CN112046101A - Laminated substrate and package - Google Patents
Laminated substrate and package Download PDFInfo
- Publication number
- CN112046101A CN112046101A CN202010509466.XA CN202010509466A CN112046101A CN 112046101 A CN112046101 A CN 112046101A CN 202010509466 A CN202010509466 A CN 202010509466A CN 112046101 A CN112046101 A CN 112046101A
- Authority
- CN
- China
- Prior art keywords
- resin layer
- protective film
- polyimide resin
- support base
- laminated
- 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 title claims abstract description 184
- 229920001721 polyimide Polymers 0.000 claims abstract description 177
- 230000001681 protective effect Effects 0.000 claims abstract description 176
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010030 laminating Methods 0.000 abstract description 11
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- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 230000003746 surface roughness Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 102220501056 E3 ubiquitin-protein ligase TRAIP_Y16F_mutation Human genes 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001646 UPILEX Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 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
- 238000007611 bar coating method Methods 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
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- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 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
- 238000007664 blowing Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
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- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
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- 238000007756 gravure coating Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 238000011068 loading method Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- NKLYMYLJOXIVFB-UHFFFAOYSA-N triethoxymethylsilane Chemical compound CCOC([SiH3])(OCC)OCC NKLYMYLJOXIVFB-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
- B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D71/00—Bundles of articles held together by packaging elements for convenience of storage or transport, e.g. portable segregating carrier for plural receptacles such as beer cans or pop bottles; Bales of material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/145—Organic substrates, e.g. plastic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68377—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support with parts of the auxiliary support remaining in the finished device
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Buffer Packaging (AREA)
- Packaging Frangible Articles (AREA)
Abstract
The present invention relates to a laminated substrate and a package. The laminated substrate is formed by laminating a polyimide resin layer and a protective film covering the polyimide resin layer on a support base material made of glass, wherein the 1 st adhesion force of the polyimide resin layer and the protective film is F1And F represents the 2 nd adhesion force of the support base material and the protective film2The 1 st adhesion force F1Is 0.001N/10mm < F ≤1Not more than 0.17N/10mm, the above-mentioned second adhesion force F2F is more than or equal to 0.05N/10mm2≤(F1(N/10mm)+0.3N/10mm)。
Description
Technical Field
The present invention relates to a laminated substrate and a package.
Background
In the manufacture of solar cells; a liquid crystal panel (LCD); an organic EL panel (OLED); a receiving sensor panel for sensing electromagnetic waves, X-rays, ultraviolet rays, visible rays, infrared rays, and the like; for example, as described in patent document 1, an embodiment using a polyimide resin layer as a substrate is disclosed. The polyimide resin layer is used in a state of a laminated substrate provided on a glass substrate, and the laminated substrate is used for the manufacture of electronic devices. After the electronic device is formed, the polyimide resin layer is separated from the glass substrate.
On the other hand, when a plurality of glass substrates are conveyed, as described in patent document 2, for example, the glass substrates are conveyed in the form of a glass plate package body in which a plurality of glass plates are stacked via a folder (input device) made of raw pulp.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-104843
Patent document 2: japanese Kokai No. 2016/104450
Disclosure of Invention
As described above, since various electronic device components constituting an electronic device are formed on the polyimide resin layer in the laminated substrate, it is desirable that the surface of the polyimide resin layer is free from scratches and foreign matters.
On the other hand, as described in patent document 2, the present inventors have attempted to convey a plurality of laminated substrates by using a package in which a plurality of laminated substrates each having a polyimide resin layer formed on a glass substrate are laminated via a paper insert made of virgin pulp, and as a result, have found that scratches are generated on the surfaces of the polyimide resin layers in the laminated substrates.
Further, the present inventors have attempted to prevent the occurrence of the above described scratches by bonding a protective film to a polyimide resin layer instead of sandwiching paper, and as a result, have found that: depending on the type of the protective film, the support base material may be damaged when the protective film is peeled off, foreign matter may be generated on the surface of the polyimide resin layer after the protective film is peeled off, or foreign matter may be generated in the outer peripheral portion of the polyimide resin layer.
Accordingly, an object of the present invention is to provide a laminate substrate in which scratches are suppressed from being generated on the surface of a polyimide resin layer even when the laminate substrate is laminated, breakage of a support base material is suppressed when a protective film is peeled, and generation of foreign matter on the polyimide resin layer is suppressed, and a package body in which a plurality of laminate substrates are mounted.
As a result of intensive studies, the present inventors have found that the above object can be achieved by the following configuration.
The 1 st aspect of the present invention provides a laminate substrate in which a polyimide resin layer and a protective film covering the polyimide resin layer are laminated on a support base made of glass, wherein the 1 st adhesion force between the polyimide resin layer and the protective film is F1F represents the 2 nd adhesion force of the support base material and the protective film21 st adhesion force F1Is 0.001N/10mm < F ≤1Not more than 0.17N/10mm, the 2 nd adhesion force F2F is more than or equal to 0.05N/10mm2≤(F1(N/10mm)+0.3N/10mm)。
The size of the protective film is preferably equal to or larger than the size of the support base material.
The thickness of the protective film is preferably 20 μm or more.
The protective film preferably includes a base material and an adhesion layer laminated on the base material and in contact with the polyimide resin layer, and the base material is preferably made of polyethylene.
The adhesion force between the support base and the polyimide resin layer is preferably greater than either of the 1 st adhesion force and the 2 nd adhesion force.
Preferably, a silane coupling agent layer is provided between the support substrate and the polyimide resin layer.
The silicone resin layer is preferably provided between the support base and the polyimide resin layer.
A package according to claim 2 of the present invention includes a tray and a plurality of laminated substrates according to claim 1 mounted on the tray.
The plurality of laminated substrates are preferably mounted on the tray in a state where a load is applied to each other.
The tray preferably has a bottom plate and a back plate standing on the bottom plate, and the laminated substrate is preferably mounted on the tray in a state in which the support base faces the surface of the back plate and is inclined.
The size of the laminated substrate is preferably 850mm or more in the short side and 1100mm or more in the long side.
According to the present invention, it is possible to provide a laminated substrate in which scratches are suppressed from being generated on the surface of a polyimide resin layer even in the case of lamination, breakage of a support base material is suppressed in the case of peeling a protective film, and generation of foreign matter on the polyimide resin layer is suppressed, and a package body in which a plurality of laminated substrates are mounted.
Drawings
Fig. 1 is a plan view schematically showing a1 st example of a laminated substrate according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view schematically showing example 1 of a laminated substrate according to an embodiment of the present invention.
Fig. 3 is a sectional view schematically showing a protective film of example 1 of a laminated substrate according to an embodiment of the present invention.
Fig. 4 is a plan view schematically showing example 2 of the laminated substrate according to the embodiment of the present invention.
Fig. 5 is a cross-sectional view schematically showing example 3 of a laminated substrate according to an embodiment of the present invention.
Fig. 6 is a side view schematically showing an example of the package according to the embodiment of the present invention.
Fig. 7 is a cross-sectional view schematically illustrating generation of a buried object of a laminated substrate according to an embodiment of the present invention.
Fig. 8 is a sectional view schematically illustrating generation of a buried object of a laminated substrate according to an embodiment of the present invention.
Fig. 9 is a cross-sectional view schematically illustrating generation of a buried object of a laminated substrate according to an embodiment of the present invention.
Fig. 10 is an SEM image showing an example of the buried structure of the laminated substrate according to the embodiment of the present invention.
Description of the symbols
10 a laminated substrate; 12 supporting the substrate; 12a surface; 12b back side; 12c an outer edge portion; 13a silicone resin layer; 13a surface; 14a polyimide resin layer; 14a surface; 16 a protective film; 18 a substrate; 19 an adhesion layer; 20, packaging the bag body; 22 a tray; 24a base plate; 24a surface; 26a back plate; 26a surface; d, foreign matters; angle beta
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 made to the following embodiments without departing from the scope of the present invention.
The numerical range represented by the term "to" means a range in which the numerical values recited before and after the term "to" are included as a lower limit value and an upper limit value.
The laminated substrate of the present invention is characterized by providing a protective film covering the polyimide resin layer. In particular, the desired effect can be obtained by adjusting the adhesion force between the protective film, the polyimide resin layer, and the support base material.
The present inventors have found that when the interleaf paper made of virgin pulp described in patent document 2 is used, the surface of the polyimide resin layer is scratched, and this is caused by the fact that the adhesion force between the interleaf paper and the polyimide resin layer is too low. That is, since the adhesion force between the interleaf paper and the polyimide resin layer is weak, friction occurs between the interleaf paper and the polyimide resin layer, and scratches occur on the surface of the polyimide resin layer. On the other hand, if the adhesion force between the polyimide resin layer and the protective film is too strong, foreign matter derived from a component of the protective film (for example, a material of the adhesion layer) remains on the polyimide resin layer when the protective film is peeled off.
In view of the above, the adhesion force between the protective film and the polyimide resin layer is adjusted.
If the adhesion force between the protective film and the support base is too weak, the protective film peels off, and foreign matter is likely to adhere to the outer peripheral portion of the polyimide resin layer. On the other hand, if the adhesion force between the protective film and the support base is too strong, a difference in peeling speed occurs between the polyimide resin layer portion and the support base portion when the protective film is peeled, and an unintended force is applied to the support base when the protective film is peeled, resulting in breakage of the support base.
In view of the above, the adhesion force between the protective film and the support base material is adjusted.
< laminated substrate >
[ 1 st example of laminated substrate ]
Fig. 1 is a plan view schematically showing a1 st example of a laminated substrate according to an embodiment of the present invention, and fig. 2 is a cross-sectional view schematically showing the 1 st example of the laminated substrate according to the embodiment of the present invention. Fig. 3 is a sectional view schematically showing a protective film of example 1 of a laminated substrate according to an embodiment of the present invention.
The laminated substrate 10 of example 1 is formed by laminating a polyimide resin layer 14 and a protective film 16 covering the polyimide resin layer 14 on a support base 12 made of glass.
As shown in fig. 2, a polyimide resin layer 14 is provided on the surface 12a of the support base 12. As shown in fig. 1, the polyimide resin layer 14 has a smaller area than the surface 12a of the support base 12, and is not provided over the entire surface 12a of the support base 12. The polyimide resin layer 14 is not provided on the outer edge portion 12c of the front surface 12a of the support base 12, i.e., on the frame portion of the support base 12.
The protective film 16 is disposed so as to cover the polyimide resin layer 14 on the support base 12. As shown in fig. 2 and 3, the protective film 16 includes a base material 18 and an adhesion layer 19 laminated on the base material 18. As shown in fig. 2, the adhesion layer 19 of the protective film 16 is in contact with the surface 14a of the polyimide resin layer 14 and the surface 12a of the support base 12. The protective film 16 is peeled off when the polyimide resin layer 14 is used as a substrate. At this time, the adhesive layer 19 of the protective film 16 may be peeled off from the state of being simultaneously in contact with the surface 14a of the polyimide resin layer 14 and the surface 12a of the support base 12.
The support base 12 is a member for supporting the polyimide resin layer 14, and functions as a reinforcing plate for reinforcing the polyimide resin layer 14. The support base material 12 also functions as a transport substrate when the laminated substrate 10 is transported.
In the laminated substrate 10, when a force is applied in a direction of separating the support base 12 and the polyimide resin layer 14, the support base 12 and the polyimide resin layer 14 are separated.
The polyimide resin layer 14 is a substrate for manufacturing an electronic device. On the surface 14a of the polyimide resin layer 14, electronic elements such as transistors, coils, and resistors, signal lines, and the like constituting electronic devices are formed.
The protective film 16 protects the support base 12 and the polyimide resin layer 14, and particularly protects the polyimide resin layer 14 from scratches, and the like caused by a bearing force from the outside. The protective film 16 is, for example, the same size as the supporting base material 12 in the laminated substrate 10 shown in fig. 1.
In the laminated substrate 10, the 1 st adhesion force of the polyimide resin layer 14 and the protective film 16 is represented as F1F represents the 2 nd adhesion force between the support base 12 and the protective film 162。
1 st adhesion force F1Is 0.001N/10mm < F ≤1Less than or equal to 0.17N/10 mm. 2 nd adhesion force F2F is more than or equal to 0.05N/10mm2≤(F1(N/10mm)+0.3N/10mm)。
The 1 st adhesion force F1And a 2 nd adhesion force F2The measurement of (2) was performed as follows. First, the protective film 16 cut into a strip shape having a width of 25mm is bonded to the polyimide resin layer 14 or the support base 12. Then, at every 1cm2The plate was left to stand for 5 days under an environment of 40 ℃ and 80% relative humidity with a load of 16g applied. Thereafter, a 90 ° peel test was performed. The pulling rate in the peeling is300 mm/min. From the load of the stably peeled region, the load at the time of peeling the protective film per unit width (10mm) was calculated.
As described above, the 1 st adhesion force F1Is 0.001N/10mm < F ≤1Less than or equal to 0.17N/10 mm. 1 st adhesion force F1If the thickness is less than 0.001N/10mm, the polyimide resin layer 14 and the protective film 16 do not sufficiently adhere to each other, friction occurs between the polyimide resin layer 14 and the protective film 16, and scratches are formed on the surface 14a of the polyimide resin layer 14.
If the 1 st adhesion force F1If the ratio is more than 0.17N/10mm, the adhesion force between the polyimide resin layer 14 and the protective film 16 becomes too strong, and a part of the adhesion layer 19 of the protective film 16 remains on the surface 14a of the polyimide resin layer 14, resulting in the generation of foreign matter. In particular, when the adhesive layer is an adhesive layer containing an adhesive, adhesive residue is generated from the adhesive. If foreign matter (particularly, adhesive residue) is generated, the heat resistance of the polyimide resin layer 14 may be lowered, or defects such as disconnection of an electronic device formed using the polyimide resin layer 14 may occur. Further, when the 1 st adhesion force F11 st adhesion force F exceeding 1.5N/10mm1If the size is too large, the supporting base material 12 may be broken.
Among these, the 1 st adhesion force F is from the viewpoint of further suppressing the generation of scratches and foreign matter on the surface 14a of the polyimide resin layer 141Preferably 0.002-0.15N/10 mm, more preferably 0.003-0.145N/10 mm.
As described above, the 2 nd adhesion force F2F is more than or equal to 0.05N/10mm2≤(F1(N/10mm) +0.3N/10 mm). 2 nd adhesion force F2Is greater than the 1 st adhesion force F1。
2 nd adhesion force F2If the thickness is less than 0.05N/10mm, the adhesion force between the protective film 16 and the support base 12 is too weak, and the protective film 16 on the outer edge portion 12c of the support base 12 is wound during transportation, so that a large amount of foreign matter adheres to the outer peripheral portion of the polyimide resin layer 14. The possibility of scratches and the like occurring in the polyimide resin layer 14 due to the foreign matter is high.
If the 2 nd adhesion force F2Exceeds F1(N/10mm) +0.3N/10mm, then protective filmThe adhesion force between the polyimide resin layer 16 and the support base 12 is too strong, and when the protective film 16 is peeled off, a difference in peeling speed occurs between the polyimide resin layer 14 and the support base 12, and an unintended force is applied to the support base 12 when the protective film 16 is peeled off, resulting in breakage of the support base 12.
In the laminated substrate 10, the 2 nd adhesion force F between the support base 12 and the protective film 162In the above range, the protective film 16 can be smoothly peeled off without causing damage to the support base 12 or the like.
Among these, the 2 nd adhesion force F is to further suppress the generation of foreign matter on the surface 14a of the polyimide resin layer 14 and the breakage of the support base 122Preferably 0.06-0.18N/10 mm, more preferably 0.07-0.17N/10 mm.
In the laminated substrate 10, the adhesion force between the support base 12 and the polyimide resin layer 14 is preferably larger than the 1 st adhesion force F1And a 2 nd adhesion force F2Either of which is large. As a method for improving the adhesion between the support base 12 and the polyimide resin layer 14, there may be mentioned a method of modifying the surface of the support base 12 (for example, a method of modifying with a silane coupling agent), that is, a method of providing a silane coupling agent layer (a layer formed using a silane coupling agent) between the support base 12 and the polyimide resin layer 14) and a method of providing a layer (for example, a silicone resin layer described later) for improving the adhesion between the support base 12 and the polyimide resin layer 14, as described later.
In the case where a layer such as a silane coupling agent layer and a silicone resin layer is provided between the support base 12 and the polyimide resin layer 14, the adhesion force between the support base 12 and the silane coupling agent layer or the silicone resin layer and the adhesion force between the polyimide resin layer 14 and the silane coupling agent layer or the silicone resin layer are preferably higher than the 1 st adhesion force F1And a 2 nd adhesion force F2Either of which is large.
[ method for producing laminated substrate 1 example ]
As a method for manufacturing the laminated substrate 10 of example 1, a method of laminating the polyimide resin layer 14 on the surface 12a of the support base 12 is preferable. Among these, it is preferable that a known silane coupling agent is applied to the surface 12a of the support base 12 before the polyimide resin layer 14 is laminated on the surface 12a of the support base 12, and then the polyimide resin layer 14 is laminated on the surface 12a of the support base 12 to which the silane coupling agent is applied. At this time, a silane coupling agent layer is provided between the supporting base 12 and the polyimide resin layer 14. In a state where the polyimide resin layer 14 is formed on the surface 12a of the support base 12, the protective film 16 is disposed so that the adhesion layer 19 faces the surface 12a of the support base 12, and the protective film 16 covering the polyimide resin layer 14 is bonded to the support base 12. This enables the laminated substrate 10 to be manufactured.
[ 2 nd example of laminated substrate ]
Fig. 4 is a plan view schematically showing example 2 of the laminated substrate according to the embodiment of the present invention. In the laminated substrate 10 of example 2 shown in fig. 4, the same constituent objects as those of the laminated substrate 10 of example 1 shown in fig. 1 and 2 are denoted by the same reference numerals, and detailed description thereof will be omitted.
The laminated substrate 10 of example 2 is similar to the laminated substrate 10 shown in fig. 1 and 2, except that the size of the protective film 16 is larger than that of the support base 12, compared to the laminated substrate 10 shown in fig. 1 and 2.
As in the laminated substrate 10 of example 2, since the size of the protective film 16 is larger than that of the support base material 12, one end portion of the protective film 16 is easily gripped when peeling off the protective film 16.
[ method for producing laminated substrate in example 2 ]
The laminated substrate 10 of example 2 can be produced in the same manner as the laminated substrate 10 of example 1, except that the protective film 16 is larger than the support base 12, and the protective film 16 is attached to the support base 12 so as to cover the polyimide resin layer 14.
[ 3 rd example of laminated substrate ]
Fig. 5 is a cross-sectional view schematically showing example 3 of a laminated substrate according to an embodiment of the present invention. In the laminated substrate 10 of example 3 shown in fig. 5, the same constituent objects as those of the laminated substrate 10 of example 1 shown in fig. 1 and 2 are denoted by the same reference numerals, and detailed description thereof will be omitted.
The laminated substrate 10 of example 3 is similar to the laminated substrate 10 shown in fig. 1 and 2, except that the silicone resin layer 13 is provided between the support base 12 and the polyimide resin layer 14, as compared with the laminated substrate 10 shown in fig. 1 and 2.
In the laminated substrate 10 of example 3, a support base 12, a silicone resin layer 13, and a polyimide resin layer 14 are laminated in this order. A silicone resin layer 13 is provided on the surface 12a of the support base 12, and a polyimide resin layer 14 is provided on the surface 13a of the silicone resin layer 13. The silicone resin layer 13 and the polyimide resin layer 14 are the same size and smaller than the surface 12a of the support base 12.
In the laminated substrate 10 of example 3, the supporting base 12 and the silicone resin layer 13 function as a reinforcing plate for reinforcing the polyimide resin layer 14.
When the laminated substrate 10 is subjected to heat treatment, the adhesion force between the support base 12 and the silicone resin layer 13 is preferably larger than the adhesion force between the silicone resin layer 13 and the polyimide resin layer 14. It can be generated by bonding the hydroxyl group of the support base 12 and the hydroxyl group of the silicone resin layer 13 by heat treatment or the like.
As a result, when a force is applied in a direction to peel the support base 12 and the polyimide resin layer 14, peeling occurs between the silicone resin layer 13 and the polyimide resin layer 14. This enables the polyimide resin layer 14 to be separated.
In the laminated substrate 10 of example 3, the size of the protective film 16 is not limited. The protective film 16 and the support base 12 may have the same size as the laminated substrate 10 shown in fig. 1, or the protective film 16 may have a size larger than the support base 12 as the laminated substrate 10 shown in fig. 4.
[ method for producing laminated substrate in example 3 ]
In the method for producing the laminated substrate 10 of example 3, the silicone resin layer 13 is preferably formed on the back surface (the surface opposite to the front surface 14 a) of the polyimide resin layer 14. Specifically, a method of producing the laminated substrate 10 is preferred in which a curable composition containing a curable silicone is applied to the back surface of the polyimide resin layer 14, the obtained coating film is cured to obtain the silicone resin layer 13, and then the support base 12 is laminated on the back surface (the surface opposite to the front surface 13 a) of the silicone resin layer 13.
More specifically, the method for manufacturing the laminated substrate 10 of example 3 includes at least: a step (resin layer forming step) of forming a curable silicone layer on the back surface (surface opposite to the front surface 14 a) of the polyimide resin layer 14 and forming a silicone resin layer 13 on the back surface of the polyimide resin layer 14; a step (laminating step) of laminating the support base 12 on the back surface (the surface opposite to the front surface 13 a) of the silicone resin layer 13; and a step of attaching the protective film 16 (attaching step). The above-described steps will be described in detail below.
(resin layer Forming step)
The resin layer forming step is a step of forming a curable silicone layer on the back surface of the polyimide resin layer 14, and forming the silicone resin layer 13 on the back surface of the polyimide resin layer 14. According to this step, a substrate with a silicone resin layer, which includes the polyimide resin layer 14 and the silicone resin layer 13 in this order, is obtained.
The substrate with the silicone resin layer can be manufactured by a so-called roll-to-roll method in which the silicone resin layer 13 is formed on the back surface of the polyimide resin layer 14 wound in a roll and then wound in a roll again, and thus the production efficiency is excellent.
In this step, the curable composition is applied to the back surface of the polyimide resin layer 14 in order to form a curable silicone layer on the back surface of the polyimide resin layer 14. Next, a cured layer is preferably formed by applying a curing treatment to the layer of curable silicone.
Specific examples of the method of applying the curable composition to the back surface of the polyimide resin layer 14 include a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, and a gravure coating method.
Next, the curable silicone applied to the back surface of the polyimide resin layer 14 is cured to form the silicone resin layer 13.
The method for curing for forming the silicone resin layer 13 is not particularly limited, and an optimum treatment is appropriately performed depending on the type of curable silicone used. For example, when a condensation reaction type silicone or an addition reaction type silicone is used, a thermosetting treatment is preferable as the curing treatment.
The conditions for the heat curing treatment are within the range of the heat resistance of the polyimide resin layer 14, and for example, the temperature conditions for the heat curing are preferably 50 to 400 ℃, and more preferably 100 to 300 ℃. The heating time is preferably 10 to 300 minutes, and more preferably 20 to 120 minutes.
The silicone resin layer 13 will be explained later.
(laminating step)
The laminating step is a step of laminating the support base 12 on the surface of the silicone resin layer 13. As a specific example of a method of laminating the support base 12 on the back surface of the silicone resin layer 13, a method of laminating the support base 12 on the back surface of the silicone resin layer 13 under an atmospheric pressure environment is given. If necessary, the support base 12 may be superposed on the back surface of the silicone resin layer 13, and then the support base 12 may be pressed against the silicone resin layer 13 by using a roller or pressing. It is preferable that the air bubbles mixed between the silicone resin layer 13 and the supporting base material 12 be easily removed by pressure bonding with a roller or pressure.
The pressure bonding by the vacuum lamination method or the vacuum pressurization method is preferable because mixing of air bubbles is suppressed and good adhesion can be achieved. By crimping under vacuum, the following advantages are also provided: even if minute bubbles remain, the bubbles are less likely to grow by the heat treatment.
When the support base 12 is laminated, the surface of the support base 12 in contact with the silicone resin layer 13 is preferably sufficiently cleaned, and the lamination is preferably performed in an environment with high cleanliness.
(bonding step)
In the bonding step, the protective film 16 is disposed so that the adhesive layer 19 faces the surface 12a of the support base 12, and the protective film 16 is bonded to the support base 12 while covering the polyimide resin layer 14. Thereby, the laminated substrate 10 is obtained.
< Package body >
Fig. 6 is a side view schematically showing an example of the package according to the embodiment of the present invention. In the package body 20 shown in fig. 6, the same constituent objects as those of the laminate substrate 10 of the 1 st embodiment shown in fig. 1 and 2 are denoted by the same reference numerals, and detailed description thereof is omitted.
The package body 20 includes the plurality of laminated substrates 10 shown in fig. 1 and a tray 22 on which the plurality of laminated substrates 10 are stacked.
When the laminated substrates 10 are 1200mm × 1000mm (G5 size) or more, it is difficult to package the laminated substrates in the case in a state where the laminated substrates are completely separated from each other, and it is preferable to package the laminated substrates 10 by loading a plurality of laminated substrates 10 on the tray 22 in a state where a load is applied to each of the laminated substrates 10 as described later.
The laminated substrate 10 is a rectangle, and as the size of the laminated substrate 10, the shorter side is preferably 850mm or more, the longer side is preferably 1100mm or more, the shorter side is more preferably 1200mm or more, the longer side is 1300mm or more, the shorter side is more preferably 1400mm or more, and the longer side is 1700mm or more. The upper limit of the size of the laminated substrate 10 is preferably 3000mm × 3000 mm.
The tray 22 has a bottom plate 24 and a back plate 26, and the back plate 26 is erected on the bottom plate 24. The surface 24a of the base plate 24 is orthogonal to the surface 26a of the back plate 26. The support base material 12 of the laminated substrate 10 is laminated on the tray 22 with the support base material 12 of the laminated substrate 10 facing the surface 26a of the back plate 26, for example, the support base material 12 of the laminated substrate 10 closest to the tray 22 side being laid over the surface 24a of the bottom plate 24 and the surface 26a of the back plate 26, and the laminated substrate 10 being inclined. The angle β formed by the back surface 12b of the support base 12 of the laminated substrate 10 and the front surface 24a of the bottom plate 24 is, for example, 45 ° to 85 °.
The support base materials 12 of the other laminated substrates 10 are stacked in contact with each other on the protective film 16 of the laminated substrate 10, and the plurality of laminated substrates 10 are stacked in contact with each other.
The tray 22 is made of resin such as polypropylene resin, and is not particularly limited.
When a load is applied to the plurality of laminated substrates 10, the plurality of laminated substrates 10 may be mounted on the tray 22 in direct contact with each other, or the plurality of laminated substrates 10 may be mounted on the tray 22 with a paper interposed between the laminated substrates 10 as described later.
In addition, the interleaf paper may be interposed for the purpose of separating the back surface 12b of the support base 12 from the surface of the protective film 16 of the adjacent laminated substrate 10. By placing the interleaf paper, adhesion between the back surface 12b of the support base 12 and the surface of the protective film 16 of the adjacent laminated substrate 10 can be reduced, and the laminated substrates 10 can be easily taken out one by one from the tray 22.
The tray 22 has a structure including a bottom plate 24 and a back plate 26, but the structure is not particularly limited as long as a plurality of laminated substrates 10 can be stacked and mounted.
The laminated substrates 10 are conveyed in the form of a package 20 mounted on a tray 22 in a state where a load is applied to the plurality of laminated substrates 10. At this time, of the plurality of laminated substrates 10, the laminated substrate 10 closest to the back plate 26 side is applied with the largest load, and the laminated substrates 10 rub against each other due to vibration during conveyance. By providing the protective film 16 as described above, even when a load is applied to the laminated substrates 10 and the laminated substrates 10 rub against each other, the occurrence of scratches and scratches on the polyimide resin layer 14 can be suppressed, and the adhesion of foreign matter can be suppressed.
In the laminated substrate 10, the 2 nd adhesion force F between the support base 12 and the protective film 162In the above range, even when the package body 20 is transported in a general environment, the protective film 16 is not peeled from the support base 12, and a large amount of foreign matter is not attached to the outer peripheral portion of the polyimide resin layer 14, so that defects are not increased.
The laminated substrate 10 mounted on the tray 22 is not limited to the laminated substrate 10 of example 1 shown in fig. 1, and may be the laminated substrate 10 of example 2 described above and the laminated substrate 10 of example 3 described above.
The laminated substrate 10 can be packaged in a glass plate packaging box (see fig. 1 to 17) described in japanese patent No. 4251290, for example.
The glass plate packing box is specifically composed of a base on which the laminated substrate 10 is placed in parallel, a bottom plate on which the base is placed, a front plate, a rear plate, two side plates arranged upright on the bottom plate, and a top plate closing the upper part.
The glass plate packing box is provided with mounting members for fitting the front plate and both side plates in the upper front edge and both side edges of the bottom plate. The mounting member has 1 pair of side plates facing each other on a bottom plate, and a front plate and both side plates are fitted between the facing side plates. In addition to the above configuration, the mounting member may be configured such that a groove opened upward is provided in the bottom plate, and the front plate and the both side plates are fitted into the groove.
In addition, in order to prevent damage when the laminated substrate is placed, a cushion material may be attached to each of the bottom receiving plate and the back receiving plate.
After the plurality of laminated substrates are placed on the base, the front side of the container made of the plurality of laminated substrates may be covered with a protective plate made of resin or the like, and corner joints (アングル members) may be disposed at both corners and bound with a tape. The strap securely binds the storage body by engaging a fixing metal fitting provided at an end of the length-adjustable strap member with the toggle clamp. In this way, by binding the storage body using the strap, the entire body can be firmly fixed by a simple mechanism. Further, if the protective plate is made of a material having cushioning properties, the toggle clamp can be further firmly bound after the laminated substrates are bound with the tape.
The support base 12, the polyimide resin layer 14, the silicone resin layer 13, and the protective film 16 constituting the laminated substrate 10 will be described in detail below.
< support substrate >
The glass support base 12 is a member for supporting and reinforcing the polyimide resin layer 14, and functions as a transport substrate. The support base material 12 is made of, for example, a glass plate.
The kind of glass is preferably alkali-free borosilicate glass, soda lime glass, high silica glass, or other oxide glass containing silicon oxide as a main component. The oxide glass is preferably a glass having a silicon oxide content of 40 to 90 mass% in terms of oxide.
More specifically, the glass plate is made of alkali-free borosilicate glass (trade name "AN 100" from AGC corporation).
As a method for producing a glass plate, there is generally mentioned a method of melting a glass raw material and molding the molten glass into a plate shape. Such a molding method may be a general method, and examples thereof include a float method, a melting method, and an overflow down-draw method.
The thickness of the support substrate 12 may be thicker or thinner than the polyimide resin layer 14. From the viewpoint of the workability of the laminated substrate 10, the thickness of the support base 12 is preferably larger than that of the polyimide resin layer 14.
The support base material 12 is required to function as a reinforcing plate and a transport substrate, and is therefore preferably non-flexible. Therefore, the thickness of the supporting base material 12 is preferably 0.3mm or more, and more preferably 0.5mm or more. On the other hand, the thickness of the supporting base material 12 is preferably 1.0mm or less.
< polyimide resin layer >
The polyimide resin layer 14 is made of a polyimide resin, and for example, a polyimide film is used. Specific examples of commercially available products of polyimide films include "XENOMAX" manufactured by toyobo co., ltd, and "UPILEX 25S" manufactured by yokeshi co.
The surface 14a of the polyimide resin layer 14 is preferably smooth in order to form high-definition wiring and the like constituting an electronic device. Specifically, the surface roughness Ra of the surface 14a of the polyimide resin layer 14 is preferably 50nm or less, more preferably 30nm or less, and still more preferably 10nm or less. The lower limit of the surface roughness Ra is 0.01nm or more.
The thickness of the polyimide resin layer 14 is preferably 1 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more, from the viewpoint of workability in the production process. From the viewpoint of flexibility, the thickness of the polyimide resin layer 14 is preferably 1mm or less, and more preferably 0.2mm or less.
When the difference between the thermal expansion coefficient of the polyimide resin layer 14 and the thermal expansion coefficient of the support base 12 is small, warpage after heating or cooling can be suppressed, and therefore, this is preferable. Specifically, polyimide resinThe difference between the thermal expansion coefficients of the grease layer 14 and the support base 12 is preferably 0 to 90 x 10-6The temperature is more preferably 0 to 30X 10-6/℃。
The area of the polyimide resin layer 14 (the area of the surface 14 a) is not particularly limited, but is preferably smaller than the area of the support base 12 in order to dispose the protective film 16. On the other hand, the area of the polyimide resin layer 14 is preferably 300cm from the viewpoint of productivity of the electronic device2The above.
The shape of the polyimide resin layer 14 is not particularly limited, and may be rectangular or circular. An orientation flat (a flat portion formed on the outer periphery of the substrate) and a notch (at least one V-shaped notch formed on the outer periphery of the substrate) may be formed in the polyimide resin layer 14.
< protective film >
The protective film 16 is preferably a laminated structure having a base material 18 and an adhesion layer 19 as shown in fig. 3.
In order to reduce the influence of the force received from the outside, the thickness of the protective film 16 is preferably 20 μm or more, more preferably 30 μm or more, and still more preferably 50 μm or more. The upper limit of the thickness of the protective film 16 is preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 100 μm or less.
In the case of a laminated structure having the base material 18 and the adhesive layer 19, the thickness of the protective film 16 is the total thickness of the base material 18 and the adhesive layer 19. The upper limit of the thickness of the protective film 16 is preferably 500 μm or less, because an excessive force may be required to peel the protective film when the thickness is too large.
The thickness of the protective film 16 is obtained by measuring the thickness of the protective film 16 at any position of 5 points or more by a contact film thickness measuring device and calculating the arithmetic mean of the thicknesses.
The base 18 of the protective film 16 is preferably made of a resin such as a polyester resin (e.g., polyethylene terephthalate (PET)), a polyolefin resin (e.g., Polyethylene (PE), polypropylene, etc.), or a polyurethane resin. Among them, polyolefin is preferable, and polyethylene or polypropylene is more preferable as the resin constituting the base material 18 of the protective film 16.
The adhesion layer 19 is only required to satisfy the 1 st adhesion force F1And a 2 nd adhesion force F2There is no particular limitation. As the adhesive layer 19, a known adhesive layer can be used. Specific examples of the adhesive constituting the adhesive layer include a (meth) acrylic adhesive, a silicone adhesive, and a urethane adhesive.
The adhesive layer 19 may be made of a resin, and specific examples of the resin include a vinyl acetate resin, an ethylene-vinyl acetate copolymer resin, a chlorinated ethylene-vinyl acetate copolymer resin, (meth) acrylic acid resin, a butyral resin, a polyurethane resin, a polystyrene elastomer, and the like.
It should be noted that (meth) acrylic acid is a concept including acrylic acid and methacrylic acid.
Depending on the type of the protective film 16, the ease with which a buried object is generated on the surface 14a of the polyimide resin layer 14 varies. Hereinafter, the mechanism thereof will be described in detail.
Here, fig. 7 to 9 are cross-sectional views schematically illustrating the generation of the buried object of the laminated substrate according to the embodiment of the present invention. Fig. 10 is an SEM image showing an example of the buried structure of the laminated substrate according to the embodiment of the present invention. In fig. 7 to 10, the same components as those of the laminated substrate 10 shown in fig. 1 and 2 are denoted by the same reference numerals, and detailed description thereof is omitted.
As shown in fig. 7, when the foreign matter D is present between the surface 14a of the polyimide resin layer 14 and the protective film 16, if the protective film 16 is hard, the protective film 16 is not easily deformed as shown in fig. 8, and the foreign matter D is embedded in the polyimide resin layer 14. As a result, a buried object is generated in the polyimide resin layer 14. Specifically, as shown in the SEM image shown in fig. 10, the foreign matter D is embedded in the polyimide resin layer 14, and the foreign matter D becomes an embedded object.
On the other hand, if the protective film 16 is flexible, the protective film 16 deforms as shown in fig. 9, and the foreign matter D adheres to the protective film 16 side, and the foreign matter D does not adhere to the polyimide resin layer 14, and the foreign matter D is not buried in the polyimide resin layer 14. Thus, even if the foreign matter D is sandwiched between the surface 14a of the polyimide resin layer 14 and the protective film 16 and stacked, the occurrence of defects in the polyimide resin layer 14 is suppressed. Therefore, the base 18 of the protective film 16 is preferably flexible.
The flexibility of the base 18 of the protective film 16 is determined by the relative relationship with the size of the foreign matter D or the hardness of the foreign matter D.
The flexibility of the protective film 16 was evaluated in examples 4 to 6 of the examples as described below.
< Silicone resin layer >
The silicone resin layer 13 is mainly composed of a silicone resin. The structure of the silicone resin is not particularly limited. The silicone resin is generally obtained by curing (crosslinking curing) a curable silicone that may be a silicone resin by a curing treatment.
Specific examples of the curable silicone include a condensation reaction type silicone, an addition reaction type silicone, an ultraviolet ray curable type silicone, and an electron beam curable type silicone depending on the curing mechanism. The weight average molecular weight of the curable silicone is preferably 5000 to 60000, and more preferably 5000 to 30000.
As a method for producing the silicone resin layer 13, the following method is preferred: a curable composition containing the above curable silicone to be the silicone resin is applied to the back surface (surface opposite to the front surface 14 a) of the polyimide resin layer 14, and the solvent is removed as necessary to form a coating film, and the curable silicone in the coating film is cured to form the silicone resin layer 13.
The curable composition may contain 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 in addition to the curable silicone. Specific examples of the metal element contained in the metal compound include a 3d transition metal, a 4d transition metal, a lanthanoid metal, bismuth, aluminum, and tin. The content of the metal compound can be appropriately adjusted.
The thickness of the silicone resin layer 13 is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 30 μm or less. On the other hand, the thickness of the silicone resin layer 13 is preferably more than 1 μm, and more preferably 4 μm or more. The thickness is obtained by measuring the thickness of the silicone resin layer 13 at any position of 5 points or more by a contact film thickness measuring device and calculating the arithmetic mean of the thickness.
< use of laminated substrate >
Applications of the laminated substrate 10 include a display device, a receiving sensor panel, a solar cell, a thin film 2-time cell, an integrated circuit, and the like, which will be described later. The polyimide resin layer may be exposed to an atmospheric atmosphere, for example, at a high temperature of 450 ℃.
Specific examples of the display device include LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, micro LED display panel, and mems (micro Electro Mechanical systems) shutter panel.
Specific examples of the receiving sensor panel include an electromagnetic wave receiving sensor panel, an X-ray receiving sensor panel, an ultraviolet ray receiving sensor panel, a visible light ray receiving sensor panel, and an infrared ray receiving sensor panel. In the case of receiving the sensor panel, the polyimide resin layer may be reinforced by a reinforcing sheet of resin or the like.
As described above, an electronic device including a polyimide resin layer and a component for an electronic device is manufactured using a laminate containing a support base and a polyimide resin layer obtained by peeling a protective film from a laminate substrate of the present invention.
Examples of the method for manufacturing an electronic device include the following methods: an electronic component member is formed on the polyimide resin layer in the obtained laminate including the support substrate and the polyimide resin layer, and the support substrate is peeled from the obtained laminate with the electronic component member, thereby obtaining an electronic component having the polyimide resin layer and the electronic component member.
The electronic component member is a member constituting at least a part of an electronic component.
Examples
The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these examples. Examples 1 to 6 described later are examples, and examples 7 to 16 are comparative examples.
< evaluation >
(evaluation of foreign matter in outer periphery)
In the evaluation of the foreign matter on the outer periphery, for each example, before the protective film was provided, positional information and an image of a defect existing on the surface of the frame region having a width of 10mm in the outer periphery of the polyimide resin layer were obtained in advance using an optical inspection apparatus manufactured by Orbotech corporation. Then, 16g/cm was applied to the protective film of the laminated substrate obtained in each example2Under the load of (3), the plate was left in an atmosphere of 40 ℃ and 80% relative humidity for 5 days. Thereafter, the protective film was peeled off, and positional information and an image of a defect present on the surface of the frame region having a width of 10mm in the outer peripheral portion of the polyimide resin layer were obtained again using an optical inspection apparatus manufactured by Orbotech.
Images before and after the protective film was provided were compared, and the presence or absence of foreign matter in the frame region was evaluated. Since defects such as adhesive residue and scratches may occur in addition to foreign matter, an image representing the foreign matter is defined in advance, and when images are compared, the presence or absence of the foreign matter is evaluated with reference to the image representing the foreign matter.
As a result of the comparison of the images, if foreign matter exists on the outer periphery, it is "present", and if foreign matter exists on the outer periphery, it is "absent".
(evaluation of residual adhesive)
In the evaluation of the residual adhesive, for each example, before the protective film was provided, positional information and an image of a defect existing on the surface of the polyimide resin layer were obtained in advance using an optical inspection apparatus manufactured by Orbotech corporation. Then, 16g/cm was applied to the protective film of the laminated substrate obtained in each example2Under the load of (3), the plate was left in an atmosphere of 40 ℃ and 80% relative humidity for 5 days. Thereafter, the protective film was peeled off, and positional information and an image of a defect present on the surface of the polyimide resin layer were obtained again using an optical inspection apparatus manufactured by Orbotech corporation.
Images before and after the protective film was set were compared to evaluate the presence or absence of residual glue. Since there is a possibility that scratches or the like are attached in addition to the residual glue, an image showing the residual glue is defined in advance, and when comparing the images, the presence or absence of the residual glue is evaluated with reference to the image showing the residual glue.
The result of the comparison of the images is "present" if there is adhesive residue and "absent" if there is no adhesive residue.
(evaluation of scratch)
In the evaluation of the scratch, for each example, before the protective film was provided, positional information and an image of a defect existing on the surface of the polyimide resin layer were obtained in advance using an optical inspection apparatus manufactured by Orbotech corporation.
Then, 23 glass plates having a thickness of 2.8mm were laminated on the protective film of the laminated substrate obtained in each example, and the laminated substrate was left under an atmosphere of 40 ℃ and 80% relative humidity for 5 days with a load applied thereto. Thereafter, the protective film was peeled off, and an image of the surface of the polyimide resin layer was obtained again using an optical inspection apparatus manufactured by Orbotech corporation.
The images before and after the application of the load were compared to evaluate the presence or absence of the scratch. Since there is a possibility that adhesive residue or the like may occur in addition to the scratch, an image indicating the scratch is defined in advance, and when comparing the images, the presence or absence of the scratch is evaluated with reference to the image indicating the scratch.
As a result of comparison of the images, "with" is the case where there is a scratch, and "without" is the case where there is no scratch.
(evaluation of breakage of supporting substrate)
When the protective film was peeled off from the laminated substrate obtained in each example, the case where the support base material was damaged was referred to as "present", and the case where no damage was generated was referred to as "absent".
(evaluation of Heat resistance test)
The heat resistance of the laminated substrate after the protective film was peeled off was evaluated as follows.
A silicon nitride film (SiNx) was formed to a thickness of 200nm on the laminated substrate for evaluation of residual adhesion by a plasma CVD method. Thereafter, heating was performed at 500 ℃ for 10 minutes under a nitrogen atmosphere. After heating, the polyimide resin layer was evaluated as "o" for the case where the polyimide resin layer was not peeled from the support substrate, and as "x" for the case where the polyimide resin layer was peeled.
(evaluation of buried foreign matter)
Evaluation was performed as follows depending on whether or not foreign matter was embedded in the polyimide resin layer.
First, before the protective film was provided, the polyimide resin layer was placed in a normal pressure and normal temperature environment in order to intentionally place a foreign substance on the polyimide resin layer, and then an optical inspection apparatus manufactured by Orbotech corporation was used to inspect a defect (foreign substance). Thereafter, a protective film was provided on the polyimide resin layer, and the laminate was placed in an atmosphere of 40 ℃ and 80% relative humidity for 5 days while applying a load by laminating 23 glass plates having a thickness of 2.8 mm. Next, the protective film was peeled off, and the surface of the polyimide resin layer was inspected again for defects (foreign matters) using an optical inspection apparatus manufactured by Orbotech corporation. By comparing the distribution of defects in an optical inspection apparatus manufactured by Orbotech corporation before and after the bonding of the protective film, it was confirmed whether or not foreign matter existing on the polyimide resin layer before the bonding was left after the peeling of the protective film, and thereafter, the surface of the foreign matter was observed using an optical microscope and a Scanning Electron Microscope (SEM) with respect to the remaining foreign matter. Whether or not the foreign object is embedded is determined by comparing the image obtained by the optical microscope with the image obtained by the scanning electron microscope.
(evaluation of Long-term storage)
When the polyimide resin film was stored with the protective film bonded and a load applied to the bonding surface, it was confirmed whether or not adhesive residue or scratches were generated on the surface of the polyimide resin layer. In each example, 3 laminated substrates for long-term storage test were prepared. In each example, before the protective film was provided, positional information and an image of a defect existing on the surface of the polyimide resin layer were obtained in advance using an optical inspection apparatus manufactured by Orbotech corporation. Then, a protective film was provided on the polyimide resin layer, and the protective film of the laminated substrate obtained in each example was coated with the protective filmAdding 16g/cm2Under the load of (3), the plate was left in an atmosphere of 40 ℃ and 80% relative humidity for 5 days. Then, the sample was taken out to an atmosphere of normal temperature and pressure, and applied with 16g/cm2Is placed in the loaded state. In each period in which the sum of the period of standing in an atmosphere at a temperature of 40 ℃ and a relative humidity of 80% and the period of taking out to normal temperature and pressure and standing thereafter was 2 months, 4 months, and 6 months, the load was removed from the 1-sheet laminated substrate to which the protective film was attached, the protective film was peeled off, and positional information and an image of a defect present on the surface of the polyimide resin layer were obtained again using an optical inspection apparatus manufactured by Orbotech. Images showing the residual glue and the scratch are defined in advance, and when images are compared, the presence or absence of the residual glue and the scratch is evaluated by referring to the images showing the residual glue and the scratch.
Images before and after the protective film was set were compared, and the presence or absence of adhesive residue and scratches was evaluated.
Examples 1 to 16 will be described below.
< example 1 >
(preparation of curable Silicone)
Triethoxymethylsilane (179g), toluene (300g) and acetic acid (5g) were charged into a 1L flask, and the mixture was stirred at 25 ℃ for 20 minutes and then heated to 60 ℃ to react for 12 hours. The obtained reaction crude liquid was cooled to 25 ℃ and then washed 3 times with water (300 g).
Chlorotrimethylsilane (70g) was added to the washed reaction crude liquid, and the mixture was stirred at 25 ℃ for 20 minutes, and then heated to 50 ℃ to react for 12 hours. The obtained reaction crude liquid was cooled to 25 ℃ and then washed 3 times with water (300 g).
Toluene was distilled off under reduced pressure from the washed reaction crude liquid to form a slurry state, and then dried overnight by a vacuum drier, thereby obtaining a white curable silicone 1 as an organopolysiloxane compound. The number of T units in the curable silicone 1: the number of M units is 87: 13 (molar ratio).
The M unit means (R)3SiO1/2The monofunctional organosiloxy unit represented. The T unit meansRSiO3/2(R represents a hydrogen atom or an organic group) or a trifunctional organosiloxy unit.
(preparation of curable composition)
Curable silicone 1 and hexane as a solvent were mixed, and bismuth (III) 2-ethylhexanoate as a metal compound was further added. The amount of the solvent was adjusted so that the solid content concentration became 50 mass%. The amount of the metal compound added was adjusted so that the amount of the metal element was 0.01 part by mass per 100 parts by mass of the resin. The obtained mixture was filtered using a filter having a pore size of 0.45 μm to obtain a curable composition.
(preparation of laminated substrate)
The obtained curable composition was applied to a polyimide film (trade name "XENOMAX" manufactured by Toyo Boseki K.K.) having a thickness of 0.015mm, and heated at 140 ℃ for 10 minutes using a hot plate to form a silicone resin layer. The thickness of the silicone resin layer was 10 μm.
Subsequently, the silicone resin layer was cleaned with AN aqueous glass cleaner ("PK-LGC 213" manufactured by Parker Corporation), and then a glass plate "AN 100" (support substrate) having a thickness of 0.5mm and cleaned with pure water was placed on the silicone resin layer and bonded thereto using a bonding apparatus to prepare a laminate.
Next, the obtained laminate was heated at 500 ℃ for 30 minutes under a nitrogen atmosphere. Thereafter, air blowing was performed to remove fine dust from the surface of the polyimide film.
The protective film 1 was bonded to the polyimide film side of the obtained laminate to obtain a laminate substrate. As the protective film 1 used, Panac Protect (registered trademark) ETK50B (trade name) having a thickness of 55 μm was used. The protective film 1 had a base material (thickness 50 μm, PET film) and an adhesive layer.
< examples 2 to 16 >
Laminated substrates of examples 2 to 16 were obtained in the same manner as in example 1 except that the type of the protective film was changed.
In example 2, Panac corporation Pana Protect (registered trademark) PX50T01a15 (trade name) having a thickness of 65 μm was used as the protective film 2. The protective film 2 has a base material (thickness 50 μm, PET film) and an adhesive layer.
In example 3, MASTACK (registered trademark) PC-751 (trade name) of Tenson industries, Inc. having a thickness of 55 μm was used as the protective film 3. The protective film 3 has a base material (thickness 50 μm, PET film) and an adhesive layer.
In example 4, a film having a substrate (PET film) with a thickness of 65 μm and an adhesive layer was used as the protective film 4.
In example 5, Sun A.Kaken PAC-3-70 (trade name) having a thickness of 70 μm was used as the protective film 5. The protective film 5 is a coextruded film of an LDPE (low density polyethylene) film and an ethylene-vinyl acetate copolymer layer.
In example 6, as the protective film 6, FSA (registered trademark) 010M (trade name) from Futamura Chemical Co., Ltd. with a thickness of 30 μ M was used. The protective film 6 is a self-adhesive protective film having biaxially oriented polypropylene (OPP) as a base material (thickness: 30 μm).
In example 7, as the protective film 7, Panac protection (registered trademark) ST50 (trade name) having a thickness of 57 μm was used. The protective film 7 has a base material (thickness 50 μm, PET film) and an adhesive layer.
In example 8, as the protective film 8, Panac protection (registered trademark) GC50 (trade name) having a thickness of 80 μm was used. The protective film 8 has a base material (thickness 50 μm, PET film) and an adhesive layer.
In example 9, Panac corporation Pana Protect (registered trademark) GS50 (trade name) having a thickness of 63 μm was used as the protective film 9. The protective film 9 has a base material (thickness 50 μm, PET film) and an adhesive layer.
In example 10, Panac Protect (registered trademark) GN50 (trade name) having a thickness of 60 μm was used as the protective film 10. The protective film 10 has a base material (thickness 50 μm, PET film) and an adhesive layer.
In example 11, a protective film 11 having a thickness of 60 μm was used, which was manufactured by Sun a.kaken JA16F (trade name). The protective film 11 has a base material (LDPE film) and an adhesive layer.
In example 12, Sun a.kaken Y16F (trade name) having a thickness of 60 μm was used as the protective film 12. The protective film 12 has a base material (LDPE film) and an adhesive layer.
In example 13, Sun A.Kaken P27 (trade name) having a thickness of 74 μm was used as the protective film 13. The protective film 13 has a base material (PE film) and an adhesive layer.
In example 14, Sun A. Kaken B35 (trade name) having a thickness of 50 μm was used as the protective film 14. The protective film 14 has a base material (PE film) and an adhesive layer.
In example 15, virgin pulp having a thickness of 50 μm was used as the protective film 15. The protective film 15 has no adhesive layer.
In example 16, a PET film having a thickness of 50 μm was used as the protective film 16. The protective film 16 has no adhesive layer.
The 1 st and 2 nd adhesion forces of the laminated substrates of the examples are summarized in tables 1 and 2. The method of measuring the adhesive force is as described above.
The column "adhesive" in tables 1 and 2 indicates the type of adhesive in the adhesive layer in the protective film, "acrylic" means that the adhesive is an acrylic adhesive, and "silicone" means that the adhesive is a silicone adhesive.
< summary of evaluation results >
As shown in tables 1 and 2, the desired effects were obtained in examples 1 to 6 satisfying the predetermined requirements.
In examples 1 to 6, the 1 st adhesion force between the protective film and the polyimide resin layer was 0.001N/10mm to 0.17N/10mm, and therefore, even when the film was conveyed in an atmospheric environment, peeling between the protective film and the polyimide resin layer did not occur, and no increase in defects was observed at the end portions of the polyimide resin layer. Furthermore, in examples 1 to 6, the 2 nd adhesion force F between the support substrate and the protective film2F is more than or equal to 0.05N/10mm2≤(F1(N/10mm) +0.3N/10mm), so that the protective film can be smoothly peeled off without causing damage to the supporting base material.
In examples 4 to 6, the protective film was cut into a size of 100mm × 100mm, and folded in two so that the adhesive surface faces the opposite side. Next, a glass substrate was used to apply 16g/cm to the film folded in two2The load of (2). After leaving under a load for 30 minutes, the glass substrate was removed. Then, it was confirmed to what extent the protective film was recovered. While examples 5 and 6 maintained the bent state (0 °), example 4 was such that the protective film was restored to 90 ° to some extent. Thus, in example 4, the restoring force of the protective film is strong and the protective film is not easily deformed following the foreign substance, and therefore, it is estimated that the foreign substance is pressed against the polyimide resin layer.
In addition, in examples 5 and 6, a long-term storage test was performed, but no adhesive residue or scratch was observed during any of the storage periods after 2 months, 4 months, and 6 months of long-term storage.
The present application is based on japanese patent application 2019-106053, filed 6.6.2019, the contents of which are incorporated herein by reference.
Claims (11)
1. A laminated substrate comprising a support base made of glass and a polyimide resin layer and a protective film covering the polyimide resin layer laminated thereon,
the 1 st adhesive force of the polyimide resin layer and the protective film is F1And F represents the 2 nd adhesion force of the support base material and the protective film2When the temperature of the water is higher than the set temperature,
the 1 st adhesion force F1Is 0.001N/10mm < F ≤1≤0.17N/10mm，
The 2 nd adhesion force F2F is more than or equal to 0.05N/10mm2≤(F1(N/10mm)+0.3N/10mm)。
2. The laminate substrate according to claim 1, wherein the protective film has a size equal to or larger than that of the support base material.
3. The laminated substrate according to claim 1 or 2, wherein the thickness of the protective film is 20 μm or more.
4. The laminate substrate according to any one of claims 1 to 3, wherein the protective film has a base material and an adhesion layer laminated on the base material and in contact with the polyimide resin layer, and the base material is composed of polyethylene.
5. The laminate substrate according to any one of claims 1 to 4, wherein the adhesion between the support base and the polyimide resin layer is greater than either one of the 1 st adhesion force and the 2 nd adhesion force.
6. The laminate substrate according to any one of claims 1 to 5, wherein a silane coupling agent layer is provided between the support base material and the polyimide resin layer.
7. The laminate substrate according to any one of claims 1 to 5, wherein a silicone resin layer is provided between the support base material and the polyimide resin layer.
8. A package comprising a tray and a plurality of the laminated substrates according to any one of claims 1 to 7 mounted on the tray.
9. The package according to claim 8, wherein the plurality of laminated substrates are loaded on the tray in a state in which a load is applied to each other.
10. The package according to claim 8 or 9, wherein the tray has a bottom plate, and a back plate standing on the bottom plate,
the laminated substrate is mounted on the tray in a state in which the support base material faces the surface of the back plate and is inclined.
11. The package according to any one of claims 8 to 10, wherein the laminated substrate has a size in which the short side is 850mm or more and the long side is 1100mm or more.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2019106053 | 2019-06-06 | ||
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| TWI811636B (en) * | 2020-03-31 | 2023-08-11 | 日商東洋紡股份有限公司 | Inorganic substrate/engineering plastic film laminate with protective film, stacking of laminates, storage method of laminates, and transportation method of laminates |
| JPWO2022186002A1 (en) * | 2021-03-04 | 2022-09-09 | ||
| CN118119507A (en) * | 2021-10-27 | 2024-05-31 | 东洋纺株式会社 | Laminate of inorganic substrate with protective film and heat-resistant polymer film |
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| KR102526049B1 (en) | 2023-04-27 |
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| TW202103913A (en) | 2021-02-01 |
| JP7115510B2 (en) | 2022-08-09 |
| JP2020199766A (en) | 2020-12-17 |
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