WO2023058408A1 - Stratifié équipé d'une bande d'aide au décollement de film protecteur - Google Patents

Stratifié équipé d'une bande d'aide au décollement de film protecteur Download PDF

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WO2023058408A1
WO2023058408A1 PCT/JP2022/033910 JP2022033910W WO2023058408A1 WO 2023058408 A1 WO2023058408 A1 WO 2023058408A1 JP 2022033910 W JP2022033910 W JP 2022033910W WO 2023058408 A1 WO2023058408 A1 WO 2023058408A1
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film
protective film
heat
polymer film
resistant polymer
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PCT/JP2022/033910
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English (en)
Japanese (ja)
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桂也 ▲徳▼田
哲雄 奥山
郷司 前田
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東洋紡株式会社
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Priority to JP2023552767A priority Critical patent/JPWO2023058408A1/ja
Priority to KR1020247011507A priority patent/KR20240087804A/ko
Priority to CN202280067438.4A priority patent/CN118076482A/zh
Publication of WO2023058408A1 publication Critical patent/WO2023058408A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a laminate of an inorganic substrate, a polymer film layer with a protective film, and a protective film peeling auxiliary tape.
  • a rigid inorganic substrate such as a glass substrate is used as a temporary support, and a polymer film is temporarily attached to the temporary support.
  • a flexible electronic device manufacturing method is known in which the polymer film is subjected to electronic device processing, and then the polymer film having the electronic device formed thereon is peeled off from the temporary support.
  • a rigid substrate such as a glass substrate is used as a temporary support
  • a polymer solution or a polymer precursor solution is applied to the temporary support, and dried.
  • a chemical reaction is caused to convert the precursor into a polymer film, thereby obtaining a laminate of the temporary support and the polymer film, and similarly forming an electronic device on the polymer film.
  • Patent Document 2 Patent Document 2
  • the laminate is often exposed to high temperatures.
  • formation of functional elements such as polysilicon and oxide semiconductors requires a process in a temperature range of about 200.degree. C. to 600.degree.
  • a temperature of about 200 to 300° C. may be applied to the film, and in order to heat and dehydrogenate the amorphous silicon to form low-temperature polysilicon, it is about 450 to 600° C. heating may be required. Therefore, the polymer film constituting the laminate is required to have heat resistance, but as a matter of fact, there are only a limited number of polymer films that can withstand such a high temperature range, and in many cases, polyimide is selected.
  • a laminate in the form of a rigid temporary support and a polymer film layer that will eventually be peeled off and become the base material of a flexible electronic device will be superimposed. Since such a laminate can be handled as a rigid plate material, it can be handled in the same manner as a glass substrate in an apparatus for manufacturing liquid crystal displays, plasma displays, organic EL displays, etc. using conventional glass substrates.
  • a method commonly used as a means of solving such problems is to protect the surface of the heat-resistant polymer film with a protective film.
  • the protective film is a slightly adhesive film obtained by applying a weakly adhesive adhesive to one side of a relatively inexpensive polymer film such as polyethylene, polypropylene, or polyester.
  • a resin film having self-adsorptive properties such as polyolefin resin may be used.
  • the surface of the polymer film can be prevented from being damaged, and the surface of the polymer film suitable for forming fine flexible electronic devices can be maintained.
  • the protective film when the protective film is peeled off from the laminate of the heat-resistant polymer film with the protective film and the inorganic substrate (hereinafter also simply referred to as the laminate), the inorganic substrate and the heat-resistant polymer film are peeled off.
  • the laminate of the inorganic substrate and the heat-resistant polymer film of the present invention is laminated with a weak adhesive force so that it can be finally peeled off after the device is produced on the surface of the heat-resistant polymer film.
  • the protective film when peeling the protective film from the sheet laminate, the protective film often lifts up at the peeling start edge of the protective film.
  • the adhesive strength between the heat-resistant polymer film and the protective film is lower than the adhesive strength between the inorganic substrate and the heat-resistant polymer film. It was found that it is difficult to peel off only the protective film when the thickness is 1/3 or more.
  • the problem to be solved by the present invention is to obtain a protective film and a heat-resistant polymer film without peeling the heat-resistant polymer film and the inorganic substrate from the laminate of the heat-resistant polymer film with the protective film and the inorganic substrate (rigid temporary support).
  • the present invention includes the following configurations.
  • a laminate with a protective film peeling auxiliary tape containing an inorganic substrate, a heat-resistant polymer film, a protective film, and a protective film peeling auxiliary tape in this order The radius of the circumscribed circle of the inorganic substrate is 330 mm or more, the inorganic substrate, the heat-resistant polymer film and the protective film are rectangular,
  • the protective film peeling auxiliary tape includes an adhesive layer and a base layer, Adhesion strength F1 between the inorganic substrate and the heat-resistant polymer film by a 90-degree peeling method; Adhesive strength F2 between the heat-resistant polymer film and the protective film by a 90-degree peeling method;
  • the adhesive strength F3 between the protective film and the protective film peeling auxiliary tape by the 90 degree peeling method is F3>F2 (1) F1>0.08N/cm (2) F2 ⁇ 0.2N/cm (3) is in the relationship of At least one side of the laminate with the protective film peeling auxiliary tape,
  • the adhesive strength (peel strength) between the heat-resistant polymer film and the protective film is 1/3 or more that of the inorganic substrate and the heat-resistant polymer film. Then, it is difficult to peel only the protective film. In particular, when the adhesion strength between the inorganic substrate and the heat-resistant polymer film is low, the inorganic substrate and the polymer film are easily peeled off when the edge of the protective film is lifted.
  • the size of the laminate is small, it is not a big problem because the peeling edge can be manually made using a protective film peeling tape, or only the edge of the protective film can be peeled off with a jig such as tweezers. Assuming that it will be handled in the air, the size of the laminate of the inorganic substrate and the heat-resistant polymer film will be about 2 ⁇ 3 m at maximum. For laminates of this size, it is assumed that the protective film will be peeled off by machine. It is difficult to exfoliate only. By adopting the configuration of the present invention, such problems can be avoided, and the laminate of the present invention can be manually or automatically peeled off only the protective film without peeling off the inorganic substrate and the heat-resistant polymer film. can.
  • FIGS. 1(a) to 1(e) are schematic diagrams of a laminate with a protective film peeling auxiliary tape according to the present invention.
  • FIG. 2(a) is a schematic diagram showing the sticking position in the laminate with the protective film peeling auxiliary tape in the present invention.
  • FIG.2(b) is a cross-sectional schematic diagram of the laminated body with a protective film peeling auxiliary tape in this invention.
  • FIG.2(c) is a schematic diagram showing another attachment position in the laminated body with the protective film peeling auxiliary tape in this invention.
  • FIG. 3 is a schematic diagram of an apparatus for measuring springback in the present invention.
  • FIG. 1(a) to 1(e) are schematic diagrams of a laminate with a protective film peeling auxiliary tape according to the present invention.
  • FIG. 2(a) is a schematic diagram showing the sticking position in the laminate with the protective film peeling auxiliary tape in the present invention.
  • FIG.2(b) is a cross-sectional schematic diagram of the laminate
  • FIG. 4 is a schematic diagram showing an angle ⁇ formed by the protective film and the heat-resistant polymer film at 10 mm from the start of peeling when the protective film is peeled from the heat-resistant polymer film in the present invention.
  • FIG. 5 is a schematic diagram schematically showing an example of a silane coupling agent treatment apparatus used in the vapor deposition method of the present invention.
  • the heat-resistant polymer film of the present invention includes polyimide-based resins such as polyimide, polyamideimide, polyetherimide, and fluorinated polyimide (eg, aromatic polyimide resin, alicyclic polyimide resin).
  • polyimide-based resins such as polyimide, polyamideimide, polyetherimide, and fluorinated polyimide (eg, aromatic polyimide resin, alicyclic polyimide resin).
  • Copolyesters such as polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate (e.g., wholly aromatic polyesters and semi-aromatic polyesters); Copolymerized (meth)acrylates typified by polymethyl methacrylate cellulose acetate; cellulose nitrate; aromatic polyamide; polyvinyl chloride; polyphenol; polyarylate; polyphenylene sulfide; However, since it is assumed that the polymer film is used in a process involving heat treatment at 300° C. or higher, the examples of polymer films that can be actually applied are limited.
  • the heat-resistant polymer film preferably contains at least one selected from the group consisting of polyimide, polyamide, and polyamideimide.
  • a polyimide resin film is prepared by applying a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent to a support for producing a polyimide film and drying it to form a green film (hereinafter referred to as (also referred to as "polyamic acid film”), and further subjecting the green film to a high-temperature heat treatment on a polyimide film-producing support or in a state in which the green film is peeled off from the support to cause a dehydration ring-closing reaction.
  • a polyamic acid polyimide precursor
  • polyamic acid (polyimide precursor) solution includes, for example, spin coating, doctor blade, applicator, comma coater, screen printing method, slit coating, reverse coating, dip coating, curtain coating, slit die coating, etc.
  • spin coating doctor blade, applicator, comma coater, screen printing method, slit coating, reverse coating, dip coating, curtain coating, slit die coating, etc.
  • application of conventionally known solutions. means can be used as appropriate.
  • the diamines that make up the polyamic acid are not particularly limited, and aromatic diamines, aliphatic diamines, alicyclic diamines, etc. that are commonly used in polyimide synthesis can be used. From the viewpoint of heat resistance, aromatic diamines are preferred. Diamines may be used alone or in combination of two or more.
  • the diamines are not particularly limited, and examples thereof include oxydianiline (bis(4-aminophenyl) ether) and paraphenylenediamine (1,4-phenylenediamine).
  • the tetracarboxylic acids constituting the polyamic acid include aromatic tetracarboxylic acids (including their acid anhydrides), aliphatic tetracarboxylic acids (including their acid anhydrides), and alicyclic tetracarboxylic acids, which are commonly used in polyimide synthesis. Acids (including anhydrides thereof) can be used. When these are acid anhydrides, one or two anhydride structures may be present in the molecule, but preferably those having two anhydride structures (dianhydrides) are good. Tetracarboxylic acids may be used alone, or two or more of them may be used in combination.
  • the tetracarboxylic acid is not particularly limited and includes, for example, pyrrolimethic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride.
  • the polyimide film may be a transparent polyimide film.
  • a colorless transparent polyimide which is an example of the polymer film, will be described. In order to avoid complication, it is simply referred to as transparent polyimide.
  • the transparency of the transparent polyimide it is preferable that the total light transmittance is 75% or more. It is more preferably 80% or more, still more preferably 85% or more, even more preferably 87% or more, and particularly preferably 88% or more.
  • the upper limit of the total light transmittance of the transparent polyimide is not particularly limited, it is preferably 98% or less, more preferably 97% or less for use as a flexible electronic device.
  • the colorless transparent polyimide in the present invention is preferably polyimide having a total light transmittance of 75% or more.
  • Aromatic tetracarboxylic acids for obtaining highly colorless and transparent polyimide 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, bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-yl)benzene-1,4 -dicarboxylate, 4,4'-[4,4'-(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl)bis(benzene-1,4-diyloxy)]dibenzene- 1,2-dicarboxylic acid, 4,4′-[(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl)bis(toluene-2,5
  • dianhydrides having two acid anhydride structures are preferred, particularly 4,4′-(2,2-hexafluoroisopropylidene)diphthalic dianhydride, 4,4′-oxydiphthalic Acid dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferred.
  • Aromatic tetracarboxylic acids may be used alone, or two or more of them may be used in combination.
  • the amount of aromatic tetracarboxylic acids to be copolymerized is, for example, preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass of the total tetracarboxylic acids when heat resistance is emphasized. More preferably, it is 70% by mass or more, particularly preferably 80% by mass or more, and particularly preferably 90% by mass or more, and may be 100% by mass.
  • 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′-bicyclohexyltetracarboxylic 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]oct-7-ene-2,3,5,6-tetracarboxylic acid, tetrahydroanthracene -2,3,6,7-tetracarboxylic acid, tetradecahydro-1,4:5,8:9,10-trimethanoanthracene-2,3,
  • dianhydrides having two acid anhydride structures are preferred, particularly 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferred, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic An acid dianhydride is more preferred, and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride is even more preferred. In addition, these may be used independently and may use 2 or more types together.
  • the amount of alicyclic tetracarboxylic acids to be copolymerized is, for example, preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass, based on the total tetracarboxylic acids when emphasis is placed on transparency. % or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass.
  • Tricarboxylic acids include aromatic tricarboxylic acids such as trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, diphenylether-3,3′,4′-tricarboxylic acid, and diphenylsulfone-3,3′,4′-tricarboxylic acid.
  • acids or hydrogenated products of the above aromatic tricarboxylic acids such as hexahydrotrimellitic acid; Glycol bistrimellitate, and their monoanhydrides and esters.
  • monoanhydrides having one acid anhydride structure are preferred, and trimellitic anhydride and hexahydrotrimellitic anhydride are particularly preferred. In addition, these may be used individually and may be used in combination.
  • Dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-oxydibenzenecarboxylic acid, or the above aromatic dicarboxylic acids such as 1,6-cyclohexanedicarboxylic acid.
  • aromatic dicarboxylic acids and hydrogenated products thereof are preferred, and terephthalic acid, 1,6-cyclohexanedicarboxylic acid, and 4,4'-oxydibenzenecarboxylic acid are particularly preferred.
  • dicarboxylic acids may be used alone or in combination.
  • Diamines or isocyanates for obtaining highly colorless and transparent polyimides are not particularly limited, and polyimide synthesis, polyamideimide synthesis, aromatic diamines, aliphatic diamines, and alicyclic diamines commonly used in polyamide synthesis. , aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and the like can be used. From the viewpoint of heat resistance, aromatic diamines are preferred, and from the viewpoint of transparency, alicyclic diamines are preferred. In addition, the use of aromatic diamines having a benzoxazole structure makes it possible to exhibit high heat resistance, high elastic modulus, low thermal shrinkage, and low coefficient of linear expansion. Diamines and isocyanates may be used alone or in combination of two or more.
  • aromatic diamines examples include 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′-ditrifluoromethyl-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,
  • some or all of the hydrogen atoms on the aromatic ring of the aromatic diamine may be substituted with a halogen atom, an alkyl or alkoxyl group having 1 to 3 carbon atoms, or a cyano group, and Some or all of the hydrogen atoms in the alkyl or alkoxyl groups of 1 to 3 may be substituted with halogen atoms.
  • aromatic diamines having a benzoxazole structure are not particularly limited, and examples thereof include 5-amino-2-(p-aminophenyl)benzoxazole, 6-amino-2-(p-aminophenyl)benzoxazole, oxazole, 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-aminobenzoxazolo)-4-(6-aminobenzoxazolo)benzene, 2,6-(4,4′-diamino diphenyl)benzo[1,2-d:5,4-d']bisoxazole, 2,6-(4,4'-diaminodiphenyl)benzo
  • aromatic diamines may be used singly or in combination.
  • Alicyclic diamines include, for example, 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propyl cyclohexane, 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, 4,4'-methylenebis(2,6-dimethylcyclohexylamine) and the like.
  • 1,4-diaminocyclohexane and 1,4-diamino-2-methylcyclohexane are particularly preferred, and 1,4-diaminocyclohexane is more preferred.
  • the alicyclic diamines may be used alone or in combination.
  • Diisocyanates include, for example, 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, 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,
  • Diisocyanates may be used alone or in combination.
  • the polymer film is preferably a polyimide film or a polyamideimide film, more preferably a polyimide film.
  • the polymer film is a polyimide film or a polyamideimide film, it has excellent heat resistance.
  • the polymer film is a polyimide film or a polyamide-imide film, it can be suitably cut with an ultraviolet laser.
  • the thickness of the polymer film is preferably 3 ⁇ m or more, more preferably 7 ⁇ m or more, still more preferably 14 ⁇ m or more, and still more preferably 20 ⁇ m or more.
  • the upper limit of the thickness of the polymer film is not particularly limited, it is preferably 250 ⁇ m or less, more preferably 100 ⁇ m or less, and still more preferably 50 ⁇ m or less for use as a flexible electronic device.
  • the average coefficient of linear expansion (CTE) of the polymer film between 30°C and 250°C is preferably 50 ppm/K or less. It is more preferably 45 ppm/K or less, still more preferably 40 ppm/K or less, even more preferably 30 ppm/K or less, and particularly preferably 20 ppm/K or less. Moreover, it is preferably -5 ppm/K or more, more preferably -3 ppm/K or more, and still more preferably 1 ppm/K or more.
  • CTE is a factor representing reversible expansion and contraction with respect to temperature.
  • 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.
  • yellowness index (hereinafter also referred to as "yellow index” or “YI”) is preferably 10 or less, more preferably 7 or less, and still more preferably 5. or less, and more preferably 3 or less.
  • the lower limit of the yellowness index of the transparent polyimide is not particularly limited, it is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more for use as a flexible electronic device. is.
  • the haze is preferably 1.0 or less, more preferably 0.8 or less, still more preferably 0.5 or less, and still more preferably 0.3 or less.
  • the lower limit is not particularly limited, but industrially, there is no problem if it is 0.01 or more, and it may be 0.05 or more.
  • the heat shrinkage rate of the polymer film between 30°C and 500°C is preferably ⁇ 0.9% or less, more preferably ⁇ 0.6% or less. Thermal shrinkage is a factor representing irreversible expansion and contraction with respect to temperature.
  • the tensile breaking strength of the polymer film is preferably 60 MPa or more, more preferably 80 MPa or more, and still more preferably 100 MPa or more. Although the upper limit of the tensile strength at break is not particularly limited, it is practically less than about 1000 MPa. When the tensile strength at break is 60 MPa or more, it is possible to prevent the polymer film from breaking when peeled from the inorganic substrate.
  • the tensile strength at break of the polymer film refers to the average value of the tensile strength at break in the machine direction (MD direction) and the tensile strength at break in the width direction (TD direction) of the polymer film.
  • the tensile elongation at break of the polymer film is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more. When the tensile elongation at break is 1% or more, the handleability is excellent.
  • the tensile elongation at break of the polymer film refers to the average value of the tensile elongation at break in the machine direction (MD direction) and the tensile elongation at break in the width direction (TD direction) of the polymer film.
  • the tensile modulus of the polymer film is preferably 2.5 GPa or more, more preferably 3 GPa or more, and still more preferably 4 GPa or more.
  • the tensile modulus is preferably 20 GPa or less, more preferably 15 GPa or less, and even more preferably 12 GPa or less.
  • the polymer film can be used as a flexible film.
  • the tensile elastic modulus of the polymer film refers to the average value of the tensile elastic modulus in the machine direction (MD direction) and the tensile elastic modulus in the width direction (TD direction) of the polymer film.
  • the thickness unevenness of the polymer film is preferably 20% or less, more preferably 12% or less, still more preferably 7% or less, and particularly preferably 4% or less. If the thickness unevenness exceeds 20%, it tends to be difficult to apply to narrow areas.
  • the polymer film is rectangular.
  • the length of the long side is preferably 300 mm or longer, more preferably 500 mm or longer, and still more preferably 1000 mm or longer.
  • the upper limit is not particularly limited, industrially, 20,000 mm or less is sufficient, and 10,000 mm or less is acceptable.
  • the radius of the circumscribed circle of the polymer film is preferably 330 mm or more, more preferably 350 mm or more, and still more preferably 400 mm or more. Industrially, 30,000 mm or less is sufficient, and 20,000 mm or less is acceptable.
  • the polymer film is preferably obtained in the form of being wound up as a long polymer film with a width of 300 mm or more and a length of 10 m or more at the time of production. More preferred are those in the form of molecular films. When the polymer film is wound into a roll, it can be easily transported in the form of a rolled polymer film.
  • a lubricant having a particle diameter of about 5 to 1000 nm is added or contained in the polymer film in an amount of about 0.03 to 3% by mass. Therefore, it is preferable to provide the surface of the polymer film with fine irregularities to ensure the slipperiness. Sufficient lubricity can be ensured by setting the particle diameter to 5 nm or more. On the other hand, by setting the particle size to 1000 nm or less, it is possible to ensure an appropriate adhesive strength between the polymer film and the inorganic substrate. Further, by setting the amount of the lubricant to be added to 0.03% by mass or more, sufficient lubricity can be ensured. On the other hand, by setting the amount of the lubricant to be added to 3% by mass or less, it is possible to appropriately secure the adhesive strength between the polymer film and the inorganic substrate.
  • the inorganic substrate of the present invention may be any plate-shaped substrate that can be used as a substrate made of an inorganic substance. , ceramic plates, semiconductor wafers, metal composites, laminates of these, those in which these are dispersed, and those in which these fibers are contained. A rigid substrate is particularly preferred.
  • the inorganic substrate in the present invention may be porous or in the form of a non-woven fabric. For example, it may be a porous ceramic laminated on a glass plate, or a non-woven fabric made of metal fibers. .
  • the inorganic substrate of the present invention is rectangular.
  • the length of the long side is preferably 300 mm or longer, more preferably 500 mm or longer, and still more preferably 1000 mm or longer.
  • the upper limit is not particularly limited, industrially, 20,000 mm or less is sufficient, and 10,000 mm or less is acceptable.
  • the radius of the circumscribed circle of the inorganic substrate must be 330 mm or more. It is preferably 350 mm or more, and more preferably 400 mm or more, because it can be used for display manufacturing equipment. For industrial purposes (display manufacturing equipment), 30,000 mm or less is sufficient, and 20,000 mm or less is acceptable.
  • the glass plate examples include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pyrex (registered trademark)), borosilicate glass (no alkali), Borosilicate glass (microsheet), aluminosilicate glass, etc. are included. Among these, those having a coefficient of linear expansion of 5 ppm/K or less are desirable. "EAGLE”, "AN100” manufactured by Asahi Glass Co., Ltd., “OA10, OA11G” manufactured by Nippon Electric Glass Co., Ltd., and "AF32” manufactured by SCHOTT are desirable.
  • the semiconductor wafer examples include, but are not limited to, silicon wafer, germanium, silicon-germanium, gallium-arsenide, aluminum-gallium-indium, nitrogen-phosphorus-arsenic-antimony, SiC, InP (indium phosphide), InGaAs, GaInNAs, Wafers of LT, LN, ZnO (zinc oxide), CdTe (cadmium telluride), ZnSe (zinc selenide), and the like can be mentioned.
  • the wafer preferably used is a silicon wafer, and particularly preferably a mirror-polished silicon wafer having a size of 8 inches or more.
  • the metals include single element metals such as W, Mo, Pt, Fe, Ni, and Au, and alloys such as Inconel, Monel, Nimonic, carbon copper, Fe—Ni system Invar alloys, and Super Invar alloys.
  • multi-layer metal plates obtained by adding other metal layers and ceramic layers are also included. In this case, if the overall coefficient of linear expansion (CTE) with the additional layer is low, Cu, Al, etc. may also be used for the main metal layer.
  • the metal used as the additional metal layer should have properties such as strong adhesion to the polyamic acid thermoset, no diffusion, good chemical resistance and heat resistance. Suitable examples include, but are not limited to, Cr, Ni, TiN, Mo-containing Cu, and the like.
  • the ceramic plate in the present invention includes Al2O3 , Mullite, ALN, SiC, crystallized glass , Cordierite, Spodumene, Pb-BSG+ CaZrO3 + Al2O3 , Crystallized glass+ Al2O3 , Crystallized Ca- BSG , BSG+Quartz, and BSG+Al. 2 O 3 , Pb-BSG+Al 2 O 3 , Glass-ceramic, Zerodur materials, and other base ceramics.
  • the thickness of the inorganic substrate is not particularly limited, the thickness is preferably 10 mm or less, more preferably 3 mm or less, and even more preferably 1.3 mm or less from the viewpoint of handleability.
  • the lower limit of the thickness is not particularly limited, it is preferably 0.07 mm or more, more preferably 0.15 mm or more, and still more preferably 0.3 mm or more. If it is too thin, it will be easily damaged and difficult to handle. On the other hand, if it is too thick, it becomes heavy and difficult to handle.
  • a surface treatment may be performed for the purpose of improving the wettability and adhesiveness of the inorganic substrate.
  • a coupling agent such as a silane coupling agent, an aluminum coupling agent, a titanate coupling agent can be used.
  • excellent properties can be obtained when a silane coupling agent is used.
  • the laminate preferably has a silane coupling agent layer (also referred to as a silane coupling agent condensed layer) between the polymer film layer and the inorganic substrate.
  • the silane coupling agent refers to a compound containing 10% by mass or more of Si (silicon) component.
  • the silane coupling agent preferably contains a large amount of a silicon oxide component because it improves heat resistance, and particularly preferably has heat resistance at a temperature of about 400°C.
  • the thickness of the silane coupling agent layer is preferably 200 nm or less (0.2 ⁇ m or less).
  • the range for use as a flexible electronic device is preferably 100 nm or less (0.1 ⁇ m or less), more preferably 50 nm or less, and even more preferably 10 nm. When normally produced, the thickness is about 0.10 ⁇ m or less. Also, in a process that requires as little silane coupling agent as possible, a thickness of 5 nm or less can be used. If the thickness is less than 0.1 nm, the adhesive strength may be lowered or there may be a portion where the adhesive is not adhered.
  • silane coupling agent in the present invention is not particularly limited, one having an amino group or an epoxy group is preferred. When heat resistance is required in the process, it is preferable to use an aromatic link between Si and an amino group.
  • the silane coupling agent is not particularly limited, it preferably contains a coupling agent having an amino group.
  • 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-butylidene)propylamine, N-phenyl-3-aminopropyl trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, aminophenyltrimethoxysilane, aminophenethyltrimeth
  • the reaction can be slightly affected by adding mixing and heating operations. You can use it after proceeding.
  • silane coupling agent that has undergone hydrolysis in advance may be used.
  • KBP-90 and KBP-64 manufactured by Shin-Etsu Silicone Co., Ltd. can be used.
  • the laminate of the present invention includes a protective film bonded to the heat-resistant polymer film.
  • the protective film laminated to the heat-resistant polymer film is usually a film for temporarily protecting the surface of the heat-resistant polymer film, especially as long as it is a peelable film that can protect the surface of the heat-resistant polymer film.
  • a film for temporarily protecting the surface of the heat-resistant polymer film is usually a film for temporarily protecting the surface of the heat-resistant polymer film, especially as long as it is a peelable film that can protect the surface of the heat-resistant polymer film.
  • heat-resistant super engineering plastic films such as PPS film, PEEK film, aromatic polyamide film, polyimide film, and polyimide benzathol film can be used. can.
  • a PET film is preferable.
  • the protective film of the present invention is rectangular.
  • the length of the long side is preferably 300 mm or longer, more preferably 500 mm or longer, and still more preferably 1000 mm or longer.
  • the upper limit is not particularly limited, industrially, 20,000 mm or less is sufficient, and 10,000 mm or less is acceptable.
  • the radius of the circumscribed circle of the protective film is preferably 200 mm or more, more preferably 300 mm or more, and still more preferably 400 mm or more. Industrially, 30,000 mm or less is sufficient, and 20,000 mm or less is acceptable.
  • the arithmetic mean waviness Wa of the protective film surface in contact with the heat-resistant polymer film is preferably 30 nm or less, more preferably 29 nm or less, still more preferably 28 nm or less, and even more preferably 27 nm or less.
  • the heat-resistant polymer film has a very smooth surface because it is assumed that a device will be formed on the surface.
  • the lower limit of the arithmetic mean waviness Wa of the protective film is not particularly limited, it is usually 5 nm or more.
  • the arithmetic mean waviness Wa is a parameter representing the magnitude (amplitude) of the waviness in the height direction. Since the undulations involved in the adhesion to the heat-resistant polymer film consist of undulations with a period of several tens of ⁇ m, the range of the measurement area of the interference microscope is 60 ⁇ m or more in both the x and y directions. When the protective film has an adhesive layer, the adhesive layer is soft and conforms to the unevenness of the surface of the heat-resistant polymer film, so Wa is not limited.
  • the arithmetic mean waviness Wa of the protective film can be controlled by the manufacturing conditions (temperature, line speed, nip roll surface waviness, nip pressure, etc.) during molding of the protective film.
  • the arithmetic mean waviness Wa tends to decrease when the molding temperature is lowered, and the arithmetic mean waviness Wa also tends to decrease when the linear velocity is increased or the nip pressure is decreased.
  • It can also be controlled by the storage conditions (temperature, humidity, storage time) of the protective film after molding.
  • a commercially available protective film it is also possible to select a suitable one by measuring the arithmetic mean waviness Wa of the protective film to be used before bonding with the transparent resin film.
  • the protective film preferably has an adhesive layer on the surface in contact with the heat-resistant polymer film layer.
  • an adhesive layer By having an adhesive layer on the protective film, self-adsorptive properties can be expressed.
  • the adhesive layer is not particularly limited, for example, a urethane-based, silicone-based, or acrylic-based adhesive layer can be used.
  • the adhesive layer can be produced by applying an adhesive dissolved in a solvent and drying it.
  • a self-adhesive resin film such as polyolefin resin may be used.
  • a polyolefin resin film is preferred.
  • Polypropylene-based resin film or polyethylene-based resin film is more preferable, and polyethylene-based resin film is even more preferable, because it is easily available and inexpensive.
  • polyethylene-based resins include high-pressure low-density polyethylene (LDPE), linear short-chain branched polyethylene (LLDPE), medium- and low-pressure high-density polyethylene (HDPE), and very low-density polyethylene (VLDPE).
  • LLDPE is preferable as the resin on the surface adjacent to the heat-resistant polymer film from the viewpoint of adhesiveness with the heat-resistant polymer film and workability.
  • the 90-degree adhesive strength F2 between the heat-resistant polymer film and the protective film is less than 0.2 N/cm. It is preferably 0.001 N/cm or more and 0.1 N/cm or less, more preferably 0.002 N/cm or more and 0.06 N/cm or less.
  • the protective film can be suitably peeled off when using the heat-resistant polymer film.
  • the 90-degree adhesive strength is 0.001 N/cm or more, the protective film is unintentionally peeled off from the heat-resistant polymer film in a stage prior to using the heat-resistant polymer film (for example, during transportation). can be suppressed.
  • the 90-degree adhesive strength F2 between the heat-resistant polymer film and the protective film refers to the value after heating the laminate at 110°C for 10 minutes.
  • the protective film may contain a substrate layer and an adhesive layer, and if necessary, the substrate layer or the adhesive layer may contain various additives.
  • the additives include fillers, antioxidants, light stabilizers, anti-gelling agents, organic wetting agents, antistatic agents, surfactants, pigments, and dyes.
  • the protective film satisfies the following numerical range in ultraviolet transmittance measurement.
  • the substrate preferably does not contain an ultraviolet absorber. Examples of the ultraviolet absorber include those described later.
  • the protective film preferably has a 50% cutoff wavelength of UV transmittance of 240 nm or more, more preferably 270 nm or more, and preferably 300 nm or more. More preferably, it is particularly preferably 340 nm or more.
  • the 50% cut-off wavelength of the UV transmittance of the protective film is 240 nm or more
  • the protective film and the heat-resistant polymer film can be more suitably cut with an UV laser. Therefore, the heat-resistant polymer film can be cut to any size from the inorganic substrate/heat-resistant polymer film/protective film laminate, or the heat-resistant polymer film with a protective film can be cut to any size with a laser. can do.
  • organic UV absorbers examples include benzotriazole-based, benzophenone-based, cyclic iminoester-based, and combinations thereof. Among them, benzotriazole-based and cyclic iminoester-based are particularly preferable from the viewpoint of durability.
  • benzotriazole-based ultraviolet absorbers examples include 2-[2′-hydroxy-5′-(methacryloyloxymethyl)phenyl]-2H-benzotriazole and 2-[2′-hydroxy-5′-(methacryloyloxyethyl).
  • benzophenone-based UV absorbers examples 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-octoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone disodium salt and the like.
  • Examples of the cyclic iminoester-based UV absorber include 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazine- 4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2-(1- or 2-naphthyl)-3,1-benzo Oxazin-4-one, 2-(4-biphenyl)-3,1-benzoxazin-4-one, 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,
  • 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)naphthalene, and 2,4,6-tri(3,1-benzoxazin-4-one-2-yl ) naphthalene 2,8-dimethyl-4H,6H-benzo(1,2-d;5,4-d′)bis-(1,3)-oxazine-4,6-dione, 2,7-dimethyl- 4H,9H-benzo(1,2-d;5,4-d′)bis-(1,3)-oxazine-4,9-dione, 2,8-diphenyl-4H,8H-benzo(1,2 -d;5,4-d')bis-(1,3)-oxazine-4,6-dione,2,7-diphenyl-4H,9H-benzo(1,2-d;5,4-d' ) bis-(1,3)-oxazine-4,6-dione, 6,6′-bis(2-methyl-4H,3,
  • the laminate of the present invention contains the inorganic substrate, the heat-resistant polymer film and the protective film in this order, and is preferably laminated in this order.
  • a protective film peeling auxiliary tape is laminated on at least a part of the protective film of the laminate.
  • the laminate with a protective film peeling auxiliary tape includes an inorganic substrate, a heat-resistant polymer film, a protective film, and a protective film peeling auxiliary tape in this order.
  • the protective film peeling auxiliary tape (hereinafter also simply referred to as peeling auxiliary tape) is for assisting the peeling of the protective film from the heat-resistant polymer film. It preferably includes a pressure-sensitive adhesive layer and is composed of a substrate layer and a pressure-sensitive adhesive layer. It is preferable that the pressure-sensitive adhesive layer surface of the auxiliary peeling tape is attached to the surface of the protective film.
  • the base material of the peeling auxiliary tape is, for example, PET film, PEN film, polyethylene film, polypropylene film, nylon film, etc., PPS film, PEEK film, aromatic polyamide film, polyimide film, polyimide benzathol film, etc.
  • Engineering plastic films can be used.
  • a self-adhesive resin film such as a polyolefin resin may be used.
  • the adhesive layer of the auxiliary release tape is not particularly limited as long as it satisfies the relationship of formula (1) described later, but for example, a urethane-based, silicone-based, or acrylic-based adhesive layer can be used.
  • the adhesive layer can be produced by applying an adhesive dissolved in a solvent and drying it.
  • a commercially available double-faced tape attached to the substrate may also be used.
  • the laminate with the protective film peeling auxiliary tape has an adhesive strength F1 between the inorganic substrate and the heat-resistant polymer film obtained by a 90-degree peeling method, and an adhesive strength F2 between the heat-resistant polymer film and the protective film obtained by a 90-degree peeling method. and the adhesion strength F3 between the protective film and the protective film peeling auxiliary tape by the 90 degree peeling method must satisfy the relationships of the following formulas (1) to (3).
  • F3 is preferably 0.2 N/cm or more, more preferably 1 N/cm or more, still more preferably 3 N/cm or more, and particularly preferably 5 N/cm or more. Also, it is preferably 30 N/cm or less, more preferably 20 N/cm or less, and even more preferably 15 N/cm or less.
  • the method for measuring F3 is according to the method described in Examples.
  • F2 is less than 0.2 N/cm, preferably 0.1 N/cm or less, more preferably 0.06 N/cm or less. Also, it is preferably 0.001 N/cm or more, more preferably 0.002 N/cm or more.
  • the method for measuring F2 is according to the method described in Examples.
  • F1 is more than 0.08 N/cm, preferably 0.09 N/cm or more, more preferably 0.1 N/cm or more. Also, it is preferably 0.3 N/cm or less, more preferably 0.2 N/cm or less, and still more preferably 0.15 N/cm or less.
  • the method for measuring F1 is according to the method described in Examples.
  • the laminate with the protective film peeling auxiliary tape of the present invention (hereinafter also simply referred to as the laminate with the peeling auxiliary tape) is preferably rectangular. At least one side of the laminate with the protective film peeling auxiliary tape has a distance D1 (mm) from the edge of the heat-resistant polymer film to the edge of the inorganic substrate, a distance D2 (mm) from the edge of the protective film to the edge of the inorganic substrate, and a protective When the distance D3 (mm) from the end of the adhesive layer of the auxiliary film peeling tape to the end of the inorganic substrate, it is necessary to satisfy either of the following (i) or (ii).
  • D1 to D3 are preferably one side of one end in the same direction of the laminate with the auxiliary peeling tape.
  • the above (i) is the case where the adhesive strength of F2 is more than 1/3 of F1. That is, this is the case where the adhesive strength F2 between the heat-resistant polymer film and the protective film is strong (strong adhesion). In this case, it is necessary to satisfy D3 ⁇ D2 ⁇ D1 (4). That is, the pressure-sensitive adhesive layer of the auxiliary peeling tape is in contact with the inorganic substrate over the length of the difference (D2-D3) between D2 and D3 in FIG. 2(a). By peeling the adhesive layer from the state in which it is in contact with the inorganic substrate, the adhesive of the auxiliary peeling tape comes into contact with the side surface of the peeled edge of the protective film, and the peeled edge of the protective film can be lifted more reliably.
  • D2-D3 is preferably 0.5 mm or more and 10 mm or less, more preferably 1 mm or more and 8 mm or less, and even more preferably 1.5 mm or more and 7 mm or less.
  • the above (ii) is the case where the adhesive strength of F2 is 1 ⁇ 3 or less of F1. That is, this is the case where the adhesive strength F2 between the heat-resistant polymer film and the protective film is weak (weak adhesion). In this case, it is necessary to satisfy D3 ⁇ D2+10(5) (unit: mm). That is, since the adhesive strength F2 between the heat-resistant polymer film and the protective film is small, the protective film can be peeled off without causing the adhesive layer of the peeling auxiliary tape to protrude onto the inorganic substrate as shown in FIG. 2(c). .
  • D3 is preferably D2 + 9 (mm) or less, more preferably D2 + 7 (mm) or less, D2 + ( 5 mm) or less.
  • the peeling auxiliary tape is attached to the end of the protective film of the laminate as shown in Fig. 2(a) or Fig. 2(c).
  • the side to be pasted may be one side as shown in FIGS. good.
  • the auxiliary peeling tape can be pasted partially protruding from the protective film as shown in Fig. 2(b). At this time, it is preferable that the adhesive layer is not exposed in the portion exceeding the preferred range of D2-D3. If the adhesive layer is exposed, the adhesive layer of the auxiliary peeling tape will contact places other than the protective film, such as the inorganic substrate, more than necessary, so the laminate may be contaminated with transfer material from the adhesive. Otherwise, the auxiliary peeling tape and the inorganic substrate may strongly adhere to each other, and the glass substrate may be deformed when the protective film is peeled off. Examples of the method of not exposing the adhesive layer more than necessary include a method of forming an adhesive layer so that D2-D3 is in a preferable range, and a method of attaching an adhesive film to an unnecessary portion.
  • the thickness of the base layer of the auxiliary peeling tape and the type of the base layer can be selected according to the springback value S of the base layer of the auxiliary peeling tape.
  • the springback value S is the force that rebounds when the substrate layer is bent and then the stress is removed.
  • S is preferably 2 gf or more and 45 gf or less, more preferably 7 gf or more and 43 gf or less.
  • the thickness of the peeling auxiliary tape base layer is not limited as long as S is within the above range, but specifically, the thickness is preferably 30 ⁇ m or more, more preferably 50 ⁇ m or more, and still more preferably 70 ⁇ m or more. Handleability is favorable in the thickness of a base material layer being 30 micrometers or more. Since the auxiliary peeling tape is easier to handle when wound in a roll, the upper limit of the thickness of the base layer is preferably 400 ⁇ m or less, more preferably 350 ⁇ m or less. The same applies to the preferred thickness of the auxiliary peeling tape when it is made of a self-adsorptive film.
  • the angle ⁇ formed by the protective film and the heat-resistant polymer film at 10 mm from the start of peeling when lifting the peeling auxiliary tape and peeling the protective film from the heat-resistant polymer film is the same as in the case of (i) above and in the case of (ii) above. can be considered separately.
  • 0.02 ⁇ S ⁇ F2 ⁇ sin ⁇ 1 (6) 0 ⁇ S ⁇ F2 ⁇ sin ⁇ 0.1 (7) ⁇ is preferably 10° or less, more preferably 8° or less.
  • the protective film When the protective film is peeled from the heat-resistant polymer film, if the radius of curvature of the protective film is sufficiently thinner than the thickness of the protective film substrate, the smaller ⁇ is, the smaller the force required for peeling is. ⁇ can be controlled by adjusting the S value, peeling speed, and angle of the auxiliary peeling tape substrate.
  • the peeling conditions, the protective film, and the auxiliary peeling tape may be selected so that S, F2 and ⁇ satisfy formula (6) or formula (7). Even when the adhesive strength between the heat-resistant polymer film and the protective film is high (above (i)), the protective film can be peeled off without peeling the heat-resistant polymer film from the inorganic substrate.
  • the protective film can be peeled off from the inorganic substrate without peeling the heat-resistant polymer film.
  • the load on the inorganic substrate at the start of peeling can be suppressed, and the protective film can be removed without causing cracks in the inorganic substrate (especially the glass substrate). Can be stripped.
  • the thickness of the adhesive layer of the peeling aid tape is preferably 7 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the thickness of the pressure-sensitive adhesive layer is 7 ⁇ m or more, it is easy to secure the adhesive strength with the protective film.
  • the thickness of the adhesive layer is preferably 120 ⁇ m or less, more preferably 100 ⁇ m or less. When the adhesive layer has a thickness of 120 ⁇ m or less, the adhesive layer does not protrude from the base material due to the pressure applied to the protective film, and the laminate is less likely to become dirty.
  • the protective film can be peeled off even when A1 ⁇ A2, the adhesive layer of the auxiliary peeling tape contacts a place other than the protective film, such as an inorganic substrate, so the laminate is not a transfer product from the adhesive. may be contaminated with
  • the 90-degree adhesive strength F3 between the protective film and the protective film peeling auxiliary tape refers to the value when the protective film is not heated after the peeling auxiliary tape is attached to the protective film.
  • the 90-degree adhesive strength F3 between the protective film and the protective film peeling auxiliary tape is not particularly limited as long as the formula (1) is satisfied.
  • FIG. 2(b) is a cross-sectional view schematically showing the laminate according to this embodiment.
  • the laminate with the auxiliary peeling tape includes the auxiliary peeling tape composed of the base material layer 23 and the adhesive layer 22, the protective film 13, and the heat-resistant polymer film 21. , and an inorganic substrate 12, and the inorganic substrate 12 and the heat-resistant polymer film 21 are laminated in contact with each other, or laminated via only a silane coupling agent layer (not shown). Also, part of the adhesive layer 22 of the auxiliary peeling tape is in contact with the surface of the inorganic substrate 12 .
  • the laminate with the auxiliary peeling tape according to this embodiment can be produced, for example, by the following procedure.
  • a heat-resistant polymer film with a protective film and an inorganic substrate are prepared.
  • peel off the protective film provided on the inorganic substrate of the heat-resistant polymer film with a protective film and the surface to be attached By doing so, a heat-resistant polymer film with a single-sided protective film can be obtained.
  • a silane coupling agent layer is provided on the laminate, at least one surface of the inorganic substrate is preferably treated with a silane coupling agent.
  • one surface of the inorganic substrate (when a silane coupling agent layer is provided, the surface treated with the silane coupling agent) and a heat-resistant polymer film with a protective film are superimposed, and both are pressed and heated.
  • a laminate heat-resistant polymer film with protective film/inorganic substrate laminate
  • the surface of the heat-resistant polymer film on which the protective film is not provided is treated with a silane coupling agent in advance, the surface treated with the silane coupling agent is superimposed on the inorganic substrate, and both are pressed and heated.
  • a laminate (heat-resistant polymer film with protective film/inorganic substrate laminate) can also be obtained by lamination by
  • a laminate with the auxiliary peeling tape can be obtained by attaching the auxiliary peeling tape to the surface of the protective film of the obtained laminate.
  • silane coupling agent treatment method known methods such as spin coating, spray coating, and dip coating can be used, and the silane coupling agent vapor generated by heating the silane coupling agent is deposited on the inorganic substrate. However, processing is possible (vapor deposition method).
  • the silane coupling agent can be diluted with a solvent and applied.
  • the solvent of the silane coupling agent solution in the present invention is one or more solvents selected from the group consisting of water, monohydric alcohols having 8 or less carbon atoms, and dihydric alcohols having 4 or less carbon atoms. is preferred. More preferably, it is one or more solvents selected from the group consisting of methanol, ethanol, normal propanol, isopropanol, butanol, ethylene glycol, propylene glycol, and water. In the present invention, a mixed solvent containing two or more solvents can be used.
  • a mixed solvent of water and alcohol a mixed solvent of water and ethylene glycol or propylene glycol, and a mixed solvent of water, an alcohol having 3 or less carbon atoms, and a diol having 3 or less carbon atoms.
  • concentration of the silane coupling agent solution is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 2% by mass or more.
  • FIG. 5 is a diagram schematically showing an example of a silane coupling agent treatment apparatus used in vapor deposition.
  • the silane coupling agent processing apparatus includes a processing chamber (chamber) 56 connected to a gas inlet 52, an exhaust port 58, and a chemical liquid tank (silane coupling agent tank) 53.
  • FIG. A chemical solution tank (silane coupling agent tank) 53 is filled with a silane coupling agent, and its temperature is controlled by a hot water tank (hot water bath) 54 having a heater 55 .
  • a gas introduction port 59 is connected to the chemical liquid tank (silane coupling agent tank) 53 so that gas can be introduced from the outside.
  • the flow rate of gas is adjusted by a flow meter 51 connected to a gas inlet 59 .
  • a flow meter 51 connected to a gas inlet 59 .
  • the gas is introduced from the gas inlet 59, the vaporized silane coupling agent in the chemical tank 53 is pushed out into the processing chamber 56, and the substrate 57 (inorganic substrate, heat-resistant polymer film, etc.) etc.) as a silane coupling agent layer.
  • Examples of the method of pressurization include ordinary pressing or lamination in the atmosphere or pressing or lamination in a vacuum. For example, above 200 mm), lamination in air is desirable. On the other hand, in the case of a laminate having a small size of about 200 mm or less, pressing in a vacuum is preferable.
  • the degree of vacuum is sufficient with a normal oil rotary pump, and about 10 Torr or less is sufficient.
  • a preferable pressure is 1 MPa to 20 MPa, more preferably 3 MPa to 10 MPa. If the pressure is high, the substrate may be damaged, and if the pressure is low, some parts may not adhere.
  • the preferred temperature is 90° C. to 300° C., more preferably 100° C. to 250° C. If the temperature is high, the film may be damaged, and if the temperature is low, adhesion may be weak.
  • the shape of the laminate is rectangular. It is preferably rectangular with a long side length of 300 mm or more, more preferably 500 mm or more, and still more preferably 1000 mm or more. Although the upper limit is not particularly limited, industrially, 20,000 mm or less is sufficient, and 10,000 mm or less is acceptable. Moreover, it is preferable that the radius of the circumscribed circle of the laminate is 330 mm or more.
  • the laminate of the present invention is more preferably 350 mm or more, more preferably 400 mm or more, because even a large-sized one (for example, a display manufacturing apparatus) can be packed in the form of a stack for storage and transportation. Industrially, 30,000 mm or less is sufficient, and 20,000 mm or less is acceptable.
  • the adhesive layer between the inorganic substrate and the heat-resistant polymer film layer of the present invention means that the Si (silicon) component is less than 10% by mass (less than 10% by mass).
  • the thickness of the adhesive layer interposed between the inorganic substrate and the polymer film layer is preferably 1 ⁇ m or less, more preferably 0.7 ⁇ m or less, and still more preferably 0.6 ⁇ m or less, Especially preferably, it is 0.5 ⁇ m or less.
  • the 90-degree adhesive strength F1 between the heat-resistant polymer film and the inorganic substrate is more than 0.08 N/cm, preferably 0.09 N/cm or more, more preferably 0.1 N/cm. cm or more.
  • the 90-degree adhesive strength F1 is preferably 0.3 N/cm or less, more preferably 0.2 N/cm or less, and even more preferably 0.15 N/cm or less.
  • the 90-degree adhesive strength F1 is more than 0.08 N/cm, it is possible to prevent the heat-resistant polymer film from peeling off from the inorganic substrate before or during device formation.
  • the 90-degree adhesive strength F1 refers to the 90-degree adhesive strength between the inorganic substrate and the heat-resistant polymer film after heat-treating the laminate at 110° C. for 10 minutes in an air atmosphere.
  • the timing of attaching the peeling auxiliary tape to the laminate in the present invention may be immediately after bonding the heat-resistant polymer film with the protective film and the inorganic substrate, or heating the laminate of the heat-resistant polymer film with the protective film and the inorganic substrate. Even after
  • ⁇ Heat-resistant polymer film G2> After replacing the inside of the reaction vessel equipped with a nitrogen inlet tube, a reflux tube, and a stirring bar with nitrogen, 33.36 parts by mass of 2,2'-bis(trifluoromethyl)benzidine (TFMB), 270.37 parts by mass of N - Methyl-2-pyrrolidone (NMP) and a dispersion obtained by dispersing colloidal silica in dimethylacetamide ("Snowtex (registered trademark) DMAC-ST" manufactured by Nissan Chemical Industries), where silica is a polymer solid in a polyamic acid solution 14% by mass in total amount and completely dissolved, then 9.81 parts by mass of 1,2,3,4-cyclobutanetetracarboxylic anhydride (CBDA), 11.34 parts by mass of 3,3′,4,4′-biphenyltetracarboxylic acid (BPDA) and 4.85 parts by mass of 4,4′-oxydiphthalic dianhydride (ODPA) were added
  • the resulting polyamic acid solution B1 was applied to the non-slip surface of polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) using a comma coater so that the final film thickness was 25 ⁇ m. It was dried at 110° C. for 10 minutes.
  • the polyamic acid film that has acquired self-supporting properties is separated from the A4100 film used as the support, passed through a pin tenter having a pin sheet with pins arranged thereon, and gripped by inserting the ends of the film into the pins so that the film does not break. and conveyed by adjusting the interval between the pin sheets so that unnecessary slack does not occur, and heated under the conditions of 200°C for 3 minutes, 250°C for 3 minutes, 300°C for 3 minutes, and 350°C for 3 minutes. to allow the imidization reaction to proceed.
  • the film was cooled to room temperature for 2 minutes, and portions of the film with poor flatness at both ends were cut off with a slitter and rolled up into a roll to obtain 500 m of polyimide film G2 with a width of 450 mm.
  • ⁇ Heat-resistant polymer film G3> After replacing the inside of the reaction vessel equipped with a nitrogen inlet tube, a reflux tube, and a stirring bar with nitrogen, 33.36 parts by mass of 2,2'-bis(trifluoromethyl)benzidine (TFMB), 270.37 parts by mass of N - Methyl-2-pyrrolidone (NMP) and a dispersion obtained by dispersing colloidal silica in dimethylacetamide ("Snowtex (registered trademark) DMAC-ST” manufactured by Nissan Chemical Industries), where silica is a polymer solid in a polyamic acid solution 1,2,3,4-cyclobutanetetracarboxylic anhydride (CBDA) of 9.81 parts by mass, 11.34 3,3',4,4'-Biphenyltetracarboxylic acid (BPDA) of 4.85 parts by mass and 4,4'-oxydiphthalic dianhydride (ODPA) of 4.85 parts by mass were added in portions as solids, and then cooled
  • the resulting polyamic acid solution B3 was applied to the non-slip surface of polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) using a comma coater so that the final film thickness was 25 ⁇ m. It was dried at 110° C. for 10 minutes.
  • the polyamic acid film that has acquired self-supporting properties is separated from the A4100 film used as the support, passed through a pin tenter having a pin sheet with pins arranged thereon, and gripped by inserting the ends of the film into the pins so that the film does not break. and conveyed by adjusting the interval between the pin sheets so that unnecessary slack does not occur, and heated under the conditions of 200°C for 3 minutes, 250°C for 3 minutes, 300°C for 3 minutes, and 350°C for 3 minutes. to allow the imidization reaction to proceed.
  • the film was cooled to room temperature for 2 minutes, and portions of the film with poor flatness at both ends were cut off with a slitter and rolled up into a roll to obtain 500 m of polyimide film G3 with a width of 450 mm.
  • ⁇ Heat-resistant polymer film G4> After replacing the inside of the reaction vessel equipped with a nitrogen inlet tube, a reflux tube, and a stirring rod with nitrogen, 470.8 parts by mass of 2,2'-bis(trifluoromethyl)benzidine (TFMB) and 6766 parts by mass of N-methyl -2-Pyrrolidone (NMP) and a dispersion obtained by dispersing colloidal silica as a lubricant in dimethylacetamide (manufactured by Nissan Chemical Industries, Ltd.
  • TFMB 2,2'-bis(trifluoromethyl)benzidine
  • NMP N-methyl -2-Pyrrolidone
  • silica is polyamic acid Add so that the total polymer solid content in the solution is 0.3% by mass, and dissolve completely, then 192.4 parts by mass of pyromellitic dianhydride (PMDA), 173.0 parts by mass of 3, 3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA) was added as a solid in portions, and then stirred at room temperature for 24 hours.
  • PMDA pyromellitic dianhydride
  • BPDA 3, 3′,4,4′-Biphenyltetracarboxylic dianhydride
  • the obtained polyamic acid solution B4 was applied to the non-slip surface of polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) using a comma coater so that the final film thickness was 25 ⁇ m. It was dried at 110° C. for 10 minutes.
  • the polyamic acid film that has acquired self-supporting properties is separated from the A4100 film used as the support, passed through a pin tenter having a pin sheet with pins arranged thereon, and gripped by inserting the ends of the film into the pins so that the film does not break. and conveyed by adjusting the interval between the pin sheets so that unnecessary slack does not occur, and heated under the conditions of 200°C for 15 minutes, 250°C for 15 minutes, 300°C for 15 minutes, and 400°C for 15 minutes. to allow the imidization reaction to proceed.
  • the film was cooled to room temperature for 2 minutes, and portions of the film with poor flatness at both ends were cut off with a slitter and rolled up into a roll to obtain 500 m of polyimide film G4 with a width of 450 mm.
  • ⁇ Heat-resistant polymer film G5> After purging the interior of a reaction vessel equipped with a nitrogen inlet tube, a thermometer, and a stirring bar, 4610 parts by mass of N,N-dimethylacetamide (DMAC) and 640.0 parts by mass of 2, are added to the reaction vessel under a nitrogen atmosphere. 2′-Bis(trifluoromethyl)benzidine (TFMB) was added and stirred to dissolve TFMB in DMAC. Next, while stirring the inside of the reaction vessel, an anhydride (6FDA) was added to 897.4 parts by mass of 4,4′-(2,2-hexafluoroisopropylidene)diphthalic acid under a nitrogen stream for about 10 minutes.
  • DMAC N,N-dimethylacetamide
  • TFMB 2′-Bis(trifluoromethyl)benzidine
  • 6FDA an anhydride
  • the polymerization reaction was carried out by continuing stirring for 6 hours while adjusting the temperature to be in the range of 20 to 40° C. to obtain a viscous polyamic acid solution.
  • 4100 parts by mass of DMAC was added to the resulting polyamic acid solution to dilute it, and then 258.3 parts by mass of isoquinoline was added as an imidization accelerator, and the polyamic acid solution was stirred at a temperature of 30 to 40°C. 1225.0 parts by mass of acetic anhydride as an imidizing agent is slowly added dropwise over about 30 minutes, and then the liquid temperature is kept at 30 to 40° C. and stirring is continued for 12 hours.
  • a chemical imidization reaction was carried out to obtain a polyimide solution b5-1.
  • 4000 parts by mass of the polyimide solution b5-1 containing the obtained imidizing agent and imidization accelerator is transferred to a reaction vessel equipped with a stirrer and a stirring blade, and stirred at a speed of 120 rpm for 15 to 15 minutes.
  • the temperature was kept at 25° C., and 60000 parts by mass of methanol was dropped at a rate of 400 parts by mass/minute.
  • turbidity of the polyimide solution was confirmed, and deposition of polyimide powder was confirmed. Subsequently, the remaining methanol was added to complete the deposition of polyimide.
  • the contents of the reaction vessel were filtered using a suction filtration device, and washed and filtered using 4000 parts by mass of methanol. After that, 2000 parts by mass of the filtered polyimide powder was dried at 50° C. for 24 hours using a dryer equipped with a local exhaust device, and further dried at 260° C. for 2 hours to remove remaining volatile components. to obtain a polyimide powder b5-2.
  • the resulting polyimide powder b5-2 had a reduced viscosity of 5.40 dl/g.
  • the resulting polyimide solution D was coated on the non-slip surface of polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) using a comma coater so that the final film thickness was 25 ⁇ m. It was dried at 110° C. for 10 minutes. After drying, the polyimide gel film that has acquired self-supporting properties is peeled off from the A4100 film used as the support, passed through a pin tenter having a pin sheet on which pins are arranged, and gripped by inserting the ends of the film into the pins so that the film does not break.
  • TFMB 2,2'-bis(trifluoromethyl)benzidine
  • DMAc N,N-dimethylacetamide
  • 6FDA 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride
  • OBBC 4,4'-oxybis(benzoyl chloride)
  • TPC terephthaloyl chloride
  • 46.3 parts by weight of -methylpyridine as an imidization accelerator and 130.4 parts by weight of acetic anhydride as an imidizing agent are added, stirred at room temperature for 30 minutes, heated to 70°C, and further 3.5 parts by weight. After stirring for hours, a polyamideimide solution b6-1 was obtained.
  • the contents of the reaction vessel were filtered using a suction filtration device, and washed and filtered using 4000 parts by mass of methanol. After that, 2000 parts by mass of the filtered polyamideimide powder was dried at 50° C. for 24 hours using a dryer with a local exhaust device, and further dried at 260° C. for 2 hours to remove the remaining volatile components. to obtain a polyamideimide powder b6-2.
  • the resulting polyamideimide powder b6-2 had a reduced viscosity of 4.50 dl/g.
  • the obtained polyamide-imide solution B6 was applied to the non-slip surface of polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) using a comma coater so that the final film thickness was 25 ⁇ m. It was dried at 110° C. for 10 minutes. After drying, the polyimide gel film that has acquired self-supporting properties is peeled off from the A4100 film used as the support, passed through a pin tenter having a pin sheet on which pins are arranged, and gripped by inserting the ends of the film into the pins so that the film does not break.
  • ⁇ Protective film PF2> In a separable flask, 55.3 parts by mass of polyol (trifunctional, polyol obtained by addition polymerization of propylene oxide and ethylene oxide to glycerin, SANNIX (registered trademark) GL3000 manufactured by Sanyo Chemical Industries, Ltd.), 4.7 parts by mass of Duranate D101 (polyisocyanate manufactured by Asahi Kasei Chemicals Co., Ltd.), 39.7 parts by mass of toluene, and 0.02 parts by mass of dibutyltin dilaurate (DBTDL) are added and heated at 45 ° C. to 55 ° C. for 2 hours with stirring to react.
  • polyol trifunctional, polyol obtained by addition polymerization of propylene oxide and ethylene oxide to glycerin, SANNIX (registered trademark) GL3000 manufactured by Sanyo Chemical Industries, Ltd.
  • Duranate D101 polyisocyanate manufactured by Asahi Kas
  • the adhesive composition C1 was applied to a polyethylene terephthalate (PET) film (A4100) manufactured by Toyobo Co., Ltd., which had been subjected to corona treatment in advance, so that the thickness of the adhesive when dry was 10 ⁇ m. After that, it was dried by heating at 130° C. for 2 minutes, and left still for 3 days in a constant temperature bath at 40° C. (aging step) to cure (crosslink) the pressure-sensitive adhesive to prepare a protective film PF2.
  • PET polyethylene terephthalate
  • an adhesive composition C3 was obtained.
  • the obtained pressure-sensitive adhesive composition C3 was applied onto a polyethylene terephthalate (PET) film (A4100) manufactured by Toyobo Co., Ltd., which had been subjected to corona treatment in advance, and dried at 100° C. to remove the solvent, thereby forming a PET film.
  • a surface protective film PF3 having a pressure-sensitive adhesive layer having a thickness of 10 ⁇ m formed thereon was obtained.
  • ⁇ Protective film peeling auxiliary tape S1> A polyethylene terephthalate (PET) film A4100 (thickness 188 ⁇ m) manufactured by Toyobo was cut into a length of 300 mm ⁇ width of 150 m. Double-faced tape VR5300 manufactured by Nitto Denko was cut into a length of 300 mm ⁇ width of 100 mm and attached to A4100 to obtain a protective film peeling auxiliary tape S1 having an adhesive surface of length of 300 mm ⁇ width of 100 mm.
  • PET polyethylene terephthalate
  • PF1 was cut into 300 mm length ⁇ 150 mm width.
  • a PET film (12 ⁇ m, E5100) manufactured by Toyobo Co., Ltd. (12 ⁇ m, E5100) having a length of 300 mm and a width of 50 mm was attached to the adhesive surface to obtain a protective film peeling auxiliary tape S2 in which the adhesive surface was exposed with a length of 300 mm and a width of 100 mm.
  • Protective film peeling auxiliary tape S4 was obtained in the same manner as S1 except that PET film A4160 (thickness: 100 ⁇ m) manufactured by Toyobo Co., Ltd. was used instead of A4100.
  • a protective film peeling auxiliary tape S5 was obtained in the same manner as S1 except that an A-PET film (thickness: 200 ⁇ m) manufactured by Naniwa Paper Industry Co., Ltd. was used instead of A4100.
  • Protective film peeling auxiliary tape S6 was obtained in the same manner as S1 except that PET film E5100 (thickness 75 ⁇ m) manufactured by Toyobo Co., Ltd. was used instead of A4100.
  • a glass substrate was prepared.
  • the glass substrate is OA10G glass (manufactured by NEG Co., Ltd.) with a thickness of 0.7 mm cut into a size of 500 mm ⁇ 500 mm (the radius of the circumscribed circle is 353.6 mm).
  • the glass substrate used was washed with pure water, dried, irradiated with a UV/O 3 irradiation device (SKR1102N-03 manufactured by LAN Technical Co., Ltd.) for 1 minute, and then washed.
  • a silane coupling agent (SCA) was applied onto the glass substrate by a vapor phase coating method to form a silane coupling agent layer, thereby obtaining a first laminate.
  • SCA silane coupling agent
  • FIG. 5 is a schematic diagram of an experimental apparatus for applying a silane coupling agent to a glass substrate.
  • 130 g of 3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903 was placed in a 1 L chemical solution tank, and the water bath outside was heated to 42°C.
  • the emerging vapors were then sent into the chamber along with clean dry air.
  • the gas flow rate was 22 L/min, and the substrate temperature was 21.degree.
  • the temperature of clean dry air was 23° C. and 1.2% RH. Since the exhaust was connected to the negative pressure exhaust port, it was confirmed by a differential pressure gauge that the chamber had a negative pressure of about 2 Pa.
  • PF1 was pasted on both sides of G1 and cut to 300 mm x 300 mm (the radius of the circumscribed circle was 212.1 mm).
  • the protective film on the surface to be attached to the support was peeled off.
  • the reason why PF1 was temporarily attached to the bonding surface with the glass substrate was to prevent scratches and adhesion of foreign matter during the cutting process. used G1 or G2.
  • the silane coupling agent layer of the glass substrate treated with the silane coupling agent and the heat-resistant polymer film with a protective film are laminated to form the glass substrate, the silane coupling agent layer, the heat-resistant polymer film, and the protective film.
  • a laminate laminated in this order was obtained.
  • a laminator (MRK-1000 manufactured by MCK Co.) was used for lamination, and the lamination conditions were air source pressure: 0.7 MPa, temperature: 22° C., humidity: 55% RH, and lamination speed: 50 mm/sec.
  • the resulting laminate laminate of heat-resistant polymer film with protective film/glass substrate
  • a peeling auxiliary tape was attached to the obtained laminate as shown in FIG. got
  • ⁇ Adhesive strength by 90 peeling method (90 degree adhesive strength)>
  • the 90-degree adhesive strength measurement of each layer of the laminate obtained as described above was performed under the following conditions.
  • the 90-degree adhesive strength F1 of inorganic substrate/heat-resistant polymer film and the 90-degree adhesive strength F2 of heat-resistant polymer film/protective film were measured by heating at 110° C. for 10 minutes and then cooling to room temperature.
  • the protective film/protective film peeling auxiliary tape was peeled in an unheated state. When only the target layer could not be peeled off, the measurement was carried out by firmly fixing the lower layer using tape. Tables 1 and 2 show the results.
  • Measuring device JSV-H1000 made by Nippon Keisoku System Measurement temperature; room temperature (25°C) Peeling speed; 100mm/min Atmosphere; air Measurement sample width; 1 cm Measurement is performed 5 times, and the average value is taken as the measured value. Also, when the measured value was 10 N/cm or more, it exceeded the upper limit of measurement, so Tables 1 and 2 described 10 N/cm.
  • ⁇ Measurement of springback value S> The protective film peeling auxiliary tape base material was cut into strips of 2 cm ⁇ 12 cm. For those in which the substrate and the adhesive layer were integrated, isopropanol was used to remove the adhesive layer before use. Using an apparatus such as that shown in FIG. 3, a strip-shaped substrate was sandwiched between slide glass substrates, and the springback value S was obtained by reading the value of an electronic balance when the distance between the slide glasses was 25 mm.
  • Example 10 Although the protective film could be peeled from the heat-resistant polymer film without peeling the heat-resistant polymer film from the glass substrate, the load on the glass substrate at the start of peeling was large, and cracks occurred in the glass substrate. rice field.
  • the laminate with the protective film peeling auxiliary tape of the present invention protects the heat resistant polymer film surface with the protective film.
  • the protective film can be easily peeled off when the surface of the heat-resistant polymer film is processed.
  • INDUSTRIAL APPLICABILITY The present invention can be effectively used in the production of flexible devices and the like by separating the polymer film from the inorganic substrate after microfabrication of the polymer film using such a laminate. In particular, it can be effectively used in display applications where the laminate size is large, for which automation of peeling of the protective film is essential.
  • protective film peeling auxiliary tape 12 inorganic substrate 13 protective film 21 heat resistant polymer film 22 protective film peeling auxiliary tape adhesive layer 23 protective film peeling auxiliary tape base layer 31 dial gauge 33 slide glass 34 electronic balance 35 micrometer head 41 Distance from protective film edge (10 mm) 51 flow meter 52 gas inlet 53 chemical tank (silane coupling agent tank) 54 Hot water tank (hot water bath) 55 heater 56 processing chamber (chamber) 57 base material 58 exhaust port

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Abstract

L'invention concerne un stratifié équipé d'une bande d'aide au décollement de film protecteur, le stratifié étant formé à partir d'un film polymère résistant à la chaleur équipé d'un film protecteur et d'un substrat inorganique (corps de support temporaire rigide), et étant tel qu'il est possible de séparer le film polymère résistant à la chaleur du film protecteur sans séparer le substrat inorganique du film polymère résistant à la chaleur.　Stratifié équipé d'une bande d'aide au décollement de film protecteur, le stratifié comprenant un substrat inorganique, un film polymère résistant à la chaleur, un film protecteur et une bande d'aide au décollement de film protecteur dans l'ordre indiqué, le rayon d'un cercle circonscrit du substrat inorganique étant de 330 mm ou plus ; le substrat inorganique, le film polymère résistant à la chaleur et le film protecteur étant rectangulaires ; la bande d'aide au décollement de film protecteur comprenant une couche adhésive sensible à la pression et une couche de matériau de base ; et la force adhésive F1 entre le substrat inorganique et le film polymère résistant à la chaleur selon un procédé de pelage à 90 degrés, la force adhésive F2 entre le film polymère résistant à la chaleur et le film protecteur selon le procédé de pelage à 90 degrés, et la force adhésive F3 entre le film protecteur et la bande d'aide au décollement de film protecteur selon le procédé de pelage à 90 degrés satisfaisant à une relation prescrite.
PCT/JP2022/033910 2021-10-08 2022-09-09 Stratifié équipé d'une bande d'aide au décollement de film protecteur WO2023058408A1 (fr)

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KR1020247011507A KR20240087804A (ko) 2021-10-08 2022-09-09 보호 필름 박리 보조 테이프를 구비한 적층체
CN202280067438.4A CN118076482A (zh) 2021-10-08 2022-09-09 带保护膜辅助剥离胶带的层叠体

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002018997A (ja) * 2000-07-11 2002-01-22 Nitto Denko Corp 光学部材の表面を保護する保護フィルム
JP2003163338A (ja) * 2001-08-22 2003-06-06 Semiconductor Energy Lab Co Ltd 剥離方法および半導体装置の作製方法
JP2013227533A (ja) * 2012-03-26 2013-11-07 Nitto Denko Corp 表面保護フィルム
JP2020100026A (ja) * 2018-12-20 2020-07-02 東洋紡株式会社 積層フィルム、積層体、及び、積層体の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5152104U (fr) 1974-10-17 1976-04-20
JPS5699606U (fr) 1979-12-27 1981-08-06

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002018997A (ja) * 2000-07-11 2002-01-22 Nitto Denko Corp 光学部材の表面を保護する保護フィルム
JP2003163338A (ja) * 2001-08-22 2003-06-06 Semiconductor Energy Lab Co Ltd 剥離方法および半導体装置の作製方法
JP2013227533A (ja) * 2012-03-26 2013-11-07 Nitto Denko Corp 表面保護フィルム
JP2020100026A (ja) * 2018-12-20 2020-07-02 東洋紡株式会社 積層フィルム、積層体、及び、積層体の製造方法

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