CN118056678A - Laminate sheet - Google Patents
Laminate sheet Download PDFInfo
- Publication number
- CN118056678A CN118056678A CN202311534500.9A CN202311534500A CN118056678A CN 118056678 A CN118056678 A CN 118056678A CN 202311534500 A CN202311534500 A CN 202311534500A CN 118056678 A CN118056678 A CN 118056678A
- Authority
- CN
- China
- Prior art keywords
- resin substrate
- intermediate layer
- length
- laminate
- extension
- 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
Links
- 239000000758 substrate Substances 0.000 claims abstract description 246
- 229920005989 resin Polymers 0.000 claims abstract description 198
- 239000011347 resin Substances 0.000 claims abstract description 198
- 229920002050 silicone resin Polymers 0.000 claims description 33
- -1 polyethylene terephthalate Polymers 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 139
- 239000011521 glass Substances 0.000 description 53
- 239000010408 film Substances 0.000 description 45
- 230000007547 defect Effects 0.000 description 43
- 238000000034 method Methods 0.000 description 22
- 229920002799 BoPET Polymers 0.000 description 21
- 229920001721 polyimide Polymers 0.000 description 21
- 229920001296 polysiloxane Polymers 0.000 description 21
- 230000001681 protective effect Effects 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000005520 cutting process Methods 0.000 description 13
- 239000012790 adhesive layer Substances 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000009719 polyimide resin Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000006482 condensation reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000002093 peripheral effect Effects 0.000 description 8
- 239000002390 adhesive tape Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000003475 lamination Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000011109 contamination Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910020388 SiO1/2 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GGVUYAXGAOIFIC-UHFFFAOYSA-K cerium(3+);2-ethylhexanoate Chemical compound [Ce+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O GGVUYAXGAOIFIC-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NKLYMYLJOXIVFB-UHFFFAOYSA-N triethoxymethylsilane Chemical compound CCOC([SiH3])(OCC)OCC NKLYMYLJOXIVFB-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
The present invention relates to a laminate sheet comprising a1 st resin substrate, an intermediate layer, and a2 nd resin substrate, wherein the 1 st resin substrate and the intermediate layer are laminated in this order, and form a laminated portion, wherein the 1 st resin substrate has a rectangular shape when viewed from a normal direction of a surface of the 1 st resin substrate, the 2 nd resin substrate has a larger area than the 1 st resin substrate and the intermediate layer, and a corner portion including a vertex at which a1 st side and a2 nd side of the 1 st resin substrate intersect perpendicularly when viewed from the normal direction of the surface of the 1 st resin substrate, and a projecting portion extending from an outer edge of the 1 st side, the vertex, and the 2 nd side has a length of 5mm to 20mm when viewed from the normal direction of the surface of the 1 st resin substrate, a length of 10mm when viewed from an intersection of the projecting portion and the 1 st side in a direction orthogonal to the 1 st side, and a length of 10mm when viewed from the intersection of the projecting portion and the 2 nd side in a direction of the parallel to the 1 st side in a direction of the 10mm to the 2mm when viewed from the projecting portion and the 2mm in a length of the projecting portion extending from the 1 st side orthogonal to the 2mm in a direction orthogonal to the 2mm to the length of the 1 st side are formed.
Description
Technical Field
The present invention relates to a laminated sheet.
Background
When manufacturing electronic devices such as solar cells, liquid crystal panels (LCDs), organic EL panels (OLEDs), and sensor panels that receive electromagnetic waves, X-rays, ultraviolet rays, visible light, infrared rays, and the like, polyimide resin layers are used as substrates. The polyimide resin layer is used in the form of a laminate provided on a glass substrate, and the laminate is used for manufacturing an electronic device.
The laminate having a polyimide resin layer is formed by providing an adsorption layer such as a silicone resin layer on a glass substrate, and forming a polyimide resin layer on the adsorption layer.
When a laminate having a polyimide resin layer is formed, a protective film is provided on an adsorption layer such as a silicone resin layer on a glass substrate.
In the production of a laminate having a polyimide resin layer, for example, a laminate of a release film, an adsorption layer, and a protective film is used. In this laminate, after the release film and the adsorption layer are cut, unnecessary portions are removed, and then the protective film is peeled off, and the adsorption layer is bonded to the glass substrate, thereby providing the adsorption layer on the glass substrate. In a state where the adsorption layer is provided on the glass substrate, a polyimide resin layer is formed on the adsorption layer as described above.
A proposal has been made for peeling off the protective film of the laminate (patent document 1). More specifically, patent document 1 discloses a double-sided adhesive sheet for electronic components, which comprises: the adhesive layer, the 1 st release sheet adhered to one surface of the adhesive layer and having at least the 1 st release layer, and the 2 nd release sheet adhered to the other surface of the adhesive layer and having at least the 2 nd release layer, the 1 st release layer is mainly composed of an olefin resin, the 2 nd release layer is mainly composed of a diene polymer material, the release force of the 1 st release sheet relative to the adhesive layer is X [ mN/20mm ], the release force of the 2 nd release sheet relative to the adhesive layer is Y [ mN/20mm ], the relation of Y-X > 50 is satisfied, and the adhesive layer, the 1 st release layer and the 2 nd release layer substantially do not contain an organosilicon compound and a halogen compound. In patent document 1, the 1 st release sheet, the adhesive layer, and the 2 nd release sheet are the same size.
Prior art literature
Patent literature
Patent document 1: international publication No. 2009/047984
Disclosure of Invention
In patent document 1, after the 1 st release sheet is released, the surface of the adhesive layer from which the 1 st release sheet is released is bonded to the coating. Then, the 2 nd release sheet was further peeled from the adhesive layer to adhere the coating to another coating. The 1 st release sheet, the adhesive layer, and the 2 nd release sheet are the same size as described above. Therefore, when the 1 st release sheet is released, a release defect such as a cohesive failure is likely to occur in the adhesive layer located at the release end portion, and improvement is required. In addition, it is also desirable that peeling defects such as peeling do not occur at the interface of each layer during processing.
The purpose of the present invention is to provide a laminated sheet which can suppress peeling defects both when peeling unnecessary parts and when handling.
The present inventors have conducted intensive studies and as a result, have found that the above-described problems can be solved by the following constitution.
(1) A laminated sheet comprising a1 st resin substrate, an intermediate layer, and a 2 nd resin substrate, wherein the 1 st resin substrate and the intermediate layer are laminated in this order, the shape and size of the 1 st resin substrate and the intermediate layer are the same, and the laminated sheet is configured such that the 1 st resin substrate has a quadrangular outer shape as viewed from the normal direction of the surface of the 1 st resin substrate, the 2 nd resin substrate has a larger area than the 1 st resin substrate and the intermediate layer, and the corner portion including the vertex at which the 1 st side and the 2 nd side of the 1 st resin substrate intersect orthogonally is provided with a protruding portion protruding from the outer edges of the 1 st side, the protruding portion has a length of 5mm to 20mm from the 1 st side in the 1 st direction protruding from the intersection point of the protruding portion and the 1 st side, a length of 10mm to 40mm from the intersection point of the protruding portion and the 1 st side in the direction protruding from the 2 nd side, and a length of 5mm to 20mm from the corner portion protruding from the 2 nd side in the direction protruding from the intersection point of the 2 nd side and the 2 nd side in the direction protruding from the intersection point of the length of the protruding portion and the 2 nd side in the direction parallel to the 2mm from the intersection point of the length of the protruding portion and the 2mm from the 2 mm.
(2) The laminate sheet according to (1), wherein an intermediate layer different from the intermediate layer and a1 st resin substrate different from the 1 st resin substrate are laminated in this order on the extension portion of the 2 nd resin substrate and are arranged separately from the laminated portion.
(3) The laminate sheet according to (1) or (2), wherein the contour of the projection portion as viewed from the normal direction of the surface of the 1 st resin substrate is composed of at least 1 of a straight line and a curved line.
(4) The laminate sheet according to any one of (1) to (3), wherein the external shape of the protruding portion as viewed from the normal direction of the surface of the 1 st resin substrate is a polygon, a sector, or an elliptical sector.
(5) The laminate sheet according to any one of (1) to (4), wherein the intermediate layer is a silicone resin layer.
(6) The laminate sheet according to any one of (1) to (5), wherein the 1 st resin substrate and the 2 nd resin substrate are polyethylene terephthalate substrates.
According to the present invention, a laminated sheet in which peeling defects at the time of peeling unnecessary portions and at the time of processing are suppressed can be provided.
Drawings
Fig. 1 is a schematic plan view showing example 1 of a laminated sheet according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view showing example 1 of a laminated sheet according to an embodiment of the present invention.
Fig. 3 is a schematic plan view showing example 2 of a laminated sheet according to the embodiment of the present invention.
Fig. 4 is a schematic cross-sectional view showing example 2 of a laminated sheet according to an embodiment of the present invention.
Fig. 5 is a schematic top view showing example 3 of a laminated sheet according to an embodiment of the present invention.
Fig. 6 is a schematic plan view showing example 4 of the laminated sheet according to the embodiment of the present invention.
Fig. 7 is a schematic plan view showing a peeling method of example 1 of a laminate sheet according to an embodiment of the present invention.
Fig. 8 is a schematic cross-sectional view showing a peeling method of example 1 of a laminated sheet according to an embodiment of the present invention.
Fig. 9 is a schematic cross-sectional view showing a state in which the 2 nd resin substrate of the 1 st example of the laminate sheet according to the embodiment of the present invention is peeled off and then bonded to a glass substrate.
Fig. 10 is a schematic plan view showing a method of peeling a2 nd resin substrate from a conventional laminate sheet.
Fig. 11 is a schematic plan view showing a method of peeling a2 nd resin substrate from a conventional laminate sheet.
Fig. 12 is a schematic plan view showing an example of a method for producing another example of the laminated sheet in the order of steps.
Fig. 13 is a schematic cross-sectional view showing an example of a manufacturing method of another example of the laminated sheet in the order of the steps.
Fig. 14 is a schematic cross-sectional view showing an example of a manufacturing method of another example of the laminated sheet in the order of the steps.
Fig. 15 is a schematic cross-sectional view showing another example of a manufacturing method of another example of a laminated sheet in the order of the steps.
Fig. 16 is a schematic cross-sectional view showing another example of a manufacturing method of another example of a laminated sheet in the order of the steps.
Fig. 17 is a schematic cross-sectional view showing a peeling method of a2 nd resin substrate of another example of a laminate sheet.
Symbol description
10. 11, 11A, 11b, 44, 100 laminate
121 St resin substrate
12A, 14a, 16a, 18a, 30a surfaces
12B, 14b back side
12E, 14e, 100f corner
13A 1 st side
13B side 2
13C 3 rd edge
13D 4 th side
13E vertex
14 Intermediate layer
15 Laminated part
16 Nd resin substrate
17 Cutting line
18 Extension part
19 Laminate
19A another intermediate layer
19B another 1 st resin substrate
20E intersection point
22 Glass substrate
30 Adsorption table
32 Mask
40 Laminate
41. 42 Area
102 Peel defect
D 1 direction 1
D 2 direction 2
Direction of Dp
M 1、M2 intersection point
D 1、d3 extension length
Length of extension of d 2 in direction parallel to side 1
Length of extension of d 4 in direction parallel to side 2
D m distance
Radius r
Tm thickness of
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the following embodiments are examples for explaining the present invention, and the present invention is not limited to the embodiments shown below. Various modifications and substitutions may be added to the following embodiments without departing from the scope of the present invention.
Hereinafter, the numerical range indicated by "to" means a range including the numerical values described before and after "to" as the lower limit value and the upper limit value.
In the following, unless otherwise specified, "orthogonal" and "parallel" include generally allowable error ranges.
Recognition of: in the laminated sheet of the present invention, the laminated sheet is formed by laminating the 1 st resin substrate, the intermediate layer, and the 2 nd resin substrate in this order, wherein the 1 st resin substrate and the intermediate layer have the same shape and size and are laminated to form a laminated portion, the 1 st resin substrate has a quadrangular outer shape as viewed from a normal direction of a surface of the 1 st resin substrate, the 2 nd resin substrate has a larger area than the 1 st resin substrate and the intermediate layer, and the 1 st resin substrate has a length of from 10mm to 40mm as viewed from a normal direction of a surface of the 1 st resin substrate, a length of from 5mm to 20mm as viewed from an intersection point of the 1 st side with the 2 nd direction, and a length of from 5mm to 20mm as viewed from an intersection point of the 2 nd side with the 2 nd direction orthogonal with the 2 nd side, and a protruding portion protruding from an outer edge of the 1 st side with the 1 st direction orthogonal with the 2 nd direction orthogonal with the 1 st side is 5mm to 20mm, and the protruding portion is peeled off from the 2 nd side as a non-parallel portion from the 2 nd side. Thus, the desired effect is obtained.
< 1 St example of laminate >
Fig. 1 is a schematic plan view showing example 1 of a laminate sheet according to an embodiment of the present invention, and fig. 2 is a schematic sectional view showing example 1 of a laminate sheet according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view taken along line A-A of fig. 1. Fig. 1 is a schematic plan view of the resin substrate 12 from the normal direction of the surface 12a of the 1 st resin substrate 12.
As shown in fig. 2, the laminated sheet 10 of example 1 shown in fig. 1 is formed by laminating a1 st resin substrate 12, an intermediate layer 14, and a2 nd resin substrate 16 in this order.
The laminated sheet 10 has an intermediate layer 14 disposed on a surface 16a of a2 nd resin substrate 16, and a1 st resin substrate 12 disposed on a surface 14a of the intermediate layer 14.
The 1 st resin substrate 12 is laminated with the intermediate layer 14 in the same shape and size to form a laminated portion 15.
As shown in fig. 1, the 1 st resin substrate 12 has a quadrangular outer shape as viewed from the normal direction of the surface 12a of the 1 st resin substrate 12.
The 2 nd resin substrate 16 has a larger area than the 1 st resin substrate 12 and the intermediate layer 14. The 2 nd resin substrate 16 has a protrusion 18 extending from the outer edges of the 1 st side 13a, the apex 13e, and the 2 nd side 13b at a corner 12e including the apex 13e where the 1 st side 13a of the 1 st resin substrate 12 orthogonally intersects with the 2 nd side 13b when viewed from the normal direction of the surface 12a of the 1 st resin substrate 12. That is, the 2 nd resin substrate 16 has a larger area than the laminated portion 15.
In the laminate sheet 10, as shown in fig. 1, the 1 st resin substrate 12 has a1 st side 13a, a 2 nd side 13b, a 3 rd side 13c, and a 4 th side 13d. The 1 st side 13a and the 3 rd side 13c are the same length and parallel. The 2 nd side 13b is the same length and parallel to the 4 th side 13d. The 1 st side 13a is orthogonal to the 2 nd side 13 b. In addition, the 3 rd side 13c is orthogonal to the 4 th side 13d.
In the laminated portion 15 shown in fig. 1, the length L 1 of the 1 st side 13a and the 3 rd side 13c is shorter than the length L 2 of the 2 nd side 13b and the 4 th side 13 d.
In the laminated portion 15, the length L 1 of the 1 st side 13a and the 3 rd side 13c may be longer than the length L 2 of the 2 nd side 13b and the 4 th side 13d, and the length L 1 of the 1 st side 13a and the 3 rd side 13c may be the same as the length L 2 of the 2 nd side 13b and the 4 th side 13 d. When the lengths L 1 of the 1 st side 13a and the 3 rd side 13c are the same as the lengths L 2 of the 2 nd side 13b and the 4 th side 13d, the outline as viewed from the normal direction of the surface 12a of the 1 st resin substrate 12 is square.
As shown in fig. 2, the laminate 10 is configured such that nothing is present on the surface 18a of the extension 18 of the 2 nd resin substrate 16.
The outline of the extension 18, as viewed from the normal direction of the surface 12a of the 1 st resin substrate 12, is, for example, a shape in which 2 quadrangles are combined as shown in fig. 1. The outline of the extension 18, as viewed from the normal direction of the surface 12a of the 1 st resin substrate 12, is L-shaped as shown in fig. 1. The vertex of the extension 18, where the side parallel to the 1 st side 13a and the side parallel to the 2 nd side 13b orthogonally intersect, is set to 18e.
The extension 18 has a length D 1 of 5mm to 20mm extending from the 1 st side 13a along the 1 st direction D 1 extending from the 1 st side 13a and a length D 2 of 10mm to 40mm extending from the intersection point M 1 of the extension 18 and the 1 st side 13a along the direction parallel to the 1 st side 13 a. The length D 3 of the extension 18 extending from the 2 nd side 13b in the 2 nd direction D 2 orthogonal to the 2 nd side 13b is 5mm to 20mm, and the length D 4 of the extension 18 extending from the intersection point M 2 of the extension 18 and the 2 nd side 13b in the direction parallel to the 2 nd side 13b is 10mm to 40mm.
The direction parallel to the 1 st side 13a is the 2 nd direction D 2, and the direction parallel to the 2 nd side 13b is the 1 st direction D 1.
The length d 1 of extension 18 and the length d 3 of extension 18 are preferably 5mm to 10mm.
The length d 2 of the protruding portion 18 in the direction parallel to the 1 st side 13a and the length d 4 of the protruding portion 18 in the direction parallel to the 2 nd side 13b are preferably 20mm to 30mm.
The length d 1 of the extension 18, the length d 2 of the extension 18 in the direction parallel to the 1 st side 13a, the length d 3 of the extension 18, and the length d 4 of the extension 18 in the direction parallel to the 2 nd side 13b are average values of distances at any 10 points corresponding to the length d 1 of the extension 18, the length d 2 of the extension 18 in the direction parallel to the 1 st side 13a, the length d 3 of the extension 18, and the length d 4 of the extension 18 in the direction parallel to the 2 nd side 13b, respectively.
The shape of the extension 18 is not particularly limited as long as the extension 18 extends over the above-mentioned range, and the extension 18 has a length d 1, a length d 2 of the extension 18 in the direction parallel to the 1 st side 13a, a length d 3 of the extension 18, and a length d 4 of the extension 18 in the direction parallel to the 2 nd side 13b, and it is preferable to consider workability such as easy-to-machine shape.
The outline of the extension 18, as viewed from the normal direction of the surface 12a of the 1 st resin substrate 12, may constitute a contour of at least 1 of a straight line and a curved line. The number of straight lines and curved lines constituting the pinna is not particularly limited, and may be 1 or a plurality of straight lines and curved lines.
In addition, the outline of the extension 18 as viewed from the normal direction of the surface 12a of the 1 st resin substrate 12 is, for example, a polygon, a fan, or an elliptical fan.
The extension portion 18 suppresses occurrence of peeling defects such as cohesive failure by satisfying the above-described ranges of the extension portion 18 extension length d 1, the extension portion 18 extension length d 2 in the direction parallel to the 1 st side 13a, the extension portion 18 extension length d 3, and the extension portion 18 extension length d 4 in the direction parallel to the 2 nd side 13b, respectively, and suppresses peeling of the laminate sheet at the time of handling such as conveying the laminate sheet.
When the length d 1 of the extension 18, the length d 2 of the extension 18 in the direction parallel to the 1 st side 13a, the length d 3 of the extension 18, and the length d 4 of the extension 18 in the direction parallel to the 2 nd side 13b exceed the upper limit values, the unintentional laminate is peeled off during handling such as transferring the laminate, and as a result, peeling defects such as cohesive failure occur.
When the length d 1 of the extension 18, the length d 2 of the extension 18 in the direction parallel to the 1 st side 13a, the length d 3 of the extension 18, and the length d 4 of the extension 18 in the direction parallel to the 2 nd side 13b are smaller than the lower limit values, peeling defects such as cohesive failure occur.
By providing the protruding portion 18 on the 2 nd resin substrate 16, the corner portion 12e having the protruding portion 18 does not become a peeling end portion when the 2 nd resin substrate 16 is peeled in the direction Dp from, for example, the corner portion 12e existing at the diagonal position of the corner portion 12e having the protruding portion 18 toward the corner portion 12e having the protruding portion 18. Therefore, peeling defects such as coagulation failure are suppressed from occurring in the corner 12e having the protruding portion 18.
The intermediate layer 14 is detached by the coagulation failure, and the detached intermediate layer 14 causes contamination in the process, but such a case is also suppressed. That is, in-process contamination can be suppressed.
< 2 Nd to 4 th cases of laminate >
Fig. 3 is a schematic plan view showing example 2 of a laminate sheet according to an embodiment of the present invention, and fig. 4 is a schematic sectional view showing example 2 of a laminate sheet according to an embodiment of the present invention.
Fig. 5 is a schematic top view showing example 3 of a laminated sheet according to an embodiment of the present invention. Fig. 6 is a schematic plan view showing example 4 of the laminated sheet according to the embodiment of the present invention.
Fig. 3, 5 and 6 are schematic plan views seen from the normal direction of the surface 12a of the 1 st resin substrate 12. Fig. 4 is a schematic cross-sectional view at line B-B of fig. 3.
In fig. 3 to 6, the same components as those of the laminated sheet 10 shown in fig. 1 and 2 are denoted by the same reference numerals, and detailed description thereof is omitted.
The laminated sheet 11 of example 2 shown in fig. 3 is similar to the laminated sheet 10 shown in fig. 1 and 2 except that, as shown in fig. 4, an intermediate layer 19a different from the intermediate layer 14 and a1 st resin substrate 19b different from the 1 st resin substrate 12 are sequentially laminated on the surface 18a of the extension 18 of the 2 nd resin substrate 16 and are arranged separately from the laminated portion 15, and the configuration is similar to that of the laminated sheet 10 shown in fig. 1 and 2. The laminate 19 is constituted by another intermediate layer 19a and another 1 st resin substrate 19 b.
In the laminate sheet 11 shown in fig. 3, the laminated portion 15 and the laminated body 19 are separated by the cut line 17. That is, the other intermediate layer 19a and the other 1 st resin substrate 19b are separated from the laminated portion 15 by the dicing line 17.
As shown in fig. 4, the dicing line 17 penetrates the 1 st resin substrate 12 and the intermediate layer 14, and reaches halfway in the thickness direction of the 2 nd resin substrate 16. The dicing line 17 is a full cut for the 1 st resin substrate 12 and the intermediate layer 14, and a half cut for the 2 nd resin substrate 16.
The other intermediate layer 19a is separated from the intermediate layer 14 by the dicing line 17, and thus may be the same as the intermediate layer 14 or may be different from the intermediate layer 14. The other 1 st resin substrate 19b is separated from the 1 st resin substrate 12 by the dicing line 17, and thus may be the same as the 1 st resin substrate 12 or may be different from the 1 st resin substrate 12.
In the laminate 11, when the 2 nd resin substrate 16 is peeled off, the laminate 19 on the surface 18a of the protruding portion 18 is peeled off before the 2 nd resin substrate 16 is peeled off. If the laminate 19 is peeled, the laminate 10 shown in fig. 1 and 2 is in a state. After the laminate 19 is peeled, the 2 nd resin substrate 16 is peeled in the same manner as the laminate 10 shown in fig. 1 and 2.
In the laminate 11, similarly to the laminate 10 shown in fig. 1 and 2, occurrence of peeling defects such as cohesive failure can be suppressed, and in-process contamination can be suppressed.
The laminated sheet 11a of example 3 shown in fig. 5 is similar to the laminated sheet 10 shown in fig. 1 and 2, except that the extension 18 of the 2 nd resin substrate 16 has a fan-shaped outer shape as viewed from the normal direction of the surface 12a of the 1 st resin substrate 12.
The external shape of the extension 18 is a fan shape having a radius r centered on the apex 13e of the 1 st resin substrate 12. The extension 18 surrounds the corner 12e including the vertex 13e where the 1 st side 13a and the 2 nd side 13b orthogonally intersect. The maximum length d 5 through the center of the sector is 2 times the radius r. The maximum length d 5 of the laminate 11a is 10mm to 40mm.
The radius r corresponds to the length D 1 of the extension 18 extending in the 1 st direction D 1 and the length D 3 of the extension 18 extending in the 2 nd direction D 2.
The maximum length d 5 of the protruding portion 18 corresponds to the length d 2 of the protruding portion 18 in the direction parallel to the 1 st side 13a and the length d 4 of the protruding portion 18 in the direction parallel to the 2 nd side 13 b.
Since the maximum length d 5 of the protruding portion 18 is 10mm to 40mm, the radius r is 5mm to 20mm.
In the laminate 11a, the outer shape of the protruding portion 18 is a sector, but may be an elliptical sector.
The laminate 11b of example 4 shown in fig. 6 is similar to the laminate 10 shown in fig. 1 and 2 except that the extension 18 of the 2 nd resin substrate 16 has a different outer shape as viewed from the normal direction of the surface 12a of the 1 st resin substrate 12.
The wheel Guo Juyou of the outer shape of the extension 18 of the laminate 11b is constituted by a curved line 20a extending from the 1 st side 13a, a straight line 20b connected to the curved line 20a and parallel to the 1 st side 13a, a curved line 20c extending from the 2 nd side 13b, and a straight line 20d connected to the curved line 20c and parallel to the 2 nd side 13b, and a straight line 20b parallel to the 1 st side 13a and a straight line 20d orthogonal to the 1 st side 13 a. The arcuate curve 20a and the arcuate curve 20c have the same length. The straight line 20b and the straight line 20d have the same length.
The distance between the 1 st side 13a and the straight line 20b in the 1 st direction D 1 is the length D 1 by which the extension 18 extends. The distance of the extension 18 from the intersection point M 1 of the curve 20a and the 1 st side 13a to the intersection point 20e of the straight line 20b and the straight line 20d in the direction parallel to the 1 st side 13a is the length d 2 of the extension 18 described above.
The distance between the 2 nd side 13b along the 2 nd direction D 2 and the straight line 20D is the length D 3 by which the extension 18 extends. The distance from the intersection point M 2 of the curve 20c and the 2 nd side 13b to the intersection point 20e in the direction parallel to the 2 nd side 13b is the length d 4 of the protruding portion 18 described above.
In the laminate 11a shown in fig. 5 and the laminate 11b of the 4 th example shown in fig. 6, the 2 nd resin substrate 16 is peeled off in the same manner as in the laminate 10 shown in fig. 1 and 2. In this case, similarly to the laminate 10 shown in fig. 1 and 2, occurrence of peeling defects such as cohesive failure can be suppressed, and in-process contamination can be suppressed.
In addition, in the laminated sheet 11a shown in fig. 5 and the laminated sheet 11b of the 4 th example shown in fig. 6, as in the laminated sheet 11 shown in fig. 4, a laminated body 19 in which another intermediate layer 19a and another 1 st resin substrate 19b are laminated in this order may be provided on the surface 18a of the extension 18.
< Method of peeling laminate >)
Fig. 7 is a schematic plan view showing the peeling method of example 1 of the laminated sheet according to the embodiment of the present invention, and fig. 8 is a schematic sectional view showing the peeling method of example 1 of the laminated sheet according to the embodiment of the present invention. Fig. 8 is a schematic cross-sectional view at line C-C of fig. 7.
In the method of peeling the laminate, the 2 nd resin substrate 16 is peeled from the diagonal side of the protruding portion 18 toward the protruding portion 18.
As shown in fig. 7 and 8, the laminate sheet 10 is placed on the surface 30a of the suction table 30 such that the surface 12a of the 1 st resin substrate 12 faces the surface 30a of the suction table 30. Then, the suction table 30 sucks the laminate sheet 10 to fix the laminate sheet 10.
At this time, a mask 32 is provided between the protruding portion 18 and the suction table 30. The contact of the extension 18 with the suction table 30 is suppressed by the mask 32.
The mask 32 may be, for example, an adhesive tape. By using an adhesive tape, the mask can be arranged at a position corresponding to the shape of the laminate sheet.
In addition to the adhesive tape described above, for example, a PET film sheet obtained by hollowing out a PET film sheet or the like to a size slightly larger than the laminate sheet 10 may be used as the mask 32. The above-described PET film or the like is placed on the suction table 30 as a mask 32.
In addition, for example, the suction hole pattern of the suction table 30 may be the same as that of the laminate 10 without providing the mask 32. Further, the suction holes used when the laminate sheet 10 is sucked by the suction table 30 may be used separately in accordance with the shape of the laminate sheet 10.
The distance d m between the mask 32 and the laminated portion 15 is more than 0mm, preferably 5mm or less, and more preferably 2mm or less.
Distance d m is the average of distances at any 10 corresponding to distance d m.
When the distance d m exceeds 5mm, the entire laminate sheet 10 may be displaced when the 2 nd resin substrate 16 is peeled off. In addition, when the 2 nd resin substrate 16 is peeled off, the air pocket (groove) becomes large, and the laminate sheet 10 may not be sufficiently sucked and fixed. As a result, when the laminate 10 is curled or when the rigidity of the laminate 10 is low, the laminate 10 is wrinkled or curled and is adhered to the glass substrate, which causes a problem.
The thickness tm of the mask 32 is, for example, the same as the thickness of the laminated portion 15. Accordingly, the thickness tm of the mask 32 is determined according to the respective thicknesses of the 1 st resin substrate 12 and the intermediate layer 14.
If the thickness tm of the mask 32 is thick, peeling defects may occur at the interface between the intermediate layer 14 and the 2 nd resin substrate 16 when the laminate sheet 10 is attracted. If a peeling defect occurs, particles adhere to the peeled portion to cause a sticking defect.
When the distance d m and the thickness tm of the mask 32 are appropriate, the 2 nd resin substrate 16 and the intermediate layer 14 are not unintentionally peeled off, and the laminate 10 can be peeled off without being displaced when the 2 nd resin substrate 16 is intentionally peeled off. Therefore, the glass substrate can be bonded to the glass substrate with good alignment accuracy without peeling defects.
The thickness tm of the mask 32 is a value obtained by measuring the thickness of the mask 32 at any position of 5 points or more by a contact film thickness measuring device and arithmetically averaging them.
Next, the 2 nd resin substrate 16 is peeled off in a direction Dp from the corner 12e located diagonally with respect to the corner 12e of the 1 st resin substrate 12 on the projecting portion 18 side toward the corner 12e on the projecting portion 18 side. At this time, the corner 12e on the projecting portion 18 side becomes a peeling end portion. Peeling defects such as condensation damage do not occur in the region of the back surface 14b of the intermediate layer 14 corresponding to the peeling terminal portion. The intermediate layer 14 is free of peeling defects.
After the 2 nd resin substrate 16 is peeled off, the back surface 14b of the exposed intermediate layer 14 is bonded to the glass substrate 22. At this time, since the interlayer 14 has no peeling defect, no lamination failure occurs after lamination to the glass substrate 22. The peeling defect was found to be a lamination failure when glass lamination was performed.
Here, fig. 10 and 11 are schematic plan views showing a conventional method for peeling a2 nd resin substrate from a laminated sheet in the order of steps.
In fig. 10 and 11, the same components as those of the laminate 10 shown in fig. 1 and 2 are denoted by the same reference numerals, and detailed description thereof is omitted.
As shown in fig. 10, the conventional laminate 100 has a structure without the extension 18 and has a quadrangular outer shape. The conventional laminate 100 is placed on the surface 30a of the suction table 30 such that the 1 st resin substrate 12 (not shown) faces the surface 30a of the suction table 30. Then, the suction table 30 sucks the conventional laminated sheet 100 and fixes the conventional laminated sheet 100.
In this fixed state, in the conventional laminated sheet 100, the 2 nd resin substrate 16 is peeled in a direction from the corner 100e toward the diagonal corner 100 f. The corner 100f is a peeling terminal portion.
After peeling, peeling defects 102 due to cohesive failure occur in the corner 14e of the back surface 14b of the intermediate layer 14 corresponding to the peeled terminal portion.
When the intermediate layer 14 having the peeling defect 102 is bonded to the glass substrate 22 shown in fig. 9, the peeling defect 102 is found as a bonding failure.
(Other examples of laminates)
Fig. 12 to 14 are a schematic plan view and a schematic sectional view showing an example of a method for manufacturing another example of a laminated sheet in the order of steps. Fig. 15 and 16 are schematic cross-sectional views showing another example of a manufacturing method of another example of a laminated sheet in the order of the steps. Fig. 17 is a schematic cross-sectional view showing a peeling method of a2 nd resin substrate of another example of a laminate sheet.
In fig. 12 to 17, the same components as those of the laminated sheet 10 shown in fig. 1 and 2 are denoted by the same reference numerals, and detailed description thereof is omitted.
As shown in fig. 12 and 13, a laminate 40 in which the 2 nd resin substrate 16, the intermediate layer 14, and the 1 st resin substrate 12 are laminated in this order is prepared.
The laminated material 40 is formed with the intermediate layer 14 on the back surface 12b of the 1 st resin substrate 12 by a spin coater or a die coater, for example. Next, the 2 nd resin substrate 16 is bonded to the back surface 14b of the intermediate layer 14. The intermediate layer 14 may be formed as a single sheet or in a roll-to-roll (roll-to-roll) system.
Next, the dicing line 17 is formed in a square frame shape from the 1 st resin substrate 12 side of the laminate 40. The region 41 surrounded by the dicing line 17 becomes a product, and the region 42 outside the dicing line 17 is an unnecessary portion. The region 42 outside the cutting line 17 is removed as an unwanted part.
As shown in fig. 13, the dicing line 17 penetrates the 1 st resin substrate 12 and the intermediate layer 14, and does not reach the 2 nd resin substrate 16. The dicing line 17 is a full cut to the 1 st resin substrate 12 and the intermediate layer 14. The cutting line 17 may be formed by, for example, laser or punching.
The width delta of the cutting line 17 is preferably 10mm to 20mm. If the width δ of the dicing line 17 is 10mm to 20mm, the occurrence of the peeling defect is suppressed, and unintentional peeling of the 1 st resin substrate 12 or the 2 nd resin substrate 16 during processing is also suppressed.
Next, as shown in fig. 14, the region 42 outside the dicing line 17 (see fig. 13) is removed, and a laminate 44 is obtained. The 1 st resin substrate 12 and the intermediate layer 14 of the laminate sheet 44 are the same size and have a quadrangular outer shape. The 2 nd resin substrate 16 is larger than the 1 st resin substrate 12 and the intermediate layer 14, and has a quadrangular outer shape. The 1 st resin substrate 12, the intermediate layer 14, and the 2 nd resin substrate 16 are arranged so that the sides are parallel to each other.
In addition, in the laminate sheet 44, a part of the surface 16a of the 2 nd resin substrate 16 is exposed.
The lamination sheet 44 peels off the 2 nd resin substrate 16, and as shown in fig. 9, the glass substrate 22 is bonded to the back surface 14b of the exposed intermediate layer 14.
As shown in fig. 15, the intermediate layer 14 is formed on the back surface 12b of the 1 st resin substrate 12 by using a spin coater or a die coater. At this time, the 1 st resin substrate 12 and the intermediate layer 14 have the same size.
Next, as shown in fig. 16, the 2 nd resin substrate 16 having a larger area than the 1 st resin substrate 12 and the intermediate layer 14 is bonded to the back surface 14b of the intermediate layer 14. Thereby, the laminate sheet 44 is obtained.
The laminated sheet 44 shown in fig. 16 is also obtained by peeling the 2 nd resin substrate 16, and bonding the glass substrate 22 to the back surface 14b of the exposed intermediate layer 14 as shown in fig. 9.
When the 2 nd resin substrate 16 of the laminate 44 is peeled off, as shown in fig. 17, the laminate 44 is placed on the surface 30a of the suction table 30 so that the 1 st resin substrate 12 faces the surface 30a of the suction table 30. A mask 32 is disposed between the 2 nd resin substrate 16 and the suction stage 30. Then, the suction table 30 sucks the laminate sheet 44 to fix the laminate sheet 44. The mask 32 is arranged in the same manner as the mask 32 shown in fig. 8, and thus a detailed description thereof is omitted.
In the state where the laminated sheet 44 is fixed to the suction table 30 shown in fig. 17, the 2 nd resin substrate 16 is peeled off from one corner (not shown) facing the diagonal line (not shown) toward the other corner (not shown) in the laminated sheet 44. At this time, the other corner is the peeling terminal portion.
Since the 2 nd resin substrate 16 has a larger area than the 1 st resin substrate 12 and the intermediate layer 14, the end portion of the intermediate layer 14 does not become a peeling terminal. Therefore, the occurrence of the peeling defect 102 shown in fig. 11 is suppressed when the 2 nd resin substrate 16 is peeled.
The fixing of the laminate sheet at the time of peeling the 2 nd resin substrate 16 is not limited to the above-described suction table 30, and may be an electrostatic chuck.
The 1 st resin substrate 12, the intermediate layer 14, and the 2 nd resin substrate 16 constituting the laminate 10 will be described in detail below.
(1 St resin substrate and 2 nd resin substrate)
The 1 st resin substrate 12 and the 2 nd resin substrate 16 protect the intermediate layer 14, and function as a protective layer, which is also called a protective film. In addition, either the 1 st resin substrate 12 or the 2 nd resin substrate 16 is peeled off from the intermediate layer 14 when being bonded to the glass substrate. Therefore, one of the 1 st resin substrate 12 and the 2 nd resin substrate 16, which is peeled off from the intermediate layer 14, is also referred to as a release film.
Examples of the material constituting the 1 st resin substrate 12 and the 2 nd resin substrate 16 include polyimide resins, polyester resins (e.g., polyethylene terephthalate, polyethylene naphthalate), polyolefin resins (e.g., polyethylene, polypropylene), and polyurethane resins. Among them, polyester resins are preferable, and polyethylene terephthalate (PET) is more preferable. Accordingly, the 1 st resin substrate 12 and the 2 nd resin substrate 16 are more preferably polyethylene terephthalate substrates.
In order to reduce the influence of the force received from the outside, the thicknesses of the 1 st resin substrate 12 and the 2 nd resin substrate 16 are preferably 20 μm or more, more preferably 30 μm or more, and still more preferably 50 μm or more. The upper limit value of the thickness of the 1 st resin substrate 12 and the 2 nd resin substrate 16 is preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 100 μm or less.
(Intermediate layer)
The intermediate layer 14 is disposed between the 1 st resin substrate 12 and the 2 nd resin substrate 16.
The intermediate layer 14 is a film for preventing peeling of a polyimide film (not shown) when the polyimide film is disposed on the intermediate layer 14.
The intermediate layer 14 may be an organic layer or an inorganic layer.
Examples of the material of the organic layer include acrylic resin, polyolefin resin, polyurethane resin, polyimide resin, silicone resin, polyimide silicone resin, and fluororesin. In addition, the intermediate layer 14 may be formed by mixing a plurality of types of resins.
Examples of the material of the inorganic layer include oxides, nitrides, oxynitrides, carbides, carbonitrides, silicides, and fluorides. Examples of the oxide (preferably metal oxide), nitride (preferably metal nitride), and oxynitride (preferably metal oxynitride) include oxides, nitrides, and oxynitrides of 1 or more elements selected from Si, hf, zr, ta, ti, Y, nb, na, co, al, zn, pb, mg, bi, la, ce, pr, sm, eu, gd, dy, er, sr, sn, in and Ba.
Examples of the carbide (preferably metal carbide) and the carbonitride (preferably metal carbonitride) include carbide, carbonitride, and oxycarbide of 1 or more elements selected from Ti, W, si, zr and Nb.
The silicide (preferably metal silicide) includes, for example, a silicide of 1 or more elements selected from Mo, W, and Cr.
Examples of the fluoride (preferably metal fluoride) include fluorides of 1 or more elements selected from Mg, Y, la and Ba.
The intermediate layer 14 may also be a plasma polymerized film.
When the intermediate layer 14 is a plasma polymerized film, examples of the material for forming the plasma polymerized film include fluorocarbon monomers such as CF4、CHF3、C2F6、C3F6、C2F2、CH3F、C4F8, hydrocarbon monomers such as methane, ethane, propane, ethylene, propylene, acetylene, benzene, toluene, hydrogen, SF 6, and the like.
Among them, the material of the intermediate layer 14 is preferably a silicone resin or a polyimide silicone resin, more preferably a silicone resin, and even more preferably a silicone resin formed of condensation-reaction type silicone, from the viewpoints of heat resistance and releasability.
Hereinafter, a manner in which the intermediate layer 14 is a silicone resin layer will be described in detail.
The silicone resin is a resin containing a predetermined organosiloxane unit, and is usually obtained by curing a curable silicone. The curable silicone is classified into addition reaction type silicone, condensation reaction type silicone, ultraviolet curing type silicone and electron beam curing type silicone according to its curing mechanism, and either can be used. Among them, condensation reaction type silicones are preferred.
As the condensation reaction type silicone, a hydrolyzable organosilane compound or a mixture thereof (monomer mixture) as a monomer or a partially hydrolyzed condensate (organopolysiloxane) obtained by subjecting a monomer or a monomer mixture to a partial hydrolytic condensation reaction can be suitably used.
By using this condensation reaction type silicone, a hydrolysis/condensation reaction (sol-gel reaction) is performed, whereby a silicone resin can be formed.
The intermediate layer 14 is preferably formed using a curable composition containing a curable silicone.
The curable composition may contain, in addition to the curable silicone, a solvent, a platinum catalyst (when an addition reaction type silicone is used as the curable silicone), a leveling agent, a metal compound, and the like. Examples of the metal element contained in the metal compound include 3d transition metal, 4d transition metal, lanthanoid metal, bismuth (Bi), aluminum (Al), and tin (Sn). The content of the metal compound is not particularly limited and may be appropriately adjusted.
The intermediate layer 14 preferably has hydroxyl groups. A portion of Si-O-Si bonds of the silicone resin constituting the intermediate layer 14 is broken, and hydroxyl groups may be exposed. In the case of using a condensation reaction type silicone, the hydroxyl group may be the hydroxyl group of the intermediate layer 14.
The thickness of the intermediate layer 14 in the normal direction of the surface 12a of the 1 st resin substrate 12 is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 12 μm or less. On the other hand, the thickness of the intermediate layer 14 is preferably more than 1. Mu.m, and is more preferably 6. Mu.m, since the foreign matter embedding property is more excellent. The thickness is a value obtained by measuring the thickness of the intermediate layer 14 at any position of 5 points or more by a contact film thickness measuring device and arithmetically averaging them.
The excellent embedding property of the foreign matter means that the foreign matter can be embedded in the intermediate layer 14 even if the foreign matter exists between the intermediate layer 14 and another substrate or the like. If the foreign matter embedding property is excellent, the intermediate layer is less likely to generate a convex portion due to the foreign matter, and when forming the component for an electronic device on the polyimide film, the risk of disconnection or the like in the component for an electronic device due to the convex portion is suppressed. Since voids formed when the convex portions were generated were observed as bubbles, the embeddability of foreign matter was evaluated by the presence or absence of bubbles.
Here, for example, when a polyimide film is formed on a glass substrate (not shown) and subjected to a high-temperature heat treatment, the polyimide film is yellowing, and thus it is difficult to use for a transparent electronic device. However, the mechanism is not clear, but yellowing of the polyimide film due to the high-temperature heat treatment can be suppressed by forming the intermediate layer 14 on the glass substrate and forming the polyimide film on the intermediate layer 14.
(Glass substrate)
The glass substrate 22 to which the intermediate layer 14 is attached is a member that supports and reinforces the 1 st resin substrate 12 and the intermediate layer 14. The glass substrate 22 functions as a transfer substrate.
The glass type is preferably alkali-free borosilicate glass, soda lime glass, silica glass, or other oxide glass containing silica as a main component. The oxide-based glass is preferably glass having a silica content of 40 to 90 mass% based on oxide conversion.
More specifically, examples of the glass plate include a glass plate made of alkali-free borosilicate glass (trade name "AN100" manufactured by AGC Co., ltd., and a linear expansion coefficient of 38X 10 -7/. Degree.C., trade name "AN-Wizus" manufactured by AGC Co., ltd.).
In general, a method for producing a glass plate is obtained by melting a glass raw material and molding the molten glass into a plate shape. Such a molding method may be a general glass molding method, and examples thereof include a float method, a fusion method, and a slot down-draw method.
The glass substrate 22 is preferably not flexible. Accordingly, the thickness of the glass substrate 22 is preferably 0.3mm or more, more preferably 0.5mm or more.
On the other hand, the thickness of the glass substrate 22 is preferably 1.0mm or less.
The surface roughness Ra of the glass substrate 22 is preferably less than 0.4nm, more preferably less than 0.25nm. If the surface roughness of the glass substrate 22 is large, the contact area between the silicone resin layer and the surface of the glass substrate increases, and water molecules are easily transferred from the glass substrate to the silicone resin layer, so that the polyimide resin layer is easily yellowing. Therefore, the surface roughness of the glass substrate 22 is preferably a constant value or less.
The shape of the glass substrate 22 when viewed from the normal direction of the surface of the glass substrate 22 is not particularly limited, and may be a quadrangle, or may be a circle, preferably a quadrangle.
The glass substrate 22 is larger than the intermediate layer 14 and the 1 st resin substrate 12, and the surface of the glass substrate 22 has a peripheral region where the intermediate layer 14 and the 1 st resin substrate 12 are not arranged, and the surface of the peripheral region of the glass substrate 22 is exposed.
The width of the peripheral region of the glass substrate 22 is not particularly limited, but is preferably 1mm to 30mm, more preferably 3mm to 10mm. The width of the peripheral region refers to the distance from the outer peripheral edge of the 1 st resin substrate 12 to the outer edge of the glass substrate 22.
If the width of the peripheral region of the glass substrate 22 is 30mm or less, the effective area for forming an electronic device or the like is larger, and the manufacturing efficiency of the electronic device is improved. In addition, since the width of the peripheral region is 1mm or more, peeling of the polyimide film is less likely to occur when the polyimide film is formed on the intermediate layer 14.
(Use of laminate)
The laminated body obtained by lamination can be used for various applications, for example, applications for manufacturing electronic components such as a panel for a display device, a PV, a thin film secondary battery, a semiconductor wafer having a circuit formed on a surface thereof, and a receiving sensor panel, which will be described later. In these applications, the laminate may be exposed to high temperature conditions (for example, 450 ℃ or higher) under an atmospheric atmosphere (for example, 20 minutes or longer).
The panel for a display device includes an LCD, an OLED (Organic LIGHT EMITTING Diode), an electronic paper, a plasma display panel, a field emission display panel, a quantum dot LED (LIGHT EMITTING Diode) panel, a Micro LED display panel, a MEMS (Micro Electro MECHANICAL SYSTEMS) shutter panel, and the like.
The receiving sensor panel includes an electromagnetic wave receiving sensor panel, an X-ray receiving sensor panel, an ultraviolet ray receiving sensor panel, a visible light receiving sensor panel, an infrared ray receiving sensor panel, and the like. The substrate used in the receiving sensor panel may be reinforced by a reinforcing sheet or the like of resin or the like.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
Examples 1 to 5 are examples, and examples 6 and 7 are comparative examples in examples 1 to 7 shown below.
[ Production of laminate ]
Preparation of curable Silicone
Triethoxymethylsilane (179 g), toluene (300 g) and acetic acid (5 g) were charged into a 1L (liter) flask, and the mixture was stirred at 25℃for 20 minutes, and then heated to 60℃to react for 12 hours, whereby a crude reaction solution was obtained.
After the obtained reaction crude liquid was cooled to 25 ℃, the reaction crude liquid was washed 3 times with water (300 g). To the reaction mixture after washing was added trimethylchlorosilane (70 g), and the mixture was stirred at 25℃for 20 minutes and then heated to 50℃to react for 12 hours. After the obtained reaction crude liquid was cooled to 25 ℃, the reaction crude liquid was washed 3 times with water (300 g).
Toluene was distilled off under reduced pressure from the reaction crude liquid after washing, and after the slurry state was reached, the slurry was dried overnight by a vacuum dryer, whereby a white curable silicone 1 was obtained as an organopolysiloxane compound.
The molar ratio of M units to T units of the curable silicone 1 was 13:87, all the organic groups were methyl groups, and the average number of OX groups was 0.02.M unit means an organosiloxane unit represented by (R) 3SiO1/2, T unit means an organosiloxane unit represented by RSiO 3/2, and R in each formula represents a hydrogen atom or an organic group. The average number of OX groups is a number indicating that several OX groups (X is a hydrogen atom or a hydrocarbon group) are bonded on average in 1 Si atom.
Preparation of curable composition
Curable silicone 1 (20 g), zirconium octoate compound ("ORGATIX ZC-200", manufactured by Matsumoto FINE CHEMICAL corporation) (0.16 g), cerium (III) 2-ethylhexanoate (manufactured by ALFA AESAR corporation, metal content 12 mass%) (0.17 g), and Isoper G (manufactured by Tonen General Sekiyu corporation) (19.7 g) as a solvent were mixed, and the obtained mixed solution was filtered using a filter having a pore size of 0.45 μm, thereby obtaining curable composition 1.
Example 1 laminate sheet
A PET film (TOYOBO master (registered trademark) film HPE, thickness 50 μm) was prepared as a1 st resin substrate (release film), and the prepared curable composition 1 was coated on the surface of the 1 st resin substrate, and heated at 140 ℃ for 10 minutes using a hot press, thereby forming a silicone resin layer on the 1 st resin substrate (release film).
A PET film (Easter (registered trademark) film HPE, thickness 50 μm) was laminated on the silicone resin layer as a2 nd resin substrate (protective film). Next, cutting was performed by using a punching machine so that an L-shaped protruding portion was formed at 1 corner of 912 (L 2)mm×722(L1) mm.
The extension is formed in such a manner that the length D 1 of the extension in the 1 st direction D 1 and the length D 3 of the extension in the 2 nd direction D 2 are 10mm and in such a manner that the length D 2 of the extension 18 in the direction parallel to the 1 st side 13a and the length D 4 of the extension 18 in the direction parallel to the 2 nd side 13b are 20 mm.
The PET film as the 1 st resin substrate (release film) and the silicone resin layer (intermediate layer) were subjected to full-cut cutting from the PET film side as the 1 st resin substrate (release film) using a cutter, and the PET film as the 2 nd resin substrate (protective film) was subjected to half-cut cutting to a mid-thickness thereof. The half-cut cutting method of the laminate sheet using the cutter is referred to as a "punching method".
Thus, a laminate sheet 1 in which the 1 st resin substrate (release film), the silicone resin layer (intermediate layer), and the 2 nd resin substrate (protective film) were laminated in this order was obtained. The thickness of the obtained laminate 1 was 110. Mu.m. The protruding portion of example 1 is in the shape shown in fig. 1.
The length D 1 of the extension in the 1 st direction D 1 and the length D 3 of the extension in the 2 nd direction D 2 are described as "the length D 1、d3 of the extension" in table 1 below.
In addition, the length d 2 of the protruding portion 18 in the direction parallel to the 1 st side 13a and the length d 4 of the protruding portion 18 in the direction parallel to the 2 nd side 13b are denoted as "protruding portion length d 2、d4" in table 1 below.
< Examples 2 to 7 >
The laminate was obtained in the same manner as in example 1 above, except that the laminate was cut so that the dimensions of the laminate, the outer shape and dimensions of the protruding portion of the laminate, and the half-cut cutting method of the laminate were set to the relationships of examples 2 to 8 shown in table 1 below.
In table 1 below, the term "-" indicates that there is no corresponding numerical value.
The extension of example 2 is of the shape shown in fig. 1.
In example 2, cutting was performed by using a laser processing machine so that an L-shaped protruding portion was formed at 1 corner portion of 912 (L 2)mm×722(L1) mm in size, instead of using a punching machine. The extension is formed in such a manner that the length D 1 of the extension in the 1 st direction D 1 and the length D 3 of the extension in the 2 nd direction D 2 are 10mm and in such a manner that the length D 2 of the extension 18 in the direction parallel to the 1 st side 13a and the length D 4 of the extension 18 in the direction parallel to the 2 nd side 13b are 20 mm.
The PET film as the 1 st resin substrate (release film) and the silicone resin layer (intermediate layer) were subjected to full-cut cutting from the PET film side as the 1 st resin substrate (release film) using a laser processing machine, and the PET film as the 2 nd resin substrate (protective film) was subjected to half-cut cutting to a halfway of the thickness thereof. The half-cut cutting method of the laminate sheet using the laser processing machine is referred to as a "laser method".
The laser processing machine uses a linear motion plotter type CO 2 laser.
The extension of example 3 is of the shape shown in fig. 1.
In example 3, laminate sheet 1 was cut by a laser processing machine so that an L-shaped extension was formed at 1 corner of 912 (L 2)mm×722(L1) mm. The extension is formed in such a manner that the length D 1 of the extension in the 1 st direction D 1 and the length D 3 of the extension in the 2 nd direction D 2 are 20mm and in such a manner that the length D 2 of the extension 18 in the direction parallel to the 1 st side 13a and the length D 4 of the extension 18 in the direction parallel to the 2 nd side 13b are 40 mm.
The extension of example 4 is of the shape shown in fig. 5.
In example 4, laminate sheet 1 was cut using a laser processing machine so that a fan-shaped extension was formed at 1 corner of 912 (L 2)mm×722(L1) mm. The protruding portion is formed in such a manner that the maximum length d 5 shown in fig. 5 is 20 mm.
The extension of example 5 is of the shape shown in fig. 6. Example 5 is denoted by "-" in the column of "appearance of extension" in table 1 below.
In example 5, laminate sheet 1 was cut using a laser processing machine so that an extension of the outer shape shown in fig. 6 was formed at 1 corner of 912 (L 2)mm×722(L1) mm. The extension is formed in such a manner that the length D 1 of the extension in the 1 st direction D 1 and the length D 3 of the extension in the 2 nd direction D 2 are 5mm and in such a manner that the length D 2 of the extension 18 in the direction parallel to the 1 st side 13a and the length D 4 of the extension 18 in the direction parallel to the 2 nd side 13b are 20 mm.
Example 6 was a structure without a protruding portion. In example 6, laminate sheet 1 was cut to a dimension 912 (L 2)mm×722(L1) mm using a laser processor.
In example 6, the column of "outline of protruding portion" in table 1 below is denoted by "-".
The protruding portion of example 7 is in the shape shown in fig. 1.
In example 7, the laminate sheet 1 was cut by a laser processing machine so that an L-shaped extension was formed at 1 corner of 912 (L 2)mm×722(L1) mm. The extension is formed in such a manner that the length D 1 of the extension in the 1 st direction D 1 and the length D 3 of the extension in the 2 nd direction D 2 are 25mm and in such a manner that the length D 2 of the extension 18 in the direction parallel to the 1 st side 13a and the length D 4 of the extension 18 in the direction parallel to the 2 nd side 13b are 50 mm.
< Peeling of the release film of the protrusion from the PET film and the Silicone resin layer >)
In examples 1 to 5 and 7, laminate sheet 1 was placed on an adsorption table with the PET film of the release film facing upward, and adhesive tape (Scotch, CM-12, 3M Co., ltd.) was applied to the extension of laminate sheet 1. Then, the PET film of the release film and the silicone resin layer were peeled off by pulling the tape by hand.
< Evaluation of handling Property >)
The short side of the laminate 1 from which the release film was peeled off was held by both hands, lifted from the table, placed on the table, and the corner of the laminate 1 was observed under a fluorescent lamp. Based on the results of the observation, the peeling defect was evaluated according to the following evaluation criteria. The results are shown in table 1 below.
A: no peeling defect was observed at the corner of the laminate sheet 1.
B: peeling defects were observed at the corners of the laminate sheet 1.
< Peeling of PET film of protective film >
A silicone film adhesive tape (626001-NB-20-50X 50, manufactured by Mitsui, inc.) was attached to the surface of a nylon net of a precision single-chip mounter (manufactured by Climb Products, SE1208 aa) so that the outer peripheral portion of the nylon net was covered with the adhesive tape at 916mm×726mm free from the center portion of the nylon net. The laminate sheet 1 having the release film peeled off was placed on the inner side of 916mm×726mm with the release film PET film and the silicone resin layer in contact with each other without masking the film, and the nylon film was sucked to fix the laminate sheet 1.
Examples 1 to 5 and 7 were peeled off from a PET adhesive tape (Scotch, CM-12, manufactured by 3M Co., ltd.) of a protective film located at the opposite corners of the extension portion of the laminate sheet 1 in the direction in which the extension portion was located.
Example 6a tape was attached to an arbitrary corner of the laminate 1, and a PET film of the protective film was peeled off.
< Evaluation of peeling Defect >)
The PET film as the 2 nd resin substrate (protective film) was peeled off from the laminate, and the peeled off terminal portion of the 2 nd resin substrate (protective film) was observed under a fluorescent lamp. Based on the results of the observation, the peeling defect was evaluated according to the following evaluation criteria. The results of the peeling defect are shown in table 1 below.
The peeling defect is a defect generated by the occurrence of a failure in the silicone resin layer (intermediate layer) without peeling at the interface between the silicone resin layer (intermediate layer) and the 2 nd resin substrate (protective film). When the 2 nd resin substrate (protective film) is peeled off, if the peeling failure occurs, a silicone resin layer (intermediate layer) is attached to the surface of the 2 nd resin substrate (protective film). Peeling defects (attached silicone resin layer (interlayer)) can be seen under fluorescent lamps.
Evaluation criterion
A: the peeling defect was not seen at the peeling end portion of the 2 nd resin substrate (protective film).
B: the peeling defect was observed at the peeling end portion of the 2 nd resin substrate (protective film).
< Fabrication of laminate >)
The glass substrate was a 920mm×730mm glass substrate "AN Wizus" (support substrate, young's modulus 85 GPa) having been cleaned with a water-based glass cleaner (PK-LCG 213, manufactured by PARKER CORPORATION, inc.) and then cleaned with pure water, and the protective film was peeled from the laminate sheet 1 of the release film-peeled PET film and the silicone resin layer, and the laminate sheet 1 was laminated with the release film-formed PET film of the silicone resin layer by using a precision uniwafer laminator (manufactured by Climb Products, SE1208 aa), to thereby produce a laminate sheet in which the glass substrate, the silicone resin layer, and the PET film were laminated in this order.
In examples 6 and 7 in which peeling defects were observed in the laminate sheet 1 in the evaluation of handling properties and peeling defects, defects in which the silicone resin was not bonded to the glass substrate were also observed at the same position of the laminate body.
TABLE 1
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From a comparison of examples 1 to 7 shown in table 1, it is clear that: examples 1 to 5 were free from peeling defects and were evaluated to be good in peeling, as compared with examples 6 and 7.
Example 6 was a structure without a protruding portion, and a peeling defect was generated.
The extension of example 7 was large and the handleability was poor.
In examples 6 and 7 in which peeling defects were observed in the laminate sheet 1 in the evaluation of handling properties and peeling defects as described above, defects in which the silicone resin was not bonded to the glass substrate were also observed at the same position of the laminate body.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various modifications and alterations can be made therein without departing from the spirit and scope thereof.
The present application is based on japanese patent application No. 2022-185672 filed on 11/21 of 2022, the contents of which are incorporated herein by reference.
Claims (6)
1. A laminated sheet comprising a 1 st resin substrate, an intermediate layer and a 2 nd resin substrate laminated in this order,
The 1 st resin substrate and the intermediate layer have the same shape and size and are laminated to form a laminated part, the 1 st resin substrate has a quadrangular external shape as viewed from the normal direction of the surface of the 1 st resin substrate,
The 2 nd resin substrate has a larger area than the 1 st resin substrate and the intermediate layer, and has a protruding portion protruding from the outer edges of the 1 st side, the apex and the 2 nd side at a corner portion including the apex where the 1 st side and the 2 nd side of the 1 st resin substrate orthogonally intersect when viewed from the normal direction of the surface of the 1 st resin substrate,
The length of the extension portion extending from the 1 st side along the 1 st direction orthogonal to the 1 st side is 5mm to 20mm, the length of the extension portion extending from the intersection point of the extension portion and the 1 st side along the direction parallel to the 1 st side is 10mm to 40mm, the length of the extension portion extending from the 2 nd side along the 2 nd direction orthogonal to the 2 nd side is 5mm to 20mm, and the length of the extension portion extending from the intersection point of the extension portion and the 2 nd side along the direction parallel to the 2 nd side is 10mm to 40mm.
2. The laminated sheet according to claim 1, wherein an intermediate layer different from the intermediate layer and a1 st resin substrate different from the 1 st resin substrate are laminated in this order on the extension portion of the 2 nd resin substrate and are arranged separately from the laminated portion.
3. The laminate sheet according to claim 1 or 2, wherein a contour of the projection portion, as viewed from the normal direction of the surface of the 1 st resin substrate, is composed of at least 1 of a straight line and a curved line.
4. The laminate sheet according to claim 1 or 2, wherein an outline of the protruding portion as viewed from the normal direction of the surface of the 1 st resin substrate is a polygon, a sector, or an elliptical sector.
5. The laminate of claim 1 or 2, wherein the intermediate layer is a silicone resin layer.
6. The laminate sheet according to claim 1 or 2, wherein the 1 st resin substrate and the 2 nd resin substrate are polyethylene terephthalate substrates.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022185672A JP2024074489A (en) | 2022-11-21 | 2022-11-21 | Laminated Sheet |
| JP2022-185672 | 2022-11-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118056678A true CN118056678A (en) | 2024-05-21 |
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ID=91069701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311534500.9A Pending CN118056678A (en) | 2022-11-21 | 2023-11-16 | Laminate sheet |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2024074489A (en) |
| CN (1) | CN118056678A (en) |
-
2022
- 2022-11-21 JP JP2022185672A patent/JP2024074489A/en active Pending
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2023
- 2023-11-16 CN CN202311534500.9A patent/CN118056678A/en active Pending
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| JP2024074489A (en) | 2024-05-31 |
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