laminate

Abstract

Provided is a laminate with a protective film peeling auxiliary tape, which includes a high molecular film with a protective film and a rigid temporary support body (inorganic substrate), and from which the protective film and the high molecular film can be peeled off without peeling the high molecular film and the temporary support body (inorganic substrate). A laminate characterized by sequentially including an inorganic substrate, a heat-resistant high molecular film, a protective film, and a protective film peeling auxiliary tape, the adhesive strength F1 between the inorganic substrate and the heat-resistant high molecular film according to a 90-degree peeling method, the adhesive strength F2 between the heat-resistant high molecular film and the protective film according to a 90-degree peeling method, and the adhesive strength F3 between the protective film and the protective film peeling auxiliary tape according to a 90-degree peeling method satisfy the relationship F3 > F1 > F2.

Description

Technical Field

[0001] This invention relates to a laminate of an inorganic substrate, a polymer film layer with a protective film, and a protective film peeling aid tape. Background Technology

[0002] As a substrate material for manufacturing flexible electronic devices, the use of heat-resistant polymer films such as polyimide (hereinafter also referred to as "polymer films") is being investigated. Since such polymer films such as polyimide are manufactured in the shape of long rolls, it is generally considered that a roll-to-roll production line is ideal for the manufacture of flexible devices.

[0003] On the other hand, most electronic devices such as display devices, sensor arrays, touch screens, and printed circuit boards in the past used rigid substrates such as glass substrates, semiconductor wafers, or glass fiber reinforced epoxy boards. The manufacturing equipment was also constructed based on the premise of using such rigid substrates.

[0004] Against this backdrop, as a means and method for manufacturing flexible electronic devices using existing manufacturing equipment, the following method is known: A flexible electronic device is manufactured by using a rigid inorganic substrate such as a glass substrate as a temporary support, operating while a polymer film is temporarily attached to the temporary support, processing electronic devices on the polymer film, and then peeling the polymer film with the electronic devices formed from the temporary support. (Patent Document 1)

[0005] In addition, as a means and method for manufacturing flexible electronic devices using existing manufacturing equipment, the following method is known: A rigid substrate such as a glass substrate is used as a temporary support; a polymer solution or polymer precursor solution is coated onto the temporary support; the solution is dried to form a precursor film; then a chemical reaction occurs to convert the precursor into a polymer film, thereby obtaining a laminate of the temporary support and the polymer film; electronic devices are then formed on the polymer film in the same manner, and finally peeled off to manufacture the flexible electronic device. (Patent Document 2)

[0006] However, in processes where desired functional elements are formed from a laminate obtained by bonding a polymer film and a support made of inorganic materials, the laminate is often exposed to high temperatures. For example, the formation of functional elements such as polycrystalline silicon and oxide semiconductors requires processes in the temperature range of approximately 200°C to 600°C. Furthermore, in the fabrication of hydrogenated amorphous silicon thin films, temperatures of approximately 200°C to 300°C are sometimes applied to the film. Further, there are cases where heating and dehydrogenation of amorphous silicon to form low-temperature polycrystalline silicon requires temperatures of approximately 450°C to 600°C. Therefore, the polymer film constituting the laminate requires heat resistance; however, as a practical problem, the number of polymer films that can withstand such high temperatures in actual use is limited, and in many cases, polyimide is chosen.

[0007] That is, in any method, a laminate is formed by overlapping a rigid temporary support and a polymer film layer that is eventually peeled off to become the substrate of a flexible electronic device. Since such a laminate can be operated as a rigid sheet material, it can be operated in the same way as glass substrates using conventional devices for manufacturing liquid crystal displays, plasma displays, or organic EL displays that use glass substrates.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent No. 5152104

[0011] Patent Document 2: Japanese Patent No. 5699606 Summary of the Invention

[0012] [The problem the invention aims to solve]

[0013] In the past, rigid inorganic substrates such as glass substrates were handled in stacks of multiple overlapping sheets during storage or transportation. During stacking, cushioning materials such as foamed polymer sheets or paper were sandwiched between the inorganic substrates to facilitate removal of the substrates from the stack after storage or transportation. This method is suitable for glass substrates with sufficient surface hardness. However, in the inorganic substrate (temporary support substrate) and polymer film laminate processed in this invention, the polymer film surface lacks sufficient surface hardness. Therefore, when the laminates are stacked, the polymer film surface rubs against the inorganic substrate surface, causing scratches on the soft polymer film surface. Furthermore, when cushioning materials such as foamed polymer sheets or paper are added, foreign matter can easily cause scratches on the polymer film surface.

[0014] A common approach to solving this problem is to protect the surface of the polymer film with a protective film. Typically, the protective film is a micro-adhesive film obtained by coating one side of a polymer film with a weakly adhesive material, such as polyethylene, polypropylene, or polyester, which are relatively inexpensive materials. Alternatively, from a cost-reduction perspective, resin films with self-adhesive properties, such as polyolefin resins, can also be used.

[0015] By using such a protective film, scratches can be prevented from forming on the surface of the polymer film, and the surface of the polymer film suitable for forming micro-flexible electronic devices can be maintained.

[0016] However, when peeling the protective film from the laminate of the polymer film and the inorganic substrate, the inventors faced the following problem: it was difficult to peel the protective film from the polymer film without separating the inorganic substrate from the polymer film. The laminate of the inorganic substrate and the polymer film of the present invention is laminated with weak adhesion because it will be peeled off after the device is fabricated on the surface of the polymer film. Therefore, it is difficult to peel off only the protective film when the peel strength between the polymer film and the protective film is equal to or greater than the peel strength between the inorganic substrate and the polymer film.

[0017] The problem to be solved by the present invention is to provide a laminate with a protective film peeling aid tape, the laminate comprising a polymer film with a protective film and a rigid temporary support (inorganic substrate), and the protective film and polymer film can be peeled off from the laminate without peeling the polymer film from the temporary support (inorganic substrate).

[0018] [Methods used to solve problems]

[0019] That is, the present invention comprises the following components.

[0020] [1] A laminated body, characterized in that it comprises, in sequence:

[0021] Inorganic substrate, heat-resistant polymer film, protective film, protective film peeling aid tape,

[0022] The adhesion strength F1 between the inorganic substrate and the heat-resistant polymer film according to the 90-degree peel method, the adhesion strength F2 between the heat-resistant polymer film and the protective film according to the 90-degree peel method, and the adhesion strength F3 between the protective film and the protective film peeling aid tape according to the 90-degree peel method satisfy the following relationship:

[0023] F3>F1>F2(1).

[0024] [2] According to the laminate described in [1], the protective film has an ultraviolet 50% cutoff wavelength of 240 nm or higher.

[0025] [3] The laminate according to [1] or [2] is characterized in that the change rate of F2 in the laminate before and after heating at 120°C for 10 minutes is less than 50%.

[0026] [4] The laminate according to any one of [1] to [3], wherein the area B1 of the protective film and the area B2 of the protective film peeling aid tape satisfy the following relationship: B1>B2.

[0027] [5] The laminate according to any one of [1] to [4] is characterized in that the arithmetic mean waviness Wa of the surface of the protective film in contact with the heat-resistant polymer film is less than 30 nm.

[0028] [6] The laminate according to any one of [1] to [5] is characterized in that the heat-resistant polymer film comprises at least one selected from the group consisting of polyimide, polyamide and polyamide-imide.

[0029] [7] The laminate according to any one of [1] to [5] is characterized in that the heat-resistant polymer film is a transparent polyimide.

[0030] [The effects of the invention]

[0031] In a laminate containing a polymer film with a protective film and a rigid temporary support (inorganic substrate), by making the adhesion strength F1 between the inorganic substrate and the polymer film greater than the adhesion strength F2 between the polymer film and the protective film, and further increasing the adhesion strength F3 between the protective film and the protective film peeling aid, the protective film can be easily peeled off without peeling the inorganic substrate from the polymer film in either manual or mechanical peeling. Attached Figure Description

[0032] [ Figure 1 ] Figure 1 (a) to (e) are schematic diagrams of the laminate (inorganic substrate / heat resistant polymer film / protective film / protective film peeling aid tape) in this invention.

[0033] [ Figure 2 ] Figure 2 (a), (b) and (c) are schematic cross-sectional views of the laminate (inorganic substrate / heat-resistant polymer film / protective film / protective film peeling aid tape) in this invention.

[0034] [ Figure 3 ] Figure 3 This is a schematic diagram illustrating an example of a silane coupling agent treatment apparatus used in the vapor phase evaporation process of the present invention.

[0035] [Figure Labels]

[0036] 11: Protective film peeling aid belt

[0037] 12: Inorganic substrate

[0038] 13: Protective film

[0039] 14: Heat-resistant polymer film

[0040] 15: Adhesive layer of protective film peel-off aid tape

[0041] 16: Substrate for protective film peel-off aid tape

[0042] 17: Protective film peel-off aid tape adhesive layer cover film

[0043] 31: Flow meter

[0044] 32: Gas inlet

[0045] 33: Chemical liquid tank (silane coupling agent tank)

[0046] 34: Warm water bath

[0047] 35: Heater

[0048] 36: Processing Chamber (Cavity)

[0049] 37: Substrate

[0050] 38: Exhaust port Detailed Implementation

[0051] Hereinafter, one embodiment of the present invention (hereinafter referred to as "the embodiment") will be described in detail. It should be noted that the present invention is not limited to the following embodiment, and various modifications and implementations can be made within the scope of the spirit of the present invention.

[0052] <Heat-resistant polymer film>

[0053] Examples of heat-resistant polymer films (hereinafter also simply referred to as polymer films) include: polyimide resins such as polyimide, polyamide-imide, polyether-imide, and fluorinated polyimide (e.g., aromatic polyimide resins and alicyclic polyimide resins); polyolefin resins such as polyethylene and polypropylene; copolyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene 2,6-naphthalenedicarboxylate (e.g., fully aromatic polyesters and semi-aromatic polyesters); copoly(meth)acrylates represented by polymethyl methacrylate; polycarbonate; polyamide; polysulfone; polyethersulfone; polyetherketone; cellulose acetate; cellulose nitrate; aromatic polyamide; polyvinyl chloride; polyphenols; polyacrylate; polyphenylene sulfide; polyphenylene ether; polystyrene, etc.

[0054] Since the polymer membrane is designed for processes involving heat treatment at temperatures above 300°C, the practical applications of the illustrated polymer membranes are limited. Preferably, the polymer membrane is made of so-called super engineering plastics, more specifically, including polyimide resins, polyamide resins, polyamide-imide resins, and pyrrole (azole) resins. Particularly preferred examples include aromatic polyimide films, aromatic amide films, aromatic amide-imide films, aromatic benzoxazole films, aromatic benzothiazole films, and aromatic benzimidazole films.

[0055] The following is a detailed description of a polyimide-based resin membrane (sometimes referred to as a polyimide membrane) as an example of the aforementioned polymer membrane. Generally, a polyimide-based resin membrane can be obtained by coating a polyamic acid (polyimide precursor) solution, obtained by reacting a diamine with a tetracarboxylic acid in a solvent, onto a support for making a polyimide membrane, drying it to form a green film (hereinafter also referred to as a "polyamic acid membrane"), and further subjecting the green film to high-temperature heat treatment on or in a state peeled from the support for making a polyimide membrane to a dehydration and ring-closing reaction.

[0056] Regarding the coating of polyamic acid (polyimide precursor) solutions, conventionally known coating methods for solutions can be appropriately used, such as spin coating, doctor blade coating, coater, comma coater, screen printing, slot coating, reverse coating, dip coating, curtain coating, and slot die coating.

[0057] There are no particular restrictions on the diamines that constitute polyamic acid; aromatic diamines, aliphatic diamines, and alicyclic diamines commonly used in polyimide synthesis can be used. From the perspective of heat resistance, aromatic diamines are preferred. Diamines can be used alone or in combination of two or more.

[0058] As a diamine, there are no particular limitations; examples include oxydianiline (bis(4-aminophenyl) ether) and p-phenylenediamine (1,4-phenylenediamine).

[0059] As the tetracarboxylic acid constituting polyamic acid, aromatic tetracarboxylic acids (including their anhydrides), aliphatic tetracarboxylic acids (including their anhydrides), and alicyclic tetracarboxylic acids (including their anhydrides) commonly used in polyimide synthesis can be used. In the case of these anhydrides, the molecule may have one anhydride structure or two anhydride structures, preferably two anhydride structures (dianhydrides). Tetracarboxylic acids can be used alone or in combination of two or more.

[0060] As a tetracarboxylic acid, there is no particular limitation; examples include pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0061] The polyimide film may be a transparent polyimide film.

[0062] A colorless transparent polyimide, as an example of a polymer film, will be described. To avoid complexity, it will also be simply referred to as transparent polyimide. Regarding the transparency of the transparent polyimide, the total light transmittance is preferably 75% or more, more preferably 80% or more, further preferably 85% or more, even more preferably 87% or more, and particularly preferably 88% or more. There is no particular upper limit to the total light transmittance of the transparent polyimide, but for use in flexible electronic devices, it is preferably 98% or less, more preferably 97% or less. The colorless transparent polyimide in this invention is preferably a polyimide with a total light transmittance of 75% or more.

[0063] Examples of aromatic tetracarboxylic acids used to obtain colorless and highly transparent polyimides include: 4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid, 4,4'-oxydiphthalic acid, bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylic acid)1,4-phenylene ester, bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-yl)phenyl-1,4-dicarboxylic acid ester, 4,4'-[4,4'-(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl)bis(phenyl-1,4-diyloxy)]diphenyl-1,2-dicarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, and 4,4'-[(3-oxo-1,3-dihydro-2-phenylene]... [3-oxo-1,1-diyl)bis(toluene-2,5-dioxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl)bis(1,4-xylene-2,5-dioxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[4,4'-(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl)bis(4-isopropyl-toluene-2,5-dioxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[4,4'-(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl)bis(naphthalene-1,4-dioxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[4,4'-(3H-2)]diphenyl-1,2-dicarboxylic acid, 4,4'-[4,4'-(3H-2)]diphenyl-1,2-dicarboxylic acid, 4,4'-[3H-2 ... 1-Benzothiocyclopentane-1,1-dioxo-3,3-diyl)bis(benzyl-1,4-diyloxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-benzophenone tetracarboxylic acid, 4,4'-[(3H-2,1-benzothiocyclopentane-1,1-dioxo-3,3-diyl)bis(toluene-2,5-diyloxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[(3H-2,1-benzothiocyclopentane-1,1-dioxo-3,3-diyl)bis(1,4-xylene-2,5-diyloxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[4,4'-(3H-2,1-benzothiocyclopentane-1,1-dioxo-3,3-diyl)bis(4-isopropyl- Toluene-2,5-dioxy)]diphenyl-1,2-dicarboxylic acid, 4,4'-[4,4'-(3H-2,1-benzoxythiacyclopentane-1,1-dioxide-3,3-diyl)bis(naphthalene-1,4-dioxy)]diphenyl-1,2-dicarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 3,3',4,4'-benzophenone Tetracarboxylic acid, 3,3',4,4'-diphenylsulfone tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, pyromellitic acid, 4,4'-[spiro(oxanthracene-9,9'-fluorene)-2,6-dimethylbis(oxycarbonyl)]diphthalic acid, 4,4'-[spiro(oxanthracene-9,9'-fluorene)-3,[6-Dimethylbis(oxycarbonyl)]diphthalic acid and other tetracarboxylic acids and their anhydrides. Among these, dianhydrides having two anhydride structures are preferred, particularly 4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid dianhydride and 4,4'-oxydiphthalic acid dianhydride. It should be noted that aromatic tetracarboxylic acids can be used alone or in combination of two or more. When heat resistance is important, the copolymerization amount of the aromatic tetracarboxylic acid is preferably 50% by mass or more of all tetracarboxylic acids, more preferably 60% by mass or more, further preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and can be 100% by mass.

[0064] Examples of alicyclic tetracarboxylic acids include: 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3',4,4'-dicyclohexyltetracarboxylic acid, bicyclo[2,2,1]heptane-2,3,5,6-tetracarboxylic acid, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic acid, bicyclo[2,2,2]-7-octen-2,3,5,6-tetracarboxylic acid, tetrahydroanthracene-2,3,6,7-tetracarboxylic acid, tetradecahydro-1,4:5,8:9,10-trimethanoylanthracene-2,3,6,7-tetracarboxylic acid, and decahydronaphthalene-2,3,6 ,7-Tetracarboxylic acid, decahydro-1,4:5,8-dibridged methylenenaphthalene-2,3,6,7-tetracarboxylic acid, decahydro-1,4-bridged ethylene-5,8-bridged methylenenaphthalene-2,3,6,7-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid (also known as “norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid”), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-(methylnorbornane)-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2”-norbornane-5,5” 6,6”-Tetracarboxylic acid (also known as "norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid"), methylnorbornane-2-spiro-α-cyclohexanone-α'-spiro-2”-(methylnorbornane)-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cyclopropanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro- α-Cyclooctanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cyclononanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cyclodecanoone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cycloundecanoone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cyclododecanoone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cyclotridecanoone-α'-spiro-2”-norbornane-5,5”,6”-Tetracarboxylic acids such as 6”-tetracarboxylic acid, norbornane-2-spiro-α-cyclotetradecanophenone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-(methylcyclopentanone)-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, norbornane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic acid, and their anhydrides. Among these, dianhydrides having two anhydride structures are preferred, particularly 1,2,3,4-cyclobutane. The alicyclic tetracarboxylic acid dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride, and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride are preferred, as are 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, and even more preferably 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride. It should be noted that these can be used alone or in combination of two or more. When transparency is important, the copolymerization amount of the alicyclic tetracarboxylic acid is preferably 50% by mass or more of all tetracarboxylic acids, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and can be 100% by mass.

[0065] Examples of tricarboxylic acids include: aromatic tricarboxylic acids such as trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, diphenyl ether-3,3',4'-tricarboxylic acid, and diphenyl sulfone-3,3',4'-tricarboxylic acid; hydrides of the above aromatic tricarboxylic acids such as hexahydrotriphenylamine; alkylene glycol bis(triphenylamine) esters such as ethylene glycol bis(triphenylamine) ester, propylene glycol bis(triphenylamine) ester, and polyethylene glycol bis(triphenylamine) ester; and their monoanhydrides and esterifications. Monoanhydrides having one anhydride structure are preferred, and trimellitic anhydride and hexahydrotriphenylamine anhydride are particularly preferred. It should be noted that they can be used alone or in combination.

[0066] Examples of dicarboxylic acids include: aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and 4,4'-dibenzoic acid oxide; or hydrides of the above aromatic dicarboxylic acids such as 1,6-cyclohexanedicarboxylic acid; oxalic acid; succinic acid; glutaric acid; adipic acid; pimelic acid; octanoic acid; azelaic acid; sebacic acid; undecanoic acid; dodecanoic acid; 2-methylsuccinic acid; and their acyl chlorides or esters. Among these, aromatic dicarboxylic acids and their hydrides are preferred, particularly terephthalic acid, 1,6-cyclohexanedicarboxylic acid, and 4,4'-dibenzoic acid oxide. It should be noted that dicarboxylic acids can be used alone or in combination.

[0067] There are no particular restrictions on the diamines or isocyanates used to obtain colorless and highly transparent polyimides. Aromatic diamines, aliphatic diamines, alicyclic diamines, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates commonly used in polyimide synthesis, polyamide-imide synthesis, and polyamide synthesis can be used. From the perspective of heat resistance, aromatic diamines are preferred, and from the perspective of transparency, alicyclic diamines are preferred. Furthermore, when using aromatic diamines with a benzoxazole structure, high heat resistance, high elastic modulus, low thermal shrinkage, and low coefficient of linear expansion are observed. Diamines and isocyanates can be used alone or in combination of two or more.

[0068] Examples of aromatic diamines include, for instance: 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1, 3,3,3-Hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4-amino-N-(4-aminophenyl)benzamide, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2'-trifluoromethyl-4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone Benzophenone, 3,4'-Diaminobenzophenone, 4,4'-Diaminobenzophenone, 3,3'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]methane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane [Phenylacetyl]butane, 1,3-bis[4-(4-aminophenoxy)phenyl]butane, 1,4-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,3-bis[4-(4-aminophenoxy)phenyl]butane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3-methylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-Bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfoxide, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene [4-(3-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 4,4'-bis[(3-aminophenoxy)benzoyl]benzene, 1,1-bis[4-(3-aminophenoxy)phenyl]propane, 1,3-bis[4-(3-aminophenoxy)phenyl]propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, bis[4-(3-aminophenoxy)phenyl]sulfoxide, 4,4'-bis[3-(4-(3-aminophenoxy)phenyl]sulfoxide, [-aminophenoxy)benzoyl]diphenyl ether, 4,4'-bis[3-(3-aminophenoxy)benzoyl]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl sulfone, bis[4-{4-(4-aminophenoxy)phenoxy}phenyl]sulfone, 1,4-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4- [Amino-6-fluorophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-methylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-cyanophenoxy)-α,α-dimethylbenzyl]benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4...4'-Diphenyloxybenzophenone, 4,4'-diamino-5,5'-diphenyloxybenzophenone, 3,4'-diamino-4,5'-diphenyloxybenzophenone, 3,3'-diamino-4-biphenyloxybenzophenone, 4,4'-diamino-5-biphenyloxybenzophenone, 3,4'-diamino-4-biphenyloxybenzophenone, 3,4'-diamino-5'-biphenyloxybenzophenone, 1,3-bis(3-amino-4-phenoxybenzoyl)benzene, 1,4-bis(3-amino-4-phenoxybenzoyl)benzene, 1,3-bis(4-amino-5-phenoxybenzoyl)benzene, 1,4-bis(4-amino-5-phenoxybenzoyl)benzene, 1,3-bis(3-amino-4-biphenyloxybenzoyl)benzene Benzene, 1,4-bis(3-amino-4-biphenoxybenzoyl)benzene, 1,3-bis(4-amino-5-biphenoxybenzoyl)benzene, 1,4-bis(4-amino-5-biphenoxybenzoyl)benzene, 2,6-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzonitrile, 4,4'-[9H-fluorene-9,9-diyl]bisaniline Other names include "9,9-bis(4-aminophenyl)fluorene", spiro(oxanthracene-9,9'-fluorene)-2,6-diylbis(oxycarbonyl)]bisaniline, 4,4'-[spiro(xanthant-9,9'-fluorene)-2,6-diylbis(oxycarbonyl)]bisaniline, and 4,4'-[spiro(oxanthracene-9,9'-fluorene)-3,6-diylbis(oxycarbonyl)]bisaniline. Furthermore, some or all of the hydrogen atoms on the aromatic ring of the above-mentioned aromatic diamines may be substituted with halogen atoms, alkyl or alkoxy groups having 1 to 3 carbon atoms, or cyano groups. Further, some or all of the hydrogen atoms in the alkyl or alkoxy groups having 1 to 3 carbon atoms may be substituted with halogen atoms. Furthermore, there is no particular limitation on the aromatic diamines having the benzoxazole structure mentioned above. Examples include: 5-amino-2-(p-aminophenyl)benzoxazole, 6-amino-2-(p-aminophenyl)benzoxazole, 5-amino-2-(m-aminophenyl)benzoxazole, 6-amino-2-(m-aminophenyl)benzoxazole, 2,2'-p-phenylenebis(5-aminobenzoxazole), 2,2'-p-phenylenebis(6-aminobenzoxazole), 1-(5-aminobenzoxazole)-4-(6-aminobenzoxazole)benzene, 2,6-(4,4'-diaminobenzoxazole)benzene, etc. (Diphenyl)benzo[1,2-d:5,4-d']biazole, 2,6-(4,4'-diaminodiphenyl)benzo[1,2-d:4,5-d']biazole, 2,6-(3,4'-diaminodiphenyl)benzo[1,2-d:5,4-d']biazole, 2,6-(3,4'-diaminodiphenyl)benzo[1,2-d:4,5-d']biazole, 2,6-(3,3'-diaminodiphenyl)benzo[1,2-d:5,4-d']biazole, 2,6-(3,3'-diaminodiphenyl)benzo[1,2-d:4,[5-d']biazole, etc. Particularly preferred are 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4-amino-N-(4-aminophenyl)benzamide, 4,4'-diaminodiphenyl sulfone, and 3,3'-diaminobenzophenone. It should be noted that aromatic diamines can be used alone or in combination.

[0069] Examples of alicyclic diamines include, for instance, 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, and 4,4'-methylenebis(2,6-dimethylcyclohexylamine). Of particular preference are 1,4-diaminocyclohexane and 1,4-diamino-2-methylcyclohexane, and more preferably 1,4-diaminocyclohexane. It should be noted that alicyclic diamines can be used alone or in combination.

[0070] Examples of diisocyanates include, for instance, diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, and 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2 4'-Diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate Ester, diphenyl sulfone-4,4'-diisocyanate, benzyl-2,4-diisocyanate, benzyl-2,6-diisocyanate, m-xylyl diisocyanate, p-xylyl diisocyanate, naphthalene-2,6-diisocyanate, 4,4'-(2,2-bis(4-phenoxyphenyl)propane)diisocyanate, 3,3'- or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'- or 2,2'-diethylbiphenyl-4, Aromatic diisocyanates such as 4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, and 3,3'-diethoxybiphenyl-4,4'-diisocyanate, as well as diisocyanates obtained by hydrogenation of any of them (e.g., isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate), etc. Among these, considering low hygroscopicity, dimensional stability, price, and polymerizability, diphenylmethane-4,4'-diisocyanate, benzyl-2,4-diisocyanate, benzyl-2,6-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate or naphthalene-2,6-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,4-cyclohexane diisocyanate are preferred. It should be noted that diisocyanates can be used alone or in combination.

[0071] In this embodiment, the polymer film is preferably a polyimide film. When the polymer film is a polyimide film, it exhibits excellent heat resistance. Furthermore, when the polymer film is a polyimide film, it can be appropriately cut using an ultraviolet laser.

[0072] The thickness of the polymer film is preferably 3 μm or more, more preferably 7 μm or more, even more preferably 14 μm or more, and even more preferably 20 μm or more. There is no particular upper limit to the thickness of the polymer film, but for use in flexible electronic devices, it is preferably 250 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less.

[0073] The average coefficient of linear expansion (CTE) of the polymer film between 30°C and 250°C is preferably 50 ppm / K or less, more preferably 45 ppm / K or less, even more preferably 40 ppm / K or less, even more preferably 30 ppm / K or less, and particularly preferably 20 ppm / K or less. Furthermore, it is preferably -5 ppm / K or more, more preferably -3 ppm / K or more, and even more preferably 1 ppm / K or more. When the CTE is within the above range, the difference in coefficient of linear expansion between the polymer film and a typical support (inorganic substrate) can be kept small, preventing the polymer film from peeling off from the inorganic substrate or warping together with the support, even when supplied to a heated process. Here, CTE represents the factor of reversible expansion and contraction with respect to temperature. It should be noted that the CTE of the polymer film refers to the average value of the CTE in the coating direction (MD direction) and the CTE in the width direction (TD direction) of the polymer solution or polymer precursor solution.

[0074] When the polymer film is a transparent polyimide film, the yellowness index (hereinafter also referred to as "yellowness index" or "YI") of the polymer film is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, and even more preferably 3 or less. There is no particular limitation on the lower limit of the yellowness index of the transparent polyimide, but for use in flexible electronic devices, it is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more.

[0075] When the polymer film is a transparent polyimide film, the haze of the polymer film is preferably 1.0 or less, more preferably 0.8 or less, even more preferably 0.5 or less, and even more preferably 0.3 or less. There is no particular limitation on the lower limit; industrially, a haze of 0.01 or more is acceptable, and 0.05 or more is permissible.

[0076] The thermal shrinkage rate of the polymer film between 30°C and 500°C is preferably less than ±0.9%, more preferably less than ±0.6%. Thermal shrinkage rate is a factor representing irreversible stretching and contraction with respect to temperature.

[0077] The tensile breaking strength of the polymer film is preferably 60 MPa or higher, more preferably 80 MPa or higher, and even more preferably 100 MPa or higher. There is no particular upper limit to the tensile breaking strength, but it is practically less than approximately 1000 MPa. When the tensile breaking strength is 60 MPa or higher, the polymer film can be prevented from breaking during peeling from the inorganic substrate. It should be noted that the tensile breaking strength of the polymer film refers to the average of the tensile breaking strength in the flow direction (MD direction) and the tensile breaking strength in the width direction (TD direction).

[0078] The tensile elongation at break of the polymer membrane is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more. When the tensile elongation at break is 1% or more, the processability is excellent. It should be noted that the tensile elongation at break of the polymer membrane refers to the average of the tensile elongation at break in the flow direction (MD direction) and the tensile elongation at break in the width direction (TD direction).

[0079] The tensile elastic modulus of the polymer film is preferably 2.5 GPa or higher, more preferably 3 GPa or higher, and even more preferably 4 GPa or higher. When the tensile elastic modulus is 2.5 GPa or higher, the polymer film exhibits less elongation deformation during peeling from the inorganic substrate, resulting in excellent processability. The tensile elastic modulus is preferably 20 GPa or lower, more preferably 15 GPa or lower, and even more preferably 12 GPa or lower. When the tensile elastic modulus is 20 GPa or lower, the polymer film can be used as a flexible film. It should be noted that the tensile elastic modulus of the polymer film refers to the average of the tensile elastic modulus in the flow direction (MD direction) and the tensile elastic modulus in the width direction (TD direction).

[0080] The thickness non-uniformity of the polymer membrane is preferably 20% or less, more preferably 12% or less, even more preferably 7% or less, and particularly preferably 4% or less. When the thickness non-uniformity is greater than 20%, it tends to be difficult to apply to narrow portions. It should be noted that the membrane thickness non-uniformity can be determined, for example, by using a contact thickness gauge, randomly selecting about 10 points from the membrane to be measured, measuring the membrane thickness, and calculating it based on the following formula.

[0081] Membrane thickness unevenness (%)

[0082] = 100 × (maximum film thickness - minimum film thickness) ÷ average film thickness

[0083] The polymer film is preferably obtained during its manufacturing in the form of a long strip of polymer film with a width of 300 mm or more and a length of 10 m or more, and more preferably in the form of a roller-shaped polymer film wound on a core. When the polymer film is wound into a roller shape, transportation of the polymer film in the form of a roller-shaped polymer film becomes easier.

[0084] In order to ensure operability and productivity, the polymer membrane is preferably made up of about 0.03 to 3% by mass of a lubricating material (particles) with a particle size of about 10 to 1000 nm, which imparts a fine texture to the surface of the polymer membrane to ensure lubricity.

[0085] <Inorganic substrate>

[0086] As the inorganic substrate, any plate-shaped inorganic substrate that can be used as a substrate formed from inorganic materials can be used. Examples include: inorganic substrates in which glass plates, ceramic plates, semiconductor wafers, metals, etc. are the main components, as well as inorganic substrates in which these glass plates, ceramic plates, semiconductor wafers, and metals are stacked, inorganic substrates in which these are dispersed, and inorganic substrates containing fibers of these materials.

[0087] The glass plates include quartz glass, high-silicate glass (96% silica), soda-lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex, a registered trademark), borosilicate glass (alkali-free), borosilicate glass (micro-plates), aluminosilicate glass, etc. Preferably, the glass plates have a coefficient of linear expansion of 5 ppm / K or less. Among commercially available products, Corning Gorilla Glass Inc.'s "Corning 7059" and "Corning 1737," "EAGLE," Asahi Glass Co., Ltd.'s "AN100," Nippon Electric Glass Co., Ltd.'s "OA10," "OA11G," and SCHOTT's "AF32," etc., are preferred for liquid crystal displays.

[0088] The semiconductor wafer is not particularly limited, and examples include silicon wafers, germanium wafers, silicon-germanium wafers, gallium-arsenic wafers, aluminum-gallium-indium wafers, nitrogen-phosphorus-arsenic-antimony wafers, SiC wafers, InP (indium phosphide), InGaAs, GaInNAs, LT wafers, LN wafers, ZnO (zinc oxide), CdTe (cadmium telluride), and ZnSe (zinc selenide). Among these, silicon wafers are preferred, and mirror-polished silicon wafers with a size of 8 inches or larger are particularly preferred.

[0089] The metals mentioned include single-element metals such as W, Mo, Pt, Fe, Ni, and Au; alloys such as Inconel, Monel, Nimonic, carbon-copper, Fe-Ni-based Invar alloy, and super Invar alloy. Furthermore, these metals also include multilayer metal plates formed by attaching other metal layers or ceramic layers to these metals. In this case, when the coefficient of linear expansion (CTE) with the attached layers is low, Cu, Al, etc., are also used in the main metal layer. There are no limitations on the metals used as attached metal layers, as long as they enhance the adhesion to the thermosetting polyamic acid, and possess properties such as non-diffusion, chemical resistance, and good heat resistance. Suitable examples include Cr, Ni, TiN, and Cu containing Mo.

[0090] The ceramic plate used in this invention includes base ceramics such as Al2O3, Mullite, ALN, SiC, crystallized glass, Cordierite, Spodumene, Pb-BSG+CaZrO3+Al2O3, Crystallized glass+Al2O3, Crystallized calcium (Cal)-BSG, BSG+Quartz, BSG+Al2O3, Pb-BSG+Al2O3, Glass-ceramic, and Zerodur.

[0091] The thickness of the inorganic substrate is not particularly limited, but from a processability perspective, a thickness of 10 mm or less is preferred, more preferably 3 mm or less, and even more preferably 1.3 mm or less. There is no particular limitation on the lower limit of the thickness, but it is preferably 0.07 mm or more, more preferably 0.15 mm or more, and even more preferably 0.3 mm or more. If it is too thin, it is prone to breakage, making handling difficult. Furthermore, if it is too thick, it becomes heavy, making handling difficult as well.

[0092] Surface treatment can be performed to improve the wettability and adhesion of inorganic substrates. Silane coupling agents, aluminum-based coupling agents, titanate-based coupling agents, and other coupling agents can be used as surface treatment agents. In particular, excellent properties can be obtained when using silane coupling agents.

[0093] <Silane Coupling Agent (SCA)>

[0094] In the laminate, a silane coupling agent layer (also called a silane coupling agent condensation layer) is preferably provided between the polymer film layer and the inorganic substrate. In this invention, the silane coupling agent refers to a compound containing 10% by mass or more Si (silicon). By using the silane coupling agent layer, the intermediate layer between the thermosetting polyamic acid layer and the inorganic substrate can be thinned, thus achieving the following effects: less degassing during heating, difficulty in dissolving even in wet processes, and even if dissolution occurs, it is limited to trace amounts. To improve heat resistance, the silane coupling agent is preferably a silane coupling agent containing a large amount of silicon oxide, and particularly preferably a silane coupling agent with heat resistance at around 400°C. The thickness of the silane coupling agent layer is preferably 200 nm or less (0.2 μm or less). As a range for use in flexible electronic devices, it is preferably 100 nm or less (0.1 μm or less), more preferably 50 nm or less, and even more preferably 10 nm. In conventional manufacturing, it is approximately 0.10 μm or less. Furthermore, in processes where it is desirable to use as little silane coupling agent as possible, it can also be used below 5 nm. At a wavelength below 0.1 nm, there is a risk of reduced peel strength or the appearance of partially unattached areas; therefore, a wavelength of 0.1 nm or more is preferred, and more preferably 0.5 nm or more.

[0095] The silane coupling agent used in this invention is not particularly limited, but silane coupling agents having amino or epoxy groups are preferred. When heat resistance is required in the process, silane coupling agents that connect Si and amino groups via aromatic linkages are preferred.

[0096] There are no particular limitations on the silane coupling agent, but silane coupling agents having an amino group are preferred. Specific examples include: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, aminophenyltrimethoxysilane, aminophenylethyltrimethoxysilane, aminophenylaminomethylphenylethyltrimethoxysilane, etc.

[0097] <Protective film>

[0098] The laminate of the present invention includes a protective film laminated (attached) to the heat-resistant polymer film. The protective film laminated (attached) to the heat-resistant polymer film is generally a film used for temporary protection of the surface of the heat-resistant polymer film, and there is no particular limitation as long as it is a peelable film capable of protecting the surface of the heat-resistant polymer film. In the present invention, considering ease of peeling in subsequent processes, a protective film satisfying formula (1) is preferred. For example, in addition to PET film, PEN film, polyethylene film, polypropylene film, nylon film, etc., heat-resistant super engineering plastic films such as PPS film, PEEK film, aromatic polyamide film, polyimide film, and polyimide benzazole film can also be used. Among these, PET film is preferred.

[0099] In the laminate of the present invention, the arithmetic mean waviness Wa of the protective film surface in contact with the heat-resistant polymer film is preferably less than 30 nm. The arithmetic mean waviness Wa is a parameter representing the magnitude (amplitude) of the waviness in the height direction. Since the waviness related to the adhesion of the heat-resistant polymer film consists of waviness with a period of tens of μm, the measurement area of ​​the interference microscope is preferably greater than 60 μm in both the x and y directions.

[0100] In this invention, the heat-resistant polymer film has a very smooth surface, as it is assumed that a device is formed on its surface. Sufficient adhesion between the protective film and the heat-resistant polymer film is ensured when the arithmetic mean waviness Wa of the protective film surface in contact with the heat-resistant polymer film is 30 nm or less. Therefore, in this invention, the arithmetic mean waviness Wa of the protective film is preferably 29 nm or less, more preferably 28 nm or less, and even more preferably 27 nm or less. There is no particular limitation on the lower limit of the arithmetic mean waviness Wa of the protective film, and it is generally 5 nm or more.

[0101] The arithmetic mean waviness Wa of a protective film can be controlled by the manufacturing conditions during its formation (temperature, linear speed, surface waviness of the kneading rollers, kneading pressure, etc.). For example, the arithmetic mean waviness Wa tends to decrease when the forming temperature is lowered, and it also tends to decrease when the linear speed is increased or the kneading pressure is decreased. Additionally, it can be controlled by the storage conditions (temperature, humidity, storage time) of the formed protective film. When using commercially available protective films, a suitable protective film can be selected by measuring its arithmetic mean waviness Wa before laminating it with a transparent resin film.

[0102] Preferably, the protective film has an adhesive layer on the surface in contact with the heat-resistant polymer film layer. By having an adhesive layer on the protective film, it can exhibit self-adhesion. There are no particular limitations on the adhesive layer; for example, polyurethane-based, silicone-based, or acrylic-based adhesive layers can be used. The adhesive layer can be prepared by coating an adhesive dissolved in a solvent and then allowing it to dry.

[0103] From the perspective of cost reduction, self-adhesive resin films (protective films) such as polyolefin resins can be used. Specifically, polyolefin resin films are preferred. From the perspective of availability and low cost, polypropylene resin films or polyethylene resin films are more preferred, and polyethylene resin films are even more preferred. In addition, as polyethylene resins, examples include: low-density polyethylene (LDPE), linear short-chain branched polyethylene (LLDPE), high-density polyethylene (HDPE), and ultra-low-density polyethylene (VLDPE). As the resin on the side adjacent to the heat-resistant polymer film, LLDPE is preferred from the perspective of adhesion to the heat-resistant polymer film and processability.

[0104] The protective film may contain various additives in the substrate layer or adhesive layer as needed. Examples of such additives include: fillers, antioxidants, light-resistant agents, anti-gelling agents, organic wetting agents, antistatic agents, surfactants, pigments, dyes, etc. Preferably, the protective film's UV transmittance is set within a range satisfying the following values ​​in UV transmittance measurements. When the protective film comprises a substrate and an adhesive layer, the substrate preferably does not contain UV absorbers. Examples of UV absorbers, described later, are examples.

[0105] Regarding the protective film, in the ultraviolet transmittance measurement, the 50% cutoff wavelength of ultraviolet transmittance is preferably 240 nm or more, more preferably 270 nm or more, further preferably 300 nm or more, and particularly preferably 340 nm or more. When the 50% cutoff wavelength of the ultraviolet transmittance of the protective film is 240 nm or more, it is more appropriate to cut the protective film and the heat-resistant polymer film by ultraviolet laser. Therefore, the heat-resistant polymer film with the protective film attached can be cut into any size from the state of the inorganic substrate / heat-resistant polymer film / protective film laminate using a laser. Preferably, the upper limit is the general wavelength region of ultraviolet light, i.e., 380 nm or less.

[0106] To achieve the desired ultraviolet transmittance, the protective film preferably contains an ultraviolet absorber. Organic ultraviolet absorbers are examples of such absorbers.

[0107] Examples of organic ultraviolet absorbers include benzotriazole-based, benzophenone-based, cyclic imino ester-based, and combinations thereof. From a durability perspective, benzotriazole-based and cyclic imino ester-based absorbers are particularly preferred.

[0108] Examples of benzotriazole-based ultraviolet absorbers include: 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxypropyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-tert-butyl-3'-( [2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, etc.

[0109] Examples of benzophenone-based ultraviolet absorbers include: 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone·2 sodium salt, etc.

[0110] Examples of cyclic imine ester-based ultraviolet absorbers include: 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2-(1- or 2-naphthyl)-3,1-benzoxazin-4-one, 2-(4-biphenyl)-3,1-benzoxazin-4-one, and 2-p-nitrophenyl-3,1-benzoxazin-4-one. 2-m-Nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p-(or m-)phthaliminophenyl-3,1-benzoxazin-4-one, 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one), 2,2'-bis(3 1-Benzoxazin-4-one), 2,2'-Ethylenebis(3,1-Benzoxazin-4-one), 2,2'-Tetramethylenebis(3,1-Benzoxazin-4-one), 2,2'-Dedecylenebis(3,1-Benzoxazin-4-one), 2,2'-p-Phenylidenebis(3,1-Benzoxazin-4-one), 2,2'-m-Phenylidenebis(3,1-Benzoxazin-4-one), 2,2'-(4,4'-Diphenylene)bis(3,1-Benzoxazin-4-one), 2,2'-(2,6- Or 1,5-naphthylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazin-4-one), 1,3,5-tris(3,1-benzoxazin-4-one-2-yl)benzene, etc.

[0111] In addition, as cyclic imine ester-based ultraviolet absorbers, 1,3,5-tris(3,1-benzoxazin-4-one-2-yl)naphthalene, 2,4,6-tris(3,1-benzoxazin-4-one-2-yl)naphthalene, 2,8-dimethyl-4H,6H-benzo(1,2-d; 5,4-d')bis-(1,3)-oxazin-4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2-d; 5,4-d')bis-(1,3)-oxazin-4,9-dione, 2,8-diphenyl-4H,8H-benzo(1,2-d; 5,4-d')bis-(1,3)-oxazin-4,6-dione, and 2,7-diphenyl-4H,9H-benzo(1,2-d; 5,4-d')bis-(1,3)-oxazin-4,6-dione, and 2,7-diphenyl-4H,9H-benzo(1,2-d)5,4-d')bis-(1,3)-oxazin-4,6-dione, 6,6'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-bis(2-ethyl-4H,3,1-benzoxazin-4-one), 6,6'-bis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-ethylidenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-Ethylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-Butylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-Butylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-Oxybis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-Oxybis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-Sulfodibis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-Sulfodibis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-Sulfodibis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,6'-Sulfodibis(2-phenyl-4H,3,1-benzoxazin-4-one), 1-Benzoxazin-4-one), 6,6'-carbonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 6,6'-carbonylbis(2-phenyl-4H,3,1-benzoxazin-4-one), 7,7'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), 7,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-ethylidenebis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-oxybis (2-Methyl-4H,3,1-benzoxazin-4-one), 7,7'-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-carbonylbis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7'-bis(2-phenyl-4H,3,1-benzoxazin-4-one), 6,7'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one), 6,7'-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one), etc.

[0112] <Removal of the auxiliary band>

[0113] In this invention, the laminate consists of an inorganic substrate, a heat-resistant polymer film, a protective film, and a protective film peeling aid tape, stacked sequentially. The protective film peeling aid tape (hereinafter also simply referred to as the peeling aid tape) is a tape used to assist in peeling the protective film from the heat-resistant polymer film. It is basically formed by a substrate and an adhesive layer disposed on the surface of the substrate. However, if the peel strength satisfies the relationship of formula (1), a resin film with self-adhesion properties, such as a polyolefin resin, can be used.

[0114] In addition to PET film, PEN film, polyethylene film, polypropylene film, and nylon film, heat-resistant engineering plastic films such as PPS film, PEEK film, aromatic polyamide film, polyimide film, and polyimidebenzazole film can also be used as the substrate for the peeling aid tape.

[0115] The adhesive layer of the release chuck is not particularly limited as long as it satisfies the relationship in formula (1). For example, polyurethane-based, silicone-based, and acrylic-based adhesive layers can be used. The adhesive layer can be made by coating an adhesive dissolved in a solvent and then drying it. As commercially available adhesive tapes, for example, Cellotape (registered trademark) manufactured by Nichiban Corporation, film cross tape, cloth adhesive tape manufactured by Nitto Denko Corporation, and vinyl tape can be used.

[0116] When the release aid tape is formed from a substrate and an adhesive layer, the substrate thickness is preferably 30 μm or more, more preferably 50 μm or more. A substrate thickness of 30 μm or more provides good operability. Regarding the release aid tape, from the perspective of ease of handling when rolled into a roll, the upper limit of the thickness is preferably 400 μm or less, more preferably 200 μm or less. Furthermore, the preferred thickness is also the same when the release aid tape is formed from a self-adhesive film.

[0117] When the release retrieval tape is formed from a substrate and an adhesive layer, the thickness of the adhesive layer is preferably 7 μm or more, more preferably 10 μm or more. When the adhesive layer thickness is 7 μm or more, adhesion to the protective film is easily ensured. Furthermore, the thickness of the adhesive layer is preferably 20 μm or less. When the adhesive layer thickness is 20 μm, the adhesive layer will not be exposed from the substrate due to pressure when applied to the protective film, and the laminate is less prone to contamination.

[0118] Preferably, the area B2 of the peeling auxiliary tape is smaller than the area B1 of the protective film (B1 > B2). When the areas B1 and B2 are equal (B1 = B2), the protective film can be peeled off as long as the relationship of formula (1) is satisfied. However, the main effect of the peeling auxiliary tape for the protective film is to lift the peeling end of the protective film. Therefore, if B1 = B2 is set, the effect may sometimes be small. In addition, when the area B1 is smaller than the area B2 (B1 < B2), the protective film can also be peeled off. However, the adhesive layer of the peeling auxiliary tape will contact places other than the protective film, such as an inorganic substrate. Therefore, there is a risk that the laminate will be contaminated by the transfer from the adhesive.

[0119] The peeling auxiliary tape is attached as Figure 1 shown to the end of the protective film of the heat-resistant polymer film / inorganic substrate laminate (inorganic substrate / heat-resistant polymer film / protective film) with the protective film attached. The side to be attached can be one side as shown in Figure 1 (a) to (d), but it can also be attached to two or more sides as shown in Figure 1 (e), and the protective film is peeled off from two or more peeling ends.

[0120] When the peeling auxiliary tape is attached by making a part of it exposed from the protective film as shown in Figure 1 shown, preferably, the adhesive layer is not exposed at the part that does not contact the protective film. When the adhesive layer is exposed, the adhesive layer of the peeling auxiliary tape will also contact places other than the protective film, such as an inorganic substrate. Therefore, there is a fear that the laminate will be contaminated by the transfer from the adhesive. As a method of not exposing the adhesive layer part, there can be mentioned: a method of forming the adhesive layer only on the width of the peeling auxiliary tape substrate that adheres to the protective film, and a method of attaching a non-adhesive film to the part exposed from the protective film.

[0121] <Laminate>

[0122] The laminate of the present invention sequentially includes the inorganic substrate, the heat-resistant polymer film, the protective film, and the peeling auxiliary tape for the protective film. The adhesive strength F1 according to the 90-degree peeling method between the inorganic substrate and the heat-resistant polymer film (hereinafter, also simply referred to as F1), the adhesive strength F2 according to the 90-degree peeling method between the heat-resistant polymer film and the protective film (hereinafter, also simply referred to as F2), and the adhesive strength F3 according to the 90-degree peeling method between the protective film and the peeling auxiliary tape for the protective film (hereinafter, also simply referred to as F3) need to satisfy the relationship of the following formula (1).

[0123] F3 > F1 > F2 (1)

[0124] By satisfying the above formula (1), in either manual or mechanical peeling, the protective film can be easily peeled off without separating the inorganic substrate from the polymer film.

[0125] In the laminate of the present invention, when the peel strength F2 between the heat-resistant polymer film and the protective film is equal to or greater than the peel strength F1 between the inorganic substrate and the heat-resistant polymer film, it sometimes becomes difficult to peel off only the protective film. In particular, when the peel strength F1 between the inorganic substrate and the heat-resistant polymer film is low, the inorganic substrate and the polymer film may easily peel off when the protective film end is lifted. In the case of a small laminate, the peeling end can be manually created using a peeling tape, or the protective film end can be peeled off only using tweezers or other clamps, so this is not a major problem. However, if it is envisioned that the operation is carried out using display manufacturing equipment, the size of the laminate of the inorganic substrate and the polymer film is at most about 2×3m. In a laminate of such size, the peeling of the protective film is envisioned to be carried out mechanically, and it is difficult to peel off only the protective film without peeling off the inorganic substrate and the protective film by subtle increases or decreases in force, as is the case with manual peeling.

[0126] By configuring the structure of this invention, such problems can be avoided, and in either manual or automatic mode, only the protective film can be peeled off without separating the inorganic substrate from the protective film.

[0127] In this specification, F1 and F2 are the 90° peel strength values ​​after heat treatment (hereinafter also referred to as heat treatment) for 10 minutes on a laminate (hereinafter also referred to as laminate precursor) formed by sequentially stacking an inorganic substrate, a heat-resistant polymer film, and a protective film at 120°C under atmospheric conditions. That is, the laminate precursor is the laminate before the release retrieval tape is laminated (attached). In addition, the lamination (attachment) of the release retrieval tape can be performed before or after the heat treatment of the laminate precursor, but since it is preferable to perform the lamination (attachment) after the heat treatment of the laminate precursor, F3 is set as the 90° peel strength value without the heat treatment.

[0128] The value of F1 is not particularly limited as long as it satisfies the formula (1), but it is preferably 0.05 N / cm or more, more preferably 0.08 N / cm or more, and even more preferably 0.1 N / cm or more. Furthermore, it is preferably 0.3 N / cm or less, more preferably 0.28 N / cm or less. When F1 is 0.05 N / cm or more, the heat-resistant polymer film can be prevented from peeling off from the inorganic substrate before or during device formation. Furthermore, when F1 is 0.3 N / cm or less, the inorganic substrate and the heat-resistant polymer film can be easily peeled off after device formation. That is, when F1 is 0.3 N / cm or less, even if the peel strength between the inorganic substrate and the heat-resistant polymer film increases slightly during device formation, they can still be easily peeled off.

[0129] The value of F2 is not particularly limited as long as it satisfies the above formula (1), but it is preferably 0.001 N / cm or more, more preferably 0.002 N / cm or more, and even more preferably 0.005 N / cm or more. It is also preferably 0.1 N / cm or less, more preferably 0.08 N / cm or less. When F2 is 0.1 N / cm or less, the protective film can be appropriately peeled off when using the heat-resistant polymer film. Furthermore, when F2 is 0.001 N / cm or more, unintentional peeling of the protective film from the heat-resistant polymer film can be prevented in the early stages of using the heat-resistant polymer film (e.g., during transport).

[0130] In this invention, preferably, the change rate of F2 before and after the heat treatment (heat treatment at 120°C for 10 minutes) is 50% or less. From the perspective of preventing the protective film from peeling off during the laminate manufacturing process, or from causing contamination of the heat-resistant polymer film due to changes (deterioration) in the adhesive of the protective film caused by heat, it is more preferably 40% or less, and even more preferably 30% or less. The lower limit is not particularly limited, but is preferably -20% or more, more preferably -10% or more, and even more preferably -5% or more. The change rate of F2 can be calculated using the following formula.

[0131] The rate of change of F2 (%) = (F2 after heat treatment - F2 before heat treatment) / F2 before heat treatment × 100

[0132] Preferably, before the heat treatment (heating at 120°C for 10 minutes), F2 also satisfies the relationship F1>F2. By satisfying the above relationship, even if the heating of the laminate is omitted, the protective film can be easily peeled off without separating the inorganic substrate from the polymer film.

[0133] F3 is not particularly limited as long as it satisfies the value of formula (1) above, but is preferably 0.1 N / cm or more, more preferably 0.15 N / cm or more, and even more preferably 0.18 N / cm or more. Furthermore, the upper limit is not particularly limited, but is preferably 15 N / cm or less, more preferably 13 N / cm or less. With F3 within the above range, the protective film can be appropriately peeled off without causing the inorganic substrate to separate from the heat-resistant polymer film.

[0134] The ratio of F1 to F2 (F1 / F2) must be greater than 1, preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. Furthermore, it is preferably 100 or less, more preferably 80 or less, and even more preferably 60 or less.

[0135] The ratio of F3 to F1 (F3 / F1) must be greater than 1, preferably 1.1 or more, more preferably 1.3 or more, and even more preferably 1.4 or more. Furthermore, it is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less.

[0136] <Manufacturing Method of Laminated Materials>

[0137] Figure 2 This is a schematic cross-sectional view of the laminated body according to this embodiment. Figure 2 (a) is an example in which the adhesive layer 15 of the protective film peel-off aid is laminated on a portion of the substrate 16 of the protective film peel-off aid (the adhesive layer 15 exists only in the overlapping portion of the substrate 16 and the protective film 13). Figure 2 (b) is an example of the adhesive layer 15 of the protective film peeling aid tape being laminated on the substrate 16 of the protective film peeling aid tape. Figure 2 (c) is an example in which the adhesive layer 15 of the protective film peeling aid is laminated on the front of the substrate 16 of the protective film peeling aid, and the adhesive layer cover film 17 of the protective film peeling aid is attached to the portion other than the overlap with the protective film 13.

[0138] like Figure 2 As shown, the laminate of this embodiment includes a protective film release aid 11, a protective film 13, a heat-resistant polymer film 14, and an inorganic substrate 12. The inorganic substrate 12 and the heat-resistant polymer film 14 are laminated in contact, or laminated only with a silane coupling agent layer (not shown) as a barrier. The protective film release aid 11 is formed by an adhesive layer 15 and a substrate 16 of the protective film release aid 11.

[0139] The laminate in this embodiment can be fabricated, for example, in the following order.

[0140] First, a heat-resistant polymer film with a protective film and an inorganic substrate are prepared. When using a heat-resistant polymer film with protective films on both sides, a heat-resistant polymer film with a single-sided protective film can be obtained by peeling off the protective film from the surface of the heat-resistant polymer film to which it is attached to the inorganic substrate. When a silane coupling agent layer is provided in the laminate, at least one surface of the inorganic substrate is pre-treated with the silane coupling agent.

[0141] Next, one surface of the inorganic substrate (the surface treated with silane coupling agent when the silane coupling agent layer is applied) is overlapped with a heat-resistant polymer film with a protective film, and both are pressurized and heated. This yields a heat-resistant polymer film / inorganic substrate laminate with a protective film (laminate). It should be noted that if the surface of the heat-resistant polymer film without the protective film is pre-treated with a silane coupling agent, and this silane-coated surface is overlapped with the inorganic substrate, and then laminated by pressurization and heating, a heat-resistant polymer film / inorganic substrate laminate with a protective film (laminate) can also be obtained. By attaching a protective film release aid to the surface of the protective film of the obtained heat-resistant polymer film / inorganic substrate with a protective film (laminate), a heat-resistant polymer film / inorganic substrate with a protective film and a release aid is obtained (laminate).

[0142] As a method for treating silane coupling agents, known methods such as spin coating, spray coating, and dip coating can be used. Alternatively, the treatment can be performed by vaporizing the silane coupling agent vapor generated by heating the silane coupling agent onto an inorganic substrate (vapor phase vapor deposition method).

[0143] Figure 3 This is a schematic diagram illustrating an example of a silane coupling agent treatment apparatus used in vapor deposition.

[0144] like Figure 3 As shown, the silane coupling agent processing apparatus includes a processing chamber (cavity) 36 connected to a gas inlet 32, an exhaust port 38, and a chemical liquid tank (silane coupling agent tank) 33. The chemical liquid tank (silane coupling agent tank) 33 is filled with silane coupling agent, and its temperature is regulated by a warm water bath 34 equipped with a heater 35. A gas inlet 39 is connected to the chemical liquid tank (silane coupling agent tank) 33, allowing gas to be introduced from the outside. The gas flow rate is regulated by a flow meter 31 connected to the gas inlet 39. When gas is introduced from the gas inlet 39, the vaporized silane coupling agent in the chemical liquid tank 33 is extruded into the processing chamber 36 and adheres to a substrate 37 (inorganic substrate or heat-resistant polymer film) disposed within the processing chamber 36, forming a silane coupling agent layer.

[0145] As a method of pressurization, examples include ordinary pressurization or lamination in the atmosphere, or pressurization or lamination in a vacuum. However, for large-sized laminates (e.g., greater than 200 mm), atmospheric lamination is preferred to obtain overall stable peel strength. Conversely, for small-sized laminates of around 200 mm or less, pressurization in a vacuum is preferred. Regarding the vacuum level, a vacuum obtained by a conventional oil rotary pump is sufficient, as long as it is below 10 Torr. A preferred pressure is 1 MPa to 20 MPa, more preferably 3 MPa to 10 MPa. High pressure may damage the substrate, while low pressure may sometimes result in incomplete adhesion. A preferred temperature is 90°C to 300°C, more preferably 100°C to 250°C. High temperatures may sometimes damage the heat-resistant polymer film, while low temperatures may sometimes result in weak adhesion.

[0146] The shape of the laminate is not particularly limited and can be square or rectangular. A rectangle is preferred, with the longest side preferably 300 mm or more, more preferably 500 mm or more, and even more preferably 1000 mm or more. There is no particular upper limit; industrially, 20,000 mm or less is sufficient, and 10,000 mm or less is also acceptable. Furthermore, the diameter of the outer circle of the inorganic substrate is preferably 310 mm or more. Regarding the laminate of the present invention, from the perspective that even large laminates can be bundled, stored, and transported in groups, 350 mm or more is more preferred, and 400 mm or more is even more preferred. Industrially, 30,000 mm or less is sufficient, and 20,000 mm or less is also acceptable.

[0147] <Adhesive>

[0148] Preferably, there is no adhesive layer substantially separating the inorganic substrate and the heat-resistant polymer film layer of the present invention. Here, the adhesive layer referred to in the present invention means a bonding base layer in which the Si (silicon) content is less than 10% (less than 10% by mass). Furthermore, "substantially not used" (not separated) means that the thickness of the adhesive layer between the inorganic substrate and the polymer film layer is preferably 0.4 μm or less, more preferably 0.3 μm or less, further preferably 0.2 μm or less, particularly preferably 0.1 μm or less, and most preferably 0 μm.

[0149] The timing of attaching the release tape to the heat-resistant polymer film / inorganic substrate laminate (laminate precursor) with protective film can be immediately after the heat-resistant polymer film with protective film is bonded to the inorganic substrate, or it can be after heating the heat-resistant polymer film / inorganic substrate laminate with protective film.

[0150] Example

[0151] The present invention will be described in more detail below with examples, but the present invention is not limited to the following examples. The methods for evaluating physical properties in the following examples are described below.

[0152] <Heat-resistant polymer film A1>

[0153] The heat-resistant polymer film A1 uses Xenomax (registered trademark) F15LR2 (a polyimide film manufactured by Toyobo Co., Ltd., with a thickness of 15μm).

[0154] <Heat-resistant polymer film A2>

[0155] In a reaction vessel equipped with a nitrogen inlet tube, Dean-Stark tube, reflux tube, thermometer, and stir bar, nitrogen gas was introduced while 19.86 parts by mass of 4,4'-diaminodiphenyl sulfone (4,4'-DDS), 4.97 parts by mass of 3,3'-diaminodiphenyl sulfone (3,3'-DDS), and 80 parts by mass of γ-butyrolactone (GBL) were added. Subsequently, 31.02 parts by mass of 4,4'-oxydiphthalic dianhydride (ODPA), 24 parts by mass of GBL, and 13 parts by mass of toluene were added at room temperature. The mixture was then heated to an internal temperature of 160°C and refluxed at 160°C for 1 hour to induce imidization. After imidization, the temperature was raised to 180°C, and the reaction continued while toluene was removed. After reacting for 12 hours, the oil bath was removed, the mixture was allowed to return to room temperature, and GBL was added to make the solid component a concentration of 20% by mass, resulting in a polyimide solution A1 with a specific viscosity of 0.70 dl / g.

[0156] Using a comma coating machine, the obtained polyimide solution A1 was coated onto the unlubricated surface of a polyethylene terephthalate film A4100 (a support manufactured by Toyobo Co., Ltd.), and the thickness was adjusted to a final film thickness of 25 μm. The polyethylene terephthalate film A4100 was then wound in a hot air oven and dried at 100°C for 10 minutes. The dried, self-supporting polyimide film was peeled from the support and fixed by inserting the film ends into the pin bars of a pin tenter equipped with pin sheets. The pin sheet spacing was adjusted to prevent the film from breaking or becoming unnecessarily loose. The film was then transported and heated at 200°C for 3 minutes, 250°C for 3 minutes, and 300°C for 6 minutes to carry out the imidization reaction. Then, after cooling to room temperature for 2 minutes, the poorly flat sections at both ends of the film are cut off using a film slitting machine and rolled into a roll. A 500m long polyimide film A2 with a width of 450mm is obtained.

[0157] <Heat-resistant polymer film A3>

[0158] After purging the reaction vessel, which is equipped with a nitrogen inlet pipe, a reflux pipe, and a stir bar, 33.36 parts by weight of 2,2'-bis(trifluoromethyl)diaminobiphenyl (TFMB), 270.37 parts by weight of N-methyl-2-pyrrolidone (NMP), and a dispersion ("Snowtex (registered trademark) DMAC-ST") made by dispersing colloidal silica in dimethylacetamide were added and completely dissolved so that the silica accounted for 0.14% by weight of the total polymer solids in the polyamic acid solution. Then, 9.81 parts by weight of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 11.34 parts by weight of 3,3',4,4'-biphenyltetracarboxylic acid (BPDA), and 4.85 parts by weight of 4,4'-oxydiphthalic dianhydride (ODPA) were added directly in batches in solid form, and the mixture was stirred at room temperature for 24 hours. Then, 165.7 parts by mass of DMAc were added for dilution to obtain a polyamic acid solution B1 with 18% by mass of solids and a specific viscosity of 2.7 dl / g (molar ratio of TFMB / / CBDA / BPDA / ODPA = 1.00 / / 0.48 / 0.37 / 0.15).

[0159] Using a comma coating machine, the obtained polyamic acid solution B1 was coated onto the unlubricated surface of a polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) to achieve a final film thickness of 25 μm. It was then dried at 110°C for 10 minutes. The dried, self-supporting polyamic acid film was peeled off from the A4100 film, which served as the support. The film ends were inserted into the needle bars to secure it using a needle-type tenter frame equipped with needle plates and needle bars. The needle plate spacing was adjusted to prevent the film from breaking or becoming unnecessarily loose. The film was then transported and heated at 200°C for 3 minutes, 250°C for 3 minutes, 300°C for 3 minutes, and 350°C for 3 minutes to induce an imidization reaction. After cooling to room temperature for 2 minutes, the poorly planar portions at both ends of the film were cut off using a film slitting machine, and the film was rolled into a roll. A 500 μm polyimide film A3 with a width of 450 mm was obtained.

[0160] <Protective Film PF1>

[0161] The following mixtures are used to obtain adhesive composition C1.

[0162] Linear polyorganosiloxane with vinyl groups only at both ends (solvent-free, Mw: 80,000): 68.30 parts by weight

[0163] Organohydrogen polysiloxane (solvent-free, Mw: 2,000): 0.41 parts by weight

[0164] Platinum catalyst (Shin-Etsu Chemical Industry Co., Ltd., PL-56): 1.00 parts by weight

[0165] Ultraviolet absorber (Cyasorb UV-3638 (manufactured by CYTEC)): 0.3 parts by weight

[0166] Reaction control agent (3-methyl-1-butyn-3-ol): 0.10 parts by weight

[0167] Toluene: 30.19 parts by weight

[0168] A polyethylene terephthalate (PET) film (A4100, 50 μm thickness) manufactured by Toyobo Co., Ltd. was subjected to corona treatment as a substrate treatment. Immediately after corona treatment, an adhesive composition C1 was coated onto the PET film. Coating was carried out to achieve a dried thickness of 10 μm at 25°C and 85% RH. Then, the film was heated in an oven at 150°C for 100 seconds to crosslink the adhesive layer, thus obtaining a protective film PF1.

[0169] <Protective film PF2>

[0170] In a separable flask, 55.3 parts by weight of a trifunctional polyol (SANNIX GL3000, manufactured by Sanyo Chemical Industry Co., Ltd., obtained by addition polymerization of propylene oxide and ethylene oxide with glycerol), 4.7 parts by weight of Durnate D101 (polyisocyanate manufactured by Asahi Kasei Chemicals Co., Ltd.), 39.7 parts by weight of toluene, and 0.02 parts by weight of dibutyltin dilaurate (DBTDL) were added. The mixture was heated at 45°C to 55°C for 2 hours with stirring to allow the reaction to proceed. After 2 hours from the start of heating, the mixture was cooled to below 40°C. After cooling, 0.28 parts by weight of an antioxidant were added, and the mixture was stirred until homogeneous to obtain composition 1 containing polyurethane polyol. To 100 parts by weight of composition 1 containing polyurethane polyol, 7.7 parts by weight of Durnate D101, 2 parts by weight of ultraviolet absorber (CyasorbUV-3638 (manufactured by CYTEC)), and 50 parts by weight of ethyl acetate were mixed and stirred thoroughly. The resulting adhesive composition was filtered through a PTFE cartridge filter (0.45 μm) to obtain adhesive composition C2.

[0171] The adhesive composition C2 was coated onto a polyethylene terephthalate (PET) film (A4100) manufactured by Toyobo Co., Ltd., which had been pre-treated with corona to achieve an adhesive film thickness of 10 μm upon drying. Then, it was heated and dried at 130°C for 2 minutes, and further cured (crosslinked) in a constant temperature bath at 40°C for 3 days to produce the protective film PF2.

[0172] <Protective Film PF3>

[0173] To obtain adhesive composition C3, 1.5 parts by weight of Coronate HX (manufactured by Tosoh Corporation, a polyisocyanate for coatings) as a polyfunctional isocyanate and 0.3 parts by weight of KP-341 (trade name, manufactured by Shin-Etsu Chemical Industry, a polyether-modified organosiloxane) as a modified organosiloxane were added to 100 parts by weight of an acrylic polymer (copolymer of 2-ethylhexyl acrylate and 4-hydroxybutyl acrylate (copolymer ratio 100:8), weight average molecular weight: 200,000).

[0174] The obtained adhesive composition C3 was coated onto a polyethylene terephthalate (PET) film (A4100) manufactured by Toyobo Co., Ltd., which had been pre-treated with corona, and dried at 100°C to remove the solvent, resulting in a surface protective film PF3 with an adhesive layer of 10 μm thickness formed on the PET film.

[0175] <Protective film PF4>

[0176] While stirring 100 parts by weight of polyurethane solvent-based adhesive US-902-50, 5.4 parts by weight of crosslinking agent N (manufactured by Lion Special Chemicals Co., Ltd.), 2 parts by weight of ultraviolet absorber (Cyasorb UV-3638 (manufactured by CYTEC)) were added to a solution containing ethyl acetate solvent (manufactured by Lion Special Chemicals Co., Ltd.), and the mixture was reacted at 40°C for 20 minutes. The resulting solution was filtered through a PTFE cartridge filter (0.45 μm), and then coated onto a pre-corona-treated polyethylene terephthalate (PET) film (A4100) manufactured by Toyobo Co., Ltd., to achieve a final film thickness of 10 μm. The film was then heated at 100°C for 2 minutes to obtain a protective film PF4.

[0177] <Protective Film PF5>

[0178] The protective film PF5 uses TORETEC (registered trademark) 7832C from Toray Film Processing Co., Ltd.

[0179] <Protective Film PF6>

[0180] The following mixtures are combined to obtain an adhesive composition.

[0181] Linear polyorganosiloxane with vinyl groups only at both ends (solvent-free, Mw: 80,000): 68.30 parts by weight

[0182] Organohydrogen polysiloxane (solvent-free, Mw: 2,000): 0.41 parts by weight

[0183] Platinum catalyst (Shin-Etsu Chemical Industry Co., Ltd., PL-56): 1.00 parts by weight

[0184] Reaction control agent (3-methyl-1-butyn-3-ol): 0.10 parts by weight

[0185] Toluene: 30.19 parts by weight

[0186] COSMOSHINE SRF (registered trademark, TA044, 80μm) manufactured by Toyobo Co., Ltd. was corona-treated as a substrate, and the adhesive composition was applied immediately after corona treatment. A raised portion was formed to achieve a dry thickness of 10μm, and the coating was performed at 25°C and 85% RH. Then, the substrate was crosslinked by heating in an oven at 150°C for 100 seconds to obtain the adhesive layer. Through the above process, a protective film PF6 was obtained.

[0187] <Protective Film PF7>

[0188] Except for using ESTEL (registered trademark) film (HB3, 50μm) manufactured by Toyobo Co., Ltd. as the substrate, it is made in the same way as the protective film PF6.

[0189] <Protective film peeling aid belt S1>

[0190] SunA.Kaken Co., Ltd.'s SUNYTECT (registered trademark) SAT type film is cut to a length of 300mm x a width of 150mm. By laminating a 300mm x 50mm length polyethylene terephthalate (PET) film (12μm, E5100) manufactured by Toyobo Co., Ltd. to the adhesive surface, a protective film peeling aid S1 is obtained with the adhesive surface exposed at a length of 300mm x a width of 100mm.

[0191] <Protective film peeling aid belt S2>

[0192] PF1 is cut into 300mm long x 150mm wide sections. By laminating a 300mm long x 50mm wide polyethylene terephthalate (PET) film (12μm, E5100) manufactured by Toyobo Co., Ltd. to the adhesive surface, a protective film peeling aid S2 with a length of 300mm x width of 100mm exposed on the adhesive surface is obtained.

[0193] <Protective film peeling aid belt S3>

[0194] Except for replacing PF1 with PF2, the process is the same as in S2, resulting in the protective film peeling aid belt S3.

[0195] <Protective film peeling aid belt S4>

[0196] Except for replacing PF1 with PF3, the process is the same as in S2, resulting in the protective film peeling aid belt S4.

[0197] <Creating Layered Objects>

[0198] (Example 1)

[0199] First, a glass substrate is prepared as the inorganic substrate. The glass substrate is OA10G glass (manufactured by NEG Corporation) cut to 500mm x 500mm dimensions and 0.7mm thick. The glass substrate is prepared by washing with pure water, drying, irradiating with a UV / O3 irradiator (SKR1102N-03 manufactured by LAN Technical) for 1 minute, and then washing again. Next, a silane coupling agent (SCA) is coated onto the glass substrate using a vapor phase coating method to form a silane coupling agent layer, resulting in the first layer stack. Specifically, the silane coupling agent is applied to the glass substrate using... Figure 3 The experimental setup shown is used. Figure 3 This is a schematic diagram of the experimental apparatus for coating a silane coupling agent onto a glass substrate. 130g of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM-903) was added to a 1L chemical liquid container, and the water bath outside the container was heated to 42°C. Then, the generated vapor was introduced into the chamber along with clean, dry air. The gas flow rate was set to 22L / min, and the substrate temperature was set to 21°C. The clean, dry air temperature was 23°C and 1.2% RH. Since the exhaust was connected to a negative pressure exhaust port, a differential pressure gauge confirmed that the chamber had a negative pressure of approximately 2Pa.

[0200] First, PF1 is attached to both sides of the polyimide film A1, and it is cut to a size of 300mm × 300mm. The protective film on the side that will be bonded to the support (glass substrate) is peeled off. PF1 is attached to the bonding surface with the glass substrate to prevent damage and foreign matter adhesion during the cutting process. The silane coupling agent layer of the glass substrate, after treatment with the silane coupling agent, is then bonded to the heat-resistant polymer film surface of the heat-resistant polymer film with the protective film attached, resulting in a laminate consisting of the glass substrate, the silane coupling agent layer, the heat-resistant polymer film, and the protective film stacked sequentially. During bonding, a laminator (MCK Corporation, MRK-1000) is used, and the bonding conditions are set as follows: air pressure: 0.7MPa, temperature: 22℃, humidity: 55%RH, lamination speed: 50mm / second.

[0201] Using an oven, heat the resulting heat-resistant polymer film / glass substrate laminate with a protective film at 120°C for 10 minutes in atmospheric conditions. Figure 1 As shown in (b), a release aid tape is attached to the obtained laminate precursor to obtain a laminate of release aid tape / protective film / heat resistant polymer film / glass substrate.

[0202] For Examples 2-9 and Comparative Examples 1-3, samples were prepared in the same manner by changing the combination of the heat-resistant polymer film, protective film, and release retrieval tape used. The combinations are shown in Table 1.

[0203] [Table 1]

[0204]

[0205] <90° peel strength>

[0206] The 90° peel strength of each layer of the laminate obtained as described above was measured under the following conditions.

[0207] The inorganic substrate / heat-resistant polymer film and the heat-resistant polymer film / protective film were peeled off after being heated at 120°C for 10 minutes, while the heat-resistant polymer film / protective film (before heating) and the protective film / protective film peeling aid tape were peeled off without heating. When it was impossible to peel off only the target layer, the underlying layer was securely fixed with adhesive tape for measurement. The results are shown in Table 1.

[0208] Measuring device: Autograph AG-IS manufactured by Shimadzu Corporation

[0209] Measurement temperature: room temperature (25℃)

[0210] Peeling speed: 100mm / min

[0211] Atmosphere: Grand

[0212] Sample width measured: 5cm

[0213] Five measurements were performed, and the average value was taken as the measured value.

[0214] The case that satisfies F3>F1>F2(1) is marked as ○, and the case that does not satisfy F3>F1>F2(1) is marked as ×.

[0215] Can the protective film be peeled off?

[0216] Using double-sided adhesive tape, secure the release retrieval aid / protective film / heat-resistant polymer film / glass substrate laminate to the worktable. Grasp the release retrieval aid and peel at approximately 180°. Record instances where the protective film can be peeled from the heat-resistant polymer film without separating it from the glass substrate as ○, and instances where the heat-resistant polymer film peels off from the glass or only the protective film peels off the release retrieval aid as ×. Evaluate the results. The results are shown in Table 1.

[0217] <Protective film's 50% UV cutoff wavelength>

[0218] UV transmittance was measured for protective films PF1 to 7. Specifically, a Shimadzu UV-3150 micrometer was used to measure UV transmittance via a transmission method. The wavelength at which 50% transmittance was achieved was defined as the 50% cutoff wavelength for ultraviolet light. The results are shown in Table 1.

[0219] <Wa of the adhesion surface between the protective film and the heat-resistant polymer film>

[0220] The surface shape of the adhesive surface between the protective film and the heat-resistant polymer film was measured at 5x magnification using a VS1800 scanning white microscope manufactured by Hitachi High Technology Co., Ltd. The measurement was performed using a film from which the protective film was peeled off at a 90° angle at a speed of 100 mm / min and allowed to stand for 5 minutes. The measured range was 1404 μm in the x-direction and 1872 μm in the y-direction. With the cutoff value set at 20 μm, the arithmetic mean waviness Wa was obtained using the waviness resolution function.

[0221] Laser cutting quality of heat-resistant polymer films with protective coatings.

[0222] Each heat-resistant polymer film with a protective film was irradiated with ultraviolet laser from the protective film side to achieve a size of 100mm × 100mm. The ultraviolet laser irradiation was performed without peeling the protective film from the heat-resistant polymer film. The ultraviolet laser used was a 355nm pulsed laser manufactured by Takei Electric. The same area was scanned three times at a power of 8.5W, a pulse frequency of 1000kHz, and a scanning speed of 500mm / second. Based on this, the first protective film and the polyimide film were cut into 100mm × 100mm sizes.

[0223] For the cut heat-resistant polymer film with a protective coating, the laser-cut end was observed under a microscope, and the width of the black powdery substance (smear) from the end was measured. Smear widths less than 300 μm were rated as ○, widths greater than 300 μm but less than 500 μm were rated as △, and widths greater than 500 μm were rated as ×. The results are shown in Table 1.

[0224] Industrial availability

[0225] As described above, the laminate of the present invention (inorganic substrate / heat-resistant polymer film / protective film / protective film peeling aid laminate) can be operated while protecting the surface of the heat-resistant polymer film using the protective film, and the protective film can be peeled off without any problems while processing the surface of the heat-resistant polymer film. The present invention can be usefully used in the manufacture of flexible devices, etc., based on such a laminate, where the polymer film is micro-processed and then peeled off from the inorganic substrate. In particular, it can be effectively used in applications where automation of protective film peeling is necessary and where the laminate size is large.

Claims

1. A laminated body, characterized in that, In order, they include: Inorganic substrate, heat-resistant polymer film, protective film, protective film peeling aid tape, The arithmetic mean waviness Wa of the surface of the protective film in contact with the heat-resistant polymer film is less than 30 nm. The adhesion strength F1 between the inorganic substrate and the heat-resistant polymer film according to the 90-degree peel method, the adhesion strength F2 between the heat-resistant polymer film and the protective film according to the 90-degree peel method, and the adhesion strength F3 between the protective film and the protective film peeling aid tape according to the 90-degree peel method satisfy the following relationship: F3>F1>F2 (1).

2. The laminated body according to claim 1, characterized in that, The protective film has an ultraviolet 50% cutoff wavelength of 240nm or higher.

3. The laminate according to claim 1 or 2, characterized in that, The rate of change of F2 in the laminate before and after heating at 120°C for 10 minutes is less than 50%.

4. The laminate according to claim 1 or 2, characterized in that, The area B1 of the protective film and the area B2 of the protective film peeling aid strip satisfy the relationship B1>B2.

5. The laminate according to claim 1 or 2, wherein, The arithmetic mean waviness Wa of the surface of the protective film in contact with the heat-resistant polymer film is above 5 nm and below 28 nm.

6. The laminate according to claim 1 or 2, characterized in that, The heat-resistant polymer film comprises at least one selected from the group consisting of polyimide, polyamide, and polyamide-imide.

7. The laminate according to claim 1 or 2, characterized in that, The heat-resistant polymer film is a transparent polyimide.

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