CN118119678A - Foldable optical adhesive sheet - Google Patents
Foldable optical adhesive sheet Download PDFInfo
- Publication number
- CN118119678A CN118119678A CN202280066149.2A CN202280066149A CN118119678A CN 118119678 A CN118119678 A CN 118119678A CN 202280066149 A CN202280066149 A CN 202280066149A CN 118119678 A CN118119678 A CN 118119678A
- Authority
- CN
- China
- Prior art keywords
- soft portion
- adhesive sheet
- optical adhesive
- hard
- foldable optical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000853 adhesive Substances 0.000 title claims abstract description 194
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 194
- 230000003287 optical effect Effects 0.000 title claims abstract description 137
- 238000002834 transmittance Methods 0.000 claims description 25
- 238000012360 testing method Methods 0.000 claims description 20
- 238000005452 bending Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 11
- 230000007423 decrease Effects 0.000 claims description 10
- 238000013459 approach Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 71
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 55
- 239000000178 monomer Substances 0.000 description 51
- 125000000217 alkyl group Chemical group 0.000 description 33
- 238000000034 method Methods 0.000 description 29
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- 238000003860 storage Methods 0.000 description 18
- 229920005601 base polymer Polymers 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- 239000004014 plasticizer Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003607 modifier Substances 0.000 description 10
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- 238000012986 modification Methods 0.000 description 9
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- 238000004519 manufacturing process Methods 0.000 description 7
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- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 5
- -1 2-ethylhexyl Chemical group 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
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- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The foldable optical adhesive sheet (1) has a shape extending in a first direction orthogonal to the thickness direction. The foldable optical adhesive sheet (1) has one end edge (11) and the other end edge (12) in a second direction orthogonal to the thickness direction and the first direction. The foldable optical adhesive sheet (1) has a soft portion (2) and two hard portions (3), and the two hard portions (3) are disposed adjacent to both sides of the soft portion (2) in the first direction and are harder than the soft portion (2). The soft portion (2) is continuously arranged in the second direction from one end edge (11) to the other end edge (12).
Description
Technical Field
The present invention relates to a foldable optical adhesive sheet.
Background
A re-bendable (foldable) optical device is known. The optical device has a plurality of optical members in order in the thickness direction. The optical member includes, for example, a pixel panel, a touch panel, a polarizing plate, and a cover film. The optical members adjacent in the thickness direction are glued (bonded) using an optical adhesive sheet. Since the above-described optical device is foldable, the optical adhesive sheet is sometimes referred to as a "foldable optical adhesive sheet".
For example, a foldable optical adhesive sheet that is homogeneous and flexible in the plane direction has been proposed (for example, refer to patent document 1 below).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2018-111754
Disclosure of Invention
Problems to be solved by the invention
Excellent handleability is required for a foldable optical adhesive sheet. The handleability is a property that enables only one foldable optical adhesive sheet to be lifted out of a laminate obtained by laminating a plurality of foldable optical adhesive sheets in the thickness direction.
In addition, excellent processability is required for the foldable optical adhesive sheet. Processability is a property that enables a foldable optical adhesive sheet to be reliably processed into a desired size and/or shape. The processing includes cutting. Workability is also a property of smoothness of the cut surface.
The invention provides a foldable optical adhesive sheet which has excellent operability and processability and is foldable.
Means for solving the problems
The present invention (1) includes a foldable optical adhesive sheet having a shape extending in a first direction orthogonal to a thickness direction and having one end edge and the other end edge in a second direction orthogonal to the thickness direction and the first direction, the foldable optical adhesive sheet having a soft portion and two hard portions disposed adjacent to both sides of the soft portion in the first direction and harder than the soft portion, the soft portions being continuously disposed in the second direction from the one end edge to the other end edge.
The foldable optical adhesive sheet has two hard portions, and therefore is excellent in handleability and workability.
The foldable optical adhesive sheet has a soft portion. Therefore, the foldable optical adhesive sheet can be bent along the soft portion. As a result, the foldable optical adhesive sheet has foldability.
The invention (2) includes (1) the foldable optical adhesive sheet, wherein the soft portion has a substantially linear shape from the one end edge to the other end edge.
The invention (3) includes the foldable optical adhesive sheet according to (1) or (2), wherein the length of the soft portion in the first direction is shorter than the lengths of the two hard portions in the first direction.
The invention (4) comprises the foldable optical adhesive sheet according to any one of (1) to (3), wherein the total light transmittance of the soft portion obtained by the following formula varies by 5% or less.
The change rate (%) = |T1-T0|/T0×100 of the total light transmittance of the soft portion
T1: total light transmittance of the soft portion after the following bending test
T0: total light transmittance of the soft portion before the bending test
Bending test: the foldable optical adhesive sheet is bent 1000 times centering on the soft portion so that the two hard portions approach each other.
The invention (5) includes the foldable optical adhesive sheet according to any one of (1) to (4), wherein the foldable optical adhesive sheet has a boundary region including a boundary between the soft portion and the hard portion, and the concentration of the material of the soft portion gradually decreases as the foldable optical adhesive sheet proceeds in the first direction from the soft portion toward the hard portion in the boundary region.
Effects of the invention
The foldable optical adhesive sheet of the present invention is excellent in handleability and workability, and has foldability.
Drawings
Fig. 1A and 1B show an embodiment of the foldable optical adhesive sheet of the present invention. Fig. 1A is a top view. Fig. 1B is a cross-sectional view.
Fig. 2 is a cross-sectional view of a coater used in the first method.
Fig. 3 shows a process of arranging two adhesive compositions in a block shape in a first method.
Fig. 4 is a process of exposing active energy rays to an adhesive composition through a photomask in a second method.
Fig. 5 shows a form in which the foldable optical adhesive sheet is bent at the soft portion.
Fig. 6 is a plan view of a foldable optical adhesive sheet according to a modification.
Fig. 7 is a cross-sectional view of a foldable optical adhesive sheet according to a modification.
Fig. 8 is a graph showing the peel force in the peel test of the foldable optical adhesive sheet of example 1.
FIG. 9 shows the IR spectrum of the foldable optical adhesive sheet of example 1.
Fig. 10A to 10C illustrate an operation test. Fig. 10A is a cross-sectional view of a sample. Fig. 10B is a form in which only one adhesive sheet with a release sheet is lifted. Fig. 10C is a form of lifting up a plurality of adhesive sheets with release sheets.
Fig. 11A to 11C illustrate a test of workability. Fig. 11A is a plan view of a sample prepared by cutting an adhesive sheet with a release sheet. Fig. 11B shows a form in which the cut portion of the sample includes a defect. Fig. 11C shows a sample in which the cut portion includes a protrusion.
Detailed Description
1. One embodiment of the foldable optical adhesive sheet
An embodiment of the foldable optical adhesive sheet of the present invention will be described with reference to fig. 1A and 1B.
As shown in fig. 1A and 1B, the foldable optical adhesive sheet 1 has a shape extending in a first direction. The first direction is orthogonal to the thickness direction. The foldable optical adhesive sheet 1 has, for example, the same thickness in the first direction. In addition, the foldable optical adhesive sheet 1 has one end edge 11 and the other end edge 12 in the second direction. The second direction is orthogonal to the thickness direction and the first direction. In the present embodiment, the foldable optical adhesive sheet 1 has a substantially rectangular shape in a plan view. In the present embodiment, one end edge 11 is spaced apart from the other end edge 12 in the second direction.
The foldable optical adhesive sheet 1 has a soft portion 2 and two hard portions 3. In the foldable optical adhesive sheet 1, one hard portion 3, a soft portion 2, and another hard portion 3 are arranged in this order in the first direction. In fig. 1A and 1B, the boundary 40 between the soft portion 2 and the hard portion 3 is drawn by a solid line, but the boundary 40 may not be actually visually observed.
1.1 Soft portion 2
The soft portion 2 is continuously arranged in the second direction from one end edge 11 to the other end edge 12 of the foldable optical adhesive sheet 1. In the present embodiment, the soft portion 2 is disposed at a substantially middle portion in the first direction. In addition, the soft portion 2 preferably has a substantially linear shape from one end edge 11 to the other end edge 12 of the foldable optical adhesive sheet 1.
1.1.1 Size of the soft portion 2
The size of the soft portion 2 is not limited. The length L1 of the soft portion 2 in the first direction is, for example, 30mm or less, preferably 20mm or less, more preferably 15mm or less, and is, for example, 2mm or more. The thickness of the soft portion 2 is, for example, 1 μm or more, preferably 10 μm or more, and is, for example, 1000 μm or less, preferably 100 μm or less.
1.1.2 Storage shear modulus G 'of Soft portion 2'
The storage shear modulus G 'of the soft portion 2 at 25℃is, for example, less than 150kPa, preferably 140kPa or less, more preferably 130kPa or less, still more preferably 125kPa or less, and the storage shear modulus G' of the soft portion 2 at 25℃is, for example, 1kPa or more, preferably 10kPa or more. The storage shear modulus G' of the soft portion 2 at 25℃was obtained by measuring the dynamic viscoelasticity at a temperature ranging from-50℃to 150℃at a temperature rise rate of 5℃per minute at a frequency of 1Hz and a measurement mode of a shear mode (torsion mode).
If the storage shear modulus G' of the soft portion 2 is equal to or less than the upper limit, the soft portion 2 can be reliably softened with respect to the two hard portions 3.
1.1.3 Elongation at break of soft portion 2
The elongation at break of the soft portion 2 at 25 ℃ is, for example, 800% or more, preferably 1000% or more, more preferably 1500% or more, still more preferably 1750% or more, and, for example, 10000% or less. The elongation at break of the soft portion 2 was determined from a stress-strain curve. The stress-strain curve is obtained by stretching the foldable optical adhesive sheet 1 at a speed of 300 mm/min.
If the elongation at break of the soft portion 2 is equal to or greater than the lower limit, the soft portion 2 can be reliably made softer than the two hard portions 3.
1.1.4 Maximum stress of soft portion 2
The maximum stress of the soft portion 2 at 25 ℃ is not limited. The maximum stress of the soft portion 2 at 25 ℃ is, for example, 100kPa or more, preferably 500kPa or more, more preferably 1000kPa or more, and is, for example, 10000kPa or less, preferably 5000kPa or less, more preferably 2000kPa or less. The maximum stress of the soft portion 2 is obtained from a stress-strain curve. The stress-strain curve is obtained by stretching the foldable optical adhesive sheet 1 at a speed of 300 mm/min.
1.1.5 Variability in total transmittance of soft portion 2
The total transmittance of the soft portion 2 obtained by the following formula varies, for example, by 5% or less, preferably by 4% or less, more preferably by 3% or less, further preferably by 2% or less, particularly preferably by 1% or less, and most preferably by 0.1% or less. The lower limit of the fluctuation ratio of the total light transmittance of the soft portion 2 is not limited. The lower limit of the fluctuation ratio of the total light transmittance of the soft portion 2 is, for example, 0.0%.
The change rate (%) = |t1-t0|/t0×100 of the total light transmittance of the soft portion 2
T1: total light transmittance of the soft portion 2 after the bending test described below
T0: total light transmittance of the soft portion 2 before the bending test described below
Bending test: as shown in fig. 5, the foldable optical adhesive sheet is bent 1000 times centering on the soft portion 2 so that two hard portions 3 (described later) approach each other. The details of the bending test are described in the examples that follow.
The total light transmittance of the soft portion 2 was measured based on JIS K7375 (2008).
If the fluctuation ratio is not more than the upper limit, the soft portion 2 is excellent in optical characteristics after repeated bending.
The total light transmittance of the soft portion 2 before the bending test is, for example, 60% or more, preferably 80% or more, more preferably 85% or more, and, for example, 100% or less. If the total light transmittance of the soft portion 2 is not less than the lower limit, the soft portion 2 is excellent in optical characteristics.
1.1.6 Haze of Soft portion 2
The haze of the soft portion 2 is 3% or less, preferably 2% or less, more preferably 1% or less, and, for example, 0% or more. The haze of the soft portion 2 was measured by using a haze meter according to JIS K7136 (year 2000). If the haze of the soft portion 2 is not more than the upper limit, the soft portion 2 is excellent in optical characteristics.
The soft portion 2 contains a base polymer. The details of the base polymer will be described later.
1.2 Hard portion 3
The two hard portions 3 are disposed adjacent to both sides of the soft portion 2 in the first direction. In the present embodiment, the two hard portions 3 are continuously arranged in the second direction from one end edge 11 to the other end edge 12 of the foldable optical adhesive sheet 1. In the present embodiment, each of the two hard portions 3 has a substantially rectangular shape in a plan view.
1.2.1 Sizes of hard portions 3
The respective sizes of the two hard portions 3 are not limited. The length L2 of each of the two hard portions 3 in the first direction is longer than the length L1 of the soft portion 2 in the first direction, for example. In other words, the length L1 of the soft portion 2 in the first direction is shorter than the length L2 of each of the two hard portions 3 in the first direction. In the case where the length L1 of the soft portion 2 in the first direction is shorter than the length L2 of each of the two hard portions 3 in the first direction, operability and workability can be sufficiently ensured, and foldability can be ensured.
The ratio (L1/L2) of the length L1 of the soft portion 2 to the length L2 of the hard portion 3 is, for example, 0.75 or less, preferably 0.5 or less, more preferably 0.25 or less, and further, for example, 0.001 or more.
The value (L2-L1) obtained by subtracting the length L1 of the soft portion 2 from the length L2 of the hard portion 3 is, for example, 10mm or more, preferably 30mm or more, more preferably 50mm or more, and 298mm or less.
Specifically, the length L2 of the hard portion 3 is, for example, 40mm or more and 300mm or less.
1.2.2 Hardness of hard portion 3
The two hard portions 3 are each harder than the soft portion 2.
In the present embodiment, the storage shear modulus G 'at 25 ℃ of each of the two hard portions 3 is higher than the storage shear modulus G' at 25 ℃ of the soft portion 2, for example. In the case where the storage shear modulus G 'at 25 ℃ of each of the two hard portions 3 is higher than the storage shear modulus G' at 25 ℃ of the soft portion 2, the foldable optical adhesive sheet 1 is excellent in handleability and workability, and has foldability. The storage shear modulus G' of the hard portion 3 at 25℃can be obtained by measuring the dynamic viscoelasticity at a temperature ranging from-50℃to 150℃at a temperature rise rate of 5℃per minute at a frequency of 1Hz and a measurement mode of a shear mode (torsion mode).
Specifically, the storage shear modulus G' at 25 ℃ of each of the two hard portions 3 is, for example, 150kPa or more, preferably 175kPa or more, more preferably 200kPa or more, and further, 1000kPa or less.
The ratio of the storage shear modulus G 'of the soft portion 2 at 25 ℃ to the storage shear modulus G' of each of the two hard portions 3 at 25 ℃ (the storage shear modulus G 'of the soft portion 2/the storage shear modulus G' of the hard portion 3) is, for example, 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less, and, for example, 0.01 or more, preferably 0.03 or more.
If the ratio is equal to or less than the upper limit, the soft portion 2 can be sufficiently softer than the hard portion 3, and therefore the foldable optical adhesive sheet 1 is excellent in foldability. If the ratio is equal to or greater than the lower limit, the soft portion 2 can be prevented from becoming too soft, and the hard portion 3 can be prevented from becoming too hard, so that the workability and workability are excellent.
The elongation at break at 25 ℃ of each of the two hard portions 3 is smaller than the elongation at break at 25 ℃ of the soft portion 2. In the case where the elongation at break at 25 ℃ of each of the two hard portions 3 is smaller than the elongation at break at 25 ℃ of the soft portion 2, the foldable optical adhesive sheet 1 is excellent in handleability and workability, and has foldability.
Specifically, the elongation at break at 25 ℃ of each of the two hard portions 3 is, for example, 750% or less, preferably 700% or less, more preferably 650% or less, and further, for example, 150% or more, preferably 200% or more.
The ratio of the elongation at break of the soft portion 2 at 25 ℃ to the elongation at break of each of the two hard portions 3 at 25 ℃ (elongation at break of the soft portion 2/elongation at break of the hard portion 3) is, for example, 1.2 or more, preferably 1.5 or more, more preferably 2.0 or more, still more preferably 2.5 or more, and, for example, 100 or less, preferably 10 or less.
If the ratio is equal to or greater than the lower limit, the soft portion 2 can be sufficiently softer than the hard portion 3, and therefore the foldable optical adhesive sheet 1 is excellent in foldability. If the ratio is equal to or less than the upper limit, the soft portion 2 can be prevented from becoming too soft, and the hard portion 3 can be prevented from becoming too hard, so that the workability and workability are excellent.
The elongation at break of each of the two hard portions 3 was obtained in the same manner as the elongation at break of the soft portion 2.
1.2.3 Maximum stress of hard portion 3
The maximum stress at 25 ℃ of each of the two hard portions 3 is not limited. The maximum stress of the hard portion 3 at 25 ℃ is, for example, 250kPa or more, preferably 500kPa or more, more preferably 700kPa or more, and 1500kPa or less, preferably 1000kPa or less, more preferably 900kPa or less. The maximum stress of each of the two hard portions 3 was obtained in the same manner as the maximum stress of the soft portion 2.
1.2.4 Thickness, total light transmittance and haze of hard portion 3
The thickness, total light transmittance, and haze of each of the two hard portions 3 are the same as those of the soft portion 2 described above.
The hard portion 3 contains a base polymer.
1.3 Base Polymer and the like
Next, a base polymer contained in the soft portion 2 and the hard portion 3 together will be described, and a component different from the soft portion 2 and the hard portion 3 will be described.
The base polymer is an adhesive component that exhibits adhesiveness in the foldable optical adhesive sheet 1. The base polymer is described in Japanese patent application laid-open No. 2018-111754, and preferably an acrylic polymer.
1.3.1 Acrylic Polymer
The acrylic polymer is a polymer containing a monomer component of an alkyl (meth) acrylate in a proportion of 50 mass% or more. "(meth) acrylic" refers to acrylic and/or methacrylic. That is, the monomer component contains an alkyl (meth) acrylate as a main component. In other words, the alkyl (meth) acrylate is the main component of the monomer component.
The alkyl (meth) acrylate is a monofunctional monomer because it has 1 functional group. The alkyl (meth) acrylate includes alkyl (meth) acrylates in which the alkyl group has 1 to 20 carbon atoms. Examples of the alkyl (meth) acrylate include those described in JP-A2018-111754.
The alkyl (meth) acrylate used for polymerizing the base polymer contained in the soft portion 2 is preferably an alkyl (meth) acrylate having 3 to 20 carbon atoms, more preferably an alkyl (meth) acrylate having 7 to 15 carbon atoms. Specifically, it is possible to list: butyl (meth) acrylate (BA/BMA), 2-ethylhexyl (meth) acrylate (2 EHA/2 EHMA) and lauryl (meth) acrylate (LA/LMA). The above alkyl (meth) acrylate is sometimes referred to as a first alkyl (meth) acrylate.
The alkyl (meth) acrylate used for polymerizing the base polymer contained in the hard portion 3 is preferably an alkyl (meth) acrylate having 6 to 20 carbon atoms, more preferably an alkyl (meth) acrylate having 7 to 18 carbon atoms, and still more preferably an alkyl (meth) acrylate having 8 to 15 carbon atoms. Specifically, 2-ethylhexyl (meth) acrylate (2 EHA/2 EHMA) may be mentioned. The above alkyl (meth) acrylate is sometimes referred to as a second alkyl (meth) acrylate.
The proportion of the alkyl (meth) acrylate in the monomer component is, for example, 50 mass% or more, preferably 55 mass% or more, more preferably 60 mass% or more, and, for example, 99 mass% or less.
1.3.2 Copolymerizable monomers
The monomer component may comprise a copolymerizable monomer capable of copolymerizing with the alkyl (meth) acrylate. Examples of the copolymerizable monomer include polar group-containing monomers.
The polar group-containing monomer is described in Japanese unexamined patent publication No. 2018-111754, and preferably includes: a monomer containing a nitrogen atom-containing ring and a hydroxyl group-containing monomer. Examples of the monomer containing a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone (NVP). Examples of the hydroxyl group-containing monomer include 4-hydroxybutyl (meth) acrylate (HBA/HBMA).
The proportion of the polar group-containing monomer in the monomer component is, for example, 0.1% by mass or more, preferably 0.3% by mass or more, and is, for example, 30% by mass or less, preferably 20% by mass or less.
1.4 Boundary region 4
In the present embodiment, as shown in fig. 1A and 1B, the foldable optical adhesive sheet 1 further has a boundary region 4 indicated by a broken line. The boundary region 4 includes a boundary 40, indicated by a solid line, between the soft portion 2 and the hard portion 3 in plan view. The boundary region 4 is continuously arranged in the second direction from one end edge 11 to the other end edge 12 of the foldable optical adhesive sheet 1. Specifically, the boundary region 4 includes: a first boundary region 4A and a second boundary region 4B, the first boundary region 4A including a boundary 40 between the soft portion 2 and the hard portion 3 disposed on one side in the first direction, and the second boundary region 4B including a boundary 40 between the soft portion 2 and the hard portion 3 disposed on the other side in the first direction.
In either of the two boundary regions 4, the concentration of the material of the soft portion 2 gradually decreases as proceeding in the first direction from the soft portion 2 toward the hard portion 3. For example, in the case where the soft portion 2 contains a polymer of a first alkyl (meth) acrylate and the hard portion 3 contains a polymer of a second alkyl (meth) acrylate, the polymer concentration of the first alkyl (meth) acrylate gradually decreases as proceeding in a first direction from the soft portion 2 toward the hard portion 3 in the boundary region 4. That is, the boundary region 4 has a gradient of the polymer concentration of the first alkyl (meth) acrylate.
Therefore, the boundary region 4 is a region from the position where the gradient of the concentration starts to the position where the gradient ends.
In the present embodiment, the length L1 of the soft portion 2 in the first direction may be defined as a distance between a midpoint of the first boundary region 4A in the first direction and a midpoint of the second boundary region 4B in the first direction. The starting points of the lengths L2 of the two hard portions 3 in the first direction may be set to the midpoint of the first boundary region 4A in the first direction and the midpoint of the second boundary region 4B in the first direction, respectively.
In the present embodiment, the physical properties (the storage shear modulus G', the elongation at break, the maximum stress, the total light transmittance, and the fluctuation in the total light transmittance) of the soft portion 2 and the hard portion 3 are physical properties of the portion (for example, the central portion in the first direction) other than the boundary region 4.
1.5 Method for producing foldable optical adhesive sheet 1
Next, a method for manufacturing the foldable optical adhesive sheet 1 will be described. The manufacturing method is not limited. The production method includes, for example, the first to third methods.
1.5.1 First method
In the first method, two adhesive compositions are simultaneously coated on the surface of the release sheet 5.
As the release sheet 5, for example, a plastic sheet is cited. Specifically, the release sheet 5 is a plastic sheet described in japanese patent application laid-open No. 2018-111754. In the present embodiment, the release sheet 5 has a substantially rectangular shape in a plan view.
The two adhesive compositions are a first adhesive composition and a second adhesive composition.
The first adhesive composition is a material of the soft portion 2. The first adhesive composition contains a polymer of a first alkyl (meth) acrylate (containing BA as a main component).
The second adhesive composition is a material of the hard portion 3. The second adhesive composition contains a polymer of a second alkyl (meth) acrylate (containing 2EHA as a main component).
The first adhesive composition and the second adhesive composition may contain at least one component selected from the group consisting of oligomers, crosslinking agents, and silane coupling agents, in addition to the base polymer. Examples of the oligomer include an acrylic oligomer described in JP 2021-055076A. Examples of the crosslinking agent include the crosslinking agent described in JP-A2018-111754, and isocyanate crosslinking agents and peroxide crosslinking agents are preferable. The silane coupling agent may be, for example, a silane coupling agent described in Japanese unexamined patent publication No. 2018-111754, and preferably an epoxy silane coupling agent. The amount of each component is, for example, 0.01 parts by mass or more and 1 part by mass or less based on 100 parts by mass of the base polymer.
In addition to the above components, additives may be added to the adhesive composition in an appropriate ratio. Examples of the additive include: adhesion promoters, deterioration inhibitors, fillers, colorants, ultraviolet absorbers, antioxidants, surfactants, and antistatic agents.
The coating method is not limited. Examples of the coating method include: roll coating, roll licking coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip die coating, and die coating.
In the above-described coating, for example, the coater 6 having the separator 61 shown in fig. 2 may be used.
The coater 6 has a discharge port 62. The discharge port 62 extends in the first direction.
Two separators 61 are disposed on the coater 6. The two separators 61 are arranged at a distance from each other in the first direction. Two baffles 61 divide the discharge opening 62 into three regions.
The three regions comprise a central region 71 and two side regions 72. The central region 71 corresponds to the soft portion 2. The two side areas 72 correspond to the two hard portions 3.
The coater 6 can simultaneously discharge the first adhesive composition from the center region 71 and the second adhesive composition from the side regions 72.
Next, the first adhesive composition and the second adhesive composition are simultaneously discharged from the coater 6, and the coater 6 is relatively moved in the second direction (see fig. 1A) with respect to the release sheet 5. Thereby forming a coating film comprising the first binder composition and the second binder composition.
Thereafter, the coating film (first binder composition and second binder composition) is dried. The drying temperature is, for example, 50℃to 200 ℃. The drying time is, for example, 5 seconds to 20 minutes.
Thereby, the foldable optical adhesive sheet 1 having the soft portion 2 and the two hard portions 3 is manufactured on the surface of the release sheet 5.
As another coating method, the following method can be also mentioned: as shown in fig. 3, one block 51 containing the first adhesive composition and two blocks 52 containing the second adhesive composition are disposed at one end portion of the surface of the release sheet 5 in the second direction with relatively thick thicknesses, respectively; thereafter, the lever 9 is moved from one end to the other end in the first direction. The rod 9 extends in a first direction. Thereby manufacturing the foldable optical adhesive sheet 1 having the soft portion 2 and the two hard portions 3.
In the boundary region 4 of the foldable optical adhesive sheet 1 manufactured by the first method, the polymer of the first alkyl (meth) acrylate in the first adhesive composition and the polymer of the second alkyl (meth) acrylate in the second adhesive composition are mixed (migrate to each other). Therefore, in the boundary region 4, the concentration of the polymer of the first alkyl (meth) acrylate gradually decreases as proceeding in the first direction from the soft portion 2 toward the hard portion 3.
1.5.2 Second method
The second method has a first process and a second process. The first step and the second step are sequentially performed.
1.5.2.1 First step
In the first step, first, an adhesive composition is coated on the surface of the release sheet 5. Thereby, a coating film containing the adhesive composition is formed. The coating film is homogeneous in the first direction.
1.5.2.2 Second step
In the second step, a modifier is blended (post-added) to a part of the coating film by coating. Examples of the modifier include a polyfunctional monomer and a plasticizer.
1.5.2.3 Multifunctional monomer
The multifunctional monomer is blended into both the first adhesive composition and the second adhesive composition at a lower blending ratio with respect to the first adhesive composition than the second adhesive composition. Thus, a larger number of cross-linked structures are introduced into the hard portion 3 than the soft portion 2, and the hard portion 3 is made harder than the soft portion 2. Therefore, the polyfunctional monomer is blended (post-added) into the coating film (adhesive composition) for forming the hard portion 3.
Examples of the polyfunctional monomer include polyfunctional (meth) acrylates. Multifunctional (meth) acrylates contain, for example, more than two ethylenically unsaturated double bonds in one molecule. As the polyfunctional (meth) acrylate, there may be mentioned: difunctional (meth) acrylates, trifunctional (meth) acrylates and multifunctional (meth) acrylates of more than tetrafunctional.
Examples of the difunctional (meth) acrylate include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate (referred to separately as hexamethylene glycol di (meth) acrylate), 1, 9-nonanediol di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and di (meth) acryl isocyanurate.
Examples of the trifunctional (meth) acrylate include: trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris ((meth) acryloxyethyl) isocyanurate.
Examples of the polyfunctional (meth) acrylate having four or more functions include: di (trimethylolpropane) tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
The amount of the polyfunctional monomer to be blended into the first adhesive composition (soft portion 2) is, for example, 0.2 parts by mass or less, preferably 0.1 parts by mass or less, more preferably 0.05 parts by mass or less, and further, for example, 0 parts by mass or more, preferably 0.005 parts by mass or more, based on 100 parts by mass of the base polymer. The amount of the polyfunctional monomer to be incorporated into the second adhesive composition (hard part 3) is, for example, greater than 0.2 parts by mass, preferably 0.25 parts by mass or more, and 2 parts by mass or less, preferably 1 part by mass or less, based on 100 parts by mass of the base polymer. The ratio of the amount of the polyfunctional monomer to be blended in the second adhesive composition to the amount of the polyfunctional monomer to be blended in the first adhesive composition is, for example, 2 or more, preferably 5 or more, and is, for example, 100 or less, preferably 50 or less.
1.5.2.4 Plasticizer
The plasticizer is a component that makes the soft portion 2 softer than the hard portion 3. Therefore, the plasticizer is blended (post-added) into the coating film (adhesive composition) for forming the soft portion 2. Examples of the plasticizer include: phthalate esters and adipate esters. Examples of the phthalate esters include dioctyl phthalate and dioctyl tin laurate. Examples of the adipic acid ester include dioctyl adipate and diisononyl adipate. The proportion of the plasticizer is, for example, 0.1 part by mass or more, preferably 0.3 part by mass or more, and is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass of the monomer component.
In the second step of coating, for example, a coater 6 shown in fig. 2 is used. The modifier is overcoated on the coating film. The modifier enters the inside of the coating film through the external coating.
Specifically, if the modifier is a multifunctional monomer, the multifunctional monomer is discharged from the both side regions 72. If the modifier is a plasticizer, the plasticizer is discharged from the central region 71. If the modifier is a multifunctional monomer and plasticizer, the multifunctional monomer is discharged from the two side regions 72 and the plasticizer is discharged from the central region 71.
In the second step, thereafter, if the modifier contains a polyfunctional monomer, the polyfunctional monomer is reacted. Examples of the reaction method include heating and ultraviolet irradiation. The hard portion 3 thus contains a crosslinked structure.
Thus, the foldable optical adhesive sheet 1 having the soft portion 2 and the two hard portions 3 was produced.
1.5.2.5 Concentration of material in soft portion 2, hard portion 3 and boundary region 4
In the second method, when the modifier is a polyfunctional monomer, the adhesive composition corresponding to the hard part 3 contains a polyfunctional monomer in addition to the alkyl (meth) acrylate (monofunctional monomer). On the other hand, the pressure-sensitive adhesive composition corresponding to the soft portion 2 contains an alkyl (meth) acrylate (monofunctional monomer) and does not contain a polyfunctional monomer. Therefore, the concentration of the polymer of the monofunctional monomer in the soft part 2 is higher than that of the polymer of the monofunctional monomer in the hard part 3.
In the boundary region 4 of the foldable optical adhesive sheet 1 manufactured by the second method in which the modifying agent is a polyfunctional monomer, the concentration of the polymer of the alkyl (meth) acrylate of the first adhesive composition gradually decreases as proceeding in the first direction from the soft portion 2 toward the hard portion 3. In the boundary region 4, the concentration of the crosslinked structure gradually increases as the progress proceeds in the first direction from the soft portion 2 toward the hard portion 3.
In the boundary region 4 of the foldable optical adhesive sheet 1 manufactured by the second method in which the modifier is a plasticizer, the concentration of the plasticizer gradually decreases as proceeding in the first direction from the soft portion 2 toward the hard portion 3 in the boundary region 4.
1.5.3 Third method
The third method includes a third step and a fourth step. The third step and the fourth step are sequentially performed.
1.5.3.1 Third step
In the third step, the adhesive composition is coated on the surface of the release sheet 5. The applied adhesive composition is homogeneous in the first direction. The coating film (adhesive composition) has a component and/or a molecular structure that can react by active energy rays. The active energy ray includes, for example, ultraviolet rays. Examples of the above-mentioned component include the above-mentioned polyfunctional monomer and the like. The proportion of the polyfunctional monomer is not limited.
1.5.3.2 Fourth procedure
As shown in fig. 4, in the fourth step, active energy rays are irradiated (exposed) to the coating film (adhesive composition) through the photomask 10.
The photomask 10 has a light shielding portion 101 and two light transmitting portions 102. The light shielding portion 101 has the same pattern as the soft portion 2. The light-transmitting portion 102 has the same pattern as the two hard portions 3.
The active energy rays transmitted through the two light transmitting portions 102 act on the above-mentioned components in the coating film (adhesive composition), and the above-mentioned components react to harden the hard portion 3.
On the other hand, the active energy ray does not pass through the light shielding portion 101. Therefore, the soft portion 2 corresponding to the light shielding portion 101 is not hardened but remains soft.
Thus, the foldable optical adhesive sheet 1 having the soft portion 2 and the two hard portions 3 was produced.
1.5 Use
The foldable optical adhesive sheet 1 is used for the adhesion of optical members. Examples of the optical member include: pixel panel, touch panel, polarizing plate and cover film.
The foldable optical adhesive sheet 1 is processed into a predetermined shape and/or size before and/or after the above-mentioned adhesion.
The optical device has a foldable optical adhesive sheet 1 and an optical member. The optical device can be repeatedly folded for use. At this time, as shown in fig. 5, the foldable optical adhesive sheet 1 is folded along the soft portion 2 so that the two hard portions 3 approach each other.
2. Effects of the foldable optical adhesive sheet 1
The foldable optical adhesive sheet 1 has two hard portions 3, and therefore has excellent handling and workability.
The foldable optical adhesive sheet 1 has a soft portion 2. Therefore, the foldable optical adhesive sheet 1 can be bent along the soft portion 2. As a result, the foldable optical adhesive sheet 1 has foldability.
The soft portion 2 has a substantially linear shape from one end edge 11 to the other end edge 12 of the foldable optical adhesive sheet 1, and therefore the foldable optical adhesive sheet 1 can be easily and reliably bent along the soft portion 2.
The soft portion 2 has an optical characteristic because the total light transmittance of the soft portion 2 varies by 5% or less.
If the length L1 of the soft portion 2 in the first direction is shorter than the length L2 of each of the two hard portions 3 in the first direction, the foldable optical adhesive sheet 1 can ensure foldability while sufficiently ensuring operability and workability.
3. Modification examples
In the following modifications, the same members and steps as those in the above-described embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. Each modification can also have the same operational effects as those of the first embodiment, except for the specific description. Further, one embodiment and the modification can be appropriately combined.
In the modification, the concentration of the material of the soft portion 2 is discontinuously shifted in the boundary region 4 of the foldable optical adhesive sheet 1. The boundary 40 is explicitly formed. Specifically, the material of the soft portion 2 is not present on one side of the boundary 40 between the soft portion 2 and the hard portion 3 arranged on one side in the first direction, and the material of the hard portion 3 is not present on the other side of the boundary 40 in the first direction.
The second method and the third method are preferably used as the method for producing the foldable optical adhesive sheet 1, and the third method is more preferably used. The above method can suppress migration which is likely to occur in the first method, and therefore can suppress the concentration of the material of the soft portion 2 from gradually decreasing toward the hard portion 3.
When comparing one embodiment with the modification, one embodiment is appropriate. In one embodiment, interfacial peeling at the boundary 40 caused by the above concentration gradient can be suppressed. The interfacial peeling includes: when stress is applied to the boundary 40 when the foldable optical adhesive sheet 1 is bent, the hard portion 3 is separated from the soft portion 2 and the soft portion 2 is separated from the hard portion 3.
As shown in fig. 6, one end edge 11 of the foldable optical adhesive sheet 1 in the second direction has a first concave portion 13. The first concave portion 13 is concave toward the other side in the second direction. The bottom of the first recess 13 forms one end edge 11 of the soft portion 2.
The other end edge 12 of the foldable optical adhesive sheet 1 in the second direction has a second concave portion 14. The second concave portion 14 is concave to one side in the second direction. The bottom of the second recess 14 forms the other end edge 12 of the soft portion 2.
In the case of the foldable optical adhesive sheet 1 shown in fig. 6, since the soft portion 2 has the first concave portion 13 and the second concave portion 14, it is possible to further suppress a decrease in operability caused by the contact of the one end edge 11 and the other end edge 12 of the soft portion 2 in the first direction with other members. That is, the foldable optical adhesive sheet 1 shown in fig. 6 is more excellent in handleability.
As shown in fig. 7, the foldable optical adhesive sheet 1 may have a plurality (two or more) of soft portions 2. The foldable optical adhesive sheet 1 may have three or more soft portions 2.
The soft portions 2 and the hard portions 3 are alternately arranged in the first direction. The hard portions 3 are disposed at both ends of the foldable optical adhesive sheet 1 in the first direction. Therefore, if the number of soft portions 2 is n (a positive number of 2 or more), the number of hard portions 3 is n+1 (a positive number of 2 or more).
According to this modification, the foldable optical adhesive sheet 1 can be wound into a roll. When the foldable optical adhesive sheet 1 is wound into a roll, the foldable optical adhesive sheet 1 is wound so that both ends in the first direction are brought close to each other.
Although not shown, the soft portion 2 may have a curved shape. The curved shape includes a curved shape.
The hardness of the two hard portions 3 may be different. For example, one hard portion 3 is harder than the other hard portion 3. Even in this case, the hard portion 3 is harder than the soft portion 2. That is, the soft portion 2, the other hard portion 3, and the one hard portion 3 are arranged in this order from soft to hard.
Examples
The present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited to the embodiments. Specific numerical values such as the blending amount (content), physical property value, and parameter described below may be replaced with upper limits (numerical values defined as "above" or "below") or lower limits (numerical values defined as "below" or "above") of the blending amount (content), physical property value, and parameter described in the above-described "specific embodiment" corresponding thereto.
< Preparation of base Polymer >
Preparation example 1
80 Parts by mass of Butyl Acrylate (BA), 10 parts by mass of 4-hydroxybutyl acrylate (4 HBA), 10 parts by mass of cyclohexyl acrylate (CHA), 0.05 part by mass of 2, 2-dimethoxy-1, 2-diphenyl-1-one (trade name "Irgacure 651" manufactured by Ciba Japan Co., ltd.), and 0.05 part by mass of 1-hydroxy-cyclohexyl-phenyl-one (trade name "Irgacure 184" manufactured by Ciba Japan Co., ltd.) were put into a four-necked flask, and were exposed to ultraviolet rays under a nitrogen atmosphere, thereby partially photopolymerization was performed, to thereby obtain a partial polymer (monomer slurry) having a polymerization rate of 10%.
Preparation example 2
62 Parts by mass of 2-ethylhexyl acrylate (2 EHA), 30 parts by mass of Lauryl Acrylate (LA), 5 parts by mass of 4-hydroxybutyl acrylate (4 HBA), 3 parts by mass of N-vinyl-2-pyrrolidone (NVP), 0.05 parts by weight of 2, 2-dimethoxy-1, 2-diphenyl-1-one (trade name "Irgacure 651" manufactured by Kagaku Co., ltd.) and 0.05 parts by weight of 1-hydroxy-cyclohexyl-phenyl-one (trade name "Irgacure 184" manufactured by Kagaku Co., ltd.) were put into a four-necked flask, and exposed to ultraviolet rays under a nitrogen atmosphere, thereby partially photopolymerization was performed, whereby a partial polymer (monomer slurry) having a polymerization rate of 8% was obtained.
Preparation example 3
75 Parts by mass of 2-ethylhexyl acrylate (2 EHA), 5 parts by mass of 4-hydroxybutyl acrylate (4 HBA), 20 parts by mass of N-vinyl-2-pyrrolidone (NVP), 0.05 parts by weight of 2, 2-dimethoxy-1, 2-diphenyl-1-one (trade name "Irgacure 651" manufactured by Ciba Japan Co., ltd.), and 0.05 parts by weight of 1-hydroxy-cyclohexyl-phenyl-one (trade name "Irgacure184" manufactured by Ciba Japan Co., ltd.) were put into a four-necked flask, and exposed to ultraviolet rays under a nitrogen atmosphere to partially carry out photopolymerization, thereby obtaining a partial polymer (monomer slurry) having a polymerization rate of 12%.
The formulations of each of preparation examples 1 to 3 are shown in Table 1.
< Preparation of acrylic oligomer >)
Preparation example 4
In a reaction vessel having a stirrer, a thermometer, a reflux condenser and a nitrogen inlet pipe, a mixture containing 95 parts by mass of cyclohexyl methacrylate (CHMA), 5 parts by mass of Acrylic Acid (AA), 10 parts by mass of α -methylstyrene dimer as a chain transfer agent, and 120 parts by mass of toluene as a solvent was stirred at room temperature under a nitrogen atmosphere for 1 hour. Thereafter, 10 parts by mass of 2,2' -Azobisisobutyronitrile (AIBN) as a thermal polymerization initiator was added to the mixture to prepare a reaction solution, which was reacted at 85 ℃ for 5 hours under a nitrogen atmosphere (formation of an acrylic oligomer). Thus, an oligomer solution (solid content concentration: 50 mass%) containing the acrylic oligomer was obtained. The weight average molecular weight of the acrylic oligomer was 4000. In addition, the glass transition temperature (Tg) of the acrylic oligomer was 84 ℃.
< Preparation of first adhesive composition >
Preparation example 5
To 100 parts by mass of the polymer solution of preparation example 1, 0.01 parts by mass of dipentaerythritol hexaacrylate was added and mixed, thereby preparing a first adhesive composition.
< Preparation of the second adhesive composition >
Preparation example 6
To 100 parts by mass of the polymer solution of preparation example 2, 0.1 parts by mass of hexamethylene glycol diacrylate was added and mixed, thereby preparing a first adhesive composition.
Preparation example 7
To 100 parts by mass of the polymer solution of preparation example 3, 0.3 parts by mass of hexamethylene glycol diacrylate was added and mixed, thereby preparing a second adhesive composition.
< Manufacturing of foldable optical adhesive sheet 1 >
Example 1
A block 51 containing the first adhesive composition of preparation example 5 and a block 52 containing the second adhesive composition of preparation example 7 were arranged at one end of the release sheet 5 in the second direction. 100 parts by volume of the block 51 was disposed at the center of the release sheet 5 in the first direction, and two 250 parts by volume of the block 52 were disposed at both ends of the release sheet 5 in the first direction.
Thereafter, the first adhesive composition and the second adhesive composition are spread by moving the rod 9 from one end portion to the other end portion in the first direction.
Thus, the foldable optical adhesive sheet 1 having the soft portion 2 and the two hard portions 3 was produced, the soft portion 2 including the polymer containing the monomer component of n-Butyl Acrylate (BA) as the main component, and the hard portion 3 including the polymer containing the monomer component of 2-ethylhexyl acrylate (2 EHA) as the main component.
The length L1 of the soft portion 2 in the first direction is 10mm. The length L2 of each of the two soft portions 3 in the first direction is 100mm.
Example 2
An optical adhesive sheet 1 for folding was produced in the same manner as in example 1. However, the first adhesive composition of preparation example 6 was used instead of the first adhesive composition of preparation example 5.
Comparative example 1
The block 51 of the first adhesive composition of preparation example 5 was disposed at the center of the release sheet 5 in the first direction.
Thereafter, the first adhesive composition is spread by moving the rod 9 from one end to the other end in the first direction.
Thus, a foldable optical adhesive sheet 1 containing the first adhesive composition of preparation example 5 was produced.
Comparative example 2
A foldable optical adhesive sheet 1 was produced in the same manner as in comparative example 1. However, the first adhesive composition of preparation example 6 was used instead of the first adhesive composition of preparation example 5.
Comparative example 3
A foldable optical adhesive sheet 1 was produced in the same manner as in comparative example 1. However, the second adhesive composition of preparation example 7 was used instead of the first adhesive composition of preparation example 5.
None of the comparative examples 1 to 3 has both the soft portion 2 and the hard portion 3.
The formulations of examples 1 to 2 and comparative examples 1 to 3 are shown in tables 1 and 3.
< Properties >
The following physical properties were measured for the foldable optical adhesive sheets 1 of each of examples 1 to 2 and comparative examples 1 to 3. The results are shown in table 3. Physical properties of the adhesive composition as the material of each of the soft portion 2 and the hard portion 3 are shown in table 2.
1. Storage shear modulus G 'at 25 ℃ of the soft portion 2 and the hard portion 3'
Sample pieces each having a thickness of 50 μm including the first adhesive composition of preparation example 5, the first adhesive composition of preparation example 6, and the second adhesive composition of preparation example 7 were produced. Then, the sample piece was cut out to a width of 30mm and a length of 80mm, and rolled up to form a cylinder having a cross-sectional area of 40mm 2. The strain-stress measurement was performed by stretching with a universal tensile tester (Autograph AG-X manufactured by Shimadzu corporation) at 300 mm/min. Thereby obtaining a stress-strain curve and finding the maximum stress and elongation at break.
2. Flexibility, total light transmittance, and fluctuation ratio of soft portion 2
Transparent polyimide films having a thickness of 75 μm were bonded to one surface and the other surface of the foldable optical adhesive sheet 1 in the thickness direction, and cut into strips of 100mm×20mm, thereby producing samples. The sample has a soft portion 2 and a hard portion 3. The sample was set on a no-load U-shaped tensile testing machine (a "bench-type endurance testing machine DLMD111LHA" and a "U-shaped tensile testing jig" manufactured by Yuasa System Co.) and a bending test was performed under the following conditions.
Environmental conditions: 25c, 55% rh,
Test speed: at 60rpm of the rotation speed of the rotating shaft,
Radius of curvature: the thickness of the film is 3mm,
Number of bending: 1000 times
The flexibility of the soft portion 2 was evaluated according to the following criteria.
The case where there was no peeling between the transparent polyimide film and the foldable optical adhesive sheet 1 was evaluated as good.
The case where there was peeling between the transparent polyimide film and the foldable optical adhesive sheet 1 was evaluated as x.
The total light transmittance of the soft portion 2 before and after bending was obtained based on JIS K7375 (2008).
3. Tension and IR determination of boundary region 4
(1) Tension force
A PET film having a thickness of 50 μm was attached to one face of the foldable optical adhesive sheet 1, and samples were cut out at 25mm wide by 100mm in the first direction. The sample was bonded to alkali glass, and then autoclaved at 50℃under 0.5MPa for 15 minutes to sufficiently adhere the sample to the alkali glass. Thereafter, a peel test was performed in a first direction at a peel angle of 180 degrees and a peel speed of 30 mm/min using a universal tensile tester (Autograph AG-X manufactured by Shimadzu corporation), and a tensile force was measured. A graph of the peel force in the peel test of example 1 is shown in fig. 8.
As can be seen from fig. 8, the peel force in the boundary region 4 gradually increases from the soft portion 2 toward the hard portion 3.
(2) IR measurement
The IR spectrum was measured at 4 points (P1, P2, P3, P4) in the boundary region 4 and the vicinity thereof of the foldable optical adhesive sheet 1 (see white circles in fig. 1A) under the following apparatus and conditions. The 4 IR spectra are shown in fig. 9, respectively.
The IR measurement was performed by the ATR method (attenuated total reflectance method) (Ge crystal) using an FT-IR spectrophotometer manufactured by Simer Feishmania technology Co.
The soft portion 2 contains a polymer of a monomer component containing BA as a main component. The hard part 3 contains a polymer of a monomer component containing 2HEA as a main component.
The point P4 is located in the hard portion 3 outside the boundary region 4. Two peaks of 2850cm -1 to 2900cm -1, clearly visible in 2-ethylhexyl acrylate (2 EHA), were observed at point P4. The point P1 is located in the soft portion 2 outside the boundary region 4. The two peaks described above are not observed at point P1. Further, it is seen that the second peak (right side) decreases from the point P3 toward the point P2.
As described above, in the boundary region 4, the concentration of the polymer of the monomer component mainly composed of 2-ethylhexyl acrylate (2 EHA) decreases from the hard portion 3 toward the soft portion 2.
< Evaluation >
The following matters were evaluated for the foldable optical adhesive sheet 1 of each of examples 1 to 2 and comparative examples 1 to 3. The results are shown in table 3.
1. Operability of
An adhesive sheet 7 with a release sheet having an optical adhesive sheet 1 for folding and two release sheets 5 sandwiching the optical adhesive sheet 1 for folding in the thickness direction was prepared. That is, one pressure-sensitive adhesive sheet 7 with a release sheet has one release sheet 5, one foldable optical pressure-sensitive adhesive sheet 1, and one release sheet 5 in this order on one side (upper side) in the thickness direction. Next, the pressure-sensitive adhesive sheet 7 with a release sheet was cut into a size of 5cm×10cm, and 10 sheets of the cut pressure-sensitive adhesive sheet 7 with a release sheet were stacked as shown in fig. 10A to prepare a sample 20. In the sample 20, the release sheet 5 disposed on the lower side of the foldable optical adhesive sheet 1 among the uppermost release sheet-attached adhesive sheets 7 is in contact with the release sheet 5 disposed on the upper side of the foldable optical adhesive sheet 1 among the second release sheet-attached adhesive sheets 7 from above.
Next, the sample 20 was stored at 50℃for 100 hours. After storage, the uppermost pressure-sensitive adhesive sheet 7 with a release sheet of the sample 20 was subjected to a lifting test using a No.31b tape (manufactured by ridong electric).
And (2) the following steps: as shown in fig. 10B, only one pressure-sensitive adhesive sheet 7 with a release sheet located uppermost is lifted. That is, only the single pressure-sensitive adhesive sheet 7 with a release sheet was lifted from the sample 20.
X: as shown in fig. 10C, the adhesive sheet 7 with a release sheet located second and thereafter from above is lifted together with the adhesive sheet 7 with a release sheet located uppermost. That is, only the single release-sheet-equipped adhesive sheet 7 was not lifted from the sample 20.
2. Workability and workability of the product
An adhesive sheet 7 with a release sheet having an optical adhesive sheet 1 for folding and two release sheets 2 sandwiching the optical adhesive sheet 1 for folding in the thickness direction was prepared. As shown by the solid line in fig. 11A, the adhesive sheet 7 with a release sheet had a first direction length of 30cm and a second direction length of 20cm. Next, as shown by the thick line in fig. 11A, the pressure-sensitive adhesive sheet 7 with a release sheet was cut into a first direction length of 10cm and a second direction length of 7cm, thereby producing a sample 15. A cutter is used in cutting. The sample 15 has one soft portion 2 and two hard portions 3.
The cut portion 30 formed at the other end edge of the sample 15 in the first direction was observed with a microscope, and workability was evaluated according to the following criteria.
O: no defect X (see fig. 11B) or no protrusion Y (see fig. 11C) was observed in the cut portion 30, and the cut portion was smooth.
X: defects X (see fig. 11B) and/or protrusions Y (see fig. 11C) are observed in the cut portion 30.
TABLE 1
TABLE 2
/>
Although the above-described invention has been provided by way of example embodiments of the invention, they are merely examples and should not be construed as limiting. Variations of the present invention that are obvious to those skilled in the art are included within the scope of the appended claims.
Industrial applicability
The foldable optical adhesive sheet is used for the adhesion of optical members.
Description of the reference numerals
1. Foldable optical adhesive sheet
2. Soft part
3. Hard part
4. Boundary region
40. Boundary of
11. An end edge
12. Another end edge
Length of the L1 soft portion in the first direction
L2 length of each of the two hard portions in the first direction
Claims (5)
1. Wherein the foldable optical adhesive sheet has a shape extending in a first direction orthogonal to a thickness direction and has one end edge and the other end edge in a second direction orthogonal to the thickness direction and the first direction,
The foldable optical adhesive sheet has a soft portion and two hard portions that are disposed adjacent to both sides of the soft portion in the first direction and are harder than the soft portion,
The soft portion is continuously arranged in the second direction from the one end edge to the other end edge.
2. The foldable optical adhesive sheet according to claim 1, wherein the soft portion has a substantially linear shape from the one end edge to the other end edge.
3. The foldable optical adhesive sheet according to claim 1, wherein a length of the soft portion in the first direction is shorter than a length of each of the two hard portions in the first direction.
4. The foldable optical adhesive sheet according to claim 1, wherein the total light transmittance of the soft portion obtained by the following formula is 5% or less,
The change rate (%) = |T1-T0|/T0×100 of the total light transmittance of the soft portion
T1: total light transmittance of the soft portion after the following bending test
T0: total light transmittance of the soft portion before the bending test
Bending test: the foldable optical adhesive sheet is bent 1000 times centering on the soft portion so that the two hard portions approach each other.
5. The foldable optical adhesive sheet according to claim 1, wherein the foldable optical adhesive sheet has a boundary region including a boundary of the soft portion and the hard portion,
In the boundary region, a concentration of the material of the soft portion gradually decreases as proceeding in the first direction from the soft portion toward the hard portion.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-164996 | 2021-10-06 | ||
| JP2021164996 | 2021-10-06 | ||
| PCT/JP2022/028701 WO2023058300A1 (en) | 2021-10-06 | 2022-07-26 | Optical adhesive sheet for foldables |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118119678A true CN118119678A (en) | 2024-05-31 |
Family
ID=85804136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280066149.2A Pending CN118119678A (en) | 2021-10-06 | 2022-07-26 | Foldable optical adhesive sheet |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2023055632A (en) |
| CN (1) | CN118119678A (en) |
| TW (1) | TW202315922A (en) |
| WO (1) | WO2023058300A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9051493B2 (en) * | 2013-03-28 | 2015-06-09 | Nokia Technologies Oy | Method and apparatus for joining together multiple functional layers of a flexible display |
| KR102268328B1 (en) * | 2014-10-21 | 2021-06-24 | 삼성디스플레이 주식회사 | Light-transmitting adhesive film and display device having employing the same |
| KR101871551B1 (en) * | 2015-10-30 | 2018-06-28 | 삼성에스디아이 주식회사 | Adhesive film, optical member comprising the same and optical display apparatus comprising the same |
| KR20170070370A (en) * | 2015-12-11 | 2017-06-22 | 삼성에스디아이 주식회사 | Adhesive sheet and optical display apparatus comprising the same |
| JP7225975B2 (en) * | 2019-03-19 | 2023-02-21 | 三菱ケミカル株式会社 | Adhesive sheet, adhesive sheet laminate with release film, laminate for constituting image display device, and image display device using the same |
| US20220332989A1 (en) * | 2019-12-10 | 2022-10-20 | Lg Chem, Ltd. | Multi-region foldable adhesive film and fabrication method therefor |
-
2022
- 2022-07-26 WO PCT/JP2022/028701 patent/WO2023058300A1/en unknown
- 2022-07-26 CN CN202280066149.2A patent/CN118119678A/en active Pending
- 2022-08-08 TW TW111129719A patent/TW202315922A/en unknown
- 2022-08-30 JP JP2022137246A patent/JP2023055632A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023055632A (en) | 2023-04-18 |
| WO2023058300A1 (en) | 2023-04-13 |
| TW202315922A (en) | 2023-04-16 |
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