを防ぐことができる。更に、前記のように積層した状態で伸縮させた場合も、前記空間部を更に調整して設けることで応力分散が可能となり応力を緩和することができ、本発明粘着シートとフレキシブル画像表示装置用構成部材との間の“剥がれ”が生じるのを防ぐことができる。
よって、空間部の空隙率（Ｘ）は３％以上であるのが好ましく、中でも４％以上、４．５％以上、５％以上、６％以上、特には８％以上、その中でも１０％以上であるのがさらに好ましい。他方、７０％以下であるのがより好ましく、中でも６０％以下、５０％以下、４８％以下、中でも４５％以下、その中でも４０％以下であるのがさらに好ましい。
特に、伸縮させた場合（ストレッチャブル性を目的とする場合）は、空間部の空隙率（Ｘ）は４％以上が好ましく、中でも４．５％以上、５％以上、６％以上、特には８％以上、その中でも１０％以上であり、他方、７０％以下であるのがより好ましく、中でも６０％以下、５０％以下、４８％以下、中でも４５％以下、その中でも４０％以下であるのがさらに好ましい。 <Space part>
In the pressure-sensitive adhesive sheet with a release film of the present invention, the space formed when sandwiched between the release films of the present invention, that is, the space formed between the release film of the present invention and the pressure-sensitive adhesive sheet of the present invention. A pressure-sensitive adhesive sheet having a porosity (X) of 3 to 70% is preferred.
When the void ratio (X) of the space is 3 to 70%, the pressure-sensitive adhesive sheet of the present invention from which the release film of the present invention has been peeled off is adhered and laminated on a component for a flexible image display device having a flat surface. Also, a space portion having the same porosity (X) can be formed between the pressure-sensitive adhesive sheet of the present invention and the constituent member for a flexible image display device. The pressure-sensitive adhesive sheet of the present invention from which the release film of the present invention has been peeled off in this way is adhered to a constituent member for a flexible image display device and laminated. It is possible to relieve the stress caused by the strain due to the difference in winding length of the adhesive sheet, and to prevent the occurrence of "floating" between the adhesive sheet of the present invention and the constituent member for a flexible image display device. Furthermore, even when the laminated state is expanded and contracted as described above, by further adjusting and providing the space portion, stress can be dispersed and the stress can be alleviated. It is possible to prevent "peeling" from occurring between the constituent members.
Therefore, the porosity (X) of the space is preferably 3% or more, especially 4% or more, 4.5% or more, 5% or more, 6% or more, particularly 8% or more, and among them 10% or more is more preferable. On the other hand, it is more preferably 70% or less, more preferably 60% or less, 50% or less, or 48% or less, especially 45% or less, and even more preferably 40% or less.
In particular, when stretched (for the purpose of stretchability), the porosity (X) of the space is preferably 4% or more, especially 4.5% or more, 5% or more, 6% or more, especially 8% or more, among which 10% or more, on the other hand, it is more preferably 70% or less, among which 60% or less, 50% or less, 48% or less, among them 45% or less, among which 40% or less is more preferred.
このように、本発明離型フィルムと本発明粘着シートとの間に空間部を形成するには、上記のように、本発明粘着シートの表面に、所定の凸部の高さを有する凹凸パターンを形成するようにすればよい。そして上記空間部の空隙率を上記範囲に調整するには、凸部の高さ（α）や凸部の最大幅（ｗ１）（μｍ）、繰り返しピッチ（ｗ２）（μｍ）、隣接する凸部との間隔（ｗ３）（μｍ）、隣接する凸部との間隔（ｗ３）に対する凸部の高さ（α）の比率（α／ｗ３）、凸部頂面幅（ｗ４）（μｍ）、粘着シートの厚み（ｂ）（μｍ）、粘着シートの厚み（ｂ）に対する凸部の高さ（α）の比率（α／ｂ）、アスペクト比（α／ｗ１）等を適宜調整することにより得られる。
Thus, in order to form a space between the release film of the present invention and the pressure-sensitive adhesive sheet of the present invention, a concavo-convex pattern having a predetermined height of protrusions is formed on the surface of the pressure-sensitive adhesive sheet of the present invention, as described above. should be formed. In order to adjust the porosity of the space portion to the above range, the height (α) of the convex portion, the maximum width (w1) (μm) of the convex portion, the repetition pitch (w2) (μm), the adjacent convex portion spacing (w3) (μm), the ratio of the height (α) of the protrusion to the spacing (w3) between the adjacent protrusions (α/w3), the top surface width of the protrusion (w4) (μm), the adhesion It can be obtained by appropriately adjusting the sheet thickness (b) (μm), the ratio (α/b) of the height (α) of the convex portion to the thickness (b) of the adhesive sheet, the aspect ratio (α/w1), etc. .
前記空隙率（％）は、以下の方法により測定することができる。
離型フィルム付き粘着シートの表面を、光学顕微鏡を用いて、単位面積当たりの凹凸面積を求め、次いで、凹凸構造を有する離型フィルム付き粘着シートの断面を、光学顕微鏡を用いて、凹凸の高さを求める。凹凸面積と凹凸高さの積より空隙率（％）を測定する。
具体的には例えば、先ず、凹凸構造を有する本発明離型フィルム付き粘着シートの表面を、離型フィルム越しに、光学顕微鏡（例えばキーエンス社製、マイクロスコープＶＨＸ－６００）を用いて、凸部の幅（ｗ２、ｗ３、ｗ４）を測定する。また、本発明離型フィルム付き粘着シートを厚さ方向に切断し、断面における凹凸の高さ（ｈ）及び粘着シート厚み（Ｈ）を、光学顕微鏡を用いて測定する。得られた結果より（（ｗ３＋（ｗ２－ｗ４））×ｈ÷２）／（ｗ２×Ｈ）より空隙率（％）を測定することができる。
但し、空間部の形状によって測定方法を変更してもよい。例えば、凸部がマイクロレンズアレイのような間欠形状の場合には、光学顕微鏡より凸部の直径、高さを測定、また粘着シート厚みＨを測定した後に、単位体積当たりの凸部の体積率より空隙率を算出することもできる。 The porosity (%) can be measured by the following method.
The surface of the pressure-sensitive adhesive sheet with a release film is examined with an optical microscope to determine the uneven area per unit area, and then the cross section of the pressure-sensitive adhesive sheet with a release film having an uneven structure is examined with an optical microscope to determine the height of the unevenness. Seek to be The porosity (%) is measured from the product of the uneven area and the uneven height.
Specifically, for example, first, the surface of the pressure-sensitive adhesive sheet with a release film of the present invention having an uneven structure, through the release film, using an optical microscope (eg, manufactured by Keyence Corporation, Microscope VHX-600), the convex portion Measure the widths (w2, w3, w4) of Also, the pressure-sensitive adhesive sheet with the release film of the present invention is cut in the thickness direction, and the height (h) of unevenness in the cross section and the thickness (H) of the pressure-sensitive adhesive sheet are measured using an optical microscope. From the obtained results, the porosity (%) can be measured from ((w3+(w2-w4))×h÷2)/(w2×H).
However, the measuring method may be changed depending on the shape of the space. For example, when the projections have an intermittent shape such as a microlens array, the diameter and height of the projections are measured with an optical microscope, and the thickness H of the adhesive sheet is measured. It is also possible to calculate the porosity.
離型フィルム付き粘着シートの表面を、光学顕微鏡を用いて、単位面積当たりの凹凸面積を求め、次いで、凹凸構造を有する離型フィルム付き粘着シートの断面を、光学顕微鏡を用いて、凹凸の高さを求める。凹凸面積と凹凸高さの積より空隙率（％）を測定する。
具体的には例えば、先ず、凹凸構造を有する本発明離型フィルム付き粘着シートの表面を、離型フィルム越しに、光学顕微鏡（例えばキーエンス社製、マイクロスコープＶＨＸ－６００）を用いて、凸部の幅（ｗ２、ｗ３、ｗ４）を測定する。また、本発明離型フィルム付き粘着シートを厚さ方向に切断し、断面における凹凸の高さ（ｈ）及び粘着シート厚み（Ｈ）を、光学顕微鏡を用いて測定する。得られた結果より（（ｗ３＋（ｗ２－ｗ４））×ｈ÷２）／（ｗ２×Ｈ）より空隙率（％）を測定することができる。
但し、空間部の形状によって測定方法を変更してもよい。例えば、凸部がマイクロレンズアレイのような間欠形状の場合には、光学顕微鏡より凸部の直径、高さを測定、また粘着シート厚みＨを測定した後に、単位体積当たりの凸部の体積率より空隙率を算出することもできる。 The porosity (%) can be measured by the following method.
The surface of the pressure-sensitive adhesive sheet with a release film is examined with an optical microscope to determine the uneven area per unit area, and then the cross section of the pressure-sensitive adhesive sheet with a release film having an uneven structure is examined with an optical microscope to determine the height of the unevenness. Seek to be The porosity (%) is measured from the product of the uneven area and the uneven height.
Specifically, for example, first, the surface of the pressure-sensitive adhesive sheet with a release film of the present invention having an uneven structure, through the release film, using an optical microscope (eg, manufactured by Keyence Corporation, Microscope VHX-600), the convex portion Measure the widths (w2, w3, w4) of Also, the pressure-sensitive adhesive sheet with the release film of the present invention is cut in the thickness direction, and the height (h) of unevenness in the cross section and the thickness (H) of the pressure-sensitive adhesive sheet are measured using an optical microscope. From the obtained results, the porosity (%) can be measured from ((w3+(w2-w4))×h÷2)/(w2×H).
However, the measuring method may be changed depending on the shape of the space. For example, when the projections have an intermittent shape such as a microlens array, the diameter and height of the projections are measured with an optical microscope, and the thickness H of the adhesive sheet is measured. It is also possible to calculate the porosity.
＜本発明粘着シート＞
本発明の実施形態の一例に係る本発明粘着シートは、粘着シート１の表裏一側又は両側の粘着面２に、凸部３Ａを有する凹凸単位３が少なくとも１つ以上設けられてなる凹凸パターン４を備えた粘着シートである。
なお、凸部３Ａとは突起した部分であり、凹部３Ｂとは窪んだ部分である。よって、仮に粘着シートの粘着面に凹部３Ｂを形成した場合、同時に凸部３Ａも形成されることになる。 <Adhesive sheet of the present invention>
The pressure-sensitive adhesive sheet of the present invention according to an embodiment of the present invention has a concave-convex pattern 4 in which at least one concave-convex unit 3 having convex portions 3A is provided on one or both sides of the pressure-sensitive adhesive surface 2 of the pressure-sensitive adhesive sheet 1. It is an adhesive sheet with
Theconvex portion 3A is a projected portion, and the concave portion 3B is a recessed portion. Therefore, if the concave portions 3B are formed on the adhesive surface of the adhesive sheet, the convex portions 3A are also formed at the same time.
本発明の実施形態の一例に係る本発明粘着シートは、粘着シート１の表裏一側又は両側の粘着面２に、凸部３Ａを有する凹凸単位３が少なくとも１つ以上設けられてなる凹凸パターン４を備えた粘着シートである。
なお、凸部３Ａとは突起した部分であり、凹部３Ｂとは窪んだ部分である。よって、仮に粘着シートの粘着面に凹部３Ｂを形成した場合、同時に凸部３Ａも形成されることになる。 <Adhesive sheet of the present invention>
The pressure-sensitive adhesive sheet of the present invention according to an embodiment of the present invention has a concave-
The
本発明粘着シートは、硬化前の状態、硬化後の状態、及び、硬化途中の状態すなわち未だ硬化される余地のある状態に硬化された状態のいずれも包含する。
The pressure-sensitive adhesive sheet of the present invention includes all of the state before curing, the state after curing, and the state in the middle of curing, that is, the state in which there is still room for curing.
本発明粘着シートは、粘着シート１の表裏一側の粘着面２に凹凸パターン４を備えていても、粘着シート１の表裏両側の粘着面２、２に凹凸パターン４を備えていてもよい。
The pressure-sensitive adhesive sheet of the present invention may have an uneven pattern 4 on the adhesive surface 2 on one of the front and back sides of the adhesive sheet 1 , or may have uneven patterns 4 on both the front and back adhesive surfaces 2 , 2 of the adhesive sheet 1 .
本発明粘着シートを上面視した際の前記凹凸パターン４の形状は、例えば、ストライプ状、円状、矩形状など、所定の平面視形状を有する凹凸単位３が、一定方向、好ましくは巻き周方向とする方向に形成されるものであればよく、好ましくは繰り返し形成されてなる形状であれば好適に採用できる（図４参照）。
この際、前記凹凸パターン４は、凹凸単位３が規則的に繰り返すように形成されていてもよいし、不規則に繰り返すように形成されていてもよい。
但し、製造のし易さなどを考慮すれば、直線状に伸びた凹状溝部又は凸状部又はこれら両方の組み合わせが一定方向、好ましくは巻き周方向に繰り返してなるストライプ状を呈するものが好ましい。
なお、前記凹凸パターン４は、１つの凹凸単位３からなる場合も包含する。例えば巻き径が顕著に大きい場合や、フォルダブルの曲率部のみに適用する場合など、凹凸パターン４が局所的に形成されていれば十分である場合があるため、そのような場合は、凹凸パターン４が１つの凹凸単位３からなる場合であっても本発明の効果を享受することができる。 When the pressure-sensitive adhesive sheet of the present invention is viewed from above, the shape of theuneven pattern 4 is such that the uneven units 3 having a predetermined plan view shape such as stripes, circles, and rectangles are arranged in a certain direction, preferably in the winding circumferential direction. Any shape may be used as long as it is formed in the direction of .
At this time, the concave-convex pattern 4 may be formed such that the concave-convex units 3 are regularly repeated, or may be formed so as to be irregularly repeated.
However, considering the ease of manufacture, it is preferable to have stripes in which linearly extending recessed grooves or protrusions or a combination of both are repeated in a certain direction, preferably in the winding direction.
In addition, theuneven pattern 4 also includes the case of being composed of one uneven unit 3 . For example, when the winding diameter is significantly large, or when applying only to the curvature part of the foldable, it may be sufficient if the uneven pattern 4 is locally formed. Even when 4 consists of one uneven unit 3, the effect of the present invention can be enjoyed.
この際、前記凹凸パターン４は、凹凸単位３が規則的に繰り返すように形成されていてもよいし、不規則に繰り返すように形成されていてもよい。
但し、製造のし易さなどを考慮すれば、直線状に伸びた凹状溝部又は凸状部又はこれら両方の組み合わせが一定方向、好ましくは巻き周方向に繰り返してなるストライプ状を呈するものが好ましい。
なお、前記凹凸パターン４は、１つの凹凸単位３からなる場合も包含する。例えば巻き径が顕著に大きい場合や、フォルダブルの曲率部のみに適用する場合など、凹凸パターン４が局所的に形成されていれば十分である場合があるため、そのような場合は、凹凸パターン４が１つの凹凸単位３からなる場合であっても本発明の効果を享受することができる。 When the pressure-sensitive adhesive sheet of the present invention is viewed from above, the shape of the
At this time, the concave-
However, considering the ease of manufacture, it is preferable to have stripes in which linearly extending recessed grooves or protrusions or a combination of both are repeated in a certain direction, preferably in the winding direction.
In addition, the
前記凹凸パターン４を構成する凹凸単位３は、粘着シートの幅方向、すなわち巻き周方向とする方向と直交する方向に伸びる凸状部又は凹状溝部又はこれらの組み合わせであるのが好ましい。
The concave-convex unit 3 constituting the concave-convex pattern 4 is preferably a convex portion or concave groove extending in the width direction of the adhesive sheet, that is, in a direction perpendicular to the winding direction, or a combination thereof.
本発明粘着シートを一定方向、例えば巻き周方向に沿って肉厚方向に切断した縦断面に見て、凹凸パターン４を構成する凹凸単位３の断面形状は、例えば三角状、四角状、台形状、半円状、半楕円状など、任意の所定形状の凹部３Ｂ又は凸部３Ａが繰返してなる形状であればよい（図５参照）。
When the pressure-sensitive adhesive sheet of the present invention is viewed in a longitudinal section cut in a thickness direction along a certain direction, for example, along the winding direction, the cross-sectional shape of the uneven unit 3 constituting the uneven pattern 4 is, for example, triangular, square, or trapezoidal. , a semicircular shape, a semielliptical shape, or any other shape in which concave portions 3B or convex portions 3A of any predetermined shape are repeated (see FIG. 5).
前記凹凸単位３における凸部３Ａの高さ（α）は７～１００μｍであるのが好ましい。
凹凸単位３における凸部３Ａの高さ（α）とは、本発明粘着シートを巻き周方向とする方向に沿って肉厚方向に切断した縦断面に見た際に、凹凸単位３における最頂部と最低部を基準とする縦長さの意味である。
凹凸単位３における凸部３Ａの高さ（α）が７μｍ以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力を緩和することができ、浮きの発生を防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより防ぐことができる。他方、１００μｍ以下であれば、成形性に優れ均一な凹凸単位３を得ることができる。
かかる観点から、凹凸単位３における凸部３Ａの高さ（α）は７．５μｍ以上であるのがより好ましく、８μｍ以上であるのがさらに好ましく、８．５μｍ以上であるのが特に好ましい。他方、１００μｍ以下であるのがより好ましく、さらに９５μｍ以下、特に９０μｍ以下であるのが好ましく、８０μｍ以下であるのが特に好ましく、７５μｍ以下であるのが殊に好ましく、７０μｍ以下であるのが最も好ましい。 It is preferable that the height (α) of theconvex portion 3A in the concave-convex unit 3 is 7 to 100 μm.
The height (α) of theconvex portion 3A in the uneven unit 3 is the topmost portion of the uneven unit 3 when viewed in a longitudinal section cut in the thickness direction along the winding circumferential direction of the pressure-sensitive adhesive sheet of the present invention. and vertical length based on the lowest part.
If the height (α) of theconvex portion 3A in the concave-convex unit 3 is 7 μm or more, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2. In addition, the stress caused by the strain caused by the winding length difference during unwinding can be alleviated, and the occurrence of floating can be prevented. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, when the thickness is 100 μm or less, it is possible to obtain uniform uneven units 3 with excellent moldability.
From this point of view, the height (α) of theconvex portion 3A in the concave-convex unit 3 is more preferably 7.5 μm or more, still more preferably 8 μm or more, and particularly preferably 8.5 μm or more. On the other hand, it is more preferably 100 μm or less, further preferably 95 μm or less, particularly preferably 90 μm or less, particularly preferably 80 μm or less, particularly preferably 75 μm or less, most preferably 70 μm or less. preferable.
凹凸単位３における凸部３Ａの高さ（α）とは、本発明粘着シートを巻き周方向とする方向に沿って肉厚方向に切断した縦断面に見た際に、凹凸単位３における最頂部と最低部を基準とする縦長さの意味である。
凹凸単位３における凸部３Ａの高さ（α）が７μｍ以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力を緩和することができ、浮きの発生を防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより防ぐことができる。他方、１００μｍ以下であれば、成形性に優れ均一な凹凸単位３を得ることができる。
かかる観点から、凹凸単位３における凸部３Ａの高さ（α）は７．５μｍ以上であるのがより好ましく、８μｍ以上であるのがさらに好ましく、８．５μｍ以上であるのが特に好ましい。他方、１００μｍ以下であるのがより好ましく、さらに９５μｍ以下、特に９０μｍ以下であるのが好ましく、８０μｍ以下であるのが特に好ましく、７５μｍ以下であるのが殊に好ましく、７０μｍ以下であるのが最も好ましい。 It is preferable that the height (α) of the
The height (α) of the
If the height (α) of the
From this point of view, the height (α) of the
本発明粘着シートの厚み（ｂ）に対する、前記凸部３Ａの高さ（α）の比率（α／ｂ）は０．０１以上１未満であるのが、好ましい。
当該比率（α／ｂ）が０．０１以上であれば、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、１未満であれば、成形性に優れ均一な凹凸単位３を得ることができる。
かかる観点から、本発明粘着シートの厚み（ｂ）に対する、前記凸部３Ａの高さ（α）の比率（α／ｂ）は０．０１５以上であるのがより好ましく、０．０１７以上であるのがさらに好ましく、０．０２以上、０．０３以上、０．０５以上、０．１以上、０．１５以上であるのが特に好ましい。他方、１未満であるのが好ましく、０．９９８以下であるのがさらに好ましく、０．９９５以下、０．９９以下、０．９５以下、０．９０以下であるのが特に好ましい。 The ratio (α/b) of the height (α) of theprojections 3A to the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is preferably 0.01 or more and less than 1.
If the ratio (α/b) is 0.01 or more, the stress derived from the strain caused by the winding length difference during winding and unwinding can be further alleviated, and the occurrence of floating can be further prevented. can. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if it is less than 1, it is possible to obtain uniformuneven units 3 with excellent moldability.
From this point of view, the ratio (α/b) of the height (α) of theprojections 3A to the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is preferably 0.015 or more, and more preferably 0.017 or more. is more preferable, and 0.02 or more, 0.03 or more, 0.05 or more, 0.1 or more, or 0.15 or more is particularly preferable. On the other hand, it is preferably less than 1, more preferably 0.998 or less, particularly preferably 0.995 or less, 0.99 or less, 0.95 or less, or 0.90 or less.
当該比率（α／ｂ）が０．０１以上であれば、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、１未満であれば、成形性に優れ均一な凹凸単位３を得ることができる。
かかる観点から、本発明粘着シートの厚み（ｂ）に対する、前記凸部３Ａの高さ（α）の比率（α／ｂ）は０．０１５以上であるのがより好ましく、０．０１７以上であるのがさらに好ましく、０．０２以上、０．０３以上、０．０５以上、０．１以上、０．１５以上であるのが特に好ましい。他方、１未満であるのが好ましく、０．９９８以下であるのがさらに好ましく、０．９９５以下、０．９９以下、０．９５以下、０．９０以下であるのが特に好ましい。 The ratio (α/b) of the height (α) of the
If the ratio (α/b) is 0.01 or more, the stress derived from the strain caused by the winding length difference during winding and unwinding can be further alleviated, and the occurrence of floating can be further prevented. can. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if it is less than 1, it is possible to obtain uniform
From this point of view, the ratio (α/b) of the height (α) of the
前記凹凸単位３を構成する凸部３Ａの最大幅（ｗ１）は１～１０００μｍであるのが好ましい。
凹凸単位３を構成する凸部３Ａの最大幅（ｗ１）とは、本発明粘着シートを巻き周方向とする方向に沿って肉厚方向に切断した縦断面に見た際に、凸部３Ａの当該巻き周方向に最長な部分の横幅の意味である。例えば、凸部３Ａが台形状の場合は底辺部の長さが最大幅（ｗ１）となる。
凸部３Ａの最大幅（ｗ１）が１μｍ以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、１０００μｍ以下であれば、巻き取った際又は伸縮時に生じる歪、応力を緩和することができる。
かかる観点から、前記凹凸単位３を構成する凸部３Ａの最大幅（ｗ１）は２μｍ以上であるのがより好ましく、５μｍ以上であるのがさらに好ましく、１０μｍ以上、５０μｍ以上、１００μｍ以上であるのが特に好ましい。他方、９００μｍ以下であるのがより好ましく、８００μｍ以下であるのがさらに好ましく、７００μｍ以下であるのが特に好ましい。 It is preferable that the maximum width (w1) of theconvex portion 3A constituting the concave-convex unit 3 is 1 to 1000 μm.
The maximum width (w1) of theconvex portion 3A constituting the concave-convex unit 3 is the width (w1) of the convex portion 3A when viewed in a longitudinal section cut in the thickness direction along the winding circumferential direction of the pressure-sensitive adhesive sheet of the present invention. It means the width of the longest portion in the winding circumferential direction. For example, when the convex portion 3A is trapezoidal, the length of the base portion is the maximum width (w1).
If the maximum width (w1) of theconvex portion 3A is 1 μm or more, a sufficient space can be provided between the component 20 (30) for the flexible image display device and the adhesive surface 2. The stress resulting from the strain caused by the winding length difference can be further alleviated, and the occurrence of floating can be further prevented. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if the thickness is 1000 μm or less, strain and stress generated during winding or expansion and contraction can be alleviated.
From this point of view, the maximum width (w1) of theconvex portion 3A constituting the concave-convex unit 3 is more preferably 2 μm or more, more preferably 5 μm or more, and is 10 μm or more, 50 μm or more, or 100 μm or more. is particularly preferred. On the other hand, it is more preferably 900 μm or less, even more preferably 800 μm or less, and particularly preferably 700 μm or less.
凹凸単位３を構成する凸部３Ａの最大幅（ｗ１）とは、本発明粘着シートを巻き周方向とする方向に沿って肉厚方向に切断した縦断面に見た際に、凸部３Ａの当該巻き周方向に最長な部分の横幅の意味である。例えば、凸部３Ａが台形状の場合は底辺部の長さが最大幅（ｗ１）となる。
凸部３Ａの最大幅（ｗ１）が１μｍ以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、１０００μｍ以下であれば、巻き取った際又は伸縮時に生じる歪、応力を緩和することができる。
かかる観点から、前記凹凸単位３を構成する凸部３Ａの最大幅（ｗ１）は２μｍ以上であるのがより好ましく、５μｍ以上であるのがさらに好ましく、１０μｍ以上、５０μｍ以上、１００μｍ以上であるのが特に好ましい。他方、９００μｍ以下であるのがより好ましく、８００μｍ以下であるのがさらに好ましく、７００μｍ以下であるのが特に好ましい。 It is preferable that the maximum width (w1) of the
The maximum width (w1) of the
If the maximum width (w1) of the
From this point of view, the maximum width (w1) of the
凹凸単位３が繰り返される場合、凹凸単位３の繰り返しピッチ（ｗ２）は２～１０００μｍであるのが好ましい。
凹凸単位３の繰り返しピッチ（ｗ２）とは、本発明粘着シートを巻き周方向とする方向に沿って肉厚方向に切断した縦断面に見た際に、隣の凹凸単位３の同一形状部分との距離の意味である。
当該繰り返しピッチ（ｗ２）が２μｍ以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、１０００μｍ以下であれば、巻き取った際又は伸縮時に生じる歪、応力を緩和することができる。
かかる観点から、前記凹凸単位３の繰り返しピッチ（ｗ２）は３μｍ以上であるのがより好ましく、５μｍ以上であるのがさらに好ましく、１０μｍ以上、５０μｍ以上、１００μｍ以上であるのが特に好ましい。他方、９００μｍ以下であるのがより好ましく、８００μｍ以下であるのがさらに好ましく、７００μｍ以下であるのが特に好ましい。
なお、繰り返しピッチ（ｗ２）は必ずしも一定である必要はない。 When the concave-convex unit 3 is repeated, the repeating pitch (w2) of the concave-convex unit 3 is preferably 2 to 1000 μm.
The repetition pitch (w2) of theuneven unit 3 is the same shape portion of the adjacent uneven unit 3 when viewed in a longitudinal section cut in the thickness direction along the winding circumferential direction of the pressure-sensitive adhesive sheet of the present invention. is the meaning of the distance between
If the repetition pitch (w2) is 2 μm or more, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2, so that the difference in winding length during winding and unwinding can be reduced. The stress resulting from the strain caused by this can be further alleviated, and the occurrence of floating can be further prevented. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if the thickness is 1000 μm or less, strain and stress generated during winding or expansion and contraction can be alleviated.
From this point of view, the repeating pitch (w2) of theuneven units 3 is more preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more, 50 μm or more, or 100 μm or more. On the other hand, it is more preferably 900 μm or less, even more preferably 800 μm or less, and particularly preferably 700 μm or less.
Note that the repetition pitch (w2) does not necessarily have to be constant.
凹凸単位３の繰り返しピッチ（ｗ２）とは、本発明粘着シートを巻き周方向とする方向に沿って肉厚方向に切断した縦断面に見た際に、隣の凹凸単位３の同一形状部分との距離の意味である。
当該繰り返しピッチ（ｗ２）が２μｍ以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、１０００μｍ以下であれば、巻き取った際又は伸縮時に生じる歪、応力を緩和することができる。
かかる観点から、前記凹凸単位３の繰り返しピッチ（ｗ２）は３μｍ以上であるのがより好ましく、５μｍ以上であるのがさらに好ましく、１０μｍ以上、５０μｍ以上、１００μｍ以上であるのが特に好ましい。他方、９００μｍ以下であるのがより好ましく、８００μｍ以下であるのがさらに好ましく、７００μｍ以下であるのが特に好ましい。
なお、繰り返しピッチ（ｗ２）は必ずしも一定である必要はない。 When the concave-
The repetition pitch (w2) of the
If the repetition pitch (w2) is 2 μm or more, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2, so that the difference in winding length during winding and unwinding can be reduced. The stress resulting from the strain caused by this can be further alleviated, and the occurrence of floating can be further prevented. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if the thickness is 1000 μm or less, strain and stress generated during winding or expansion and contraction can be alleviated.
From this point of view, the repeating pitch (w2) of the
Note that the repetition pitch (w2) does not necessarily have to be constant.
凹凸単位３が繰り返される場合、前記凹凸単位３を構成する凸部３Ａと隣接する凸部３Ａとの間隔（ｗ３）は１～１０００μｍであるのが好ましい。
凸部３Ａと隣接する凸部３Ａとの間隔（ｗ３）とは、本発明粘着シートを巻き周方向とする方向に沿って肉厚方向に切断した縦断面に見た際に、凸部３Ａと隣接する凸部３Ａとの間の平面部の巻き周方向長さの意味である。
当該間隔（ｗ３）が１μｍ以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、１０００μｍ以下であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な粘着性が確保できるため好ましい。
かかる観点から、前記凹凸単位３を構成する凸部３Ａと隣接する凸部３Ａとの間隔（ｗ３）は２μｍ以上であるのがより好ましく、５μｍ以上であるのがさらに好ましく、１０μｍ以上、３０μｍ以上であるのが特に好ましい。他方、９００μｍ以下であるのがより好ましく、８００μｍ以下であるのがさらに好ましく、７００μｍ以下、５００μｍ以下、２００μｍ以下であるのが特に好ましい。
なお、図５（Ｄ）のように、隣接する凸部３Ａとの間隔（ｗ３）がゼロの場合もある。 When the concave-convex unit 3 is repeated, the interval (w3) between the convex portion 3A forming the concave-convex unit 3 and the adjacent convex portion 3A is preferably 1 to 1000 μm.
The interval (w3) between theconvex portion 3A and the adjacent convex portion 3A is the distance between the convex portion 3A and the adjacent convex portion 3A when viewed in a longitudinal section cut in the thickness direction along the winding circumferential direction of the pressure-sensitive adhesive sheet of the present invention. It means the length in the winding circumferential direction of the plane portion between the adjacent convex portions 3A.
If the interval (w3) is 1 μm or more, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2. The stress resulting from the generated distortion can be further relieved, and the occurrence of floating can be further prevented. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if the thickness is 1000 μm or less, sufficient adhesiveness can be ensured between the component 20 (30) for the flexible image display device and the adhesive surface 2, which is preferable.
From this point of view, the distance (w3) between theconvex portion 3A constituting the concave-convex unit 3 and the adjacent convex portion 3A is more preferably 2 μm or more, further preferably 5 μm or more, 10 μm or more, and 30 μm or more. is particularly preferred. On the other hand, it is more preferably 900 μm or less, even more preferably 800 μm or less, and particularly preferably 700 μm or less, 500 μm or less, or 200 μm or less.
In addition, as shown in FIG. 5(D), the interval (w3) between adjacentconvex portions 3A may be zero.
凸部３Ａと隣接する凸部３Ａとの間隔（ｗ３）とは、本発明粘着シートを巻き周方向とする方向に沿って肉厚方向に切断した縦断面に見た際に、凸部３Ａと隣接する凸部３Ａとの間の平面部の巻き周方向長さの意味である。
当該間隔（ｗ３）が１μｍ以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、１０００μｍ以下であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な粘着性が確保できるため好ましい。
かかる観点から、前記凹凸単位３を構成する凸部３Ａと隣接する凸部３Ａとの間隔（ｗ３）は２μｍ以上であるのがより好ましく、５μｍ以上であるのがさらに好ましく、１０μｍ以上、３０μｍ以上であるのが特に好ましい。他方、９００μｍ以下であるのがより好ましく、８００μｍ以下であるのがさらに好ましく、７００μｍ以下、５００μｍ以下、２００μｍ以下であるのが特に好ましい。
なお、図５（Ｄ）のように、隣接する凸部３Ａとの間隔（ｗ３）がゼロの場合もある。 When the concave-
The interval (w3) between the
If the interval (w3) is 1 μm or more, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2. The stress resulting from the generated distortion can be further relieved, and the occurrence of floating can be further prevented. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if the thickness is 1000 μm or less, sufficient adhesiveness can be ensured between the component 20 (30) for the flexible image display device and the adhesive surface 2, which is preferable.
From this point of view, the distance (w3) between the
In addition, as shown in FIG. 5(D), the interval (w3) between adjacent
前記凹凸単位３を構成する凸部３Ａの頂面幅（ｗ４）は、１～１０００μｍであるのが好ましい。
凸部３Ａの頂面幅（ｗ４）とは、本発明粘着シートを巻き周方向とする方向に沿って肉厚方向に切断した縦断面に見た際に、凸部頂上部の平面部の巻き周方向長さの意味である。
凸部３Ａの頂面幅（ｗ４）が１μｍ以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、１０００μｍ以下であれば、巻き取った際又は伸縮時に生じる歪、応力を緩和することができる。
かかる観点から、凸部３Ａの頂面幅（ｗ４）は２μｍ以上であるのがより好ましく、５μｍ以上であるのがさらに好ましく、１０μｍ以上であるのが特に好ましい。他方、９００μｍ以下であるのがより好ましく、８００μｍ以下であるのがさらに好ましく、７００μｍ以下であるのが特に好ましい。
なお、図５（Ｃ）のように、凸部３Ａの頂面幅（ｗ４）がゼロの場合もある。 It is preferable that the top surface width (w4) of theconvex portion 3A constituting the concave-convex unit 3 is 1 to 1000 μm.
The top surface width (w4) of theconvex portion 3A is the winding width of the flat portion of the top portion of the convex portion when viewed in a longitudinal section cut in the thickness direction along the winding circumferential direction of the pressure-sensitive adhesive sheet of the present invention. It means circumferential length.
If the top surface width (w4) of theconvex portion 3A is 1 μm or more, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2, so that the winding and unwinding can be performed. It is possible to further reduce the stress derived from the strain caused by the winding length difference, and to further prevent the occurrence of floating. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if the thickness is 1000 μm or less, strain and stress generated during winding or expansion and contraction can be alleviated.
From this point of view, the top surface width (w4) of theprojection 3A is more preferably 2 μm or more, even more preferably 5 μm or more, and particularly preferably 10 μm or more. On the other hand, it is more preferably 900 μm or less, even more preferably 800 μm or less, and particularly preferably 700 μm or less.
Note that, as shown in FIG. 5C, the top surface width (w4) of theconvex portion 3A may be zero.
凸部３Ａの頂面幅（ｗ４）とは、本発明粘着シートを巻き周方向とする方向に沿って肉厚方向に切断した縦断面に見た際に、凸部頂上部の平面部の巻き周方向長さの意味である。
凸部３Ａの頂面幅（ｗ４）が１μｍ以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、１０００μｍ以下であれば、巻き取った際又は伸縮時に生じる歪、応力を緩和することができる。
かかる観点から、凸部３Ａの頂面幅（ｗ４）は２μｍ以上であるのがより好ましく、５μｍ以上であるのがさらに好ましく、１０μｍ以上であるのが特に好ましい。他方、９００μｍ以下であるのがより好ましく、８００μｍ以下であるのがさらに好ましく、７００μｍ以下であるのが特に好ましい。
なお、図５（Ｃ）のように、凸部３Ａの頂面幅（ｗ４）がゼロの場合もある。 It is preferable that the top surface width (w4) of the
The top surface width (w4) of the
If the top surface width (w4) of the
From this point of view, the top surface width (w4) of the
Note that, as shown in FIG. 5C, the top surface width (w4) of the
本発明粘着シートの厚み（ｂ）は１０μｍ～１００μｍであるのが好ましい。
本発明粘着シートの厚み（ｂ）は、凹凸パターン４の厚みを含めた厚みである。
本発明粘着シートの厚み（ｂ）が１０μｍ以上であれば、所望の粘着力を発現することができ、１００μｍ以下であれば、巻き長差分（ΔＬ／ｂ）が小さくなり、それによる歪をより一層抑えることができる。
かかる観点から、本発明粘着シートの厚み（ｂ）は１５μｍ以上であるのがより好ましく、２０μｍ以上であるのがさらに好ましく、２５μｍ以上であるのが特に好ましい。他方、９０μｍ以下であるのがより好ましく、８５μｍ以下であるのがさらに好ましく、８０μｍ以下であるのが特に好ましい。 The thickness (b) of the adhesive sheet of the present invention is preferably 10 μm to 100 μm.
The thickness (b) of the pressure-sensitive adhesive sheet of the present invention is the thickness including the thickness of theuneven pattern 4 .
If the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is 10 μm or more, the desired adhesive strength can be expressed, and if it is 100 μm or less, the winding length difference (ΔL/b) becomes small, and the resulting distortion is reduced. can be suppressed further.
From this point of view, the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is more preferably 15 µm or more, still more preferably 20 µm or more, and particularly preferably 25 µm or more. On the other hand, it is more preferably 90 μm or less, even more preferably 85 μm or less, and particularly preferably 80 μm or less.
本発明粘着シートの厚み（ｂ）は、凹凸パターン４の厚みを含めた厚みである。
本発明粘着シートの厚み（ｂ）が１０μｍ以上であれば、所望の粘着力を発現することができ、１００μｍ以下であれば、巻き長差分（ΔＬ／ｂ）が小さくなり、それによる歪をより一層抑えることができる。
かかる観点から、本発明粘着シートの厚み（ｂ）は１５μｍ以上であるのがより好ましく、２０μｍ以上であるのがさらに好ましく、２５μｍ以上であるのが特に好ましい。他方、９０μｍ以下であるのがより好ましく、８５μｍ以下であるのがさらに好ましく、８０μｍ以下であるのが特に好ましい。 The thickness (b) of the adhesive sheet of the present invention is preferably 10 μm to 100 μm.
The thickness (b) of the pressure-sensitive adhesive sheet of the present invention is the thickness including the thickness of the
If the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is 10 μm or more, the desired adhesive strength can be expressed, and if it is 100 μm or less, the winding length difference (ΔL/b) becomes small, and the resulting distortion is reduced. can be suppressed further.
From this point of view, the thickness (b) of the pressure-sensitive adhesive sheet of the present invention is more preferably 15 µm or more, still more preferably 20 µm or more, and particularly preferably 25 µm or more. On the other hand, it is more preferably 90 μm or less, even more preferably 85 μm or less, and particularly preferably 80 μm or less.
本発明粘着シートにおいて、粘着シートの厚み（ｂ）に対する凸部の高さ（α）の比率（α／ｂ）は、０．０１以上１未満であるのが好ましい。
比率（α／ｂ）が上記下限値以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、上記上限値未満であれば、巻き取った際又は伸縮時に生じる歪、応力を緩和することができる。
かかる観点から、比率（α／ｂ）は０．０１５以上であるのがより好ましく、０．０１７以上であるのがさらに好ましく、０．０３以上、０．０５以上、０．１以上、０．１５以上であるのが特に好ましい。他方、０．９９８以下であるのがさらに好ましく、０．９９５以下、０．９９以下、０．９５以下、０．９０以下であるのが特に好ましい。 In the pressure-sensitive adhesive sheet of the present invention, the ratio (α/b) of the height (α) of the projections to the thickness (b) of the pressure-sensitive adhesive sheet is preferably 0.01 or more and less than 1.
If the ratio (α/b) is equal to or higher than the above lower limit, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2. The stress resulting from the strain caused by the length difference can be further alleviated, and the occurrence of floating can be further prevented. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if it is less than the above upper limit, strain and stress generated during winding or expansion and contraction can be alleviated.
From this point of view, the ratio (α/b) is more preferably 0.015 or more, still more preferably 0.017 or more, 0.03 or more, 0.05 or more, 0.1 or more, 0.01 or more. 15 or more is particularly preferred. On the other hand, it is more preferably 0.998 or less, particularly preferably 0.995 or less, 0.99 or less, 0.95 or less, or 0.90 or less.
比率（α／ｂ）が上記下限値以上であれば、フレキシブル画像表示装置用構成部材２０（３０）と粘着面２の間に十分な空間を設けることができるため、巻き取り及び巻き戻し時に巻き長差分により生じる歪みに由来する応力をより一層緩和することができ、浮きの発生をより一層防ぐことができる。また、伸縮時の応力を緩和することができ、剥がれをより一層防ぐことができる。他方、上記上限値未満であれば、巻き取った際又は伸縮時に生じる歪、応力を緩和することができる。
かかる観点から、比率（α／ｂ）は０．０１５以上であるのがより好ましく、０．０１７以上であるのがさらに好ましく、０．０３以上、０．０５以上、０．１以上、０．１５以上であるのが特に好ましい。他方、０．９９８以下であるのがさらに好ましく、０．９９５以下、０．９９以下、０．９５以下、０．９０以下であるのが特に好ましい。 In the pressure-sensitive adhesive sheet of the present invention, the ratio (α/b) of the height (α) of the projections to the thickness (b) of the pressure-sensitive adhesive sheet is preferably 0.01 or more and less than 1.
If the ratio (α/b) is equal to or higher than the above lower limit, a sufficient space can be provided between the flexible image display device component 20 (30) and the adhesive surface 2. The stress resulting from the strain caused by the length difference can be further alleviated, and the occurrence of floating can be further prevented. In addition, stress during expansion and contraction can be relaxed, and peeling can be further prevented. On the other hand, if it is less than the above upper limit, strain and stress generated during winding or expansion and contraction can be alleviated.
From this point of view, the ratio (α/b) is more preferably 0.015 or more, still more preferably 0.017 or more, 0.03 or more, 0.05 or more, 0.1 or more, 0.01 or more. 15 or more is particularly preferred. On the other hand, it is more preferably 0.998 or less, particularly preferably 0.995 or less, 0.99 or less, 0.95 or less, or 0.90 or less.
更に、凹凸パターンにおける凸部のアスペクト比、すなわち前記凹凸単位を構成する凸部の最大幅（ｗ１）に対する、凸部の高さ（α）に比率（α／ｗ１）は０．０３～０．３であることが好ましい。
凸部のアスペクト比（α／ｗ１）が０．０３以上であれば空間を維持することが可能であり、０．３以下であれば伸縮時の応力を緩和することができ、剥がれを一層防ぐことができることから好ましい。
よって、凸部のアスペクト比（α／ｗ１）は０．０３２以上であるのがさらに好ましく、中でも０．０３４以上、その中でも０．０３５以上であるのがさらに好ましい。他方、０．２９以下であるのがさらに好ましく、中でも０．２８以下、その中でも０．２６以下であるのがさらに好ましい。 Furthermore, the aspect ratio of the protrusions in the uneven pattern, that is, the ratio (α/w1) of the height (α) of the protrusions to the maximum width (w1) of the protrusions constituting the uneven unit is 0.03 to 0.03. 3 is preferred.
If the aspect ratio (α/w1) of the convex portion is 0.03 or more, it is possible to maintain the space, and if it is 0.3 or less, the stress during expansion and contraction can be relaxed, and peeling can be further prevented. It is preferable because it can
Therefore, the aspect ratio (α/w1) of the projections is more preferably 0.032 or more, more preferably 0.034 or more, and most preferably 0.035 or more. On the other hand, it is more preferably 0.29 or less, more preferably 0.28 or less, and even more preferably 0.26 or less.
凸部のアスペクト比（α／ｗ１）が０．０３以上であれば空間を維持することが可能であり、０．３以下であれば伸縮時の応力を緩和することができ、剥がれを一層防ぐことができることから好ましい。
よって、凸部のアスペクト比（α／ｗ１）は０．０３２以上であるのがさらに好ましく、中でも０．０３４以上、その中でも０．０３５以上であるのがさらに好ましい。他方、０．２９以下であるのがさらに好ましく、中でも０．２８以下、その中でも０．２６以下であるのがさらに好ましい。 Furthermore, the aspect ratio of the protrusions in the uneven pattern, that is, the ratio (α/w1) of the height (α) of the protrusions to the maximum width (w1) of the protrusions constituting the uneven unit is 0.03 to 0.03. 3 is preferred.
If the aspect ratio (α/w1) of the convex portion is 0.03 or more, it is possible to maintain the space, and if it is 0.3 or less, the stress during expansion and contraction can be relaxed, and peeling can be further prevented. It is preferable because it can
Therefore, the aspect ratio (α/w1) of the projections is more preferably 0.032 or more, more preferably 0.034 or more, and most preferably 0.035 or more. On the other hand, it is more preferably 0.29 or less, more preferably 0.28 or less, and even more preferably 0.26 or less.
凹凸パターン４は、粘着シートの粘着面全面に均等に形成することもできるし、曲率がかかる部分にのみ形成することもできる。
The concave-convex pattern 4 can be formed evenly over the entire adhesive surface of the adhesive sheet, or can be formed only on the portion where the curvature is applied.
＜本発明粘着剤組成物＞
本発明粘着シートは、（メタ）アクリル系重合体（Ａ）及び光重合開始剤（Ｂ）、必要に応じてさらに架橋剤（Ｃ）、さらにその他の成分を含有する光硬化性粘着剤組成物（「本発明粘着剤組成物」とも称する）から形成することができる。 <Pressure-sensitive adhesive composition of the present invention>
The pressure-sensitive adhesive sheet of the present invention is a photocurable pressure-sensitive adhesive composition containing a (meth)acrylic polymer (A) and a photopolymerization initiator (B), optionally a cross-linking agent (C), and other components. (also referred to as "the adhesive composition of the present invention").
本発明粘着シートは、（メタ）アクリル系重合体（Ａ）及び光重合開始剤（Ｂ）、必要に応じてさらに架橋剤（Ｃ）、さらにその他の成分を含有する光硬化性粘着剤組成物（「本発明粘着剤組成物」とも称する）から形成することができる。 <Pressure-sensitive adhesive composition of the present invention>
The pressure-sensitive adhesive sheet of the present invention is a photocurable pressure-sensitive adhesive composition containing a (meth)acrylic polymer (A) and a photopolymerization initiator (B), optionally a cross-linking agent (C), and other components. (also referred to as "the adhesive composition of the present invention").
（(メタ)アクリル系重合体（Ａ））
本発明粘着剤組成物において、(メタ)アクリル系重合体（Ａ）を含有し、とりわけ主成分樹脂として含有するものである。
すなわち、(メタ)アクリル系重合体（Ａ）は、本発明粘着剤組成物を構成する不揮発成分の中で最も質量割合が高い成分である。この際、本発明粘着剤組成物を構成する不揮発成分のうち、(メタ)アクリル系重合体（Ａ）の質量割合は５０質量％以上、中でも７０質量％以上、その中でも８０質量％以上、その中でも９０質量％以上であってもよい。 ((Meth) acrylic polymer (A))
The pressure-sensitive adhesive composition of the present invention contains a (meth)acrylic polymer (A), especially as a main component resin.
That is, the (meth)acrylic polymer (A) is the component having the highest mass ratio among the non-volatile components constituting the pressure-sensitive adhesive composition of the present invention. At this time, among the non-volatile components constituting the pressure-sensitive adhesive composition of the present invention, the (meth)acrylic polymer (A) has a mass ratio of 50% by mass or more, especially 70% by mass or more, especially 80% by mass or more. Above all, it may be 90% by mass or more.
本発明粘着剤組成物において、(メタ)アクリル系重合体（Ａ）を含有し、とりわけ主成分樹脂として含有するものである。
すなわち、(メタ)アクリル系重合体（Ａ）は、本発明粘着剤組成物を構成する不揮発成分の中で最も質量割合が高い成分である。この際、本発明粘着剤組成物を構成する不揮発成分のうち、(メタ)アクリル系重合体（Ａ）の質量割合は５０質量％以上、中でも７０質量％以上、その中でも８０質量％以上、その中でも９０質量％以上であってもよい。 ((Meth) acrylic polymer (A))
The pressure-sensitive adhesive composition of the present invention contains a (meth)acrylic polymer (A), especially as a main component resin.
That is, the (meth)acrylic polymer (A) is the component having the highest mass ratio among the non-volatile components constituting the pressure-sensitive adhesive composition of the present invention. At this time, among the non-volatile components constituting the pressure-sensitive adhesive composition of the present invention, the (meth)acrylic polymer (A) has a mass ratio of 50% by mass or more, especially 70% by mass or more, especially 80% by mass or more. Above all, it may be 90% by mass or more.
前記（メタ）アクリル系重合体（Ａ）としては、次の式１（式中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は炭素原子数４～１８の直鎖もしくは分岐状のアルキル基または脂環式炭化水素を表す。）で示される化合物由来の構造単位を含むものであり、当該モノマー成分を５０質量％以上含む重合成分を重合したものが好ましい。
As the (meth)acrylic polymer (A), the following formula 1 (wherein R 1 represents a hydrogen atom or a methyl group and R 2 represents a linear or branched alkyl having 4 to 18 carbon atoms group or an alicyclic hydrocarbon), and is preferably obtained by polymerizing a polymer component containing 50% by mass or more of the monomer component.
中でも、（メタ）アクリル系重合体（Ａ）は、前記モノマー成分を重合成分として５５質量％以上含み重合したものがさらに好ましく、その中でも６０質量％以上含み重合したものが特に好ましい。
Above all, the (meth)acrylic polymer (A) is more preferably polymerized to contain 55% by mass or more of the monomer component as a polymerization component, and particularly preferably polymerized to contain 60% by mass or more.
なお、本発明において、「（メタ）アクリル」とは、アクリル及びメタクリルを、「（メタ）アクリロイル」とは、アクリロイル及びメタクリロイルを、「（メタ）アクリレート」とはアクリレート及びメタクリレートをそれぞれ包括する意味であり、「（共）重合体」とは、重合体及び共重合体を包括する意味である。
In the present invention, "(meth)acrylic" means acrylic and methacrylic, "(meth)acryloyl" means acryloyl and methacryloyl, and "(meth)acrylate" means acrylate and methacrylate, respectively. and "(co)polymer" is meant to include polymers and copolymers.
前記式１で表されるモノマーとしては、例えばｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリート、イソオクチル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｔ－ブチルシクロヘキシル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、３，５，５－トリメチルシクロヘキサン（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート等を挙げることができる。これらは１種又は２種以上を組み合わせて使用してもよい。前記の中でも、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ラウリル（メタ）アクリレートの何れか１種以上を含むことが特に好ましい。
Examples of the monomer represented by Formula 1 include n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl ( meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate , tetradecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, isobornyl (meth)acrylate, 3,5,5-trimethylcyclohexane (meth)acrylate, dicyclopentanyl ( meth)acrylate, dicyclopentenyl (meth)acrylate and the like can be mentioned. These may be used singly or in combination of two or more. Among them, one or more of butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate and lauryl (meth)acrylate is particularly preferable.
前記（メタ）アクリル系重合体（Ａ）は、前記モノマー成分以外の「他の共重合性モノマー」を共重合成分として有する共重合体であるのが好ましい。
The (meth)acrylic polymer (A) is preferably a copolymer having "another copolymerizable monomer" other than the monomer component as a copolymerization component.
前記「他の共重合性モノマー」は、（メタ）アクリル系重合体（Ａ）中に、１～３０質量％含むことが好ましく、中でも２質量％以上或いは２５質量％以下の割合で含まれることがより好ましい。
The above-mentioned "other copolymerizable monomer" is preferably contained in the (meth)acrylic polymer (A) in an amount of 1 to 30% by mass, and is contained in a proportion of 2% by mass or more or 25% by mass or less. is more preferred.
当該「他の共重合性モノマー」としては、例えば（ａ）カルボキシル基含有モノマー（以下「共重合性モノマーａ１」とも称する。）、（ｂ）水酸基含有モノマー（以下「共重合性モノマーａ２」とも称する。）、（ｃ）アミノ基含有モノマー（以下「共重合性モノマーａ３」とも称する。）、（ｄ）エポキシ基含有モノマー（以下「共重合性モノマーａ４」とも称する。）、（ｅ）アミド基含有モノマー（以下「共重合性モノマーａ５」とも称する。）、（ｆ）ビニルモノマー（以下「共重合性モノマーａ６」とも称する。）、（ｇ）アルキル基の炭素数が１～３の（メタ）アクリレートモノマー（以下「共重合性モノマーａ７」とも称する。）、（ｈ）マクロモノマー（以下「共重合性モノマーａ８」とも称する。）、（ｉ）芳香族含有モノマー（以下「共重合性モノマーａ９」と称する）や、（ｊ）その他官能基含有モノマー（以下「共重合性モノマーａ１０」）を挙げることができる。上記の中でも、（ａ）カルボキシル基含有モノマーや、（ｂ）水酸基含有モノマー、（ｈ）マクロモノマーを含有することが好ましい。これらは１種又は２種以上を組み合わせてもよい。
Examples of the "other copolymerizable monomer" include (a) a carboxyl group-containing monomer (hereinafter also referred to as "copolymerizable monomer a1"), (b) a hydroxyl group-containing monomer (hereinafter also referred to as "copolymerizable monomer a2"). ), (c) amino group-containing monomer (hereinafter also referred to as "copolymerizable monomer a3"), (d) epoxy group-containing monomer (hereinafter also referred to as "copolymerizable monomer a4"), (e) amide Group-containing monomer (hereinafter also referred to as "copolymerizable monomer a5"), (f) vinyl monomer (hereinafter also referred to as "copolymerizable monomer a6"), (g) alkyl group having 1 to 3 carbon atoms ( meth) acrylate monomer (hereinafter also referred to as “copolymerizable monomer a7”), (h) macromonomer (hereinafter also referred to as “copolymerizable monomer a8”), (i) aromatic-containing monomer (hereinafter also referred to as “copolymerizable (hereinafter referred to as "monomer a9") and (j) other functional group-containing monomers (hereinafter referred to as "copolymerizable monomer a10"). Among the above, it is preferable to contain (a) a carboxyl group-containing monomer, (b) a hydroxyl group-containing monomer, and (h) a macromonomer. These may be used alone or in combination of two or more.
前記共重合性モノマーａ１としては、例えば（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシプロピル（メタ）アクリレート、カルボキシブチル（メタ）アクリレート、ω－カルボキシポリカプロラクトンモノ（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシプロピルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシプロピルフタル酸、２－（メタ）アクリロイルオキシエチルマレイン酸、２－（メタ）アクリロイルオキシプロピルマレイン酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－（メタ）アクリロイルオキシプロピルコハク酸、クロトン酸、フマル酸、マレイン酸、イタコン酸を挙げることができる。これらは１種又は２種以上を組み合わせてもよい。
Examples of the copolymerizable monomer a1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypropyl (meth)acrylate, carboxybutyl (meth)acrylate, ω-carboxypolycaprolactone mono(meth)acrylate, 2- (Meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxypropyl hexahydrophthalate, 2-(meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxypropyl phthalate, 2-(meth) ) acryloyloxyethyl maleate, 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxypropyl succinate, crotonic acid, fumaric acid, maleic acid, itacon Mention may be made of acids. These may be used alone or in combination of two or more.
前記共重合性モノマーａ２としては、例えば２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ－１－メチルエチルアクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート、ポリエチレングリコールポリプロピレングリコールモノ(メタ)アクリレート、ポリエチレングリコールポリブチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールポリブチレングリコールモノ(メタ)アクリレート、ヒドロキシフェニル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類を挙げることができる。これらは１種又は２種以上を組み合わせてもよい。
Examples of the copolymerizable monomer a2 include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol Hydroxyalkyl (meth)acrylates such as polybutylene glycol mono(meth)acrylate, polypropylene glycol polybutylene glycol mono(meth)acrylate and hydroxyphenyl(meth)acrylate can be mentioned. These may be used alone or in combination of two or more.
前記共重合性モノマーａ８としてのマクロモノマーは、末端の官能基と高分子量骨格成分とを有する高分子単量体である。
前記「他の共重合性モノマー」が共重合性モノマーａ８である場合、前記（メタ）アクリル系重合体（Ａ）は、マクロモノマー由来の構造単位を含む共重合体である。 The macromonomer as the copolymerizable monomer a8 is a macromonomer having a terminal functional group and a high-molecular-weight skeleton component.
When the "other copolymerizable monomer" is the copolymerizable monomer a8, the (meth)acrylic polymer (A) is a copolymer containing a macromonomer-derived structural unit.
前記「他の共重合性モノマー」が共重合性モノマーａ８である場合、前記（メタ）アクリル系重合体（Ａ）は、マクロモノマー由来の構造単位を含む共重合体である。 The macromonomer as the copolymerizable monomer a8 is a macromonomer having a terminal functional group and a high-molecular-weight skeleton component.
When the "other copolymerizable monomer" is the copolymerizable monomer a8, the (meth)acrylic polymer (A) is a copolymer containing a macromonomer-derived structural unit.
本樹脂組成物においては、前記マクロモノマーとしては、炭素数１～３の直鎖もしくは分岐状のアルキル基を持つ（メタ）アクリレートが共重合されたマクロモノマーであることで、加工性や保管安定性を向上させることができるから良好である。
かかるマクロモノマーの数平均分子量としては、好ましくは１０００～１００００、特に好ましくは１５００以上或いは５０００以下、更に好ましくは２０００以上或いは４０００以下である。 In the present resin composition, the macromonomer is a macromonomer obtained by copolymerizing a (meth)acrylate having a linear or branched alkyl group having 1 to 3 carbon atoms. It is good because it can improve the properties.
The number average molecular weight of such a macromonomer is preferably 1,000 to 10,000, particularly preferably 1,500 or more or 5,000 or less, and still more preferably 2,000 or more or 4,000 or less.
かかるマクロモノマーの数平均分子量としては、好ましくは１０００～１００００、特に好ましくは１５００以上或いは５０００以下、更に好ましくは２０００以上或いは４０００以下である。 In the present resin composition, the macromonomer is a macromonomer obtained by copolymerizing a (meth)acrylate having a linear or branched alkyl group having 1 to 3 carbon atoms. It is good because it can improve the properties.
The number average molecular weight of such a macromonomer is preferably 1,000 to 10,000, particularly preferably 1,500 or more or 5,000 or less, and still more preferably 2,000 or more or 4,000 or less.
特に本樹脂組成物においては、（メタ）アクリル系重合体（Ａ）におけるマクロモノマーの共重合割合が３０質量％以下であることがホットメルト時の流動性付与の点で好ましく、より好ましくは２質量％以上或いは１５質量％以下、さらに好ましくは３質量％以上或いは１０質量％以下、とくに好ましくは４質量％以上或いは７質量％以下である。
In particular, in the present resin composition, the copolymerization ratio of the macromonomer in the (meth)acrylic polymer (A) is preferably 30% by mass or less in terms of imparting fluidity during hot-melt, more preferably 2 % by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less, particularly preferably 4% by mass or more and 7% by mass or less.
前記（メタ）アクリル系重合体（Ａ）は、金属腐食防止性及び耐湿熱白化性などの観点から、前記「共重合性モノマーａ１」を含まない又は実質的に含まないものであるのが好ましい。
なお、「共重合性モノマーａ１を含まない又は実質的に含まない」とは、完全に含まない場合のみならず、（メタ）アクリル酸エステル（共）重合体中に、共重合性モノマーａ１が０．５質量％未満、好ましくは、０．１質量％未満で含むものを許容する意である。 The (meth)acrylic polymer (A) preferably does not contain or substantially does not contain the "copolymerizable monomer a1" from the viewpoint of metal corrosion resistance and wet heat whitening resistance. .
In addition, "does not contain or substantially does not contain copolymerizable monomer a1" means not only the case where it does not contain completely, but also the case where copolymerizable monomer a1 is contained in the (meth)acrylic acid ester (co)polymer. It is intended to allow a content of less than 0.5% by mass, preferably less than 0.1% by mass.
なお、「共重合性モノマーａ１を含まない又は実質的に含まない」とは、完全に含まない場合のみならず、（メタ）アクリル酸エステル（共）重合体中に、共重合性モノマーａ１が０．５質量％未満、好ましくは、０．１質量％未満で含むものを許容する意である。 The (meth)acrylic polymer (A) preferably does not contain or substantially does not contain the "copolymerizable monomer a1" from the viewpoint of metal corrosion resistance and wet heat whitening resistance. .
In addition, "does not contain or substantially does not contain copolymerizable monomer a1" means not only the case where it does not contain completely, but also the case where copolymerizable monomer a1 is contained in the (meth)acrylic acid ester (co)polymer. It is intended to allow a content of less than 0.5% by mass, preferably less than 0.1% by mass.
（メタ）アクリル系重合体（Ａ）のガラス転移温度は－７０～０℃であるのが好ましい。
The (meth)acrylic polymer (A) preferably has a glass transition temperature of -70 to 0°C.
なお、共重合体成分のガラス転移温度とは、当該共重合体各成分のホモポリマーから得られるポリマーのガラス転移温度と構成比率から、Ｆｏｘの計算式によって算出される値を意味する。
Ｆｏｘの計算式とは、以下の式により求められる計算値であり、ポリマーハンドブック〔ＰｏｌｙｍｅｒＨａｎｄＢｏｏｋ，Ｊ．Ｂｒａｎｄｒｕｐ，Ｉｎｔｅｒｓｃｉｅｎｃｅ，１９８９〕に記載されている値を用いて求めることができる。
１／（２７３＋Ｔｇ）＝Σ（Ｗｉ／（２７３＋Ｔｇｉ））
［式中、Ｗｉはモノマーｉの重量分率、ＴｇｉはモノマーｉのホモポリマーのＴｇ（℃）を示す。］ The glass transition temperature of the copolymer component means a value calculated by the Fox formula from the glass transition temperature of the polymer obtained from the homopolymer of each component of the copolymer and the composition ratio.
The Fox calculation formula is a calculated value obtained by the following formula, which is described in Polymer Handbook [Polymer Handbook, J. Am. Brandrup, Interscience, 1989].
1/(273+Tg)=Σ(Wi/(273+Tgi))
[In the formula, Wi is the weight fraction of the monomer i, and Tgi is the Tg (° C.) of the homopolymer of the monomer i. ]
Ｆｏｘの計算式とは、以下の式により求められる計算値であり、ポリマーハンドブック〔ＰｏｌｙｍｅｒＨａｎｄＢｏｏｋ，Ｊ．Ｂｒａｎｄｒｕｐ，Ｉｎｔｅｒｓｃｉｅｎｃｅ，１９８９〕に記載されている値を用いて求めることができる。
１／（２７３＋Ｔｇ）＝Σ（Ｗｉ／（２７３＋Ｔｇｉ））
［式中、Ｗｉはモノマーｉの重量分率、ＴｇｉはモノマーｉのホモポリマーのＴｇ（℃）を示す。］ The glass transition temperature of the copolymer component means a value calculated by the Fox formula from the glass transition temperature of the polymer obtained from the homopolymer of each component of the copolymer and the composition ratio.
The Fox calculation formula is a calculated value obtained by the following formula, which is described in Polymer Handbook [Polymer Handbook, J. Am. Brandrup, Interscience, 1989].
1/(273+Tg)=Σ(Wi/(273+Tgi))
[In the formula, Wi is the weight fraction of the monomer i, and Tgi is the Tg (° C.) of the homopolymer of the monomer i. ]
上記（メタ）アクリル系重合体（Ａ）を得るに際しては、（メタ）アクリル系重合体（Ａ）が有する（メタ）アクリル酸エステル由来の繰り返し単位のうち、少なくとも１つの繰り返し単位のガラス転移温度は－７０～０℃であるのが好ましい。
When obtaining the (meth)acrylic polymer (A), the glass transition temperature of at least one of the (meth)acrylic acid ester-derived repeating units of the (meth)acrylic polymer (A) is preferably -70 to 0°C.
また、（メタ）アクリル系重合体（Ａ）が有する（メタ）アクリル酸エステル由来の繰り返し単位のうち、少なくとも１つの繰り返し単位のガラス転移温度が２０～１２０℃である場合には、優れた加工性や保管安定性を保持できる為好ましい。具体的には、本発明粘着シートのホットメルト温度に影響するため、このガラス転移温度（Ｔｇ）は３０℃～１２０℃であるのが好ましく、中でも４０℃以上或いは１１０℃以下、その中でも５０℃以上或いは１００℃以下であるのがさらに好ましい。
このようなガラス転移温度（Ｔｇ）を有する繰り返し単位があれば、分子量を調整することにより、優れた加工性や保管安定性を保持できると共に、５０℃以上でホットメルトするように調整することができる。 Further, when the glass transition temperature of at least one of the repeating units derived from the (meth)acrylic acid ester of the (meth)acrylic polymer (A) is 20 to 120° C., excellent processing is achieved. It is preferable because it can maintain the properties and storage stability. Specifically, the glass transition temperature (Tg) is preferably 30° C. to 120° C., especially 40° C. or higher or 110° C. or lower, especially 50° C., because it affects the hot-melt temperature of the pressure-sensitive adhesive sheet of the present invention. It is more preferable that the temperature is 100° C. or higher or 100° C. or lower.
If there is a repeating unit having such a glass transition temperature (Tg), it is possible to maintain excellent workability and storage stability by adjusting the molecular weight, and to adjust it so that it hot melts at 50 ° C. or higher. can.
このようなガラス転移温度（Ｔｇ）を有する繰り返し単位があれば、分子量を調整することにより、優れた加工性や保管安定性を保持できると共に、５０℃以上でホットメルトするように調整することができる。 Further, when the glass transition temperature of at least one of the repeating units derived from the (meth)acrylic acid ester of the (meth)acrylic polymer (A) is 20 to 120° C., excellent processing is achieved. It is preferable because it can maintain the properties and storage stability. Specifically, the glass transition temperature (Tg) is preferably 30° C. to 120° C., especially 40° C. or higher or 110° C. or lower, especially 50° C., because it affects the hot-melt temperature of the pressure-sensitive adhesive sheet of the present invention. It is more preferable that the temperature is 100° C. or higher or 100° C. or lower.
If there is a repeating unit having such a glass transition temperature (Tg), it is possible to maintain excellent workability and storage stability by adjusting the molecular weight, and to adjust it so that it hot melts at 50 ° C. or higher. can.
（重合開始剤（Ｂ））
重合開始剤（Ｂ）は、本発明粘着シートに活性エネルギー線硬化性を付与するものであり、活性エネルギー線によってラジカルを発生する化合物であればよい。
重合開始剤（Ｂ）は、ラジカル発生機構によって大きく２つに分類され、重合開始剤自身の単結合を開裂分解してラジカルを発生させることができる開裂型光開始剤と、励起した開始剤と系中の水素供与体とが励起錯体を形成し、水素供与体の水素を転移させることができる水素引抜型光開始剤と、に大別される。
なお、（メタ）アクリル系重合体（Ａ）が、例えば、ベンゾフェノン構造等のように、活性エネルギー線照射により励起し、その励起状態において、系中の水素ラジカルを引き抜くことができる構造を有する場合や、活性エネルギー線として電子線を用いる場合は、必ずしも重合開始剤（Ｂ）を含む必要はない。 (Polymerization initiator (B))
The polymerization initiator (B) imparts active energy ray curability to the pressure-sensitive adhesive sheet of the present invention, and may be any compound that generates radicals by means of active energy rays.
The polymerization initiator (B) is roughly classified into two groups according to the mechanism of radical generation: a cleavage-type photoinitiator capable of cleaving and decomposing a single bond of the polymerization initiator itself to generate radicals, and an excited initiator. and a hydrogen abstraction type photoinitiator capable of forming an exciplex with a hydrogen donor in the system and transferring hydrogen of the hydrogen donor.
When the (meth)acrylic polymer (A) has a structure, such as a benzophenone structure, which is excited by active energy ray irradiation and can extract hydrogen radicals in the system in the excited state. Alternatively, when an electron beam is used as the active energy ray, the polymerization initiator (B) is not necessarily included.
重合開始剤（Ｂ）は、本発明粘着シートに活性エネルギー線硬化性を付与するものであり、活性エネルギー線によってラジカルを発生する化合物であればよい。
重合開始剤（Ｂ）は、ラジカル発生機構によって大きく２つに分類され、重合開始剤自身の単結合を開裂分解してラジカルを発生させることができる開裂型光開始剤と、励起した開始剤と系中の水素供与体とが励起錯体を形成し、水素供与体の水素を転移させることができる水素引抜型光開始剤と、に大別される。
なお、（メタ）アクリル系重合体（Ａ）が、例えば、ベンゾフェノン構造等のように、活性エネルギー線照射により励起し、その励起状態において、系中の水素ラジカルを引き抜くことができる構造を有する場合や、活性エネルギー線として電子線を用いる場合は、必ずしも重合開始剤（Ｂ）を含む必要はない。 (Polymerization initiator (B))
The polymerization initiator (B) imparts active energy ray curability to the pressure-sensitive adhesive sheet of the present invention, and may be any compound that generates radicals by means of active energy rays.
The polymerization initiator (B) is roughly classified into two groups according to the mechanism of radical generation: a cleavage-type photoinitiator capable of cleaving and decomposing a single bond of the polymerization initiator itself to generate radicals, and an excited initiator. and a hydrogen abstraction type photoinitiator capable of forming an exciplex with a hydrogen donor in the system and transferring hydrogen of the hydrogen donor.
When the (meth)acrylic polymer (A) has a structure, such as a benzophenone structure, which is excited by active energy ray irradiation and can extract hydrogen radicals in the system in the excited state. Alternatively, when an electron beam is used as the active energy ray, the polymerization initiator (B) is not necessarily included.
重合開始剤（Ｂ）としては、開裂型光開始剤及び水素引抜型光開始剤のいずれであってもよく、それぞれ単独に使用しても両者を混合して使用してもよく、さらに、各々について１種又は２種以上を併用してもよい。
光開始剤として水素引抜型光開始剤を用いた場合、（メタ）アクリル系重合体からも水素引抜反応を起こして、活性エネルギー線硬化性化合物のみならず（メタ）アクリル系重合体も架橋構造に取り込まれ、架橋点が多い架橋構造を形成することができる点で好ましい。
また、重合開始剤（Ｂ）として開裂型光開始剤を用いた場合、一度ラジカル発生させると分解して失活することから、硬化後に予期せぬ反応や劣化をおこす恐れがない点で好ましい。 The polymerization initiator (B) may be either a cleavage photoinitiator or a hydrogen abstraction photoinitiator, each of which may be used alone or a mixture of both may be used. may be used alone or in combination of two or more.
When a hydrogen abstraction type photoinitiator is used as a photoinitiator, a hydrogen abstraction reaction also occurs from the (meth)acrylic polymer, and not only the active energy ray-curable compound but also the (meth)acrylic polymer has a crosslinked structure. It is preferable in terms of being able to form a crosslinked structure with many crosslinked points.
In addition, when a cleavage type photoinitiator is used as the polymerization initiator (B), it is decomposed and deactivated once radicals are generated, which is preferable in that there is no risk of unexpected reaction or deterioration after curing.
光開始剤として水素引抜型光開始剤を用いた場合、（メタ）アクリル系重合体からも水素引抜反応を起こして、活性エネルギー線硬化性化合物のみならず（メタ）アクリル系重合体も架橋構造に取り込まれ、架橋点が多い架橋構造を形成することができる点で好ましい。
また、重合開始剤（Ｂ）として開裂型光開始剤を用いた場合、一度ラジカル発生させると分解して失活することから、硬化後に予期せぬ反応や劣化をおこす恐れがない点で好ましい。 The polymerization initiator (B) may be either a cleavage photoinitiator or a hydrogen abstraction photoinitiator, each of which may be used alone or a mixture of both may be used. may be used alone or in combination of two or more.
When a hydrogen abstraction type photoinitiator is used as a photoinitiator, a hydrogen abstraction reaction also occurs from the (meth)acrylic polymer, and not only the active energy ray-curable compound but also the (meth)acrylic polymer has a crosslinked structure. It is preferable in terms of being able to form a crosslinked structure with many crosslinked points.
In addition, when a cleavage type photoinitiator is used as the polymerization initiator (B), it is decomposed and deactivated once radicals are generated, which is preferable in that there is no risk of unexpected reaction or deterioration after curing.
開裂型光開始剤としては、例えば２,２－ジメトキシ－１,２－ジフェニルエタン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－（４－（２－ヒドロキシエトキシ）フェニル）－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－ヒロドキシ－１－［４－｛４－（２－ヒドロキシ－２－メチル－プロピオニル）ベンジル｝フェニル］－２－メチル－プロパン－１－オン、オリゴ（２－ヒドロキシ－２－メチル－１－（４－（１－メチルビニル）フェニル）プロパノン）、フェニルグリオキシリック酸メチル、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－（ジメチルアミノ）－２－[（４－メチルフェニル）メチル]－１－[４－（４－モルホリニル）フェニル]－１－ブタノン、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、（２，４，６－トリメチルベンゾイル）エトキシフェニルホスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）２，４，４－トリメチルペンチルフォスフィンオキサイドや、それらの誘導体などを挙げることができる。
Examples of cleavage-type photoinitiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one. , 1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2- Methyl-propionyl)benzyl}phenyl]-2-methyl-propan-1-one, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone), phenylglyoxylic acid methyl, 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)-phenyl Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, bis(2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine Fin oxides and their derivatives can be mentioned.
水素引抜型光開始剤としては、例えばベンゾフェノン、４－メチル－ベンゾフェノン、２，４，６－トリメチルベンゾフェノン、４－フェニルベンゾフェノン、３，３’－ジメチル－４－メトキシベンゾフェノン、４－（メタ）アクリロイルオキシベンゾフェノン、２－ベンゾイル安息香酸メチル、ベンゾイル蟻酸メチル、ビス（２－フェニル－２－オキソ酢酸）オキシビスエチレン、４－（１，３－アクリロイル－１，４，７，１０，１３－ペンタオキソトリデシル）ベンゾフェノン、チオキサントン、２－クロロチオキサントン、３－メチルチオキサントン、２，４－ジメチルチオキサントン、２－メチルアントラキノン、２－エチルアントラキノン、２－ｔｅｒｔ－ブチルアントラキノン、２－アミノアントラキノンやその誘導体などを挙げることができる。
Hydrogen abstraction photoinitiators include, for example, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(meth)acryloyl Oxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis(2-phenyl-2-oxoacetic acid)oxybisethylene, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxo tridecyl)benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone and derivatives thereof, etc. can be mentioned.
上記重合開始剤（Ｂ）の含有量は特に制限されるものではない。目安としては、（メタ）アクリル系重合体（Ａ）１００質量部に対して０．５質量部以上５質量部以下、中でも１質量部以上或いは４質量部以下、その中でも１．２質量部以上或いは３質量部以下の割合で含有するのが好ましい。
The content of the polymerization initiator (B) is not particularly limited. As a guideline, 0.5 parts by mass or more and 5 parts by mass or less, especially 1 part by mass or more or 4 parts by mass or less, and among them 1.2 parts by mass or more per 100 parts by mass of the (meth)acrylic polymer (A) Alternatively, it is preferably contained in a proportion of 3 parts by mass or less.
（架橋剤（Ｃ））
架橋剤（Ｃ）は、本発明粘着剤組成物に架橋構造を形成する化合物乃至組成物であり、２以上の架橋性官能基を有する化合物である。
本発明粘着剤組成物が、架橋剤（Ｃ）を含むことにより、本発明粘着剤組成物が架橋構造を形成し、本発明粘着シートに耐久性を付与することができる。
但し、（メタ）アクリル系重合体（Ａ）が重合開始剤（Ｂ）等の作用によって水素引抜反応を起こして、（メタ）アクリル系重合体（Ａ）内及び／又は（メタ）アクリル系重合体（Ａ）間で十分な架橋構造を形成することができる場合は、必ずしも架橋剤（Ｃ）を含む必要はない。 (Crosslinking agent (C))
The cross-linking agent (C) is a compound or composition that forms a cross-linked structure in the pressure-sensitive adhesive composition of the present invention, and is a compound having two or more cross-linkable functional groups.
By including the cross-linking agent (C) in the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive composition of the present invention forms a crosslinked structure, and durability can be imparted to the pressure-sensitive adhesive sheet of the present invention.
However, the (meth)acrylic polymer (A) causes a hydrogen abstraction reaction by the action of the polymerization initiator (B) or the like, and the (meth)acrylic polymer (A) and/or the (meth)acrylic polymer If a sufficient crosslinked structure can be formed between coalescence (A), the crosslinker (C) does not necessarily need to be included.
架橋剤（Ｃ）は、本発明粘着剤組成物に架橋構造を形成する化合物乃至組成物であり、２以上の架橋性官能基を有する化合物である。
本発明粘着剤組成物が、架橋剤（Ｃ）を含むことにより、本発明粘着剤組成物が架橋構造を形成し、本発明粘着シートに耐久性を付与することができる。
但し、（メタ）アクリル系重合体（Ａ）が重合開始剤（Ｂ）等の作用によって水素引抜反応を起こして、（メタ）アクリル系重合体（Ａ）内及び／又は（メタ）アクリル系重合体（Ａ）間で十分な架橋構造を形成することができる場合は、必ずしも架橋剤（Ｃ）を含む必要はない。 (Crosslinking agent (C))
The cross-linking agent (C) is a compound or composition that forms a cross-linked structure in the pressure-sensitive adhesive composition of the present invention, and is a compound having two or more cross-linkable functional groups.
By including the cross-linking agent (C) in the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive composition of the present invention forms a crosslinked structure, and durability can be imparted to the pressure-sensitive adhesive sheet of the present invention.
However, the (meth)acrylic polymer (A) causes a hydrogen abstraction reaction by the action of the polymerization initiator (B) or the like, and the (meth)acrylic polymer (A) and/or the (meth)acrylic polymer If a sufficient crosslinked structure can be formed between coalescence (A), the crosslinker (C) does not necessarily need to be included.
前記架橋性官能基としては、例えばイソシアネート基、エポキシ基、（メタ）アクリロイル基、チオイソシアネート基、１級もしくは２級のアミノ基及びチオール基を挙げることができる。これらは適当な保護基で保護されていてもよい。
Examples of the crosslinkable functional groups include isocyanate groups, epoxy groups, (meth)acryloyl groups, thioisocyanate groups, primary or secondary amino groups, and thiol groups. These may be protected with a suitable protecting group.
架橋剤に含まれる架橋性官能基の好ましい組み合わせとしては、エポキシ基のみ、イソシアネート基のみ、（メタ）アクリロイル基のみ、チオイソシアネート基のみ、チオール基のみ、１級もしくは２級のアミノ基のみ、エポキシ基と（メタ）アクリロイル基、イソシアネート基と（メタ）アクリロイル基の組み合わせを挙げることができる。
中でも、本発明粘着シートが活性エネルギー線を照射されることにより硬化する性質を担保する観点から、架橋剤（Ｃ）として、（メタ）アクリロイル基を２つ以上有する多官能（メタ）アクリレート（ｃ１）であるのが好ましい。 Preferred combinations of crosslinkable functional groups contained in the crosslinker include only epoxy groups, only isocyanate groups, only (meth)acryloyl groups, only thioisocyanate groups, only thiol groups, only primary or secondary amino groups, epoxy A combination of a group and a (meth)acryloyl group, and an isocyanate group and a (meth)acryloyl group can be mentioned.
Among them, from the viewpoint of securing the property that the pressure-sensitive adhesive sheet of the present invention is cured by being irradiated with an active energy ray, a polyfunctional (meth)acrylate (c1 ) is preferred.
中でも、本発明粘着シートが活性エネルギー線を照射されることにより硬化する性質を担保する観点から、架橋剤（Ｃ）として、（メタ）アクリロイル基を２つ以上有する多官能（メタ）アクリレート（ｃ１）であるのが好ましい。 Preferred combinations of crosslinkable functional groups contained in the crosslinker include only epoxy groups, only isocyanate groups, only (meth)acryloyl groups, only thioisocyanate groups, only thiol groups, only primary or secondary amino groups, epoxy A combination of a group and a (meth)acryloyl group, and an isocyanate group and a (meth)acryloyl group can be mentioned.
Among them, from the viewpoint of securing the property that the pressure-sensitive adhesive sheet of the present invention is cured by being irradiated with an active energy ray, a polyfunctional (meth)acrylate (c1 ) is preferred.
多官能（メタ）アクリレート（ｃ１）の含有質量は、(メタ)アクリル系重合体（Ａ）１００質量部に対して、０．５質量部以上であるのが好ましく、中でも１質量部以上、その中で１．５質量部以上である方がより好ましい。
上限値に関しては、適度な柔軟性を維持して折り曲げ時の被着体への追従性を担保する観点から、２０質量部以下であるのが好ましく、１５質量部以下であるのがより好ましく、１０質量部以下であるのがさらに好ましく、さらにその中でも５質量部以下、その中でも３質量部以下、特に２質量部以下である方が好ましい。 The content of the polyfunctional (meth)acrylate (c1) is preferably 0.5 parts by mass or more, preferably 1 part by mass or more, based on 100 parts by mass of the (meth)acrylic polymer (A). Among them, 1.5 parts by mass or more is more preferable.
Regarding the upper limit, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, from the viewpoint of maintaining appropriate flexibility and ensuring followability to the adherend when bent. It is more preferably 10 parts by mass or less, more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less.
上限値に関しては、適度な柔軟性を維持して折り曲げ時の被着体への追従性を担保する観点から、２０質量部以下であるのが好ましく、１５質量部以下であるのがより好ましく、１０質量部以下であるのがさらに好ましく、さらにその中でも５質量部以下、その中でも３質量部以下、特に２質量部以下である方が好ましい。 The content of the polyfunctional (meth)acrylate (c1) is preferably 0.5 parts by mass or more, preferably 1 part by mass or more, based on 100 parts by mass of the (meth)acrylic polymer (A). Among them, 1.5 parts by mass or more is more preferable.
Regarding the upper limit, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, from the viewpoint of maintaining appropriate flexibility and ensuring followability to the adherend when bent. It is more preferably 10 parts by mass or less, more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less.
多官能（メタ）アクリレート（ｃ１）としては、例えば１，４－ブタンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、グリセリングリシジルエーテルジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、トリシクロデカンジメタクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ビスフェノールＡポリエトキシジ（メタ）アクリレート、ビスフェノールＡポリプロポキシジ（メタ）アクリレート、ビスフェノールＦポリエトキシジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、ε－カプロラクトン変性トリス（２－ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、プロポキシ化ペンタエリスリトールトリ（メタ）アクリレート、エトキシ化ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、プロポキシ化ペンタエリスリトールテトラ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート、（トリス（アクリロキシエチル）イソシアヌレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、ヒドロキシビバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ヒドロキシビバリン酸ネオペングリコールのε－カプロラクトン付加物のジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート等の紫外線硬化型の多官能（メタ）アクリル系モノマーの他、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、ポリエーテル（メタ）アクリレート等の多官能（メタ）アクリル系オリゴマーを挙げることができる。中でも、プロポキシ化ペンタエリスリトールトリ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート、が好ましい。これらは１種又は２種以上を組み合わせて使用してもよい。
Polyfunctional (meth)acrylates (c1) include, for example, 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin glycidyl ether di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethacrylate, tricyclodecanedimethanol di(meth)acrylate, bisphenol A polyethoxydi(meth)acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ε-caprolactone modified tris (2-hydroxyethyl) isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate (Meth)acrylate, (tris(acryloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate) , neopentyl glycol di(meth)acrylate hydroxybivalate, di(meth)acrylate of ε-caprolactone adduct of neopentyl hydroxybivalate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri ( In addition to UV-curable polyfunctional (meth)acrylic monomers such as meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyether ( Polyfunctional (meth)acrylic oligomers such as meth)acrylates can be mentioned. Among them, propoxylated pentaerythritol tri(meth)acrylate and polytetramethylene glycol di(meth)acrylate are preferable. These may be used singly or in combination of two or more.
（単官能（メタ）アクリレート成分（Ｄ））
本発明粘着剤組成物は、さらに、（メタ）アクリロイル基を１つ有する単官能（メタ）アクリレート成分（Ｄ）を含んでいてもよい。単官能（メタ）アクリレート成分を含むことにより、硬化物の架橋点間分子量を大きくすることができるため、分子鎖の運動自由度が増し、本発明粘着シートを介して画像表示装置構成部材を貼り合わせた積層体を高温又は低温環境下で折り曲げた際に、本発明粘着剤組成物からなる本発明粘着シートはそれに追随して変形することができる。 (Monofunctional (meth)acrylate component (D))
The pressure-sensitive adhesive composition of the present invention may further contain a monofunctional (meth)acrylate component (D) having one (meth)acryloyl group. By including a monofunctional (meth)acrylate component, the molecular weight between cross-linking points of the cured product can be increased, so that the degree of freedom of movement of the molecular chains is increased, and the components constituting the image display device can be pasted via the pressure-sensitive adhesive sheet of the present invention. When the combined laminate is folded in a high-temperature or low-temperature environment, the pressure-sensitive adhesive sheet of the present invention made of the pressure-sensitive adhesive composition of the present invention can be deformed accordingly.
本発明粘着剤組成物は、さらに、（メタ）アクリロイル基を１つ有する単官能（メタ）アクリレート成分（Ｄ）を含んでいてもよい。単官能（メタ）アクリレート成分を含むことにより、硬化物の架橋点間分子量を大きくすることができるため、分子鎖の運動自由度が増し、本発明粘着シートを介して画像表示装置構成部材を貼り合わせた積層体を高温又は低温環境下で折り曲げた際に、本発明粘着剤組成物からなる本発明粘着シートはそれに追随して変形することができる。 (Monofunctional (meth)acrylate component (D))
The pressure-sensitive adhesive composition of the present invention may further contain a monofunctional (meth)acrylate component (D) having one (meth)acryloyl group. By including a monofunctional (meth)acrylate component, the molecular weight between cross-linking points of the cured product can be increased, so that the degree of freedom of movement of the molecular chains is increased, and the components constituting the image display device can be pasted via the pressure-sensitive adhesive sheet of the present invention. When the combined laminate is folded in a high-temperature or low-temperature environment, the pressure-sensitive adhesive sheet of the present invention made of the pressure-sensitive adhesive composition of the present invention can be deformed accordingly.
単官能（メタ）アクリレート成分（Ｄ）としては、例えばエチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、イソドデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ベへニル（メタ）アクリレート、シクロプロピル（メタ）アクリレート、シクロブチル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、シクロヘプチル（メタ）アクリレート、シクロオクチル（メタ）アクリレート、シクロノニル（メタ）アクリレート、シクロデシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、トリシクロデカンジメタノールアクリレート、エトキシ化－ｏ－フェニルフェノールアクリレート、２－ヒドロキシ－ｏ－フェニルフェノールプロピルアクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、フェノキシエチレングリコール（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、２－ヒドロキシ－ｏ－フェニルフェノールプロピルアクリレート、２－（メタ）アクリロイルオキシエチルコハク酸、２－（メタ）アクリロイルオキシエチルテトラヒドロフタル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシプロピルフタル酸、２－（メタ）アクリロイルオキシプロピルヒドロフタル酸、２－（メタ）アクリロイルオキシプロピルヘキサヒドロフタル酸等ベンジル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシエチレングリコール（メタ）アクリレート、２－ナフチル（メタ）アクリレート、９－アントラセニル（メタ）アクリレート、１－ピレニルメチル（メタ）アクリレート、ベンジル（メタ）アクリレート、トリシクロデカンジメタノールモノアクリレートモノカルボン酸、ジシクロペンタニルアクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、トリメチロールプロパンモノ（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、ペンタエリスリトールモノ（メタ）アクリレート、ジグリセリンモノ（メタ）アクリレート、ジトリメチロールプロパンモノ（メタ）アクリレート、ジペンタエリスリトールモノ（メタ）アクリレート、エトキシ化トリメチロールプロパンモノ（メタ）アクリレート、プロポキシ化トリメチロールプロパンモノ（メタ）アクリレート、エトキシ化グリセリンモノ（メタ）アクリレート、プロポキシ化グリセリンモノ（メタ）アクリレート、エトキシ化ペンタエリスリトールモノ（メタ）アクリレート、プロポキシ化ペンタエリスリトールモノ（メタ）アクリレート、エトキシ化ジトリメチロールプロパンモノ（メタ）アクリレート、プロポキシ化ジトリメチロールプロパンモノ（メタ）アクリレート、アルキレンオキサイド変性ジグリセリンモノ（メタ）アクリレート及びアルキレンオキサイド変性ジペンタエリスリトールモノ（メタ）アクリレート等の他、単官能ウレタン（メタ）アクリレート、単官能エポキシ（メタ）アクリレート、単官能ポリエステル（メタ）アクリレート等の単官能オリゴマー類を挙げることができる。これらは１種又は２種以上を組み合わせて使用してもよい。
Examples of the monofunctional (meth)acrylate component (D) include ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, Acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate Acrylate, dodecyl (meth)acrylate, isododecyl (meth)acrylate, tetradecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclobutyl ( meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, cyclononyl (meth)acrylate, cyclodecyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl ( meth)acrylate, adamantyl (meth)acrylate, tricyclodecanedimethanol acrylate, ethoxylated-o-phenylphenol acrylate, 2-hydroxy-o-phenylphenolpropyl acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate ) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, 2-hydroxy-o-phenylphenolpropyl acrylate , 2-(meth) acryloyloxyethyl succinate, 2-(meth) acryloyloxyethyl tetrahydrophthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxypropyl phthalate, 2- (meth)acryloyloxypropylhydrophthalic acid, 2-(meth)acryloyloxypropylhexahydrophthalic acid, etc. benzyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethylene glycol (meth)acrylate, 2-naphthyl (meth)acrylate, 9-anthracenyl (meth)acrylate, 1-pyrenylmethyl (meth)acrylate, benzyl (meth)acrylate, tricyclodecane dimethanol monoacrylate monocarboxylic acid, dicyclopentanyl acrylate, 2-hydroxy Ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane mono (meth)acrylate , glycerin mono(meth)acrylate, pentaerythritol mono(meth)acrylate, diglycerin mono(meth)acrylate, ditrimethylolpropane mono(meth)acrylate, dipentaerythritol mono(meth)acrylate, ethoxylated trimethylolpropane mono(meth)acrylate ) acrylate, propoxylated trimethylolpropane mono(meth)acrylate, ethoxylated glycerin mono(meth)acrylate, propoxylated glycerin mono(meth)acrylate, ethoxylated pentaerythritol mono(meth)acrylate, propoxylated pentaerythritol mono(meth)acrylate In addition to acrylates, ethoxylated ditrimethylolpropane mono(meth)acrylate, propoxylated ditrimethylolpropane mono(meth)acrylate, alkylene oxide-modified diglycerin mono(meth)acrylate and alkylene oxide-modified dipentaerythritol mono(meth)acrylate, Monofunctional oligomers such as monofunctional urethane (meth)acrylate, monofunctional epoxy (meth)acrylate and monofunctional polyester (meth)acrylate can be mentioned. These may be used singly or in combination of two or more.
単官能（メタ）アクリレート成分（Ｄ）を含む場合、多官能（メタ）アクリレート（ｃ１）と単官能（メタ）アクリレート成分（Ｄ）の含有質量比率は、多官能（メタ）アクリレート（ｃ１）：単官能（メタ）アクリレート（Ｄ）＝１：０．１～１：９であるのが好ましく、１：１～１：９であるのがより好ましく、１：２～１：９であるのがさらに好ましい。この範囲にあることで単官能（メタ）アクリレート成分が多すぎず、光に対する感度が落ちて生産性が低下するおそれもない。
When the monofunctional (meth)acrylate component (D) is included, the content ratio by mass of the polyfunctional (meth)acrylate (c1) and the monofunctional (meth)acrylate component (D) is the polyfunctional (meth)acrylate (c1): Monofunctional (meth)acrylate (D) is preferably 1:0.1 to 1:9, more preferably 1:1 to 1:9, and preferably 1:2 to 1:9. More preferred. Within this range, the amount of the monofunctional (meth)acrylate component is not too large, and there is no concern that the sensitivity to light will decrease and the productivity will decrease.
（その他の成分）
本発明粘着剤組成物に含まれる前記以外の「その他の成分」として、例えば、必要に応じて、シランカップリング剤や、粘着付与樹脂、可塑剤、酸化防止剤、光安定化剤、金属不活性化剤、老化防止剤、吸湿剤、重合禁止剤、紫外線吸収剤、防錆剤、無機粒子、増感剤、顔料などの各種の添加剤を適宜含有させることが可能である。これら添加剤の量は、典型的には、粘着シートの硬化に悪影響を与えないように、又は、粘着シートの物理的特性に悪影響を与えないように選択するのが好ましい。
また、必要に応じて、三級アミン系化合物、四級アンモニウム系化合物、ラウリル酸スズ化合物などの反応触媒を適宜含有してもよい。 (other ingredients)
"Other components" other than those described above contained in the pressure-sensitive adhesive composition of the present invention include, for example, silane coupling agents, tackifier resins, plasticizers, antioxidants, light stabilizers, metal inerts, if necessary. Various additives such as activators, antioxidants, hygroscopic agents, polymerization inhibitors, ultraviolet absorbers, rust preventives, inorganic particles, sensitizers and pigments can be incorporated as appropriate. The amounts of these additives are typically preferably selected so as not to adversely affect the curing of the adhesive sheet or adversely affect the physical properties of the adhesive sheet.
Moreover, if necessary, a reaction catalyst such as a tertiary amine compound, a quaternary ammonium compound, a tin laurate compound, or the like may be appropriately contained.
本発明粘着剤組成物に含まれる前記以外の「その他の成分」として、例えば、必要に応じて、シランカップリング剤や、粘着付与樹脂、可塑剤、酸化防止剤、光安定化剤、金属不活性化剤、老化防止剤、吸湿剤、重合禁止剤、紫外線吸収剤、防錆剤、無機粒子、増感剤、顔料などの各種の添加剤を適宜含有させることが可能である。これら添加剤の量は、典型的には、粘着シートの硬化に悪影響を与えないように、又は、粘着シートの物理的特性に悪影響を与えないように選択するのが好ましい。
また、必要に応じて、三級アミン系化合物、四級アンモニウム系化合物、ラウリル酸スズ化合物などの反応触媒を適宜含有してもよい。 (other ingredients)
"Other components" other than those described above contained in the pressure-sensitive adhesive composition of the present invention include, for example, silane coupling agents, tackifier resins, plasticizers, antioxidants, light stabilizers, metal inerts, if necessary. Various additives such as activators, antioxidants, hygroscopic agents, polymerization inhibitors, ultraviolet absorbers, rust preventives, inorganic particles, sensitizers and pigments can be incorporated as appropriate. The amounts of these additives are typically preferably selected so as not to adversely affect the curing of the adhesive sheet or adversely affect the physical properties of the adhesive sheet.
Moreover, if necessary, a reaction catalyst such as a tertiary amine compound, a quaternary ammonium compound, a tin laurate compound, or the like may be appropriately contained.
＜本発明粘着シートの製造方法＞
次に、本発明粘着シートの製造方法について説明する。ただし、以下の説明は、本発明粘着シートを製造する方法の一例であり、本発明粘着シートはかかる製造方法により製造されるものに限定されるものではない。 <Method for producing the pressure-sensitive adhesive sheet of the present invention>
Next, a method for producing the pressure-sensitive adhesive sheet of the present invention will be described. However, the following description is an example of the method for producing the pressure-sensitive adhesive sheet of the present invention, and the pressure-sensitive adhesive sheet of the present invention is not limited to those produced by such a production method.
次に、本発明粘着シートの製造方法について説明する。ただし、以下の説明は、本発明粘着シートを製造する方法の一例であり、本発明粘着シートはかかる製造方法により製造されるものに限定されるものではない。 <Method for producing the pressure-sensitive adhesive sheet of the present invention>
Next, a method for producing the pressure-sensitive adhesive sheet of the present invention will be described. However, the following description is an example of the method for producing the pressure-sensitive adhesive sheet of the present invention, and the pressure-sensitive adhesive sheet of the present invention is not limited to those produced by such a production method.
本発明粘着シートの作製においては、(メタ)アクリル系重合体（Ａ）のほか、好ましくは、光重合開始剤（Ｂ）、さらに好ましくは架橋剤（Ｃ）、さらに必要に応じて他の成分をそれぞれ所定量混合することにより、本発明粘着剤組成物を調製し、当該粘着剤組成物をシート状に成形し、必要に応じて硬化性化合物を架橋すなわち重合反応させて硬化させて、凹凸パターンを形成して、本発明粘着シートを作製すればよい。ただし、この方法に限定するものではない。
また、本発明粘着剤組成物をシート状に成形して、凹凸パターンを形成した後に硬化させて作製することもできる。 In the preparation of the pressure-sensitive adhesive sheet of the present invention, in addition to the (meth)acrylic polymer (A), preferably a photopolymerization initiator (B), more preferably a cross-linking agent (C), and optionally other components By mixing each predetermined amount, the pressure-sensitive adhesive composition of the present invention is prepared, the pressure-sensitive adhesive composition is formed into a sheet, and if necessary, the curable compound is crosslinked, that is, polymerized to be cured to form unevenness. A pattern may be formed to produce the pressure-sensitive adhesive sheet of the present invention. However, it is not limited to this method.
Alternatively, the pressure-sensitive adhesive composition of the present invention can be formed into a sheet, formed with an uneven pattern, and then cured.
また、本発明粘着剤組成物をシート状に成形して、凹凸パターンを形成した後に硬化させて作製することもできる。 In the preparation of the pressure-sensitive adhesive sheet of the present invention, in addition to the (meth)acrylic polymer (A), preferably a photopolymerization initiator (B), more preferably a cross-linking agent (C), and optionally other components By mixing each predetermined amount, the pressure-sensitive adhesive composition of the present invention is prepared, the pressure-sensitive adhesive composition is formed into a sheet, and if necessary, the curable compound is crosslinked, that is, polymerized to be cured to form unevenness. A pattern may be formed to produce the pressure-sensitive adhesive sheet of the present invention. However, it is not limited to this method.
Alternatively, the pressure-sensitive adhesive composition of the present invention can be formed into a sheet, formed with an uneven pattern, and then cured.
本発明粘着剤組成物を調製する際、上記原料を、温度調節可能な混練機（例えば、一軸押出機、二軸押出機、プラネタリーミキサー、二軸ミキサー、加圧ニーダー等）を用いて混練すればよい。
なお、種々の原料を混合する際、シランカップリング剤、酸化防止剤等の各種添加剤は、予め樹脂とともにブレンドしてから混練機に供給してもよいし、予め全ての材料を溶融混合してから供給してもよいし、添加剤のみを予め樹脂に濃縮したマスターバッチを作製し供給してもよい。 When preparing the pressure-sensitive adhesive composition of the present invention, the raw materials are kneaded using a temperature-controllable kneader (e.g., single-screw extruder, twin-screw extruder, planetary mixer, twin-screw mixer, pressure kneader, etc.). do it.
When mixing various raw materials, various additives such as silane coupling agents and antioxidants may be blended in advance with the resin and then supplied to the kneader, or all the materials may be melted and mixed in advance. Alternatively, a masterbatch in which only the additive is concentrated in the resin in advance may be prepared and supplied.
なお、種々の原料を混合する際、シランカップリング剤、酸化防止剤等の各種添加剤は、予め樹脂とともにブレンドしてから混練機に供給してもよいし、予め全ての材料を溶融混合してから供給してもよいし、添加剤のみを予め樹脂に濃縮したマスターバッチを作製し供給してもよい。 When preparing the pressure-sensitive adhesive composition of the present invention, the raw materials are kneaded using a temperature-controllable kneader (e.g., single-screw extruder, twin-screw extruder, planetary mixer, twin-screw mixer, pressure kneader, etc.). do it.
When mixing various raw materials, various additives such as silane coupling agents and antioxidants may be blended in advance with the resin and then supplied to the kneader, or all the materials may be melted and mixed in advance. Alternatively, a masterbatch in which only the additive is concentrated in the resin in advance may be prepared and supplied.
本発明粘着剤組成物をシート状に成形する方法としては、公知の方法、例えばウェットラミネーション法、ドライラミネート法、Ｔダイを用いる押出キャスト法、押出ラミネート法、カレンダー法やインフレーション法、射出成型、注液硬化法等を採用することができる。中でも、シートを製造する場合は、ウェットラミネーション法、押出キャスト法、押出ラミネート法が好適である。
Methods for forming the pressure-sensitive adhesive composition of the present invention into a sheet include known methods such as wet lamination, dry lamination, extrusion casting using a T-die, extrusion lamination, calendering, inflation, injection molding, An injection curing method or the like can be employed. Among them, the wet lamination method, the extrusion casting method, and the extrusion lamination method are suitable for producing a sheet.
（硬化方法）
シート状に成形された本発明粘着剤組成物若しくは粘着シートを硬化する場合、その硬化方法としては、熱および／又は活性エネルギー線を照射して硬化させることにより硬化物とする方法を挙げることができる。
例えば、シート状に成形された本発明粘着剤組成物若しくは粘着シートに対して、熱および／又は活性エネルギー線を照射することにより硬化させることができる。 (Curing method)
When curing the pressure-sensitive adhesive composition or pressure-sensitive adhesive sheet of the present invention molded into a sheet, examples of the curing method include a method of curing by irradiation with heat and/or active energy rays to obtain a cured product. can.
For example, the pressure-sensitive adhesive composition or pressure-sensitive adhesive sheet of the present invention molded into a sheet can be cured by irradiating heat and/or active energy rays.
シート状に成形された本発明粘着剤組成物若しくは粘着シートを硬化する場合、その硬化方法としては、熱および／又は活性エネルギー線を照射して硬化させることにより硬化物とする方法を挙げることができる。
例えば、シート状に成形された本発明粘着剤組成物若しくは粘着シートに対して、熱および／又は活性エネルギー線を照射することにより硬化させることができる。 (Curing method)
When curing the pressure-sensitive adhesive composition or pressure-sensitive adhesive sheet of the present invention molded into a sheet, examples of the curing method include a method of curing by irradiation with heat and/or active energy rays to obtain a cured product. can.
For example, the pressure-sensitive adhesive composition or pressure-sensitive adhesive sheet of the present invention molded into a sheet can be cured by irradiating heat and/or active energy rays.
ここで、照射する活性エネルギー線としては、α線、β線、γ線、中性子線、電子線などの電離性放射線、紫外線、可視光線などを挙げることができ、中でも光学装置構成部材へのダメージ抑制や反応制御の観点から紫外線が好適である。
また、活性エネルギー線の照射エネルギー、照射時間、照射方法などに関しては特に限定されず、開始剤を活性化させて（メタ）アクリレート成分を重合できればよい。 Here, the active energy rays to be irradiated include α rays, β rays, γ rays, ionizing radiation such as neutron rays and electron beams, ultraviolet rays, visible rays, and the like. Ultraviolet rays are preferable from the viewpoint of suppression and reaction control.
Moreover, the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as the initiator can be activated to polymerize the (meth)acrylate component.
また、活性エネルギー線の照射エネルギー、照射時間、照射方法などに関しては特に限定されず、開始剤を活性化させて（メタ）アクリレート成分を重合できればよい。 Here, the active energy rays to be irradiated include α rays, β rays, γ rays, ionizing radiation such as neutron rays and electron beams, ultraviolet rays, visible rays, and the like. Ultraviolet rays are preferable from the viewpoint of suppression and reaction control.
Moreover, the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as the initiator can be activated to polymerize the (meth)acrylate component.
（他の製造方法）
また、本発明粘着シートを形成するための粘着シートの別の実施態様として、本発明粘着剤組成物を適切な溶剤に溶解させ、各種コーティング手法を用いて実施することもできる。
コーティング手法を用いた場合、上記の活性エネルギー線照射硬化の他、熱硬化させることにより粘着シートを得ることもできる。 (Other manufacturing methods)
Moreover, as another embodiment of the pressure-sensitive adhesive sheet for forming the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive composition of the present invention can be dissolved in a suitable solvent, and various coating techniques can be used.
When a coating method is used, the pressure-sensitive adhesive sheet can also be obtained by thermal curing in addition to the active energy ray irradiation curing described above.
また、本発明粘着シートを形成するための粘着シートの別の実施態様として、本発明粘着剤組成物を適切な溶剤に溶解させ、各種コーティング手法を用いて実施することもできる。
コーティング手法を用いた場合、上記の活性エネルギー線照射硬化の他、熱硬化させることにより粘着シートを得ることもできる。 (Other manufacturing methods)
Moreover, as another embodiment of the pressure-sensitive adhesive sheet for forming the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive composition of the present invention can be dissolved in a suitable solvent, and various coating techniques can be used.
When a coating method is used, the pressure-sensitive adhesive sheet can also be obtained by thermal curing in addition to the active energy ray irradiation curing described above.
コーティングの場合、粘着シートの厚みは塗工厚みと塗工液の固形分濃度によって調整できる。
In the case of coating, the thickness of the adhesive sheet can be adjusted by the coating thickness and the solid content concentration of the coating liquid.
（凹凸パターンの形成方法）
前記凹凸パターン４は、粘着シートの粘着面に金型の凹凸面を押圧して、金型の凹凸構造を粘着シートの粘着面に転写することにより、形成することができる。そして、凹凸パターンが形成された本発明粘着シートが得られる。 (Method for forming uneven pattern)
Theuneven pattern 4 can be formed by pressing the uneven surface of a mold against the adhesive surface of the adhesive sheet to transfer the uneven structure of the mold to the adhesive surface of the adhesive sheet. Then, the pressure-sensitive adhesive sheet of the present invention on which an uneven pattern is formed is obtained.
前記凹凸パターン４は、粘着シートの粘着面に金型の凹凸面を押圧して、金型の凹凸構造を粘着シートの粘着面に転写することにより、形成することができる。そして、凹凸パターンが形成された本発明粘着シートが得られる。 (Method for forming uneven pattern)
The
前記金型は、平板状のものであっても、円柱状、円筒状のものであってもよい。
前記金型の材質は、金属、樹脂、ガラスなど任意である。 The mold may be flat, columnar, or cylindrical.
The material of the mold is arbitrary, such as metal, resin, and glass.
前記金型の材質は、金属、樹脂、ガラスなど任意である。 The mold may be flat, columnar, or cylindrical.
The material of the mold is arbitrary, such as metal, resin, and glass.
粘着シートの粘着面に金型の凹凸面を押圧する際、その圧力は０．００００１～１ＭＰａとするのが好ましく、中でも０．００００５ＭＰａ以上或いは０．９ＭＰａ以下、その中でも０．０００１ＭＰａ以上或いは０．８ＭＰａ以下とするのがさらに好ましい。
また、粘着シートの粘着面に金型の凹凸面を押圧した状態で１～５００秒の間静置するのが好ましく、中でも２秒以上或いは４００秒以下、その中でも３秒以上或いは３００秒以下の間静置するのがさらに好ましい。 When the uneven surface of the mold is pressed against the adhesive surface of the adhesive sheet, the pressure is preferably 0.00001 to 1 MPa, especially 0.00005 MPa or more or 0.9 MPa or less, among which 0.0001 MPa or more or 0.001 MPa or more. 8 MPa or less is more preferable.
In addition, it is preferable to leave the uneven surface of the mold pressed against the adhesive surface of the adhesive sheet for 1 to 500 seconds. It is more preferable to leave it still for a while.
また、粘着シートの粘着面に金型の凹凸面を押圧した状態で１～５００秒の間静置するのが好ましく、中でも２秒以上或いは４００秒以下、その中でも３秒以上或いは３００秒以下の間静置するのがさらに好ましい。 When the uneven surface of the mold is pressed against the adhesive surface of the adhesive sheet, the pressure is preferably 0.00001 to 1 MPa, especially 0.00005 MPa or more or 0.9 MPa or less, among which 0.0001 MPa or more or 0.001 MPa or more. 8 MPa or less is more preferable.
In addition, it is preferable to leave the uneven surface of the mold pressed against the adhesive surface of the adhesive sheet for 1 to 500 seconds. It is more preferable to leave it still for a while.
粘着シートの粘着面に金型の凹凸面を押圧する際、必要に応じて、金型を加熱するようにしてもよい。この際、加熱温度は、２０～１００℃とするのが好ましく、中でも３０℃以上或いは９０℃以下、その中でも４０℃以上或いは８０℃以下とするのがより好ましい。
When pressing the uneven surface of the mold against the adhesive surface of the adhesive sheet, the mold may be heated as necessary. At this time, the heating temperature is preferably 20 to 100° C., more preferably 30° C. or higher or 90° C. or lower, and more preferably 40° C. or higher or 80° C. or lower.
＜本発明粘着シートの層構成＞
本発明粘着シートは、本発明粘着剤組成物からなる粘着剤層（「本発明粘着剤層」とも称する）からなる単層構成であっても、本発明粘着剤層を備えた２層以上の複数層構成であってもよい。
本発明粘着シートが２層以上の複数層構成である場合、本発明粘着剤層以外の層の組成は任意である。ただし、例えば中間層や最表層或いは最裏層を本発明粘着剤層以外の層で形成する場合、層間接着性をより高める観点から、本発明粘着剤層以外の層を形成する粘着剤組成物も、（メタ）アクリル系重合体を含む粘着剤組成物から形成するのが好ましく、中でも、本発明粘着剤層と同じ（メタ）アクリル系重合体（Ａ）を含むのがより好ましい。さらには、本発明粘着剤層以外の層も、光重合開始剤（Ｂ）および／又は架橋剤（Ｃ）を含むのがより好ましい。 <Layer structure of the pressure-sensitive adhesive sheet of the present invention>
The pressure-sensitive adhesive sheet of the present invention may have a single-layer structure composed of a pressure-sensitive adhesive layer (also referred to as "the pressure-sensitive adhesive layer of the present invention") made of the pressure-sensitive adhesive composition of the present invention, or two or more layers comprising the pressure-sensitive adhesive layer of the present invention. A multilayer structure may be used.
When the pressure-sensitive adhesive sheet of the present invention has a multilayer structure of two or more layers, the composition of layers other than the pressure-sensitive adhesive layer of the present invention is arbitrary. However, for example, when the intermediate layer, the outermost layer, or the outermost layer is formed of a layer other than the pressure-sensitive adhesive layer of the present invention, the pressure-sensitive adhesive composition that forms the layer other than the pressure-sensitive adhesive layer of the present invention from the viewpoint of further increasing the interlayer adhesion. is preferably formed from a pressure-sensitive adhesive composition containing a (meth)acrylic polymer, more preferably containing the same (meth)acrylic polymer (A) as the pressure-sensitive adhesive layer of the present invention. Furthermore, it is more preferable that layers other than the pressure-sensitive adhesive layer of the present invention also contain a photopolymerization initiator (B) and/or a cross-linking agent (C).
本発明粘着シートは、本発明粘着剤組成物からなる粘着剤層（「本発明粘着剤層」とも称する）からなる単層構成であっても、本発明粘着剤層を備えた２層以上の複数層構成であってもよい。
本発明粘着シートが２層以上の複数層構成である場合、本発明粘着剤層以外の層の組成は任意である。ただし、例えば中間層や最表層或いは最裏層を本発明粘着剤層以外の層で形成する場合、層間接着性をより高める観点から、本発明粘着剤層以外の層を形成する粘着剤組成物も、（メタ）アクリル系重合体を含む粘着剤組成物から形成するのが好ましく、中でも、本発明粘着剤層と同じ（メタ）アクリル系重合体（Ａ）を含むのがより好ましい。さらには、本発明粘着剤層以外の層も、光重合開始剤（Ｂ）および／又は架橋剤（Ｃ）を含むのがより好ましい。 <Layer structure of the pressure-sensitive adhesive sheet of the present invention>
The pressure-sensitive adhesive sheet of the present invention may have a single-layer structure composed of a pressure-sensitive adhesive layer (also referred to as "the pressure-sensitive adhesive layer of the present invention") made of the pressure-sensitive adhesive composition of the present invention, or two or more layers comprising the pressure-sensitive adhesive layer of the present invention. A multilayer structure may be used.
When the pressure-sensitive adhesive sheet of the present invention has a multilayer structure of two or more layers, the composition of layers other than the pressure-sensitive adhesive layer of the present invention is arbitrary. However, for example, when the intermediate layer, the outermost layer, or the outermost layer is formed of a layer other than the pressure-sensitive adhesive layer of the present invention, the pressure-sensitive adhesive composition that forms the layer other than the pressure-sensitive adhesive layer of the present invention from the viewpoint of further increasing the interlayer adhesion. is preferably formed from a pressure-sensitive adhesive composition containing a (meth)acrylic polymer, more preferably containing the same (meth)acrylic polymer (A) as the pressure-sensitive adhesive layer of the present invention. Furthermore, it is more preferable that layers other than the pressure-sensitive adhesive layer of the present invention also contain a photopolymerization initiator (B) and/or a cross-linking agent (C).
本発明粘着シートが２層以上の複数層構成である場合、少なくとも、最表層、最裏層又はその両層が本発明粘着剤層に該当する層であるのが好ましい。全ての層が本発明粘着剤層に該当する層であってもよい。
When the pressure-sensitive adhesive sheet of the present invention has a multilayer structure of two or more layers, it is preferable that at least the outermost layer, the backmost layer, or both layers correspond to the pressure-sensitive adhesive layer of the present invention. All layers may be layers corresponding to the pressure-sensitive adhesive layer of the present invention.
本発明粘着シートが２層以上の複数層構成である場合、本発明粘着剤層に該当する層の厚みが、本発明粘着シート全体の厚みに対して１０％以上１００％以下を占めるのが好ましく、中でも１４％以上或いは７０％以下、その中でも２０％以上或いは５０％以下の割合で占めるのがさらに好ましい。
When the pressure-sensitive adhesive sheet of the present invention has a multilayer structure of two or more layers, the thickness of the layer corresponding to the pressure-sensitive adhesive layer of the present invention preferably accounts for 10% or more and 100% or less of the total thickness of the pressure-sensitive adhesive sheet of the present invention. , above all, 14% or more or 70% or less, more preferably 20% or more or 50% or less.
＜粘着シートの粘弾性＞
本発明粘着シートは、凹凸形状を維持する観点から、周波数１Ｈｚ、温度２３℃における貯蔵弾性率が、１×１０３～１×１０６Ｐａであることが好ましく、中でも１×１０３Ｐａ以上或いは０．５×１０６Ｐａ以下、その中でも１×１０４Ｐａ以上或いは１×１０５Ｐａ以下であることが好ましい。
なお、前記貯蔵弾性率は、例えば、レオメトリックス社製の粘弾性測定装置「ダイナミックアナライザー ＲＤＡＩＩ」を用いて剪断法により、次の条件で測定することができる。但し、この測定方法に限定するものではない。
・治具：Φ２５ｍｍパラレルプレート
・歪み：０．５％
・周波数：１Ｈｚ
・温度：－７０～２００℃（－７０℃から昇温速度３℃／ｍｉｎで測定）
・試料厚さ：５００μｍ
なお、測定する粘着シートの厚みが５００μｍに満たない場合は、それぞれ５００μｍの厚さになるまで粘着剤層を積層することで調整することができる。 <Viscoelasticity of Adhesive Sheet>
From the viewpoint of maintaining the uneven shape, the pressure-sensitive adhesive sheet of the present invention preferably has a storage elastic modulus of 1×10 3 to 1×10 6 Pa at a frequency of 1 Hz and a temperature of 23° C., especially 1×10 3 Pa or more, or 0.5×10 6 Pa or less, preferably 1×10 4 Pa or more or 1×10 5 Pa or less.
The storage elastic modulus can be measured, for example, by a shear method using a viscoelasticity measuring device "Dynamic Analyzer RDAII" manufactured by Rheometrics Co., Ltd. under the following conditions. However, it is not limited to this measuring method.
・Jig: Φ25mm parallel plate ・Distortion: 0.5%
・Frequency: 1Hz
・Temperature: -70 to 200°C (measured at a temperature increase rate of 3°C/min from -70°C)
・Sample thickness: 500 μm
In addition, when the thickness of the pressure-sensitive adhesive sheet to be measured is less than 500 μm, the thickness can be adjusted by laminating pressure-sensitive adhesive layers until each thickness reaches 500 μm.
本発明粘着シートは、凹凸形状を維持する観点から、周波数１Ｈｚ、温度２３℃における貯蔵弾性率が、１×１０３～１×１０６Ｐａであることが好ましく、中でも１×１０３Ｐａ以上或いは０．５×１０６Ｐａ以下、その中でも１×１０４Ｐａ以上或いは１×１０５Ｐａ以下であることが好ましい。
なお、前記貯蔵弾性率は、例えば、レオメトリックス社製の粘弾性測定装置「ダイナミックアナライザー ＲＤＡＩＩ」を用いて剪断法により、次の条件で測定することができる。但し、この測定方法に限定するものではない。
・治具：Φ２５ｍｍパラレルプレート
・歪み：０．５％
・周波数：１Ｈｚ
・温度：－７０～２００℃（－７０℃から昇温速度３℃／ｍｉｎで測定）
・試料厚さ：５００μｍ
なお、測定する粘着シートの厚みが５００μｍに満たない場合は、それぞれ５００μｍの厚さになるまで粘着剤層を積層することで調整することができる。 <Viscoelasticity of Adhesive Sheet>
From the viewpoint of maintaining the uneven shape, the pressure-sensitive adhesive sheet of the present invention preferably has a storage elastic modulus of 1×10 3 to 1×10 6 Pa at a frequency of 1 Hz and a temperature of 23° C., especially 1×10 3 Pa or more, or 0.5×10 6 Pa or less, preferably 1×10 4 Pa or more or 1×10 5 Pa or less.
The storage elastic modulus can be measured, for example, by a shear method using a viscoelasticity measuring device "Dynamic Analyzer RDAII" manufactured by Rheometrics Co., Ltd. under the following conditions. However, it is not limited to this measuring method.
・Jig: Φ25mm parallel plate ・Distortion: 0.5%
・Frequency: 1Hz
・Temperature: -70 to 200°C (measured at a temperature increase rate of 3°C/min from -70°C)
・Sample thickness: 500 μm
In addition, when the thickness of the pressure-sensitive adhesive sheet to be measured is less than 500 μm, the thickness can be adjusted by laminating pressure-sensitive adhesive layers until each thickness reaches 500 μm.
＜接着性＞
本発明粘着シートは、フレキシブル画像表示装置用構成部材の代替部材としてのポリエチレンテレフタレートシートに対する９０℃剥離による粘着力（剥離速度３００ｍｍ／ｍｉｎ）を０．５～３０Ｎ／２０ｍｍとすることができる。かかる粘着力は伸縮時の剥れにくさの点から０．５Ｎ／２０ｍｍ以上、更には１．０Ｎ／２０ｍｍ以上、特には１．５Ｎ／２０ｍｍ以上、殊には２．０Ｎ／２０ｍｍ以上が好ましく、一方、形状保持性の点から３０Ｎ／２０ｍｍ以下、更には２８Ｎ／２０ｍｍ以下、特には２５Ｎ／２０ｍｍ以下が好ましい。
この際、前記フレキシブル画像表示装置用構成部材の代替部材としてのポリエチレンテレフタレートシートは、２軸延伸シートであるのが好ましい。また、その厚みは５０～３００μｍであるのが好ましい。 <Adhesion>
The pressure-sensitive adhesive sheet of the present invention can have an adhesive strength of 0.5 to 30 N/20 mm when peeled at 90° C. (peeling speed: 300 mm/min) to a polyethylene terephthalate sheet as a substitute member for flexible image display devices. Such adhesive strength is preferably 0.5 N/20 mm or more, further 1.0 N/20 mm or more, particularly 1.5 N/20 mm or more, particularly 2.0 N/20 mm or more, from the viewpoint of resistance to peeling during stretching. On the other hand, it is preferably 30 N/20 mm or less, more preferably 28 N/20 mm or less, and particularly preferably 25 N/20 mm or less from the viewpoint of shape retention.
In this case, the polyethylene terephthalate sheet as a substitute member for the flexible image display device is preferably a biaxially oriented sheet. Also, the thickness is preferably 50 to 300 μm.
本発明粘着シートは、フレキシブル画像表示装置用構成部材の代替部材としてのポリエチレンテレフタレートシートに対する９０℃剥離による粘着力（剥離速度３００ｍｍ／ｍｉｎ）を０．５～３０Ｎ／２０ｍｍとすることができる。かかる粘着力は伸縮時の剥れにくさの点から０．５Ｎ／２０ｍｍ以上、更には１．０Ｎ／２０ｍｍ以上、特には１．５Ｎ／２０ｍｍ以上、殊には２．０Ｎ／２０ｍｍ以上が好ましく、一方、形状保持性の点から３０Ｎ／２０ｍｍ以下、更には２８Ｎ／２０ｍｍ以下、特には２５Ｎ／２０ｍｍ以下が好ましい。
この際、前記フレキシブル画像表示装置用構成部材の代替部材としてのポリエチレンテレフタレートシートは、２軸延伸シートであるのが好ましい。また、その厚みは５０～３００μｍであるのが好ましい。 <Adhesion>
The pressure-sensitive adhesive sheet of the present invention can have an adhesive strength of 0.5 to 30 N/20 mm when peeled at 90° C. (peeling speed: 300 mm/min) to a polyethylene terephthalate sheet as a substitute member for flexible image display devices. Such adhesive strength is preferably 0.5 N/20 mm or more, further 1.0 N/20 mm or more, particularly 1.5 N/20 mm or more, particularly 2.0 N/20 mm or more, from the viewpoint of resistance to peeling during stretching. On the other hand, it is preferably 30 N/20 mm or less, more preferably 28 N/20 mm or less, and particularly preferably 25 N/20 mm or less from the viewpoint of shape retention.
In this case, the polyethylene terephthalate sheet as a substitute member for the flexible image display device is preferably a biaxially oriented sheet. Also, the thickness is preferably 50 to 300 μm.
＜本発明離型フィルム＞
本発明離型フィルムの材質としては、例えばポリエステルフィルム、ポリオレフィンフィルム、ポリカーボネートフィルム、ポリスチレンフィルム、アクリルフィルム、トリアセチルセルロースフィルム、フッ素樹脂フィルム等を挙げることができる。これらの中でも、ポリエステルフィルム及びポリオレフィンフィルムが特に好ましい。 <Release film of the present invention>
Examples of materials for the release film of the present invention include polyester films, polyolefin films, polycarbonate films, polystyrene films, acrylic films, triacetylcellulose films, and fluororesin films. Among these, polyester films and polyolefin films are particularly preferred.
本発明離型フィルムの材質としては、例えばポリエステルフィルム、ポリオレフィンフィルム、ポリカーボネートフィルム、ポリスチレンフィルム、アクリルフィルム、トリアセチルセルロースフィルム、フッ素樹脂フィルム等を挙げることができる。これらの中でも、ポリエステルフィルム及びポリオレフィンフィルムが特に好ましい。 <Release film of the present invention>
Examples of materials for the release film of the present invention include polyester films, polyolefin films, polycarbonate films, polystyrene films, acrylic films, triacetylcellulose films, and fluororesin films. Among these, polyester films and polyolefin films are particularly preferred.
本発明離型フィルムの表面、特に本発明粘着シートを貼り合わせる側の表面は平坦面であるのが好ましい。
The surface of the release film of the present invention, particularly the surface to which the adhesive sheet of the present invention is attached, is preferably flat.
本発明離型フィルムの厚みは、特に制限するものではない。中でも、例えば加工性及びハンドリング性の観点からは、２５μｍ～５００μｍであるのが好ましく、その中でも３８μｍ以上或いは２５０μｍ以下、その中でも５０μｍ以上或いは２００μｍ以下であるのがさらに好ましい。
The thickness of the release film of the present invention is not particularly limited. Among them, for example, from the viewpoint of workability and handleability, the thickness is preferably 25 μm to 500 μm, more preferably 38 μm or more or 250 μm or less, and more preferably 50 μm or more or 200 μm or less.
本発明離型フィルム付き粘着シートは、本発明離型フィルムがポリエステル系フィルムであることが好ましく、また、活性エネルギー線を照射した後にも剥離し易いものであるものが離型性の点から好ましい。かかる観点から、波長３６５ｎｍの活性エネルギー線を積算光量２０００～４０００ｍＪ／ｃｍ２照射した時の本発明粘着シートに対する剥離力が、剥離角１８０°、剥離速度３００ｍｍ／分において、０．１Ｎ／ｃｍ以下となるものであることが好ましい。
In the pressure-sensitive adhesive sheet with a release film of the present invention, the release film of the present invention is preferably a polyester-based film, and from the standpoint of releasability, it is preferable that the release film is easy to peel even after irradiation with active energy rays. . From this point of view, the peel force for the pressure-sensitive adhesive sheet of the present invention when irradiated with an active energy ray having a wavelength of 365 nm with an accumulated light amount of 2000 to 4000 mJ/cm 2 is 0.1 N/cm or less at a peel angle of 180 ° and a peel speed of 300 mm / min. It is preferable that
＜＜本発明フレキシブル積層体＞＞
本発明の実施形態の一例であるフレキシブル画像表示装置用積層体（「本発明フレキシブル積層体」と称する）は、本発明粘着シートと、フレキシブル画像表示装置用構成部材とが積層してなる構成を備えたものである。
なお、本発明フレキシブル積層体における本発明粘着シートは、硬化前の状態、硬化後の状態、及び、硬化途中の状態すなわち未だ硬化される余地のある状態に硬化された状態のいずれも包含する。 <<Flexible laminate of the present invention>>
A laminate for a flexible image display device (referred to as "the flexible laminate of the present invention"), which is an example of an embodiment of the present invention, has a configuration in which the pressure-sensitive adhesive sheet of the present invention and a constituent member for a flexible image display device are laminated. It is prepared.
The pressure-sensitive adhesive sheet of the present invention in the flexible laminate of the present invention includes all of a state before curing, a state after curing, and a state in the middle of curing, that is, a state in which there is still room for curing.
本発明の実施形態の一例であるフレキシブル画像表示装置用積層体（「本発明フレキシブル積層体」と称する）は、本発明粘着シートと、フレキシブル画像表示装置用構成部材とが積層してなる構成を備えたものである。
なお、本発明フレキシブル積層体における本発明粘着シートは、硬化前の状態、硬化後の状態、及び、硬化途中の状態すなわち未だ硬化される余地のある状態に硬化された状態のいずれも包含する。 <<Flexible laminate of the present invention>>
A laminate for a flexible image display device (referred to as "the flexible laminate of the present invention"), which is an example of an embodiment of the present invention, has a configuration in which the pressure-sensitive adhesive sheet of the present invention and a constituent member for a flexible image display device are laminated. It is prepared.
The pressure-sensitive adhesive sheet of the present invention in the flexible laminate of the present invention includes all of a state before curing, a state after curing, and a state in the middle of curing, that is, a state in which there is still room for curing.
前述のように、本発明離型フィルム付き粘着シートにおいて、本発明離型フィルムと本発明粘着シートとの間に所定の空隙率（Ｘ）を有する空間部が形成されていれば、本発明離型フィルムを剥離した本発明粘着シートを、表面平坦なフレキシブル画像表示装置用構成部材に貼着して本発明フレキシブル積層体を形成した場合にも、本発明粘着シートとフレキシブル画像表示装置用構成部材との間に同様の空隙率（Ｘ）を有する空間部を形成することができ、本発明フレキシブル積層体を巻き取り、巻き戻して広げた時に、本発明粘着シートとフレキシブル画像表示装置用構成部材との間に“浮き”が生じるのを防ぐことができる。また、本発明フレキシブル積層体伸縮させた場合も、本発明粘着シートとフレキシブル画像表示装置用構成部材との間の“剥がれ”が生じるのを防ぐことができる。
よって、本発明フレキシブル積層体において、フレキシブル画像表示装置用構成部材と本発明粘着シートとの間に形成された空間部の空隙率（Ｘ）は３％以上、更に４％以上であるのが好ましく、中でも４．５％以上、５％以上、６％以上、中でも８％以上、その中でも１０％以上であるのがさらに好ましい。他方、７０％以下であるのがより好ましく、中でも６０％以下、５０％以下、４８％以下、中でも４５％以下、その中でも４０％以下であるのがさらに好ましい。
特に、伸縮させた場合（ストレッチャブル性を目的とする場合）は、空間部の空隙率（Ｘ）は４％以上が好ましく、中でも４．５％以上、５％以上、６％以上、特には８％以上、その中でも１０％以上であり、他方、７０％以下であるのがより好ましく、中でも６０％以下、５０％以下、４８％以下、中でも４５％以下、その中でも４０％以下であるのがさらに好ましい。 As described above, in the pressure-sensitive adhesive sheet with the release film of the present invention, if a space portion having a predetermined porosity (X) is formed between the release film of the present invention and the pressure-sensitive adhesive sheet of the present invention, the release film of the present invention can be used. Even when the flexible laminate of the present invention is formed by sticking the pressure-sensitive adhesive sheet of the present invention from which the mold film has been peeled off to a structural member for a flexible image display device having a flat surface, the pressure-sensitive adhesive sheet of the present invention and the structural member for a flexible image display device are formed. A space having the same porosity (X) can be formed between and, when the flexible laminate of the present invention is wound up, unwound and spread, the pressure-sensitive adhesive sheet of the present invention and a component for a flexible image display device It is possible to prevent “floating” from occurring between In addition, even when the flexible laminate of the present invention is stretched, it is possible to prevent "peeling" between the adhesive sheet of the present invention and the constituent members for a flexible image display device.
Therefore, in the flexible laminate of the present invention, the porosity (X) of the space formed between the component for a flexible image display device and the pressure-sensitive adhesive sheet of the present invention is preferably 3% or more, more preferably 4% or more. , 4.5% or more, 5% or more, 6% or more, 8% or more, more preferably 10% or more. On the other hand, it is more preferably 70% or less, more preferably 60% or less, 50% or less, or 48% or less, especially 45% or less, and even more preferably 40% or less.
In particular, when stretched (for the purpose of stretchability), the porosity (X) of the space is preferably 4% or more, especially 4.5% or more, 5% or more, 6% or more, especially 8% or more, among which 10% or more, on the other hand, it is more preferably 70% or less, among which 60% or less, 50% or less, 48% or less, among them 45% or less, among which 40% or less is more preferred.
よって、本発明フレキシブル積層体において、フレキシブル画像表示装置用構成部材と本発明粘着シートとの間に形成された空間部の空隙率（Ｘ）は３％以上、更に４％以上であるのが好ましく、中でも４．５％以上、５％以上、６％以上、中でも８％以上、その中でも１０％以上であるのがさらに好ましい。他方、７０％以下であるのがより好ましく、中でも６０％以下、５０％以下、４８％以下、中でも４５％以下、その中でも４０％以下であるのがさらに好ましい。
特に、伸縮させた場合（ストレッチャブル性を目的とする場合）は、空間部の空隙率（Ｘ）は４％以上が好ましく、中でも４．５％以上、５％以上、６％以上、特には８％以上、その中でも１０％以上であり、他方、７０％以下であるのがより好ましく、中でも６０％以下、５０％以下、４８％以下、中でも４５％以下、その中でも４０％以下であるのがさらに好ましい。 As described above, in the pressure-sensitive adhesive sheet with the release film of the present invention, if a space portion having a predetermined porosity (X) is formed between the release film of the present invention and the pressure-sensitive adhesive sheet of the present invention, the release film of the present invention can be used. Even when the flexible laminate of the present invention is formed by sticking the pressure-sensitive adhesive sheet of the present invention from which the mold film has been peeled off to a structural member for a flexible image display device having a flat surface, the pressure-sensitive adhesive sheet of the present invention and the structural member for a flexible image display device are formed. A space having the same porosity (X) can be formed between and, when the flexible laminate of the present invention is wound up, unwound and spread, the pressure-sensitive adhesive sheet of the present invention and a component for a flexible image display device It is possible to prevent “floating” from occurring between In addition, even when the flexible laminate of the present invention is stretched, it is possible to prevent "peeling" between the adhesive sheet of the present invention and the constituent members for a flexible image display device.
Therefore, in the flexible laminate of the present invention, the porosity (X) of the space formed between the component for a flexible image display device and the pressure-sensitive adhesive sheet of the present invention is preferably 3% or more, more preferably 4% or more. , 4.5% or more, 5% or more, 6% or more, 8% or more, more preferably 10% or more. On the other hand, it is more preferably 70% or less, more preferably 60% or less, 50% or less, or 48% or less, especially 45% or less, and even more preferably 40% or less.
In particular, when stretched (for the purpose of stretchability), the porosity (X) of the space is preferably 4% or more, especially 4.5% or more, 5% or more, 6% or more, especially 8% or more, among which 10% or more, on the other hand, it is more preferably 70% or less, among which 60% or less, 50% or less, 48% or less, among them 45% or less, among which 40% or less is more preferred.
本発明フレキシブル積層体の一例として、２つのフレキシブル画像表示装置用構成部材が、本発明粘着シートからなる硬化性を有する粘着層を介して積層してなる構成を備えたフレキシブル画像表示装置用積層体を挙げることができる。
As an example of the flexible laminate of the present invention, a laminate for a flexible image display device having a configuration in which two constituent members for a flexible image display device are laminated via a curable adhesive layer made of the adhesive sheet of the present invention. can be mentioned.
本発明フレキシブル積層体の他例として、２つのフレキシブル画像表示装置用構成部材が、本発明粘着シートが硬化されてなる粘着層を介して積層してなる構成を備えたフレキシブル画像表示装置用積層体を挙げることができる。
As another example of the flexible laminate of the present invention, a laminate for a flexible image display device having a configuration in which two constituent members for a flexible image display device are laminated via an adhesive layer formed by curing the adhesive sheet of the present invention. can be mentioned.
具体的な例としては、フレキシブル積層体は、第１のフレキシブル画像表示装置構成用部材（以下「第１の部材」と称することがある）と、本発明粘着シートと、第２のフレキシブル画像表示装置構成用部材（以下「第２の部材」と称することがある）とが、この順で積層されてなる構成を備えた積層体であるのが好ましい。
さらに、第１の部材、第２の部材及び第３のフレキシブル画像表示装置構成用部材（以下「第３の部材」と称することがある）とが、それぞれ本発明粘着シートを介してこの順で積層されてなる構成を備えた積層体であってもよい。積層する２以上の部材は同じでもよいし、異なるものでもよい。 As a specific example, the flexible laminate includes a first flexible image display device constituent member (hereinafter sometimes referred to as "first member"), the pressure-sensitive adhesive sheet of the present invention, and a second flexible image display It is preferable that the device-constituting member (hereinafter sometimes referred to as "second member") is a laminate having a configuration in which the members are laminated in this order.
Furthermore, the first member, the second member, and the third member for constituting a flexible image display device (hereinafter sometimes referred to as the "third member") are placed in this order via the pressure-sensitive adhesive sheet of the present invention. It may be a laminate having a laminated structure. Two or more members to be laminated may be the same or different.
さらに、第１の部材、第２の部材及び第３のフレキシブル画像表示装置構成用部材（以下「第３の部材」と称することがある）とが、それぞれ本発明粘着シートを介してこの順で積層されてなる構成を備えた積層体であってもよい。積層する２以上の部材は同じでもよいし、異なるものでもよい。 As a specific example, the flexible laminate includes a first flexible image display device constituent member (hereinafter sometimes referred to as "first member"), the pressure-sensitive adhesive sheet of the present invention, and a second flexible image display It is preferable that the device-constituting member (hereinafter sometimes referred to as "second member") is a laminate having a configuration in which the members are laminated in this order.
Furthermore, the first member, the second member, and the third member for constituting a flexible image display device (hereinafter sometimes referred to as the "third member") are placed in this order via the pressure-sensitive adhesive sheet of the present invention. It may be a laminate having a laminated structure. Two or more members to be laminated may be the same or different.
本発明フレキシブル積層体の厚みは、特に制限されるものではない。例えば、画像表示装置に使用される場合の一例としては、本発明フレキシブル積層体はシート状であり、その厚みが０．０２ｍｍ以上であれば、ハンドリング性が良好であり、また、厚みが１．０ｍｍ以下であれば、積層体の薄型化に寄与することができる。
よって、本発明フレキシブル積層体の厚みは、０．０２ｍｍ以上であるのが好ましく、中でも０．０３ｍｍ以上、特に０．０５ｍｍ以上であるのがより好ましい。一方、上限に関しては、１．０ｍｍ以下であるのが好ましく、中でも０．７ｍｍ以下、特に０．５ｍｍ以下であるのがさらに好ましい。 The thickness of the flexible laminate of the present invention is not particularly limited. For example, when used in an image display device, the flexible laminate of the present invention is in the form of a sheet. If it is 0 mm or less, it can contribute to thinning of the laminate.
Therefore, the thickness of the flexible laminate of the present invention is preferably 0.02 mm or more, more preferably 0.03 mm or more, particularly 0.05 mm or more. On the other hand, the upper limit is preferably 1.0 mm or less, more preferably 0.7 mm or less, particularly 0.5 mm or less.
よって、本発明フレキシブル積層体の厚みは、０．０２ｍｍ以上であるのが好ましく、中でも０．０３ｍｍ以上、特に０．０５ｍｍ以上であるのがより好ましい。一方、上限に関しては、１．０ｍｍ以下であるのが好ましく、中でも０．７ｍｍ以下、特に０．５ｍｍ以下であるのがさらに好ましい。 The thickness of the flexible laminate of the present invention is not particularly limited. For example, when used in an image display device, the flexible laminate of the present invention is in the form of a sheet. If it is 0 mm or less, it can contribute to thinning of the laminate.
Therefore, the thickness of the flexible laminate of the present invention is preferably 0.02 mm or more, more preferably 0.03 mm or more, particularly 0.05 mm or more. On the other hand, the upper limit is preferably 1.0 mm or less, more preferably 0.7 mm or less, particularly 0.5 mm or less.
本発明粘着シートを、第１の部材、第２の部材及び／又は第３の部材に貼着することにより、本発明フレキシブル積層体を作製することができる。ただし、このような製造方法に限定するものではない。
By attaching the adhesive sheet of the present invention to the first member, the second member and/or the third member, the flexible laminate of the present invention can be produced. However, it is not limited to such a manufacturing method.
（フレキシブル画像表示装置構成部材）
フレキシブル画像表示装置の構成や本発明粘着シートの位置にも依るが、第１の部材、第２の部材及び第３の部材（これらをまとめて「本部材」と称する場合がある）としては、例えばカバーレンズ、偏光板、位相差フィルム、バリアフィルム、タッチセンサーフィルム、発光素子、ＰＳＡ等を挙げることができる。 (Flexible image display device component)
Depending on the configuration of the flexible image display device and the position of the pressure-sensitive adhesive sheet of the present invention, the first member, the second member and the third member (these may be collectively referred to as "this member") include: Examples thereof include cover lenses, polarizing plates, retardation films, barrier films, touch sensor films, light-emitting elements, PSA, and the like.
フレキシブル画像表示装置の構成や本発明粘着シートの位置にも依るが、第１の部材、第２の部材及び第３の部材（これらをまとめて「本部材」と称する場合がある）としては、例えばカバーレンズ、偏光板、位相差フィルム、バリアフィルム、タッチセンサーフィルム、発光素子、ＰＳＡ等を挙げることができる。 (Flexible image display device component)
Depending on the configuration of the flexible image display device and the position of the pressure-sensitive adhesive sheet of the present invention, the first member, the second member and the third member (these may be collectively referred to as "this member") include: Examples thereof include cover lenses, polarizing plates, retardation films, barrier films, touch sensor films, light-emitting elements, PSA, and the like.
フレキシブル画像表示装置構成部材の一例として、ローラブル部材、すなわち、巻き取り、巻き戻しが可能な部材や、ストレッチャブル部材、すなわち、伸縮可能な部材を挙げることができる。具体的には、例えば反射シート、導光板と光源、拡散フィルム、プリズムシート、液晶パネル、位相差板、ガラス基板、偏光板、有機ＥＬパネル、電極、反射防止フィルム、カラーフィルター、タッチセンサー、カバーガラス、カバープラスチック、又は、これらのうちの２種類以上の部材が複合一体化されたものや、表面保護フィルムなどを挙げることができる。なお、前記部材以外にも、帯電防止層やハードコート層、アンカー層、離型層、易接着層、保護層、ブリーディング防止層及び平坦化層等、必要に応じて他の層を介在していてもよい。
Examples of flexible image display device constituent members include a rollable member, that is, a member that can be wound up and rewound, and a stretchable member, that is, a member that can be expanded and contracted. Specifically, for example, a reflective sheet, a light guide plate and a light source, a diffusion film, a prism sheet, a liquid crystal panel, a retardation plate, a glass substrate, a polarizing plate, an organic EL panel, an electrode, an antireflection film, a color filter, a touch sensor, and a cover. Examples include glass, cover plastic, or a composite and integrated product of two or more of these members, a surface protective film, and the like. In addition to the above members, other layers such as an antistatic layer, a hard coat layer, an anchor layer, a release layer, an easy adhesion layer, a protective layer, an anti-bleeding layer and a flattening layer are interposed as necessary. may
また、画像表示の構成を考慮すると、第１の部材は、タッチ入力機能を有することが好ましい。本発明粘着シートが前述した第２の部材、第３の部材を有する場合、第２の部材乃至第３の部材がタッチ入力機能を有していてもよい。
また、本部材のうちの少なくとも一つは、本発明粘着シートとの接触面に、配線、印刷、パターン現像や表面処理、エンボス加工等により種々の凹凸が賦形されていてもよい。 Also, considering the configuration of image display, the first member preferably has a touch input function. When the adhesive sheet of the present invention has the second member and the third member described above, the second member to the third member may have a touch input function.
In addition, at least one of the members may have various irregularities formed by wiring, printing, pattern development, surface treatment, embossing, etc. on the contact surface with the pressure-sensitive adhesive sheet of the present invention.
また、本部材のうちの少なくとも一つは、本発明粘着シートとの接触面に、配線、印刷、パターン現像や表面処理、エンボス加工等により種々の凹凸が賦形されていてもよい。 Also, considering the configuration of image display, the first member preferably has a touch input function. When the adhesive sheet of the present invention has the second member and the third member described above, the second member to the third member may have a touch input function.
In addition, at least one of the members may have various irregularities formed by wiring, printing, pattern development, surface treatment, embossing, etc. on the contact surface with the pressure-sensitive adhesive sheet of the present invention.
貼り合わせるフレキシブル画像表示装置構成用部材（第１の部材、第２の部材及び第３の部材を包含する）のうちの少なくとも一つは、ウレタン樹脂、シクロオレフィン樹脂、トリアセチルセルロース樹脂、（メタ）アクリレート樹脂、エポキシ樹脂及びポリイミド樹脂からなる群から選択される一種若しくは二種以上の樹脂を主成分とする樹脂シート又は薄膜ガラスであってもよい。
ここで「主成分」とは、フレキシブル画像表示装置構成用部材を構成する成分のうち最も多い質量比率を占める成分であることをいい、具体的には、フレキシブル画像表示装置構成用部材の５０質量％以上を占めるもの、中でも５５質量％以上を占めるもの、中でも６０質量％以上を占めるのを想定することができる。 At least one of the flexible image display device constituent members (including the first member, the second member, and the third member) to be laminated is made of urethane resin, cycloolefin resin, triacetylcellulose resin, (meta ) It may be a resin sheet or a thin film glass mainly composed of one or more resins selected from the group consisting of acrylate resins, epoxy resins and polyimide resins.
Here, the "main component" refers to a component occupying the largest mass ratio among the components constituting the flexible image display device constituent member, specifically, 50 mass of the flexible image display device constituent member. % or more, especially 55 mass % or more, especially 60 mass % or more.
ここで「主成分」とは、フレキシブル画像表示装置構成用部材を構成する成分のうち最も多い質量比率を占める成分であることをいい、具体的には、フレキシブル画像表示装置構成用部材の５０質量％以上を占めるもの、中でも５５質量％以上を占めるもの、中でも６０質量％以上を占めるのを想定することができる。 At least one of the flexible image display device constituent members (including the first member, the second member, and the third member) to be laminated is made of urethane resin, cycloolefin resin, triacetylcellulose resin, (meta ) It may be a resin sheet or a thin film glass mainly composed of one or more resins selected from the group consisting of acrylate resins, epoxy resins and polyimide resins.
Here, the "main component" refers to a component occupying the largest mass ratio among the components constituting the flexible image display device constituent member, specifically, 50 mass of the flexible image display device constituent member. % or more, especially 55 mass % or more, especially 60 mass % or more.
本発明粘着シートは、活性エネルギー線による硬化後においてホットメルトすることも可能である。かかるホットメルトにより、被着体の被着面に凹凸を有する場合であっても、該凹凸に追随しかつ凹凸を吸収するように貼合することができ、その表面を平滑にすることもできる。そのため、２つのフレキシブル画像表示装置構成用部材を、本発明粘着シートを介して貼合する際、一方又は両方のフレキシブル画像表示装置構成用部材が光を透過しない部材であっても、該凹凸を吸収しつつ２つのフレキシブル画像表示装置構成用部材を貼合することができる。
The adhesive sheet of the present invention can be hot-melted after being cured by active energy rays. With such a hot melt, even if the adherend surface of the adherend has unevenness, it can be laminated so as to follow the unevenness and absorb the unevenness, and the surface can be smoothed. . Therefore, when two members for constituting a flexible image display device are laminated via the pressure-sensitive adhesive sheet of the present invention, even if one or both of the members for constituting a flexible image display device do not transmit light, the unevenness can be eliminated. It is possible to bond two members for constituting a flexible image display device while absorbing.
（本発明フレキシブル積層体の製造方法）
本発明フレキシブル積層体は、例えば、凹凸パターン形成時に活性エネルギー線を照射して硬化してなる本発明粘着シートの一方を、フレキシブル画像表示装置構成用部材１に貼合し、次に、本発明粘着シートの他方の表面にフレキシブル画像表示装置構成用部材２を貼合して積層体とすることが挙げられる。
また、本発明フレキシブル積層体は、例えば、フレキシブル画像表示装置構成用部材１に、本発明粘着シートの一方の表面を貼合し、活性エネルギー線を照射して本発明粘着シートを硬化させ、次に、硬化後の本発明粘着シートの他方の表面にフレキシブル画像表示装置構成用部材２を貼合して積層体とすることができる。
また、本発明フレキシブル積層体は、例えば、フレキシブル画像表示装置構成用部材１に、本発明粘着シートの一方の表面を貼合し、本発明粘着シートの他方の表面にフレキシブル画像表示装置構成用部材２を貼合して積層体とした後、一方のフレキシブル画像表示装置構成用部材を通して、活性エネルギー線を照射して本発明粘着シートを硬化させることもできる。 (Method for producing the flexible laminate of the present invention)
For the flexible laminate of the present invention, for example, one side of the pressure-sensitive adhesive sheet of the present invention, which is cured by irradiating an active energy ray at the time of forming an uneven pattern, is attached to themember 1 for constituting a flexible image display device, and then the adhesive sheet of the present invention is laminated. For example, the flexible image display device-constituting member 2 is attached to the other surface of the pressure-sensitive adhesive sheet to form a laminate.
Further, the flexible laminate of the present invention can be obtained, for example, by bonding one surface of the pressure-sensitive adhesive sheet of the present invention to the flexible image display deviceconstituent member 1, and curing the pressure-sensitive adhesive sheet of the present invention by irradiating an active energy ray. Secondly, the member 2 for constituting a flexible image display device can be adhered to the other surface of the cured pressure-sensitive adhesive sheet of the present invention to form a laminate.
Further, the flexible laminate of the present invention can be obtained, for example, by laminating one surface of the pressure-sensitive adhesive sheet of the present invention to the flexible image display deviceconstituent member 1, and attaching the flexible image display device constituent member to the other surface of the pressure-sensitive adhesive sheet of the present invention. After laminating 2 to form a laminate, the pressure-sensitive adhesive sheet of the present invention can be cured by irradiating active energy rays through one of the members for constituting a flexible image display device.
本発明フレキシブル積層体は、例えば、凹凸パターン形成時に活性エネルギー線を照射して硬化してなる本発明粘着シートの一方を、フレキシブル画像表示装置構成用部材１に貼合し、次に、本発明粘着シートの他方の表面にフレキシブル画像表示装置構成用部材２を貼合して積層体とすることが挙げられる。
また、本発明フレキシブル積層体は、例えば、フレキシブル画像表示装置構成用部材１に、本発明粘着シートの一方の表面を貼合し、活性エネルギー線を照射して本発明粘着シートを硬化させ、次に、硬化後の本発明粘着シートの他方の表面にフレキシブル画像表示装置構成用部材２を貼合して積層体とすることができる。
また、本発明フレキシブル積層体は、例えば、フレキシブル画像表示装置構成用部材１に、本発明粘着シートの一方の表面を貼合し、本発明粘着シートの他方の表面にフレキシブル画像表示装置構成用部材２を貼合して積層体とした後、一方のフレキシブル画像表示装置構成用部材を通して、活性エネルギー線を照射して本発明粘着シートを硬化させることもできる。 (Method for producing the flexible laminate of the present invention)
For the flexible laminate of the present invention, for example, one side of the pressure-sensitive adhesive sheet of the present invention, which is cured by irradiating an active energy ray at the time of forming an uneven pattern, is attached to the
Further, the flexible laminate of the present invention can be obtained, for example, by bonding one surface of the pressure-sensitive adhesive sheet of the present invention to the flexible image display device
Further, the flexible laminate of the present invention can be obtained, for example, by laminating one surface of the pressure-sensitive adhesive sheet of the present invention to the flexible image display device
本発明粘着シートの貼合方法としては、ロール貼合、平行平板によるプレス貼合、ダイヤフラム貼合等の既知の方式を用いることができる。
貼合環境としては、常圧で貼り合わせる大気貼合方式と、減圧下で貼り合わせる真空貼合方式がある。貼合時の気泡を防止する観点からは、減圧環境下で平行平板にて貼合する方法が好ましい。また、貼合温度を適宜調整してもよい。 As a method for laminating the pressure-sensitive adhesive sheet of the present invention, known methods such as roll lamination, press lamination using a parallel plate, and diaphragm lamination can be used.
As the lamination environment, there are an air lamination method in which lamination is performed under normal pressure and a vacuum lamination method in which lamination is performed under reduced pressure. From the viewpoint of preventing air bubbles during lamination, a method of laminating with a parallel plate under a reduced pressure environment is preferable. Moreover, you may adjust bonding temperature suitably.
貼合環境としては、常圧で貼り合わせる大気貼合方式と、減圧下で貼り合わせる真空貼合方式がある。貼合時の気泡を防止する観点からは、減圧環境下で平行平板にて貼合する方法が好ましい。また、貼合温度を適宜調整してもよい。 As a method for laminating the pressure-sensitive adhesive sheet of the present invention, known methods such as roll lamination, press lamination using a parallel plate, and diaphragm lamination can be used.
As the lamination environment, there are an air lamination method in which lamination is performed under normal pressure and a vacuum lamination method in which lamination is performed under reduced pressure. From the viewpoint of preventing air bubbles during lamination, a method of laminating with a parallel plate under a reduced pressure environment is preferable. Moreover, you may adjust bonding temperature suitably.
本発明粘着シートを貼合する際、必要に応じて、本発明粘着シート、又は画像表示装置構成用部材１又は画像表示装置構成用部材２を加熱するようにしてもよい。
この際の加熱は、例えば、画像表示装置構成用部材１／本発明粘着シート／画像表示装置構成用部材２からなる画像表示装置用積層体を、両側から、所定温度に加熱されたプレス板で加圧する方法などを挙げることができる。
また、この際の加熱温度は、温度５０℃以上８０℃以下であるのが好ましい。すなわち、５０℃以上８０℃以下に画像表示装置構成用部材１及び／又は画像表示装置構成用部材２を加熱して前記粘着シートをホットメルトさせながら、画像表示装置構成用部材２を貼合するのが好ましい。
また、プレス板で加圧する際のプレス圧は、０．０１ＭＰａ以上或いは０．４ＭＰａ以下、その中でも０．０２ＭＰａ以上或いは０．３５ＭＰａ以下であるのがさらに好ましい。 When laminating the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive sheet of the present invention, the image display device-constitutingmember 1, or the image display device-constituting member 2 may be heated, if necessary.
In this heating, for example, the image display device laminate composed of image display deviceconstituent member 1/the pressure-sensitive adhesive sheet of the present invention/image display device constituent member 2 is heated from both sides with a press plate heated to a predetermined temperature. A method of pressurizing can be mentioned.
Moreover, the heating temperature at this time is preferably 50° C. or higher and 80° C. or lower. That is, the image display deviceconstituent member 1 and/or the image display device constituent member 2 are heated to 50° C. or more and 80° C. or less to hot-melt the adhesive sheet, and the image display device constituent member 2 is bonded. is preferred.
Further, the press pressure when pressing with the press plate is preferably 0.01 MPa or more or 0.4 MPa or less, more preferably 0.02 MPa or more or 0.35 MPa or less.
この際の加熱は、例えば、画像表示装置構成用部材１／本発明粘着シート／画像表示装置構成用部材２からなる画像表示装置用積層体を、両側から、所定温度に加熱されたプレス板で加圧する方法などを挙げることができる。
また、この際の加熱温度は、温度５０℃以上８０℃以下であるのが好ましい。すなわち、５０℃以上８０℃以下に画像表示装置構成用部材１及び／又は画像表示装置構成用部材２を加熱して前記粘着シートをホットメルトさせながら、画像表示装置構成用部材２を貼合するのが好ましい。
また、プレス板で加圧する際のプレス圧は、０．０１ＭＰａ以上或いは０．４ＭＰａ以下、その中でも０．０２ＭＰａ以上或いは０．３５ＭＰａ以下であるのがさらに好ましい。 When laminating the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive sheet of the present invention, the image display device-constituting
In this heating, for example, the image display device laminate composed of image display device
Moreover, the heating temperature at this time is preferably 50° C. or higher and 80° C. or lower. That is, the image display device
Further, the press pressure when pressing with the press plate is preferably 0.01 MPa or more or 0.4 MPa or less, more preferably 0.02 MPa or more or 0.35 MPa or less.
活性エネルギー線を照射して本発明粘着シートを製造する際、活性エネルギー線としては、紫外線及び可視光線が好適である。
活性エネルギー線を照射する際の光源については、例えば高圧水銀ランプ、メタルハライドランプ、キセノンランプ、ハロゲンランプ、ＬＥＤランプ、蛍光ランプなどの中から、照射する光の波長や照射量に応じて使い分けることができる。
照射時間や照射手段に関しては特に限定されないが、例えば紫外線照射であれば、波長３６５ｎｍにおける積算光量が１０００ｍＪ／ｃｍ２以上、更に２０００ｍＪ／ｃｍ２以上、特に３０００ｍＪ／ｃｍ２以上となるように照射するのが好ましい。なお、積算光量の上限は通常１００００ｍＪ／ｃｍ２である。 When the pressure-sensitive adhesive sheet of the present invention is produced by irradiating an active energy ray, ultraviolet rays and visible rays are suitable as the active energy ray.
As for the light source when irradiating the active energy ray, it is possible to use properly according to the wavelength and irradiation amount of the light to be irradiated from, for example, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a halogen lamp, an LED lamp, a fluorescent lamp, etc. can.
The irradiation time and irradiation means are not particularly limited. For example, in the case of ultraviolet irradiation, irradiation is performed so that the integrated light amount at a wavelength of 365 nm is 1000 mJ/cm 2 or more, further 2000 mJ/cm 2 or more, particularly 3000 mJ/cm 2 or more. is preferred. Note that the upper limit of the integrated amount of light is usually 10000 mJ/cm 2 .
活性エネルギー線を照射する際の光源については、例えば高圧水銀ランプ、メタルハライドランプ、キセノンランプ、ハロゲンランプ、ＬＥＤランプ、蛍光ランプなどの中から、照射する光の波長や照射量に応じて使い分けることができる。
照射時間や照射手段に関しては特に限定されないが、例えば紫外線照射であれば、波長３６５ｎｍにおける積算光量が１０００ｍＪ／ｃｍ２以上、更に２０００ｍＪ／ｃｍ２以上、特に３０００ｍＪ／ｃｍ２以上となるように照射するのが好ましい。なお、積算光量の上限は通常１００００ｍＪ／ｃｍ２である。 When the pressure-sensitive adhesive sheet of the present invention is produced by irradiating an active energy ray, ultraviolet rays and visible rays are suitable as the active energy ray.
As for the light source when irradiating the active energy ray, it is possible to use properly according to the wavelength and irradiation amount of the light to be irradiated from, for example, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a halogen lamp, an LED lamp, a fluorescent lamp, etc. can.
The irradiation time and irradiation means are not particularly limited. For example, in the case of ultraviolet irradiation, irradiation is performed so that the integrated light amount at a wavelength of 365 nm is 1000 mJ/cm 2 or more, further 2000 mJ/cm 2 or more, particularly 3000 mJ/cm 2 or more. is preferred. Note that the upper limit of the integrated amount of light is usually 10000 mJ/cm 2 .
（巻き取り）
本発明フレキシブル積層体は、例えば図１に示すように、巻き芯などに巻き付けて巻き取り、その後、巻き戻して広げたときに、本発明粘着シートの巻き長差分による歪みに由来する応力を緩和することができ、粘着シートとフレキシブル画像表示装置用構成部材との間に“浮き”が生じるのを防ぐことができる。よって、本発明フレキシブル積層体は、フレキシブル性に優れ、更にはローラブル性にも優れたものである。
なお、本発明粘着シートにおいて、凹凸形状の凸部が片方に形成されている場合、凸部を外向きに巻き取っても内向きに巻き取っても同様の効果が得られる。 (Take-up)
For example, as shown in FIG. 1, the flexible laminate of the present invention is wound around a winding core or the like, and then unwound and unrolled to relax the stress derived from the strain due to the difference in winding length of the pressure-sensitive adhesive sheet of the present invention. It is possible to prevent "floating" between the pressure-sensitive adhesive sheet and the component for a flexible image display device. Therefore, the flexible laminate of the present invention is excellent in flexibility and also in rollability.
In addition, in the pressure-sensitive adhesive sheet of the present invention, in the case where uneven convex portions are formed on one side, the same effect can be obtained whether the convex portions are wound outward or inward.
本発明フレキシブル積層体は、例えば図１に示すように、巻き芯などに巻き付けて巻き取り、その後、巻き戻して広げたときに、本発明粘着シートの巻き長差分による歪みに由来する応力を緩和することができ、粘着シートとフレキシブル画像表示装置用構成部材との間に“浮き”が生じるのを防ぐことができる。よって、本発明フレキシブル積層体は、フレキシブル性に優れ、更にはローラブル性にも優れたものである。
なお、本発明粘着シートにおいて、凹凸形状の凸部が片方に形成されている場合、凸部を外向きに巻き取っても内向きに巻き取っても同様の効果が得られる。 (Take-up)
For example, as shown in FIG. 1, the flexible laminate of the present invention is wound around a winding core or the like, and then unwound and unrolled to relax the stress derived from the strain due to the difference in winding length of the pressure-sensitive adhesive sheet of the present invention. It is possible to prevent "floating" between the pressure-sensitive adhesive sheet and the component for a flexible image display device. Therefore, the flexible laminate of the present invention is excellent in flexibility and also in rollability.
In addition, in the pressure-sensitive adhesive sheet of the present invention, in the case where uneven convex portions are formed on one side, the same effect can be obtained whether the convex portions are wound outward or inward.
本発明フレキシブル積層体の巻き取り径ｃ、すなわち、巻芯５０の直径は５～５００ｍｍであるのが好ましい。
当該巻き取り径ｃが５ｍｍ以上であれば、巻き取った際に生じる歪をより一層緩和することができ、５００ｍｍ以下であれば、ハンドリング性に優れる。
かかる観点から、本発明フレキシブル積層体の巻き取り径ｃは６ｍｍ以上であるのがより好ましく、７ｍｍ以上であるのがさらに好ましく、１０ｍｍ以上であるのが特に好ましい。他方、４５０ｍｍ以下であるのがより好ましく、４００ｍｍ以下であるのがさらに好ましく、３５０ｍｍ以下であるのが特に好ましい。 The winding diameter c of the flexible laminate of the present invention, that is, the diameter of the windingcore 50 is preferably 5 to 500 mm.
If the winding diameter c is 5 mm or more, the strain generated during winding can be further alleviated, and if it is 500 mm or less, the handleability is excellent.
From this point of view, the winding diameter c of the flexible laminate of the present invention is more preferably 6 mm or more, still more preferably 7 mm or more, and particularly preferably 10 mm or more. On the other hand, it is more preferably 450 mm or less, even more preferably 400 mm or less, and particularly preferably 350 mm or less.
当該巻き取り径ｃが５ｍｍ以上であれば、巻き取った際に生じる歪をより一層緩和することができ、５００ｍｍ以下であれば、ハンドリング性に優れる。
かかる観点から、本発明フレキシブル積層体の巻き取り径ｃは６ｍｍ以上であるのがより好ましく、７ｍｍ以上であるのがさらに好ましく、１０ｍｍ以上であるのが特に好ましい。他方、４５０ｍｍ以下であるのがより好ましく、４００ｍｍ以下であるのがさらに好ましく、３５０ｍｍ以下であるのが特に好ましい。 The winding diameter c of the flexible laminate of the present invention, that is, the diameter of the winding
If the winding diameter c is 5 mm or more, the strain generated during winding can be further alleviated, and if it is 500 mm or less, the handleability is excellent.
From this point of view, the winding diameter c of the flexible laminate of the present invention is more preferably 6 mm or more, still more preferably 7 mm or more, and particularly preferably 10 mm or more. On the other hand, it is more preferably 450 mm or less, even more preferably 400 mm or less, and particularly preferably 350 mm or less.
＜本フレキシブル画像表示装置＞
本発明フレキシブル積層体を組み込むことで、例えば本発明フレキシブル積層体を他の画像表示装置構成部材に積層することで、本発明フレキシブル積層体を備えたフレキシブル画像表示装置（「本フレキシブル画像表示装置」とも称する）を形成することができる。
フレキシブル画像表示装置とは、繰り返し折り曲げや湾曲操作、巻き取り操作をしても曲げ跡を残さず、折り曲げ状態や湾曲状態、巻き取り状態を解放した際には折り曲げや湾曲操作、巻き取り操作をする前の状態まで素早く回復することができ、歪みなく画像を表示できる画像表示装置をいう。とりわけ、本発明においては、ローラブル用に好適なフレキシブル画像表示装置を得ることができる。
また、本発明においては、伸ばしたり、縮めたり等の伸縮操作が繰り返し行われても画像表示装置構成部材の剥がれ等が生じることのない、ストレッチャブル用にも好適なフレキシブル画像表示装置を得ることができる。 <This flexible image display device>
By incorporating the flexible laminate of the present invention, for example, by laminating the flexible laminate of the present invention to other constituent members of an image display device, a flexible image display device equipped with the flexible laminate of the present invention ("this flexible image display device") ) can be formed.
A flexible image display device leaves no trace of bending even after repeated bending, bending, or winding operations, and can be bent, bent, or wound up when the bending, bending, or winding state is released. It is an image display device that can quickly recover to the state before the display and can display an image without distortion. Especially, in the present invention, a flexible image display device suitable for rollable can be obtained.
In addition, in the present invention, it is possible to obtain a flexible image display device suitable for stretchable use, in which even when expansion and contraction operations such as stretching and contracting are repeatedly performed, peeling of the constituent members of the image display device does not occur. can be done.
本発明フレキシブル積層体を組み込むことで、例えば本発明フレキシブル積層体を他の画像表示装置構成部材に積層することで、本発明フレキシブル積層体を備えたフレキシブル画像表示装置（「本フレキシブル画像表示装置」とも称する）を形成することができる。
フレキシブル画像表示装置とは、繰り返し折り曲げや湾曲操作、巻き取り操作をしても曲げ跡を残さず、折り曲げ状態や湾曲状態、巻き取り状態を解放した際には折り曲げや湾曲操作、巻き取り操作をする前の状態まで素早く回復することができ、歪みなく画像を表示できる画像表示装置をいう。とりわけ、本発明においては、ローラブル用に好適なフレキシブル画像表示装置を得ることができる。
また、本発明においては、伸ばしたり、縮めたり等の伸縮操作が繰り返し行われても画像表示装置構成部材の剥がれ等が生じることのない、ストレッチャブル用にも好適なフレキシブル画像表示装置を得ることができる。 <This flexible image display device>
By incorporating the flexible laminate of the present invention, for example, by laminating the flexible laminate of the present invention to other constituent members of an image display device, a flexible image display device equipped with the flexible laminate of the present invention ("this flexible image display device") ) can be formed.
A flexible image display device leaves no trace of bending even after repeated bending, bending, or winding operations, and can be bent, bent, or wound up when the bending, bending, or winding state is released. It is an image display device that can quickly recover to the state before the display and can display an image without distortion. Especially, in the present invention, a flexible image display device suitable for rollable can be obtained.
In addition, in the present invention, it is possible to obtain a flexible image display device suitable for stretchable use, in which even when expansion and contraction operations such as stretching and contracting are repeatedly performed, peeling of the constituent members of the image display device does not occur. can be done.
本フレキシブル画像表示装置においては、液晶パネルなどの画像表示パネルの視認側に本発明粘着シートを配置することもできるし、また、画像表示パネルの視認側とは反対側、すなわち光源側に配置することもできる。
In this flexible image display device, the pressure-sensitive adhesive sheet of the present invention can be placed on the viewing side of an image display panel such as a liquid crystal panel, or can be placed on the side opposite to the viewing side of the image display panel, that is, on the light source side. can also
＜＜用語の説明＞＞
本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。
また、画像表示パネル、保護パネル等のように「パネル」と表現する場合、板体、シート及びフィルムを包含するものである。 <<explanation of terms>>
In the present invention, the term "film" includes the "sheet", and the term "sheet" includes the "film".
In addition, the expression "panel" such as an image display panel, a protective panel, etc. includes a plate, a sheet and a film.
本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。
また、画像表示パネル、保護パネル等のように「パネル」と表現する場合、板体、シート及びフィルムを包含するものである。 <<explanation of terms>>
In the present invention, the term "film" includes the "sheet", and the term "sheet" includes the "film".
In addition, the expression "panel" such as an image display panel, a protective panel, etc. includes a plate, a sheet and a film.
本発明において、「Ｘ～Ｙ」（Ｘ，Ｙは任意の数字）と記載した場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」或いは「好ましくはＹより小さい」の意も包含するものである。
また、「Ｘ以上」（Ｘは任意の数字）と記載した場合、特にことわらない限り「好ましくはＸより大きい」の意を包含し、「Ｙ以下」（Ｙは任意の数字）と記載した場合、特にことわらない限り「好ましくはＹより小さい」の意も包含するものである。
さらに、「Ｘ及び／又はＹ（Ｘ，Ｙは任意の構成）」とは、Ｘ及びＹの少なくとも一方を意味するものであって、Ｘのみ、Ｙのみ、Ｘ及びＹ、の３通りを意味するものである。 In the present invention, when "X to Y" (X and Y are arbitrary numbers), unless otherwise specified, "X or more and Y or less" and "preferably larger than X" or "preferably Y It also includes the meaning of "less than".
In addition, when described as "X or more" (X is an arbitrary number), it includes the meaning of "preferably greater than X" unless otherwise specified, and is described as "Y or less" (Y is an arbitrary number). If not otherwise specified, it also includes the meaning of "preferably smaller than Y".
Furthermore, "X and/or Y (X and Y are arbitrary configurations)" means at least one of X and Y, and means only X, only Y, and X and Y. It is something to do.
また、「Ｘ以上」（Ｘは任意の数字）と記載した場合、特にことわらない限り「好ましくはＸより大きい」の意を包含し、「Ｙ以下」（Ｙは任意の数字）と記載した場合、特にことわらない限り「好ましくはＹより小さい」の意も包含するものである。
さらに、「Ｘ及び／又はＹ（Ｘ，Ｙは任意の構成）」とは、Ｘ及びＹの少なくとも一方を意味するものであって、Ｘのみ、Ｙのみ、Ｘ及びＹ、の３通りを意味するものである。 In the present invention, when "X to Y" (X and Y are arbitrary numbers), unless otherwise specified, "X or more and Y or less" and "preferably larger than X" or "preferably Y It also includes the meaning of "less than".
In addition, when described as "X or more" (X is an arbitrary number), it includes the meaning of "preferably greater than X" unless otherwise specified, and is described as "Y or less" (Y is an arbitrary number). If not otherwise specified, it also includes the meaning of "preferably smaller than Y".
Furthermore, "X and/or Y (X and Y are arbitrary configurations)" means at least one of X and Y, and means only X, only Y, and X and Y. It is something to do.
本発明において、「（メタ）アクリル」とは、「アクリル」及び「メタクリル」を、「（メタ）アクリレート」とは、「アクリレート」及び「メタクリレート」を、「（メタ）アクリロイル」とは、「アクリロイル」及び「メタクリロイル」を、それぞれ包括する意味である。
また、「アクリル系重合体」とは、（メタ）アクリレート由来の単量体単位を含むものを意味し、（メタ）アクリル系共重合体を包含する意味である。 In the present invention, "(meth)acrylic" means "acrylic" and "methacrylic", "(meth)acrylate" means "acrylate" and "methacrylate", and "(meth)acryloyl" means " It is a meaning that encompasses "acryloyl" and "methacryloyl" respectively.
The term "acrylic polymer" means one containing a (meth)acrylate-derived monomer unit, and includes (meth)acrylic copolymers.
また、「アクリル系重合体」とは、（メタ）アクリレート由来の単量体単位を含むものを意味し、（メタ）アクリル系共重合体を包含する意味である。 In the present invention, "(meth)acrylic" means "acrylic" and "methacrylic", "(meth)acrylate" means "acrylate" and "methacrylate", and "(meth)acryloyl" means " It is a meaning that encompasses "acryloyl" and "methacryloyl" respectively.
The term "acrylic polymer" means one containing a (meth)acrylate-derived monomer unit, and includes (meth)acrylic copolymers.
以下、実施例を挙げて本発明をさらに具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。
なお、下記において「部」、「％」とあるのは、質量基準を意味する。 EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In the following, "parts" and "%" mean mass standards.
なお、下記において「部」、「％」とあるのは、質量基準を意味する。 EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In the following, "parts" and "%" mean mass standards.
＜粘着シートの原料＞
次の原料を使用して粘着シートを作製した。 <Raw material for adhesive sheet>
A pressure-sensitive adhesive sheet was produced using the following raw materials.
次の原料を使用して粘着シートを作製した。 <Raw material for adhesive sheet>
A pressure-sensitive adhesive sheet was produced using the following raw materials.
（（メタ）アクリル系重合体（Ａ））
・（メタ）アクリル系重合体（Ａ－１）：数平均分子量２８００のポリメタクリル酸メチルマクロモノマー（Ｔｇ１０５℃）６質量部と、ブチルアクリレート（Ｔｇ－５５℃）９０質量部と、アクリル酸（Ｔｇ１０６℃）４質量部とが共重合してなるアクリル系グラフト共重合体（質量平均分子量：２２万、Ｔｇ－４５℃）
・（メタ）アクリル系重合体（Ａ－２）：数平均分子量２８００のポリメタクリル酸メチルマクロモノマー（Ｔｇ１０５℃）１５質量部と、ブチルアクリレート（Ｔｇ－５５℃）８１質量部と、アクリル酸（１０６℃）４質量部とが共重合してなるアクリル系グラフト共重合体（質量平均分子量：１６万、Ｔｇ－３６℃） ((Meth) acrylic polymer (A))
- (Meth) acrylic polymer (A-1): 6 parts by mass of polymethyl methacrylate macromonomer (Tg 105 ° C.) having a number average molecular weight of 2800, 90 parts by mass of butyl acrylate (Tg -55 ° C.), acrylic acid ( Tg 106° C.) 4 parts by mass of acrylic graft copolymer (mass average molecular weight: 220,000, Tg −45° C.)
- (Meth) acrylic polymer (A-2): 15 parts by mass of polymethyl methacrylate macromonomer (Tg 105 ° C.) having a number average molecular weight of 2800, 81 parts by mass of butyl acrylate (Tg -55 ° C.), and acrylic acid ( 106° C.) 4 parts by mass of acrylic graft copolymer (mass average molecular weight: 160,000, Tg −36° C.)
・（メタ）アクリル系重合体（Ａ－１）：数平均分子量２８００のポリメタクリル酸メチルマクロモノマー（Ｔｇ１０５℃）６質量部と、ブチルアクリレート（Ｔｇ－５５℃）９０質量部と、アクリル酸（Ｔｇ１０６℃）４質量部とが共重合してなるアクリル系グラフト共重合体（質量平均分子量：２２万、Ｔｇ－４５℃）
・（メタ）アクリル系重合体（Ａ－２）：数平均分子量２８００のポリメタクリル酸メチルマクロモノマー（Ｔｇ１０５℃）１５質量部と、ブチルアクリレート（Ｔｇ－５５℃）８１質量部と、アクリル酸（１０６℃）４質量部とが共重合してなるアクリル系グラフト共重合体（質量平均分子量：１６万、Ｔｇ－３６℃） ((Meth) acrylic polymer (A))
- (Meth) acrylic polymer (A-1): 6 parts by mass of polymethyl methacrylate macromonomer (Tg 105 ° C.) having a number average molecular weight of 2800, 90 parts by mass of butyl acrylate (Tg -55 ° C.), acrylic acid ( Tg 106° C.) 4 parts by mass of acrylic graft copolymer (mass average molecular weight: 220,000, Tg −45° C.)
- (Meth) acrylic polymer (A-2): 15 parts by mass of polymethyl methacrylate macromonomer (Tg 105 ° C.) having a number average molecular weight of 2800, 81 parts by mass of butyl acrylate (Tg -55 ° C.), and acrylic acid ( 106° C.) 4 parts by mass of acrylic graft copolymer (mass average molecular weight: 160,000, Tg −36° C.)
（光重合開始剤（Ｂ））
・開始剤（Ｂ－１）：２，４，６－トリメチルベンゾフェノン及び４－メチルベンゾフェノンの混合物（ＩＧＭ社製「Ｅｓａｃｕｒｅ ＴＺＴ」） (Photoinitiator (B))
- Initiator (B-1): a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone ("Esacure TZT" manufactured by IGM)
・開始剤（Ｂ－１）：２，４，６－トリメチルベンゾフェノン及び４－メチルベンゾフェノンの混合物（ＩＧＭ社製「Ｅｓａｃｕｒｅ ＴＺＴ」） (Photoinitiator (B))
- Initiator (B-1): a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone ("Esacure TZT" manufactured by IGM)
（架橋剤（Ｃ））
・開始剤（Ｃ－１）：プロポキシ化ペンタエリスリトールトリアクリレート (Crosslinking agent (C))
- Initiator (C-1): propoxylated pentaerythritol triacrylate
・開始剤（Ｃ－１）：プロポキシ化ペンタエリスリトールトリアクリレート (Crosslinking agent (C))
- Initiator (C-1): propoxylated pentaerythritol triacrylate
（その他）
・防錆剤：１，２，３－ベンゾトリアゾール (others)
・Rust inhibitor: 1,2,3-benzotriazole
・防錆剤：１，２，３－ベンゾトリアゾール (others)
・Rust inhibitor: 1,2,3-benzotriazole
＜離型フィルム付き粘着シート１の作製＞
（メタ）アクリル系重合体（Ａ－２）１００質量部、開始剤（Ｂ－１）２．５質量部、架橋剤（Ｃ－１）３質量部、防錆剤０．５質量部を混合し、粘着剤組成物を得た。
次に、得られた粘着剤組成物を１００℃に加熱してホットメルトし、シリコーン離型処理された１００μｍの離型フィルム（三菱ケミカル社製ＰＥＴフィルム、厚さ１００μｍ）と、シリコーン離型処理された７５μｍの離型フィルム（三菱ケミカル社製ＰＥＴフィルム、厚さ７５μｍ）、すなわち２枚の離型フィルムの間に挟んで、厚さ５０μｍのシート状に成形し、離型フィルム／粘着シート／離型フィルムからなる離型フィルム付き粘着シート１（凹凸パターン形成前）を得た。
なお、粘着シート１は、光を照射することにより硬化する活性エネルギー線硬化性を備えた粘着シートであった。 <Preparation of pressure-sensitive adhesive sheet 1 with release film>
(Meth)acrylic polymer (A-2) 100 parts by mass, initiator (B-1) 2.5 parts by mass, cross-linking agent (C-1) 3 parts by mass, rust inhibitor 0.5 parts by mass. to obtain an adhesive composition.
Next, the obtained pressure-sensitive adhesive composition was heated to 100 ° C. to hot-melt, and a 100 µm release film (PET film manufactured by Mitsubishi Chemical Corporation, thickness 100 µm) subjected to silicone release treatment, and silicone release treatment 75 μm release film (PET film manufactured by Mitsubishi Chemical Corporation, thickness 75 μm), that is, sandwiched between two release films, formed into a sheet with a thickness of 50 μm, release film / adhesive sheet / A release film-attached pressure-sensitive adhesive sheet 1 (before formation of the uneven pattern) was obtained.
Theadhesive sheet 1 was an active energy ray-curing adhesive sheet that was cured by irradiation with light.
（メタ）アクリル系重合体（Ａ－２）１００質量部、開始剤（Ｂ－１）２．５質量部、架橋剤（Ｃ－１）３質量部、防錆剤０．５質量部を混合し、粘着剤組成物を得た。
次に、得られた粘着剤組成物を１００℃に加熱してホットメルトし、シリコーン離型処理された１００μｍの離型フィルム（三菱ケミカル社製ＰＥＴフィルム、厚さ１００μｍ）と、シリコーン離型処理された７５μｍの離型フィルム（三菱ケミカル社製ＰＥＴフィルム、厚さ７５μｍ）、すなわち２枚の離型フィルムの間に挟んで、厚さ５０μｍのシート状に成形し、離型フィルム／粘着シート／離型フィルムからなる離型フィルム付き粘着シート１（凹凸パターン形成前）を得た。
なお、粘着シート１は、光を照射することにより硬化する活性エネルギー線硬化性を備えた粘着シートであった。 <Preparation of pressure-
(Meth)acrylic polymer (A-2) 100 parts by mass, initiator (B-1) 2.5 parts by mass, cross-linking agent (C-1) 3 parts by mass, rust inhibitor 0.5 parts by mass. to obtain an adhesive composition.
Next, the obtained pressure-sensitive adhesive composition was heated to 100 ° C. to hot-melt, and a 100 µm release film (PET film manufactured by Mitsubishi Chemical Corporation, thickness 100 µm) subjected to silicone release treatment, and silicone release treatment 75 μm release film (PET film manufactured by Mitsubishi Chemical Corporation, thickness 75 μm), that is, sandwiched between two release films, formed into a sheet with a thickness of 50 μm, release film / adhesive sheet / A release film-attached pressure-sensitive adhesive sheet 1 (before formation of the uneven pattern) was obtained.
The
＜離型フィルム付き粘着シート２の作製＞
（メタ）アクリル系重合体（Ａ－１）１００質量部、開始剤（Ｂ－１）２．５質量部、架橋剤（Ｃ－１）３質量部、防錆剤０．５質量部を混合して粘着剤組成物を得た以外は、前記離型フィルム付き粘着シート１と同様にして離型フィルム付き粘着シート２（凹凸パターン形成前）を作製した。 <Preparation of adhesive sheet 2 with release film>
(Meth)acrylic polymer (A-1) 100 parts by mass, initiator (B-1) 2.5 parts by mass, cross-linking agent (C-1) 3 parts by mass, rust inhibitor 0.5 parts by mass. A pressure-sensitive adhesive sheet 2 with a release film (before formation of the uneven pattern) was produced in the same manner as the pressure-sensitive adhesive sheet 1 with a release film, except that a pressure-sensitive adhesive composition was obtained.
（メタ）アクリル系重合体（Ａ－１）１００質量部、開始剤（Ｂ－１）２．５質量部、架橋剤（Ｃ－１）３質量部、防錆剤０．５質量部を混合して粘着剤組成物を得た以外は、前記離型フィルム付き粘着シート１と同様にして離型フィルム付き粘着シート２（凹凸パターン形成前）を作製した。 <Preparation of adhesive sheet 2 with release film>
(Meth)acrylic polymer (A-1) 100 parts by mass, initiator (B-1) 2.5 parts by mass, cross-linking agent (C-1) 3 parts by mass, rust inhibitor 0.5 parts by mass. A pressure-sensitive adhesive sheet 2 with a release film (before formation of the uneven pattern) was produced in the same manner as the pressure-
＜凹凸付き金型Ｘ、及び、凹凸付き金型Ｙの作製＞
精密平板加工機に、被削材に銅めっきを使用した平板金型を取り付け、先端５０ｍｍＲの単結晶ダイヤモンドバイトを用いて鏡面加工を行った。次に、先端に２００μｍフラット部を有する挟み角３０°の単結晶ダイヤモンドバイトを用いて、送りピッチ３００μｍで切込み量５０μｍの溝加工を行うことで、図６に示すように、底幅２００μｍ、深さ５０μｍの台形状の複数の溝が、７４μｍの間隔をおいてピッチ３００μｍで繰り返し形成されてなる凹凸構造を金型表面に有する凹凸付き金型Ｘを得た。
次いで、無電解ニッケルめっき処理を行い、凹凸表面に１．０μｍ厚みの無電解ニッケルめっきを有する凹凸付き金型Ｙを得た。 <Production of mold X with unevenness and mold Y with unevenness>
A flat plate mold using copper plating as a work material was attached to a precision flat plate processing machine, and mirror finishing was performed using a single crystal diamond cutting tool with a tip radius of 50 mm. Next, using a single-crystal diamond cutting tool with a flat portion of 200 μm at the tip and an included angle of 30°, grooving was performed with a feed pitch of 300 μm and a depth of cut of 50 μm. An uneven mold X having an uneven structure in which a plurality of trapezoidal grooves with a thickness of 50 μm are repeatedly formed at intervals of 74 μm at a pitch of 300 μm on the surface of the mold was obtained.
Then, an electroless nickel plating treatment was performed to obtain a mold Y with unevenness having a 1.0 μm-thick electroless nickel plating on the uneven surface.
精密平板加工機に、被削材に銅めっきを使用した平板金型を取り付け、先端５０ｍｍＲの単結晶ダイヤモンドバイトを用いて鏡面加工を行った。次に、先端に２００μｍフラット部を有する挟み角３０°の単結晶ダイヤモンドバイトを用いて、送りピッチ３００μｍで切込み量５０μｍの溝加工を行うことで、図６に示すように、底幅２００μｍ、深さ５０μｍの台形状の複数の溝が、７４μｍの間隔をおいてピッチ３００μｍで繰り返し形成されてなる凹凸構造を金型表面に有する凹凸付き金型Ｘを得た。
次いで、無電解ニッケルめっき処理を行い、凹凸表面に１．０μｍ厚みの無電解ニッケルめっきを有する凹凸付き金型Ｙを得た。 <Production of mold X with unevenness and mold Y with unevenness>
A flat plate mold using copper plating as a work material was attached to a precision flat plate processing machine, and mirror finishing was performed using a single crystal diamond cutting tool with a tip radius of 50 mm. Next, using a single-crystal diamond cutting tool with a flat portion of 200 μm at the tip and an included angle of 30°, grooving was performed with a feed pitch of 300 μm and a depth of cut of 50 μm. An uneven mold X having an uneven structure in which a plurality of trapezoidal grooves with a thickness of 50 μm are repeatedly formed at intervals of 74 μm at a pitch of 300 μm on the surface of the mold was obtained.
Then, an electroless nickel plating treatment was performed to obtain a mold Y with unevenness having a 1.0 μm-thick electroless nickel plating on the uneven surface.
＜実施例１＞
図７に示すように、離型フィルム付き粘着シート１の一方の離型フィルム１２を剥離した貼着面に、金型Ｘの凹凸側を積層し、金型Ｘとは反対側の離型フィルム１２表面をローラーで貼合した後、当該離型フィルム１２表面にガラス板を載せて、金型温度２３℃、圧力０．００１ＭＰａで荷重（Ｐ）を掛けた状態で３０分静置した。次いで、ＵＶランプ（Ｆｕｓｉｏｎ社製、Ｈバルブ）を用いて、金型Ｘの反対側から離型フィルム１２を通して粘着シート１０に対して、２００～５００ｎｍ波長の光を積算光量４０００ｍＪ／ｃｍ２露光して粘着シート１０を硬化させた。露光後に、金型Ｘを離し、更に離型フィルム１３を積層することで、凹凸パターン形成された離型フィルム付き粘着シート１（本発明粘着シート）を得た。 <Example 1>
As shown in FIG. 7, the uneven side of the mold X is laminated on the sticking surface from which one of therelease films 12 of the pressure-sensitive adhesive sheet 1 with a release film has been peeled off, and the release film on the side opposite to the mold X is laminated. After laminating the surface of 12 with a roller, a glass plate was placed on the surface of the release film 12 and allowed to stand for 30 minutes while applying a load (P) at a mold temperature of 23° C. and a pressure of 0.001 MPa. Then, using a UV lamp (manufactured by Fusion, H bulb), the pressure-sensitive adhesive sheet 10 is exposed to light with a wavelength of 200 to 500 nm through the release film 12 from the opposite side of the mold X with an integrated light amount of 4000 mJ/cm 2 . to cure the adhesive sheet 10. After the exposure, the mold X was released, and a release film 13 was further laminated to obtain a release film-attached pressure-sensitive adhesive sheet 1 (the pressure-sensitive adhesive sheet of the present invention) having an uneven pattern.
図７に示すように、離型フィルム付き粘着シート１の一方の離型フィルム１２を剥離した貼着面に、金型Ｘの凹凸側を積層し、金型Ｘとは反対側の離型フィルム１２表面をローラーで貼合した後、当該離型フィルム１２表面にガラス板を載せて、金型温度２３℃、圧力０．００１ＭＰａで荷重（Ｐ）を掛けた状態で３０分静置した。次いで、ＵＶランプ（Ｆｕｓｉｏｎ社製、Ｈバルブ）を用いて、金型Ｘの反対側から離型フィルム１２を通して粘着シート１０に対して、２００～５００ｎｍ波長の光を積算光量４０００ｍＪ／ｃｍ２露光して粘着シート１０を硬化させた。露光後に、金型Ｘを離し、更に離型フィルム１３を積層することで、凹凸パターン形成された離型フィルム付き粘着シート１（本発明粘着シート）を得た。 <Example 1>
As shown in FIG. 7, the uneven side of the mold X is laminated on the sticking surface from which one of the
得られた凹凸パターンが形成された離型フィルム付き粘着シート１（本発明粘着シート）には、フィルム幅方向すなわちＴＤ方向に伸びた凸状部からなる凹凸単位が、フィルム長さ方向すなわちＭＤ方向に適宜間隔を置いて繰り返し形成されてなる凹凸パターンが形成された。当該凹凸パターンは、図９に示すように、本発明粘着シートをＭＤ方向、すなわち巻き周方向とする方向に沿って肉厚方向に切断した縦断面において、表１に記載の通りの形状を有するものであった。
In the obtained pressure-sensitive adhesive sheet 1 with a release film (the pressure-sensitive adhesive sheet of the present invention) on which the uneven pattern is formed, the uneven unit composed of the convex portions extending in the film width direction, that is, the TD direction, is arranged in the film length direction, that is, the MD direction. A concave-convex pattern formed repeatedly at appropriate intervals was formed. As shown in FIG. 9, the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
＜実施例２＞
実施例１において、離型フィルム付き粘着シート２を用いて、金型温度２３℃、圧力０．００１ＭＰａで荷重を掛けた状態で３０分静置した以外は、実施例１と同様にして、凹凸パターンが形成された離型フィルム付き粘着シート２（本発明粘着シート）を得た。 <Example 2>
In Example 1, unevenness was formed in the same manner as in Example 1, except that the pressure-sensitive adhesive sheet 2 with a release film was used and the mold temperature was 23 ° C. and the load was applied at a pressure of 0.001 MPa for 30 minutes. A release film-attached pressure-sensitive adhesive sheet 2 (the pressure-sensitive adhesive sheet of the present invention) in which a pattern was formed was obtained.
実施例１において、離型フィルム付き粘着シート２を用いて、金型温度２３℃、圧力０．００１ＭＰａで荷重を掛けた状態で３０分静置した以外は、実施例１と同様にして、凹凸パターンが形成された離型フィルム付き粘着シート２（本発明粘着シート）を得た。 <Example 2>
In Example 1, unevenness was formed in the same manner as in Example 1, except that the pressure-sensitive adhesive sheet 2 with a release film was used and the mold temperature was 23 ° C. and the load was applied at a pressure of 0.001 MPa for 30 minutes. A release film-attached pressure-sensitive adhesive sheet 2 (the pressure-sensitive adhesive sheet of the present invention) in which a pattern was formed was obtained.
得られた凹凸パターンが形成された離型フィルム付き粘着シート２（本発明粘着シート）には、フィルム幅方向すなわちＴＤ方向に伸びた断面台形状の凸状部からなる凹凸単位が、フィルム長さ方向すなわちＭＤ方向に適宜間隔を置いて繰り返し形成されてなる凹凸パターンが形成された。当該凹凸パターンは、図９に示すように、本発明粘着シートをＭＤ方向、すなわち巻き周方向とする方向に沿って肉厚方向に切断した縦断面において、表１に記載の通りの形状を有するものであった。
In the obtained pressure-sensitive adhesive sheet 2 with a release film (the pressure-sensitive adhesive sheet of the present invention) on which the uneven pattern is formed, the uneven unit consisting of the convex portion having a trapezoidal cross section extending in the film width direction, that is, the TD direction, extends along the length of the film. A concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the MD direction. As shown in FIG. 9, the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
＜実施例３＞
実施例２において、金型温度６０℃、圧力０．００１ＭＰａで荷重を掛けた状態で３０分静置した以外は、実施例２と同様にして、凹凸パターンが形成された離型フィルム付き粘着シート３（本発明粘着シート）を得た。 <Example 3>
In Example 2, the pressure-sensitive adhesive sheet with a release film having an uneven pattern was formed in the same manner as in Example 2, except that the mold temperature was 60 ° C. and the load was applied at a pressure of 0.001 MPa for 30 minutes. 3 (the pressure-sensitive adhesive sheet of the present invention) was obtained.
実施例２において、金型温度６０℃、圧力０．００１ＭＰａで荷重を掛けた状態で３０分静置した以外は、実施例２と同様にして、凹凸パターンが形成された離型フィルム付き粘着シート３（本発明粘着シート）を得た。 <Example 3>
In Example 2, the pressure-sensitive adhesive sheet with a release film having an uneven pattern was formed in the same manner as in Example 2, except that the mold temperature was 60 ° C. and the load was applied at a pressure of 0.001 MPa for 30 minutes. 3 (the pressure-sensitive adhesive sheet of the present invention) was obtained.
得られた凹凸パターンが形成された離型フィルム付き粘着シート３（本粘接着シート）には、フィルム幅方向すなわちＴＤ方向に伸びた断面台形状の凸状部からなる凹凸単位が、フィルム長さ方向すなわちＭＤ方向に適宜間隔を置いて繰り返し形成されてなる凹凸パターンが形成された。当該凹凸パターンは、図９に示すように、本発明粘着シートをＭＤ方向、すなわち巻き周方向とする方向に沿って肉厚方向に切断した縦断面において、表１に記載の通りの形状を有するものであった。
In the obtained pressure-sensitive adhesive sheet 3 with a release film (the present pressure-sensitive adhesive sheet) on which the uneven pattern is formed, the unevenness unit consisting of a convex portion having a trapezoidal cross section extending in the film width direction, that is, the TD direction, extends over the length of the film. A concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the longitudinal direction, that is, the MD direction. As shown in FIG. 9, the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
＜実施例４＞
実施例２において、金型温度２３℃、圧力０．００１ＭＰａで荷重を掛けた状態で３０分静置した以外は、実施例２と同様にして、凹凸パターンが形成された離型フィルム付き粘着シート４（本発明粘着シート）を得た。 <Example 4>
In Example 2, the pressure-sensitive adhesive sheet with a release film having an uneven pattern was formed in the same manner as in Example 2, except that the mold temperature was 23 ° C. and the pressure was 0.001 MPa and the pressure was applied for 30 minutes. 4 (the pressure-sensitive adhesive sheet of the present invention) was obtained.
実施例２において、金型温度２３℃、圧力０．００１ＭＰａで荷重を掛けた状態で３０分静置した以外は、実施例２と同様にして、凹凸パターンが形成された離型フィルム付き粘着シート４（本発明粘着シート）を得た。 <Example 4>
In Example 2, the pressure-sensitive adhesive sheet with a release film having an uneven pattern was formed in the same manner as in Example 2, except that the mold temperature was 23 ° C. and the pressure was 0.001 MPa and the pressure was applied for 30 minutes. 4 (the pressure-sensitive adhesive sheet of the present invention) was obtained.
得られた凹凸パターンが形成された離型フィルム付き粘着シート４（本発明粘着シート）には、フィルム幅方向すなわちＴＤ方向に伸びた断面台形状の凸状部からなる凹凸単位が、フィルム長さ方向すなわちＭＤ方向に適宜間隔を置いて繰り返し形成されてなる凹凸パターンが形成された。当該凹凸パターンは、図９に示すように、本発明粘着シートをＭＤ方向、すなわち巻き周方向とする方向に沿って肉厚方向に切断した縦断面において、表１に記載の通りの形状を有するものであった。
In the obtained pressure-sensitive adhesive sheet 4 with a release film (the pressure-sensitive adhesive sheet of the present invention) on which the uneven pattern is formed, the uneven unit consisting of the convex portion having a trapezoidal cross section extending in the film width direction, that is, the TD direction, extends along the length of the film. A concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the MD direction. As shown in FIG. 9, the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
＜実施例５＞
実施例２において、金型温度２３℃、圧力０．００５ＭＰａで荷重を掛けた状態で３０分静置した以外は、実施例２と同様にして、凹凸パターンが形成された離型フィルム付き粘着シート５（本発明粘着シート）を得た。 <Example 5>
In Example 2, the pressure-sensitive adhesive sheet with a release film having an uneven pattern was formed in the same manner as in Example 2, except that the mold temperature was 23 ° C. and the load was applied at a pressure of 0.005 MPa for 30 minutes. 5 (the pressure-sensitive adhesive sheet of the present invention) was obtained.
実施例２において、金型温度２３℃、圧力０．００５ＭＰａで荷重を掛けた状態で３０分静置した以外は、実施例２と同様にして、凹凸パターンが形成された離型フィルム付き粘着シート５（本発明粘着シート）を得た。 <Example 5>
In Example 2, the pressure-sensitive adhesive sheet with a release film having an uneven pattern was formed in the same manner as in Example 2, except that the mold temperature was 23 ° C. and the load was applied at a pressure of 0.005 MPa for 30 minutes. 5 (the pressure-sensitive adhesive sheet of the present invention) was obtained.
得られた凹凸パターンが形成された離型フィルム付き粘着シート５（本発明粘着シート）には、フィルム幅方向すなわちＴＤ方向に伸びた断面台形状の凸状部からなる凹凸単位が、フィルム長さ方向すなわちＭＤ方向に適宜間隔を置いて繰り返し形成されてなる凹凸パターンが形成された。当該凹凸パターンは、図９に示すように、本発明粘着シートをＭＤ方向、すなわち巻き周方向とする方向に沿って肉厚方向に切断した縦断面において、表１に記載の通りの形状を有するものであった。
In the obtained pressure-sensitive adhesive sheet 5 with a release film (the pressure-sensitive adhesive sheet of the present invention) on which the uneven pattern is formed, the uneven unit consisting of the convex portion having a trapezoidal cross section extending in the film width direction, that is, in the TD direction, extends along the length of the film. A concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the MD direction. As shown in FIG. 9, the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
＜比較例１＞
離型フィルム付き粘着シート１をそのまま、比較例１の粘着シート１’（比較粘着シート）とした。 <Comparative Example 1>
The pressure-sensitive adhesive sheet 1 with a release film was used as the pressure-sensitive adhesive sheet 1′ of Comparative Example 1 (comparative pressure-sensitive adhesive sheet).
離型フィルム付き粘着シート１をそのまま、比較例１の粘着シート１’（比較粘着シート）とした。 <Comparative Example 1>
The pressure-
＜比較例２＞
離型フィルム付き粘着シート１を用いて、金型温度２３℃、圧力０．００００１ＭＰａで荷重を掛けた状態で３０分静置した以外は、実施例１と同様にして、凹凸パターンが形成された離型フィルム付き粘着シート２’（比較粘着シート）を得た。 <Comparative Example 2>
A concavo-convex pattern was formed in the same manner as in Example 1, except that the pressure-sensitive adhesive sheet 1 with a release film was used and allowed to stand for 30 minutes with a mold temperature of 23 ° C. and a pressure of 0.00001 MPa. A release film-attached pressure-sensitive adhesive sheet 2' (comparative pressure-sensitive adhesive sheet) was obtained.
離型フィルム付き粘着シート１を用いて、金型温度２３℃、圧力０．００００１ＭＰａで荷重を掛けた状態で３０分静置した以外は、実施例１と同様にして、凹凸パターンが形成された離型フィルム付き粘着シート２’（比較粘着シート）を得た。 <Comparative Example 2>
A concavo-convex pattern was formed in the same manner as in Example 1, except that the pressure-
得られた凹凸パターンが形成された離型フィルム付き粘着シート２’（比較粘着シート）には、フィルム幅方向すなわちＴＤ方向に伸びた断面台形状の凸状部からなる凹凸単位が、フィルム長さ方向すなわちＭＤ方向に適宜間隔を置いて繰り返し形成されてなる凹凸パターンが形成された。当該凹凸パターンは、図９に示すように、本発明粘着シートをＭＤ方向、すなわち巻き周方向とする方向に沿って肉厚方向に切断した縦断面において、表１に記載の通りの形状を有するものであった。
In the obtained pressure-sensitive adhesive sheet 2′ with a release film (comparative pressure-sensitive adhesive sheet) on which the concave-convex pattern is formed, the concave-convex unit consisting of a convex portion having a trapezoidal cross section extending in the film width direction, that is, the TD direction, extends over the length of the film. A concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the MD direction. As shown in FIG. 9, the uneven pattern has a shape as shown in Table 1 in a longitudinal section of the adhesive sheet of the present invention cut in the thickness direction along the MD direction, that is, the winding direction. It was something.
＜測定方法及び評価方法＞
実施例の粘着シート１～５（本発明粘着シート）及び比較例の粘着シート１’～２’（比較粘着シート）の各種物性値の測定方法及び評価方法について説明する。 <Measurement method and evaluation method>
Methods for measuring and evaluating various physical property values ofPSA sheets 1 to 5 of Examples (the PSA sheets of the present invention) and PSA sheets 1′ and 2′ of Comparative Examples (comparative PSA sheets) will be described.
実施例の粘着シート１～５（本発明粘着シート）及び比較例の粘着シート１’～２’（比較粘着シート）の各種物性値の測定方法及び評価方法について説明する。 <Measurement method and evaluation method>
Methods for measuring and evaluating various physical property values of
＜凹凸パターン各部の測定＞
実施例の粘着シート１～５（本発明粘着シート）及び比較例の粘着シート１’～２’（比較粘着シート）のＭＤ方向、すなわち巻き周方向とする方向に沿って肉厚方向に切断した縦断面を、レーザー顕微鏡（ＬＥＸＴ、オリンパス社製）を用いて観察し、粘着面に形成された凹凸パターンの各形状を測定した。測定結果は表１の通りであった。 <Measurement of each part of the uneven pattern>
Theadhesive sheets 1 to 5 of the examples (the adhesive sheets of the present invention) and the adhesive sheets 1' to 2' of the comparative examples (comparative adhesive sheets) were cut in the thickness direction along the MD direction, that is, the winding circumferential direction. The longitudinal section was observed using a laser microscope (LEXT, manufactured by Olympus Corporation) to measure each shape of the uneven pattern formed on the adhesive surface. The measurement results are shown in Table 1.
実施例の粘着シート１～５（本発明粘着シート）及び比較例の粘着シート１’～２’（比較粘着シート）のＭＤ方向、すなわち巻き周方向とする方向に沿って肉厚方向に切断した縦断面を、レーザー顕微鏡（ＬＥＸＴ、オリンパス社製）を用いて観察し、粘着面に形成された凹凸パターンの各形状を測定した。測定結果は表１の通りであった。 <Measurement of each part of the uneven pattern>
The
＜離型フィルム付き粘着シートの空間部の空隙率の測定＞
上記で得られた凹凸パターンが形成された離型フィルム付き粘着シートに関し、粘着シートの凹凸パターンが形成された粘着面と、離型フィルムとの間に存在する空間部の空隙率を次のように測定した。測定結果は表１の通りであった。
凹凸構造を有する本発明離型フィルム付き粘着シートの表面を、離型フィルム越しに、光学顕微鏡（キーエンス社製、マイクロスコープＶＨＸ－６００）を用いて、凸部の幅（ｗ２、ｗ３、ｗ４）を測定した。また、本発明離型フィルム付き粘着シートを厚さ方向に切断し、断面における凹凸の高さ（ｈ）及び粘着シート厚み（Ｈ）を、光学顕微鏡を用いて測定した。得られた結果より（（ｗ３＋（ｗ２－ｗ４））×ｈ÷２）／（ｗ２×Ｈ）より空隙率（％）を測定した。 <Measurement of the void ratio of the space of the pressure-sensitive adhesive sheet with release film>
Regarding the pressure-sensitive adhesive sheet with a release film on which the uneven pattern is formed, the void ratio of the space existing between the adhesive surface of the pressure-sensitive adhesive sheet on which the uneven pattern is formed and the release film is as follows. measured to The measurement results are shown in Table 1.
The surface of the pressure-sensitive adhesive sheet with the release film of the present invention having an uneven structure is examined through the release film using an optical microscope (Microscope VHX-600, manufactured by Keyence Corporation) to determine the width of the protrusions (w2, w3, w4). was measured. In addition, the pressure-sensitive adhesive sheet with the release film of the present invention was cut in the thickness direction, and the height (h) of unevenness in the cross section and the thickness (H) of the pressure-sensitive adhesive sheet were measured using an optical microscope. From the obtained results, the porosity (%) was measured from ((w3+(w2-w4))×h÷2)/(w2×H).
上記で得られた凹凸パターンが形成された離型フィルム付き粘着シートに関し、粘着シートの凹凸パターンが形成された粘着面と、離型フィルムとの間に存在する空間部の空隙率を次のように測定した。測定結果は表１の通りであった。
凹凸構造を有する本発明離型フィルム付き粘着シートの表面を、離型フィルム越しに、光学顕微鏡（キーエンス社製、マイクロスコープＶＨＸ－６００）を用いて、凸部の幅（ｗ２、ｗ３、ｗ４）を測定した。また、本発明離型フィルム付き粘着シートを厚さ方向に切断し、断面における凹凸の高さ（ｈ）及び粘着シート厚み（Ｈ）を、光学顕微鏡を用いて測定した。得られた結果より（（ｗ３＋（ｗ２－ｗ４））×ｈ÷２）／（ｗ２×Ｈ）より空隙率（％）を測定した。 <Measurement of the void ratio of the space of the pressure-sensitive adhesive sheet with release film>
Regarding the pressure-sensitive adhesive sheet with a release film on which the uneven pattern is formed, the void ratio of the space existing between the adhesive surface of the pressure-sensitive adhesive sheet on which the uneven pattern is formed and the release film is as follows. measured to The measurement results are shown in Table 1.
The surface of the pressure-sensitive adhesive sheet with the release film of the present invention having an uneven structure is examined through the release film using an optical microscope (Microscope VHX-600, manufactured by Keyence Corporation) to determine the width of the protrusions (w2, w3, w4). was measured. In addition, the pressure-sensitive adhesive sheet with the release film of the present invention was cut in the thickness direction, and the height (h) of unevenness in the cross section and the thickness (H) of the pressure-sensitive adhesive sheet were measured using an optical microscope. From the obtained results, the porosity (%) was measured from ((w3+(w2-w4))×h÷2)/(w2×H).
＜ＰＥＴフィルム基材に貼り合わせた際に形成される空間部の空隙率の測定＞
フレキシブル画像表示装置用構成部材の代替材料としてのＰＥＴフィルム基材に、粘着シートを貼り合わせた際に、粘着シートの凹凸パターンが形成された粘着面と、ＰＥＴフィルム基材との間に存在する空間部の空隙率を、上記の空隙率測定方法に準じて測定した結果、いずれの実施例・比較例においても、粘着シートの凹凸パターンが形成された粘着面と、離型フィルムとの間に存在する空間部の空隙率と同じ値であった。 <Measurement of porosity of space formed when bonded to PET film substrate>
When an adhesive sheet is attached to a PET film substrate as an alternative material for a component of a flexible image display device, it exists between the adhesive surface of the adhesive sheet on which the uneven pattern is formed and the PET film substrate. As a result of measuring the porosity of the space according to the above porosity measuring method, in all of the examples and comparative examples, the adhesive surface of the adhesive sheet on which the uneven pattern was formed and the release film It was the same value as the porosity of the existing space.
フレキシブル画像表示装置用構成部材の代替材料としてのＰＥＴフィルム基材に、粘着シートを貼り合わせた際に、粘着シートの凹凸パターンが形成された粘着面と、ＰＥＴフィルム基材との間に存在する空間部の空隙率を、上記の空隙率測定方法に準じて測定した結果、いずれの実施例・比較例においても、粘着シートの凹凸パターンが形成された粘着面と、離型フィルムとの間に存在する空間部の空隙率と同じ値であった。 <Measurement of porosity of space formed when bonded to PET film substrate>
When an adhesive sheet is attached to a PET film substrate as an alternative material for a component of a flexible image display device, it exists between the adhesive surface of the adhesive sheet on which the uneven pattern is formed and the PET film substrate. As a result of measuring the porosity of the space according to the above porosity measuring method, in all of the examples and comparative examples, the adhesive surface of the adhesive sheet on which the uneven pattern was formed and the release film It was the same value as the porosity of the existing space.
＜粘着力＞
図１０に示すように、実施例の粘着シート１～５（本発明粘着シート）及び比較例の粘着シート１’～２’（比較粘着シート）を幅２０ｍｍ×長さ１００ｍｍにカットし、凹凸パターンが形成された粘着剤表面側の離型フィルム１３を剥がした後、粘着剤表面を、２軸延伸フィルムであるＰＥＴフィルム基材１１（ダイアホイル、三菱ケミカル社製、「Ｔ９１３Ｅ１２５Ｃ」厚み１２５μｍ）にローラーで貼り付けて、離型フィルム１２／粘着シート１０／ＰＥＴフィルム基材１１の層構成の積層体とした。なお、粘着シートを貼り合わる際、意図的に加熱及び加圧はしていない。
そして、粘着シート１０とＰＥＴフィルム基材１１との界面において、ＪＩＳ Ｚ ０２３７：２０００に準じて、剥離速度３００ｍｍ／ｍｉｎで９０度剥離試験を行い、粘着力（Ｎ／２０ｍｍ）を測定した。 <Adhesive strength>
As shown in FIG. 10, pressure-sensitive adhesive sheets 1 to 5 of Examples (the pressure-sensitive adhesive sheets of the present invention) and pressure-sensitive adhesive sheets 1' to 2' of Comparative Examples (comparative pressure-sensitive adhesive sheets) were cut into a width of 20 mm and a length of 100 mm. After peeling off the release film 13 on the adhesive surface side on which is formed, the adhesive surface is applied to the PET film base material 11 (Diafoil, manufactured by Mitsubishi Chemical Co., Ltd., "T913E125C" thickness 125 μm), which is a biaxially stretched film. A laminate having a layer structure of release film 12/adhesive sheet 10/PET film substrate 11 was formed by sticking with a roller. It should be noted that when the pressure-sensitive adhesive sheets were attached together, they were not intentionally heated or pressurized.
At the interface between theadhesive sheet 10 and the PET film substrate 11, a 90 degree peel test was performed at a peel rate of 300 mm/min according to JIS Z 0237:2000 to measure the adhesive strength (N/20 mm).
図１０に示すように、実施例の粘着シート１～５（本発明粘着シート）及び比較例の粘着シート１’～２’（比較粘着シート）を幅２０ｍｍ×長さ１００ｍｍにカットし、凹凸パターンが形成された粘着剤表面側の離型フィルム１３を剥がした後、粘着剤表面を、２軸延伸フィルムであるＰＥＴフィルム基材１１（ダイアホイル、三菱ケミカル社製、「Ｔ９１３Ｅ１２５Ｃ」厚み１２５μｍ）にローラーで貼り付けて、離型フィルム１２／粘着シート１０／ＰＥＴフィルム基材１１の層構成の積層体とした。なお、粘着シートを貼り合わる際、意図的に加熱及び加圧はしていない。
そして、粘着シート１０とＰＥＴフィルム基材１１との界面において、ＪＩＳ Ｚ ０２３７：２０００に準じて、剥離速度３００ｍｍ／ｍｉｎで９０度剥離試験を行い、粘着力（Ｎ／２０ｍｍ）を測定した。 <Adhesive strength>
As shown in FIG. 10, pressure-
At the interface between the
＜ローラブル性の評価＞
図１０に示すように、実施例の粘着シート１～５（本発明粘着シート）及び比較例の粘着シート１’～２’（比較粘着シート）の凹凸パターンが形成された粘着剤表面側の離型フィルム１３を剥がした後、粘着剤表面を、２軸延伸フィルムであるＰＥＴフィルム基材１１（ダイアホイル、三菱ケミカル社製、「Ｔ９１３Ｅ１２５Ｃ」厚み１２５μｍ）にローラーで貼り付けて、離型フィルム１２／粘着シート１０／ＰＥＴフィルム基材１１の層構成の積層体とした。なお、粘着シートを貼り合わる際、意図的に加熱及び加圧はしていない。
かかる積層体を８０ｍｍ×１００ｍｍサイズにカットし、直径１０ｍｍの丸棒に巻き付けた。この際、実施例１～２、４～５及び比較例１～２は、粘着シート１０の外側にＰＥＴフィルム基材１１が来るように巻き付ける一方、実施例３は、粘着シートの内側にＰＥＴフィルム基材が来るように巻き付けた。
そして、巻き付け状態を１０秒間保持した後、巻き戻して展開し、外観を目視観察し、以下の基準で評価した。
○・・・ＰＥＴフィルム基材に浮きは見られなかった。
×・・・ＰＥＴフィルム基材に浮きが発生していた。 <Evaluation of rollability>
As shown in FIG. 10, the pressure-sensitive adhesive sheets 1 to 5 of the examples (the pressure-sensitive adhesive sheets of the present invention) and the pressure-sensitive adhesive sheets 1′ to 2′ of the comparative examples (comparative pressure-sensitive adhesive sheets) were separated from the pressure-sensitive adhesive surface side on which the uneven pattern was formed. After peeling off the mold film 13, the surface of the pressure-sensitive adhesive was pasted on a PET film substrate 11 (Diafoil, manufactured by Mitsubishi Chemical Corporation, “T913E125C” thickness 125 μm), which is a biaxially stretched film, with a roller. A laminate having a layer configuration of /adhesive sheet 10/PET film substrate 11 was obtained. It should be noted that when the pressure-sensitive adhesive sheets were attached together, they were not intentionally heated or pressurized.
This laminate was cut into a size of 80 mm×100 mm and wound around a round bar with a diameter of 10 mm. At this time, in Examples 1-2, 4-5 and Comparative Examples 1-2, thePET film substrate 11 is wound on the outside of the adhesive sheet 10, while in Example 3, the PET film is wrapped inside the adhesive sheet. It was wound so that the base material came.
Then, after holding the wound state for 10 seconds, it was unwound and unfolded, and the appearance was visually observed and evaluated according to the following criteria.
Good: No lift was observed on the PET film substrate.
×: Lifting occurred on the PET film substrate.
図１０に示すように、実施例の粘着シート１～５（本発明粘着シート）及び比較例の粘着シート１’～２’（比較粘着シート）の凹凸パターンが形成された粘着剤表面側の離型フィルム１３を剥がした後、粘着剤表面を、２軸延伸フィルムであるＰＥＴフィルム基材１１（ダイアホイル、三菱ケミカル社製、「Ｔ９１３Ｅ１２５Ｃ」厚み１２５μｍ）にローラーで貼り付けて、離型フィルム１２／粘着シート１０／ＰＥＴフィルム基材１１の層構成の積層体とした。なお、粘着シートを貼り合わる際、意図的に加熱及び加圧はしていない。
かかる積層体を８０ｍｍ×１００ｍｍサイズにカットし、直径１０ｍｍの丸棒に巻き付けた。この際、実施例１～２、４～５及び比較例１～２は、粘着シート１０の外側にＰＥＴフィルム基材１１が来るように巻き付ける一方、実施例３は、粘着シートの内側にＰＥＴフィルム基材が来るように巻き付けた。
そして、巻き付け状態を１０秒間保持した後、巻き戻して展開し、外観を目視観察し、以下の基準で評価した。
○・・・ＰＥＴフィルム基材に浮きは見られなかった。
×・・・ＰＥＴフィルム基材に浮きが発生していた。 <Evaluation of rollability>
As shown in FIG. 10, the pressure-
This laminate was cut into a size of 80 mm×100 mm and wound around a round bar with a diameter of 10 mm. At this time, in Examples 1-2, 4-5 and Comparative Examples 1-2, the
Then, after holding the wound state for 10 seconds, it was unwound and unfolded, and the appearance was visually observed and evaluated according to the following criteria.
Good: No lift was observed on the PET film substrate.
×: Lifting occurred on the PET film substrate.
なお、ＰＥＴフィルム基材を、画像表示装置用構成部材、中でもフレキシブル画像表示装置用構成部材の代替部材として使用して、各種評価を行うこととしたが、本発明の特徴が粘着シートの凹凸形状にあることから、基材や部材が多少異なっても、適切な評価が得られるものであると認識される。
Various evaluations were carried out using the PET film substrate as a constituent member for an image display device, especially as a substitute member for a constituent member for a flexible image display device. Therefore, it is recognized that appropriate evaluation can be obtained even if the base materials and members are slightly different.
上記実施例・比較例の結果、並びに、これまで本発明者が行ってきた試験結果から、粘着シートの少なくとも表裏一側の粘着面に、離型フィルムで挟持された際に形成される空間部の空隙率が所定範囲にあれば、粘着シートの当該粘着面にフレキシブル画像表示装置用構成部材を積層した状態で巻き取り、巻き戻して広げたときに、粘着シートとフレキシブル画像表示装置用構成部材との間に“浮き”が生じるのを防ぐことができることが分かった。
前記のように積層状態のまま、巻き取り、その後、巻き戻して展開したときに、粘着シートとフレキシブル画像表示装置用構成部材とが一部剥離して“浮き”が発生する原因は、粘着シートの厚みｂに対する、巻き取った際に生じる粘着シート１０の内側単位円周長（内側巻き長）Ｌ１と外側単位円周長（外側巻き長）Ｌ２との巻き長差（ΔＬ）の比率すなわち巻き長分（ΔＬ／ｂ）による歪のためであると考えられる。そこで、フレキシブル画像表示装置用構成部材を積層する側の粘着面に、所定の凸部の高さを有する凹凸パターンを形成した結果、巻き取った際に生じる巻き長分による歪を緩和することができ、浮きが生じるのを防ぐことができたと推察される。 From the results of the above Examples and Comparative Examples and the results of the tests conducted by the present inventors, the space formed when the release film is sandwiched between at least one of the front and back sides of the adhesive sheet. If the porosity is within a predetermined range, the adhesive sheet and the flexible image display device component are wound up in a state in which the flexible image display device component is laminated on the adhesive surface of the adhesive sheet, and when unwound and spread, the adhesive sheet and the flexible image display device component It was found that it is possible to prevent the occurrence of "floating" between
As described above, when the pressure-sensitive adhesive sheet and the constituent members for a flexible image display device are partially separated from each other when the pressure-sensitive adhesive sheet and the flexible image display device components are partially peeled off when the pressure-sensitive adhesive sheet is wound up in the laminated state and then unwound and unfolded, the pressure-sensitive adhesive sheet is caused to occur. The ratio of the winding length difference (ΔL) between the inner unit circumference length (inner winding length) L1 and the outer unit circumference length (outer winding length) L2 of the pressure-sensitive adhesive sheet 10 when wound with respect to the thickness b of the winding This is believed to be due to the distortion due to the length (ΔL/b). Therefore, as a result of forming a concavo-convex pattern having a predetermined convex portion height on the adhesive surface on which the constituent members for a flexible image display device are laminated, it is possible to relax the distortion due to the winding length generated when the adhesive is wound. It is presumed that it was possible to prevent the occurrence of floating.
前記のように積層状態のまま、巻き取り、その後、巻き戻して展開したときに、粘着シートとフレキシブル画像表示装置用構成部材とが一部剥離して“浮き”が発生する原因は、粘着シートの厚みｂに対する、巻き取った際に生じる粘着シート１０の内側単位円周長（内側巻き長）Ｌ１と外側単位円周長（外側巻き長）Ｌ２との巻き長差（ΔＬ）の比率すなわち巻き長分（ΔＬ／ｂ）による歪のためであると考えられる。そこで、フレキシブル画像表示装置用構成部材を積層する側の粘着面に、所定の凸部の高さを有する凹凸パターンを形成した結果、巻き取った際に生じる巻き長分による歪を緩和することができ、浮きが生じるのを防ぐことができたと推察される。 From the results of the above Examples and Comparative Examples and the results of the tests conducted by the present inventors, the space formed when the release film is sandwiched between at least one of the front and back sides of the adhesive sheet. If the porosity is within a predetermined range, the adhesive sheet and the flexible image display device component are wound up in a state in which the flexible image display device component is laminated on the adhesive surface of the adhesive sheet, and when unwound and spread, the adhesive sheet and the flexible image display device component It was found that it is possible to prevent the occurrence of "floating" between
As described above, when the pressure-sensitive adhesive sheet and the constituent members for a flexible image display device are partially separated from each other when the pressure-sensitive adhesive sheet and the flexible image display device components are partially peeled off when the pressure-sensitive adhesive sheet is wound up in the laminated state and then unwound and unfolded, the pressure-sensitive adhesive sheet is caused to occur. The ratio of the winding length difference (ΔL) between the inner unit circumference length (inner winding length) L1 and the outer unit circumference length (outer winding length) L2 of the pressure-
＜実施例６＞
図７に示すように、離型フィルム付き粘着シート２（凹凸パターン形成前）の一方の離型フィルム１２を剥離した貼着面に、金型Ｙの凹凸側を積層し、金型Ｙとは反対側の離型フィルム１２表面をローラーで貼合した後、当該離型フィルム１２表面にガラス板を載せて、金型温度２３℃、圧力０．０１ＭＰａで荷重（Ｐ）を掛けた状態で３０分静置した。次いで、ＵＶランプ（Ｆｕｓｉｏｎ社製、Ｈバルブ）を用いて、金型Ｙの反対側から離型フィルム１２を通して粘着シート１０に対して、２００～５００ｎｍ波長の光を積算光量４０００ｍＪ／ｃｍ２露光して粘着シート１０を硬化させた。露光後に、金型Ｙを離し、更に離型フィルム１３を積層することで、凹凸パターンが形成された離型フィルム付き粘着シート６（本発明粘着シート）を得た。 <Example 6>
As shown in FIG. 7, the uneven side of the mold Y is laminated on the adhesion surface from which one of therelease films 12 of the adhesive sheet 2 with a release film (before forming the uneven pattern) is peeled off. After bonding the surface of the release film 12 on the opposite side with a roller, a glass plate was placed on the surface of the release film 12, and a load (P) was applied at a mold temperature of 23 ° C. and a pressure of 0.01 MPa. Let stand for a minute. Then, using a UV lamp (manufactured by Fusion, H bulb), the pressure-sensitive adhesive sheet 10 is exposed to light with a wavelength of 200 to 500 nm through the release film 12 from the opposite side of the mold Y with an integrated light amount of 4000 mJ/cm 2 . to cure the adhesive sheet 10. After the exposure, the mold Y was released, and a release film 13 was further laminated to obtain a release film-attached pressure-sensitive adhesive sheet 6 (the pressure-sensitive adhesive sheet of the present invention) on which an uneven pattern was formed.
図７に示すように、離型フィルム付き粘着シート２（凹凸パターン形成前）の一方の離型フィルム１２を剥離した貼着面に、金型Ｙの凹凸側を積層し、金型Ｙとは反対側の離型フィルム１２表面をローラーで貼合した後、当該離型フィルム１２表面にガラス板を載せて、金型温度２３℃、圧力０．０１ＭＰａで荷重（Ｐ）を掛けた状態で３０分静置した。次いで、ＵＶランプ（Ｆｕｓｉｏｎ社製、Ｈバルブ）を用いて、金型Ｙの反対側から離型フィルム１２を通して粘着シート１０に対して、２００～５００ｎｍ波長の光を積算光量４０００ｍＪ／ｃｍ２露光して粘着シート１０を硬化させた。露光後に、金型Ｙを離し、更に離型フィルム１３を積層することで、凹凸パターンが形成された離型フィルム付き粘着シート６（本発明粘着シート）を得た。 <Example 6>
As shown in FIG. 7, the uneven side of the mold Y is laminated on the adhesion surface from which one of the
得られた凹凸パターンが形成された離型フィルム付き粘着シート６（本発明粘着シート）には、フィルム幅方向すなわちＴＤ方向に伸びた凸状部からなる凹凸単位が、フィルム長さ方向すなわちＭＤ方向に適宜間隔を置いて繰り返し形成されてなる凹凸パターンが形成された。当該凹凸パターンは、図９に示すように、本発明粘着シートをＭＤ方向、すなわち巻き周方向とする方向に沿って肉厚方向に切断した縦断面において、表２に記載の通りの形状を有するものであった。
In the obtained pressure-sensitive adhesive sheet 6 with a release film (the pressure-sensitive adhesive sheet of the present invention) on which the uneven pattern is formed, the uneven unit consisting of the convex portions extending in the film width direction, that is, the TD direction, extends in the film length direction, that is, the MD direction. A concave-convex pattern formed repeatedly at appropriate intervals was formed. As shown in FIG. 9, the uneven pattern has a shape as shown in Table 2 in a longitudinal section obtained by cutting the adhesive sheet of the present invention in the MD direction, that is, in the direction of the winding circumference in the thickness direction. It was something.
＜参考例１＞
図７に示すように、離型フィルム付き粘着シート２（凹凸パターン形成前）の一方の離型フィルム１２を剥離した貼着面に、金型Ｙの凹凸側を積層し、金型Ｙとは反対側の離型フィルム１２表面をローラーで貼合した後、当該離型フィルム１２表面にガラス板を載せて、金型温度２３℃、圧力０．０１ＭＰａで荷重（Ｐ）を掛けた状態で３０分静置した。次いで、ＵＶランプ（Ｆｕｓｉｏｎ社製、Ｈバルブ）を用いて、金型Ｙの反対側から離型フィルム１２を通して粘着シート１０に対して、２００～５００ｎｍ波長の光を積算光量４０００ｍＪ／ｃｍ２露光して粘着シート１０を硬化させた。露光後に、金型Ｙを離し、更に離型フィルム１３を積層することで、凹凸パターンが形成された離型フィルム付き粘着シート３’（比較粘着シート）を得た。 <Reference example 1>
As shown in FIG. 7, the uneven side of the mold Y is laminated on the adhesion surface from which one of therelease films 12 of the adhesive sheet 2 with a release film (before forming the uneven pattern) is peeled off. After bonding the surface of the release film 12 on the opposite side with a roller, a glass plate was placed on the surface of the release film 12, and a load (P) was applied at a mold temperature of 23 ° C. and a pressure of 0.01 MPa. Let stand for a minute. Then, using a UV lamp (manufactured by Fusion, H bulb), the pressure-sensitive adhesive sheet 10 is exposed to light with a wavelength of 200 to 500 nm through the release film 12 from the opposite side of the mold Y with an integrated light amount of 4000 mJ/cm 2 . to cure the adhesive sheet 10. After the exposure, the mold Y was released, and a release film 13 was further laminated to obtain a release film-attached pressure-sensitive adhesive sheet 3′ (comparative pressure-sensitive adhesive sheet) on which an uneven pattern was formed.
図７に示すように、離型フィルム付き粘着シート２（凹凸パターン形成前）の一方の離型フィルム１２を剥離した貼着面に、金型Ｙの凹凸側を積層し、金型Ｙとは反対側の離型フィルム１２表面をローラーで貼合した後、当該離型フィルム１２表面にガラス板を載せて、金型温度２３℃、圧力０．０１ＭＰａで荷重（Ｐ）を掛けた状態で３０分静置した。次いで、ＵＶランプ（Ｆｕｓｉｏｎ社製、Ｈバルブ）を用いて、金型Ｙの反対側から離型フィルム１２を通して粘着シート１０に対して、２００～５００ｎｍ波長の光を積算光量４０００ｍＪ／ｃｍ２露光して粘着シート１０を硬化させた。露光後に、金型Ｙを離し、更に離型フィルム１３を積層することで、凹凸パターンが形成された離型フィルム付き粘着シート３’（比較粘着シート）を得た。 <Reference example 1>
As shown in FIG. 7, the uneven side of the mold Y is laminated on the adhesion surface from which one of the
得られた凹凸パターン形成された離型フィルム付き粘着シート３’（比較粘着シート）の粘着面には、フィルム幅方向すなわちＴＤ方向に伸びた凸状部からなる凹凸単位が、フィルム長さ方向すなわちＭＤ方向に適宜間隔を置いて繰り返し形成されてなる凹凸パターンが形成された。当該凹凸パターンは、図９に示すように、本発明粘着シートをＭＤ方向、すなわち巻き周方向とする方向に沿って肉厚方向に切断した縦断面において、表２に記載の通りの形状を有するものであった。
On the adhesive surface of the obtained pressure-sensitive adhesive sheet 3′ with a release film (comparative pressure-sensitive adhesive sheet) having an uneven pattern formed thereon, uneven units composed of convex portions extending in the film width direction, that is, the TD direction, are formed in the film length direction, that is, A concavo-convex pattern was formed which was repeatedly formed at appropriate intervals in the MD direction. As shown in FIG. 9, the uneven pattern has a shape as shown in Table 2 in a longitudinal section obtained by cutting the adhesive sheet of the present invention in the MD direction, that is, in the direction of the winding circumference in the thickness direction. It was something.
＜測定方法及び評価方法＞
実施例の粘着シート６（本発明粘着シート）及び参考例の粘着シート３’（比較粘着シート）の各種物性値の測定方法及び評価方法について説明する。 <Measurement method and evaluation method>
Methods for measuring and evaluating various physical property values of PSA sheet 6 of Example (the PSA sheet of the present invention) andPSA sheet 3′ of Reference Example (comparative PSA sheet) will be described.
実施例の粘着シート６（本発明粘着シート）及び参考例の粘着シート３’（比較粘着シート）の各種物性値の測定方法及び評価方法について説明する。 <Measurement method and evaluation method>
Methods for measuring and evaluating various physical property values of PSA sheet 6 of Example (the PSA sheet of the present invention) and
＜凹凸パターン各部の測定＞
上記と同様の方法により、粘着面に形成された凹凸パターンの各形状を測定した。測定結果は表２の通りであった。 <Measurement of each part of the uneven pattern>
Each shape of the concavo-convex pattern formed on the adhesive surface was measured by the same method as described above. The measurement results are shown in Table 2.
上記と同様の方法により、粘着面に形成された凹凸パターンの各形状を測定した。測定結果は表２の通りであった。 <Measurement of each part of the uneven pattern>
Each shape of the concavo-convex pattern formed on the adhesive surface was measured by the same method as described above. The measurement results are shown in Table 2.
＜離型フィルム付き粘着シートの空間部の空隙率の測定＞
上記で得られた離型フィルム付き粘着シートに関し、上記と同様の方法により、粘着シート１０の凹凸パターンが形成された粘着面と、離型フィルム１３との間に存在する空間部の空隙率を測定した。測定結果は表２の通りであった。 <Measurement of the void ratio of the space of the pressure-sensitive adhesive sheet with release film>
Regarding the pressure-sensitive adhesive sheet with a release film obtained above, the void ratio of the space existing between the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet 10 on which the uneven pattern is formed and the release film 13 is determined by the same method as described above. It was measured. The measurement results are shown in Table 2.
上記で得られた離型フィルム付き粘着シートに関し、上記と同様の方法により、粘着シート１０の凹凸パターンが形成された粘着面と、離型フィルム１３との間に存在する空間部の空隙率を測定した。測定結果は表２の通りであった。 <Measurement of the void ratio of the space of the pressure-sensitive adhesive sheet with release film>
Regarding the pressure-sensitive adhesive sheet with a release film obtained above, the void ratio of the space existing between the pressure-sensitive adhesive surface of the pressure-
＜ＰＥＴフィルム基材に貼り合わせた際に形成される空間部の空隙率の測定＞
フレキシブル画像表示装置用構成部材の代替材料としてのＰＥＴフィルム基材１１に、粘着シート１０を貼り合わせた際に、粘着シート１０の凹凸パターンが形成された粘着面と、ＰＥＴフィルム基材１１との間に存在する空間部の空隙率を上記と同様の方法により測定した結果、いずれの実施例及び参考例においても、粘着シート１０の凹凸パターンが形成された粘着面と、離型フィルム１３との間に存在する空間部の空隙率と同じ値であった。 <Measurement of porosity of space formed when bonded to PET film substrate>
When theadhesive sheet 10 is attached to the PET film substrate 11 as an alternative material for a component of a flexible image display device, the adhesive surface of the adhesive sheet 10 on which the uneven pattern is formed and the PET film substrate 11 are separated. As a result of measuring the porosity of the space existing between them by the same method as described above, in any of the examples and reference examples, the adhesive surface of the adhesive sheet 10 on which the uneven pattern was formed and the release film 13 It was the same value as the porosity of the space existing between them.
フレキシブル画像表示装置用構成部材の代替材料としてのＰＥＴフィルム基材１１に、粘着シート１０を貼り合わせた際に、粘着シート１０の凹凸パターンが形成された粘着面と、ＰＥＴフィルム基材１１との間に存在する空間部の空隙率を上記と同様の方法により測定した結果、いずれの実施例及び参考例においても、粘着シート１０の凹凸パターンが形成された粘着面と、離型フィルム１３との間に存在する空間部の空隙率と同じ値であった。 <Measurement of porosity of space formed when bonded to PET film substrate>
When the
＜粘着力＞
上記と同様の方法により、粘着力（Ｎ／２０ｍｍ）を測定した。測定結果は表２の通りであった。 <Adhesive strength>
Adhesion (N/20 mm) was measured by the same method as above. The measurement results are shown in Table 2.
上記と同様の方法により、粘着力（Ｎ／２０ｍｍ）を測定した。測定結果は表２の通りであった。 <Adhesive strength>
Adhesion (N/20 mm) was measured by the same method as above. The measurement results are shown in Table 2.
＜ストレッチャブル性の評価＞
図１０に示すように、実施例の粘着シート６（本発明粘着シート）及び参考例の粘着シート３’（比較粘着シート）の凹凸パターンが形成された粘着剤表面側の離型フィルム１３を剥がした後、粘着剤表面を、２軸延伸フィルムであるＰＥＴフィルム基材１１（ダイアホイル、三菱ケミカル社製、「Ｔ９１３Ｅ１２５Ｃ」厚み１２５μｍ）にローラーで貼り付けて、離型フィルム１２／粘着シート１０／ＰＥＴフィルム基材１３の層構成の積層体とした。なお、粘着シート１０を貼り合わる際、意図的に加熱及び加圧はしていない。
かかる積層体を２０ｍｍ×１００ｍｍサイズにカットし、引張試験機を用いて５ｍｍ／ｍｉｎの速度で５０％の一軸引張を行った。
そして、引張試験後の外観を目視観察し、以下の基準で評価した。
○・・・ＰＥＴフィルム基材に剥がれが見られなかった。
×・・・ＰＥＴフィルム基材に剥がれが発生していた。 <Evaluation of stretchability>
As shown in FIG. 10, therelease film 13 on the pressure-sensitive adhesive surface side on which the concave-convex pattern is formed of the pressure-sensitive adhesive sheet 6 of the example (the pressure-sensitive adhesive sheet of the present invention) and the pressure-sensitive adhesive sheet 3' of the reference example (comparative pressure-sensitive adhesive sheet) is peeled off. After that, the adhesive surface is pasted with a roller to a PET film base material 11 (Diafoil, manufactured by Mitsubishi Chemical Corporation, "T913E125C" thickness 125 μm), which is a biaxially stretched film, to form a release film 12 / adhesive sheet 10 / A laminate having a layer structure of the PET film substrate 13 was formed. It should be noted that when the adhesive sheet 10 is adhered to each other, no heat or pressure is intentionally applied.
This laminate was cut into a size of 20 mm×100 mm and subjected to 50% uniaxial tension at a speed of 5 mm/min using a tensile tester.
The appearance after the tensile test was visually observed and evaluated according to the following criteria.
○: No peeling was observed on the PET film substrate.
×: Peeling occurred in the PET film substrate.
図１０に示すように、実施例の粘着シート６（本発明粘着シート）及び参考例の粘着シート３’（比較粘着シート）の凹凸パターンが形成された粘着剤表面側の離型フィルム１３を剥がした後、粘着剤表面を、２軸延伸フィルムであるＰＥＴフィルム基材１１（ダイアホイル、三菱ケミカル社製、「Ｔ９１３Ｅ１２５Ｃ」厚み１２５μｍ）にローラーで貼り付けて、離型フィルム１２／粘着シート１０／ＰＥＴフィルム基材１３の層構成の積層体とした。なお、粘着シート１０を貼り合わる際、意図的に加熱及び加圧はしていない。
かかる積層体を２０ｍｍ×１００ｍｍサイズにカットし、引張試験機を用いて５ｍｍ／ｍｉｎの速度で５０％の一軸引張を行った。
そして、引張試験後の外観を目視観察し、以下の基準で評価した。
○・・・ＰＥＴフィルム基材に剥がれが見られなかった。
×・・・ＰＥＴフィルム基材に剥がれが発生していた。 <Evaluation of stretchability>
As shown in FIG. 10, the
This laminate was cut into a size of 20 mm×100 mm and subjected to 50% uniaxial tension at a speed of 5 mm/min using a tensile tester.
The appearance after the tensile test was visually observed and evaluated according to the following criteria.
○: No peeling was observed on the PET film substrate.
×: Peeling occurred in the PET film substrate.
なお、ＰＥＴフィルム基材を、画像表示装置用構成部材、中でもフレキシブル画像表示装置用構成部材の代替部材として使用して、各種評価を行うこととしたが、本発明の特徴が粘着シートの凹凸形状にあることから、基材や部材が多少異なっても、適切な評価が得られるものであると認識される。
Various evaluations were carried out using the PET film substrate as a constituent member for an image display device, especially as a substitute member for a constituent member for a flexible image display device. Therefore, it is recognized that appropriate evaluation can be obtained even if the base materials and members are slightly different.
上記実施例、比較例及び参考例の結果、並びに、これまで本発明者が行ってきた試験結果から、粘着シートの少なくとも表裏一側の粘着面に、離型フィルムで挟持された際に形成される空間部の空隙率が所定範囲にあれば、粘着シートの当該粘着面にフレキシブル画像表示装置用構成部材を積層した状態で伸ばしたり、縮めたりしたときに、粘着シートとフレキシブル画像表示装置用構成部材との間に“剥がれ”が生じるのを防ぐことができることが分かった。
前記のように積層状態のまま、伸縮したときに、粘着シートとフレキシブル画像表示装置用構成部材とが一部剥離するなどの原因は、引張応力が生じた際に応力分散ができずフィルム端部よりフィルムの剥がれが生じたものであると考えられる。そこで、所定の空間部の空隙率を調整することにより、伸縮しても剥がれが生じるのを防ぐことができる粘着シートとなると推察される。 From the results of the above Examples, Comparative Examples, and Reference Examples, as well as the results of the tests conducted by the present inventors, it was found that the pressure-sensitive adhesive sheet formed when it was sandwiched with a release film on at least one of the front and back sides of the pressure-sensitive adhesive sheet. If the porosity of the space portion of the adhesive sheet is within a predetermined range, when the flexible image display device component is laminated on the adhesive surface of the adhesive sheet and stretched or contracted, the adhesive sheet and the flexible image display device configuration It was found that it is possible to prevent "peeling" from occurring between the material and the member.
As described above, when the pressure-sensitive adhesive sheet and the constituent members for a flexible image display device are partially peeled off when the adhesive sheet is stretched in a laminated state, the stress cannot be dispersed when the tensile stress is generated, and the film ends It is considered that the peeling of the film occurred more. Therefore, it is presumed that by adjusting the porosity of the predetermined space portion, the pressure-sensitive adhesive sheet can be prevented from being peeled off even when it is stretched.
前記のように積層状態のまま、伸縮したときに、粘着シートとフレキシブル画像表示装置用構成部材とが一部剥離するなどの原因は、引張応力が生じた際に応力分散ができずフィルム端部よりフィルムの剥がれが生じたものであると考えられる。そこで、所定の空間部の空隙率を調整することにより、伸縮しても剥がれが生じるのを防ぐことができる粘着シートとなると推察される。 From the results of the above Examples, Comparative Examples, and Reference Examples, as well as the results of the tests conducted by the present inventors, it was found that the pressure-sensitive adhesive sheet formed when it was sandwiched with a release film on at least one of the front and back sides of the pressure-sensitive adhesive sheet. If the porosity of the space portion of the adhesive sheet is within a predetermined range, when the flexible image display device component is laminated on the adhesive surface of the adhesive sheet and stretched or contracted, the adhesive sheet and the flexible image display device configuration It was found that it is possible to prevent "peeling" from occurring between the material and the member.
As described above, when the pressure-sensitive adhesive sheet and the constituent members for a flexible image display device are partially peeled off when the adhesive sheet is stretched in a laminated state, the stress cannot be dispersed when the tensile stress is generated, and the film ends It is considered that the peeling of the film occurred more. Therefore, it is presumed that by adjusting the porosity of the predetermined space portion, the pressure-sensitive adhesive sheet can be prevented from being peeled off even when it is stretched.
本発明の粘着シートは、フレキシブル性、特にローラブル性、ストレッチャブル性に優れた粘着シートであり、例えば、有機発光ダイオード（ＯＬＥＤ）や量子ドット（ＱＤ）を用いたフレキシブル画像表示装置などに有用である。
The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having excellent flexibility, particularly rollability and stretchability, and is useful, for example, for flexible image display devices using organic light-emitting diodes (OLEDs) and quantum dots (QDs). be.
１ 粘着シート
２ 粘着面
３ 凹凸単位
３Ａ 凸部
３Ｂ 凹部
４ 凹凸パターン
１０ 粘着シート
１１ ＰＥＴフィルム基材
１２ 離型フィルム
１３ 離型フィルム
２０ フレキシブル画像表示装置用構成部材
３０ フレキシブル画像表示装置用構成部材
５０ 巻芯
Ｘ，Ｙ 金型
Ｐ 荷重 REFERENCE SIGNSLIST 1 Adhesive sheet 2 Adhesive surface 3 Concave and convex unit 3A Convex part 3B Concave part 4 Concave and convex pattern 10 Adhesive sheet 11 PET film substrate 12 Release film 13 Release film 20 Component for flexible image display device 30 Component for flexible image display device 50 Core X, Y Mold P Load
２ 粘着面
３ 凹凸単位
３Ａ 凸部
３Ｂ 凹部
４ 凹凸パターン
１０ 粘着シート
１１ ＰＥＴフィルム基材
１２ 離型フィルム
１３ 離型フィルム
２０ フレキシブル画像表示装置用構成部材
３０ フレキシブル画像表示装置用構成部材
５０ 巻芯
Ｘ，Ｙ 金型
Ｐ 荷重 REFERENCE SIGNS
Claims (22)
- 離型フィルムと粘着シートを備えた離型フィルム付き粘着シートであって、
離型フィルムと粘着シートとの間に空間部を有し、当該空間部の空隙率（Ｘ）が３～７０％である離型フィルム付き粘着シート。 A release film-attached pressure-sensitive adhesive sheet comprising a release film and a pressure-sensitive adhesive sheet,
A pressure-sensitive adhesive sheet with a release film having a space between the release film and the pressure-sensitive adhesive sheet, wherein the space has a porosity (X) of 3 to 70%. - 前記粘着シートの少なくとも表裏一側の粘着面に、凸部を有する凹凸単位が少なくとも１つ設けられてなる凹凸パターンを備える、請求項１に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to claim 1, wherein at least one of the front and back sides of the pressure-sensitive adhesive sheet has an uneven pattern in which at least one uneven unit having a convex portion is provided.
- 前記凹凸単位における凸部の高さ（α）が７～１００μｍである、請求項２に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to claim 2, wherein the height (α) of the convex portion in the concave-convex unit is 7 to 100 µm.
- 前記凹凸単位を構成する凸部の最大幅（ｗ１）が１～１０００μｍである、請求項２又は３に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to claim 2 or 3, wherein the maximum width (w1) of the protrusions constituting the uneven unit is 1 to 1000 µm.
- 粘着シートの厚み（ｂ）に対する、前記凸部の高さ（α）の比率（α／ｂ）が０．０１以上１未満である、請求項２～４の何れか一項に記載の離型フィルム付き粘着シート。 The release according to any one of claims 2 to 4, wherein the ratio (α/b) of the height (α) of the protrusions to the thickness (b) of the adhesive sheet is 0.01 or more and less than 1. Adhesive sheet with film.
- 前記凹凸単位が繰り返される凹凸パターンを備えるものであり、前記凹凸単位の繰り返しピッチ（ｗ２）が２～１０００μｍである、請求項２～５の何れか一項に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to any one of claims 2 to 5, which comprises an uneven pattern in which the uneven units are repeated, and the repeating pitch (w2) of the uneven units is 2 to 1000 μm.
- 前記凹凸単位を構成する凸部と隣接する凸部との間隔（ｗ３）が１～１０００μｍである、請求項２～６の何れか一項に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to any one of claims 2 to 6, wherein the distance (w3) between the convex portion constituting the concave-convex unit and the adjacent convex portion is 1 to 1000 µm.
- 前記凹凸単位における凸部の頂面は平坦面であり、前記凸部頂面幅（ｗ４）が１～１０００μｍである、請求項２～７の何れか一項に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to any one of claims 2 to 7, wherein the top surface of the protrusion in the uneven unit is a flat surface, and the top surface width (w4) of the protrusion is 1 to 1000 µm. .
- 前記凹凸単位を構成する凸部の最大幅（ｗ１）に対する、凸部の高さ（α）の比率（α／ｗ１）が０．０３～０．３である、請求項２～８の何れか一項に記載の離型フィルム付き粘着シート。 Any one of claims 2 to 8, wherein the ratio (α/w1) of the height (α) of the convex portion to the maximum width (w1) of the convex portion constituting the concave/convex unit is 0.03 to 0.3. 1. The pressure-sensitive adhesive sheet with a release film according to item 1.
- ポリエチレンテレフタレートシートに対する９０℃剥離による粘着力（剥離速度３００ｍｍ／ｍｉｎ）が０．５～３０Ｎ／２０ｍｍである、請求項１～９の何れか一項に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to any one of claims 1 to 9, wherein the pressure-sensitive adhesive force (peeling speed: 300 mm/min) when peeled at 90°C from a polyethylene terephthalate sheet is 0.5 to 30 N/20 mm.
- 粘着シートの厚み（ｂ）が１０～１００μｍである、請求項１～１０の何れか一項に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to any one of claims 1 to 10, wherein the thickness (b) of the pressure-sensitive adhesive sheet is 10 to 100 µm.
- 前記粘着シートが、（メタ）アクリル系重合体（Ａ）及び光重合開始剤（Ｂ）を含有する光硬化性粘着剤組成物から形成される粘着シートである、請求項１～１１の何れか一項に記載の離型フィルム付き粘着シート。 Any one of claims 1 to 11, wherein the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet formed from a photocurable pressure-sensitive adhesive composition containing a (meth)acrylic polymer (A) and a photopolymerization initiator (B). 1. The pressure-sensitive adhesive sheet with a release film according to item 1.
- 光硬化性粘着剤組成物が架橋剤（Ｃ）を含有する、請求項１２に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to claim 12, wherein the photocurable pressure-sensitive adhesive composition contains a cross-linking agent (C).
- フレキシブル画像表示装置用構成部材を貼り合わせるために用いられる、請求項１～１３の何れか一項に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to any one of claims 1 to 13, which is used for bonding constituent members for a flexible image display device.
- 前記フレキシブル画像表示装置用構成部材がローラブル部材である、請求項１４に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to claim 14, wherein the constituent member for a flexible image display device is a rollable member.
- 前記フレキシブル画像表示装置用構成部材がストレッチャブル部材である、請求項１４に記載の離型フィルム付き粘着シート。 The pressure-sensitive adhesive sheet with a release film according to claim 14, wherein the component for a flexible image display device is a stretchable member.
- 請求項１～１６の何れか一項に記載の離型フィルム付き粘着シートの粘着シートと、フレキシブル画像表示装置用構成部材とが積層してなる構成を備えたフレキシブル画像表示装置用積層体。 A laminate for a flexible image display device, comprising a configuration in which the pressure-sensitive adhesive sheet of the pressure-sensitive adhesive sheet with a release film according to any one of claims 1 to 16 and a constituent member for a flexible image display device are laminated.
- 請求項１～１６の何れか一項に記載の離型フィルム付き粘着シートの粘着シートが硬化してなる硬化後粘着シートと、フレキシブル画像表示装置用構成部材とが積層してなる構成を備えたフレキシブル画像表示装置用積層体。 A configuration in which a cured adhesive sheet obtained by curing the adhesive sheet of the adhesive sheet with a release film according to any one of claims 1 to 16 and a component for a flexible image display device are laminated. A laminate for a flexible image display device.
- フレキシブル画像表示装置用構成部材と粘着シートとが積層してなる構成を備えたフレキシブル画像表示装置用積層体であって、
フレキシブル画像表示装置用構成部材と粘着シートとの間に形成された空間部の空隙率（Ｘ）が３～７０％であるフレキシブル画像表示装置用積層体。 A laminate for a flexible image display device having a configuration in which a component for a flexible image display device and an adhesive sheet are laminated,
A laminate for a flexible image display device, wherein a void ratio (X) of a space formed between a component for a flexible image display device and an adhesive sheet is 3 to 70%. - 前記粘着シートは、請求項１～１６の何れか一項に記載の離型フィルム付き粘着シートの粘着シートである、請求項１９に記載のフレキシブル画像表示装置用積層体。 The laminate for a flexible image display device according to claim 19, wherein the adhesive sheet is the adhesive sheet of the adhesive sheet with a release film according to any one of claims 1 to 16.
- 請求項１７～２０の何れか一項に記載のフレキシブル画像表示装置用積層体を備えたフレキシブル画像表示装置。 A flexible image display device comprising the laminate for a flexible image display device according to any one of claims 17 to 20.
- フレキシブル画像表示装置用構成部材を貼り合わせるために使用する粘着シートであって、
前記粘着シートの少なくとも表裏一側の粘着面に、凸部を有する凹凸単位が少なくとも１つ設けられてなる凹凸パターンを備え、
前記凹凸単位における凸部の高さ（α）が７～１００μｍであり、
前記凹凸単位を構成する凸部の最大幅（ｗ１）が１～１０００μｍである粘着シート。
A pressure-sensitive adhesive sheet used for bonding constituent members for a flexible image display device,
An uneven pattern in which at least one uneven unit having a convex portion is provided on at least one of the front and back adhesive surfaces of the adhesive sheet,
The height (α) of the convex portion in the concave-convex unit is 7 to 100 μm,
The pressure-sensitive adhesive sheet, wherein the maximum width (w1) of the protrusions constituting the uneven unit is 1 to 1000 μm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020247009128A KR20240127328A (en) | 2021-12-21 | 2022-12-05 | Adhesive sheet having a release film, laminate for a flexible image display device, flexible image display device and adhesive sheet |
| JP2023569258A JPWO2023120136A1 (en) | 2021-12-21 | 2022-12-05 | |
| CN202280071324.7A CN118159617A (en) | 2021-12-21 | 2022-12-05 | Release film-attached pressure-sensitive adhesive sheet, laminate for flexible image display device, and pressure-sensitive adhesive sheet |
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| JP2021206952 | 2021-12-21 | ||
| JP2021-206952 | 2021-12-21 | ||
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| PCT/JP2022/044730 WO2023120136A1 (en) | 2021-12-21 | 2022-12-05 | Adhesive sheet with release film, laminate for flexible image display device, flexible image display device, and adhesive sheet |
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| JP (1) | JPWO2023120136A1 (en) |
| KR (1) | KR20240127328A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017193685A (en) * | 2016-04-22 | 2017-10-26 | 住友化学株式会社 | Separate film with adhesive layer, optical member with separate film, and method for producing the same |
| WO2019228953A1 (en) * | 2018-05-28 | 2019-12-05 | Tesa Se | Removable pressure-sensitive adhesive strip |
| WO2020137578A1 (en) * | 2018-12-27 | 2020-07-02 | Dic株式会社 | Adhesive tape and adhesive tape manufacturing method |
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- 2022-12-05 JP JP2023569258A patent/JPWO2023120136A1/ja active Pending
- 2022-12-05 KR KR1020247009128A patent/KR20240127328A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017193685A (en) * | 2016-04-22 | 2017-10-26 | 住友化学株式会社 | Separate film with adhesive layer, optical member with separate film, and method for producing the same |
| WO2019228953A1 (en) * | 2018-05-28 | 2019-12-05 | Tesa Se | Removable pressure-sensitive adhesive strip |
| WO2020137578A1 (en) * | 2018-12-27 | 2020-07-02 | Dic株式会社 | Adhesive tape and adhesive tape manufacturing method |
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| TW202339953A (en) | 2023-10-16 |
| KR20240127328A (en) | 2024-08-22 |
| JPWO2023120136A1 (en) | 2023-06-29 |
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