CN110099974B - Composition for forming protective layer on substrate - Google Patents

Composition for forming protective layer on substrate Download PDF

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CN110099974B
CN110099974B CN201780080618.5A CN201780080618A CN110099974B CN 110099974 B CN110099974 B CN 110099974B CN 201780080618 A CN201780080618 A CN 201780080618A CN 110099974 B CN110099974 B CN 110099974B
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substrate
protective layer
resin substrate
composition
forming
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CN110099974A (en
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江原和也
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/002—Pretreatement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Paints Or Removers (AREA)

Abstract

Provided is a composition for forming a substrate protective layer, which is a composition for forming a substrate protective layer, comprising: a resin substrate that is formed on a base and is peeled off from the base to produce a resin substrate, the resin substrate being interposed between the base and the resin substrate, having easy peelability from the base, and functioning as a protective layer for the resin substrate after peeling; which comprises a polyamic acid and an organic solvent.

Description

Composition for forming protective layer on substrate
Technical Field
The present invention relates to a composition for forming a substrate protective layer.
Background
In recent years, electronic devices are required to have a function of being bendable in addition to characteristics of being thinner and lighter. In view of this, it is required to use a lightweight flexible plastic substrate instead of a conventional heavy, fragile, and inflexible glass substrate.
In particular, for the next generation of displays, development of an active matrix type full-color TFT display panel using a lightweight flexible plastic substrate (hereinafter referred to as a resin substrate) is required. The technology related to this new-generation display is expected to be transferred to various fields such as flexible displays, flexible smart phones, mirror displays, and the like.
Therefore, various methods for manufacturing electronic devices using a resin film as a substrate have been studied, and for a new-generation display, a process capable of using an existing device for manufacturing a TFT display panel has been studied.
For example, patent documents 1,2, and 3 disclose the following methods: after an amorphous silicon thin film layer is formed on a glass substrate and a plastic substrate is formed on the thin film layer, laser light is irradiated from the glass substrate side to crystallize amorphous silicon, and the plastic substrate is peeled from the glass substrate by hydrogen gas generated along with the crystallization.
Patent document 4 discloses a method of: a liquid crystal display device is completed by attaching a layer to be peeled (described as a "layer to be transferred" in patent document 4) to a plastic film by using the techniques disclosed in patent documents 1 to 3.
However, the methods disclosed in patent documents 1 to 4, particularly the method disclosed in patent document 4, have the following problems: in order to transmit laser light, a substrate having high light transmittance must be used; irradiation with laser light of relatively large energy sufficient to cause hydrogen contained in amorphous silicon to be released through the substrate; the layer to be peeled may be damaged by laser irradiation.
Further, when the layer to be peeled has a large area, the laser processing requires a long time, and thus it is difficult to improve the productivity of device fabrication.
As a means for solving such a problem, patent document 5 adopts the following manufacturing process: a conventional glass substrate is used as a base (hereinafter referred to as a glass base), a release layer is formed on the glass base using a polymer such as a cyclic olefin copolymer, a heat-resistant resin film (resin substrate) such as a polyimide film is formed on the release layer, an ITO transparent electrode, a TFT, and the like are formed and sealed on the film by a vacuum process, and then the glass base is finally peeled and removed.
However, at present, a low-temperature polysilicon TFT having a mobility 2 times faster than that of an amorphous silicon TFT is used as a TFT. In the low-temperature polysilicon TFT, after amorphous silicon vapor deposition, dehydrogenation annealing and irradiation of a pulse laser to crystallize silicon are required to be performed at 400 ℃ or higher (hereinafter, these are referred to as TFT steps), and the temperature in the dehydrogenation annealing step is not lower than the glass transition temperature (hereinafter, referred to as Tg) of a conventional polymer.
However, with respect to existing polymers, it is known that: when the resin substrate is heated to a temperature of Tg or higher, the adhesion is improved (for example, see patent document 6), and the adhesion between the release layer and the base and the resin substrate is improved after the heat treatment, and it may be difficult to peel the resin substrate from the base.
The heat-resistant polymer that can be used in such a step is limited to a partially highly heat-resistant polymer compound such as polyimide, but cannot be dissolved in a general solvent. Therefore, when the polyimide is used for the release layer, it is difficult to remove the release layer remaining in the glass substrate after the resin substrate is peeled and reuse the glass substrate.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 10-125929
Patent document 2: japanese laid-open patent publication No. 10-125931
Patent document 3: international publication No. 2005/050754
Patent document 4: japanese laid-open patent publication No. 10-125930
Patent document 5: japanese patent laid-open publication No. 2010-111853
Patent document 6 Japanese laid-open patent publication No. 2008-188792
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a protective layer on a substrate, which can facilitate the reuse of a base, can be peeled off from the base together with a resin substrate of a flexible electronic device, and does not damage the resin substrate nor significantly change the properties.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that: when a resin substrate is produced by peeling off the resin substrate after forming the resin substrate on a base, a substrate protective layer having appropriate adhesiveness to the base and appropriate peelability and excellent adhesiveness to a resin substrate used in a flexible electronic device can be formed by using a composition containing a polyamic acid and an organic solvent as a composition for forming a substrate protective layer which is interposed between the base and the resin substrate, has easy peelability from the base, and functions as a protective layer of the peeled resin substrate, and the present invention has been completed.
Namely, the present invention provides:
1. a composition for forming a substrate protective layer, which is a composition for forming a substrate protective layer comprising: a resin substrate which is formed on a base and is interposed between the base and the resin substrate when the resin substrate is peeled from the base together with the resin substrate, has releasability from the base, and functions as a protective layer for the resin substrate after peeling; the polyamic acid solution is characterized by comprising polyamic acid and an organic solvent.
2.1A composition for forming a protective layer on a substrate, which comprises a polyamic acid represented by the following formula (1) and an organic solvent,
[ solution 1]
Figure BDA0002107328430000031
(wherein X represents an aromatic group represented by the following formula (2), Y represents a 2-valent aromatic group having a fluorine atom, and n represents a natural number.)
[ solution 2]
Figure BDA0002107328430000041
3.2A composition for forming a protective layer on a substrate, wherein Y is an aromatic group represented by the following formula (3),
[ solution 3]
Figure BDA0002107328430000042
4.2 or 3, wherein Y is an aromatic group represented by the following formula (4),
[ solution 4]
Figure BDA0002107328430000043
5.1 to 4, wherein the organic solvent is at least one selected from the group consisting of organic solvents having structures represented by the following formulae (S1) to (S7),
[ solution 5]
Figure BDA0002107328430000044
(in the formula, R1～R8Independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R9And R10Independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms, b and n represent natural numbers)
6.1 the composition for forming a protective layer for a substrate, which has releasability from the base when an electronic component is further produced on the resin substrate and the electronic component is peeled off from the base together with the resin substrate, and which functions as a protective layer for the resin substrate after peeling,
7. a substrate protective layer obtained from the composition for forming a substrate protective layer of any one of 1 to 6,
8. a method of manufacturing a flexible electronic device, comprising:
a step of applying 6 the substrate protective layer forming composition on a base and firing the composition at a maximum temperature of 500 ℃ or higher to form a substrate protective layer having releasability from the base;
applying a resin substrate-forming composition to the substrate protective layer, and firing the composition at a maximum temperature of 500 ℃ or higher to form a resin substrate;
a step of manufacturing an electronic component on the resin substrate; and
a step of peeling the electronic component together with the substrate protective layer and the resin substrate from the base body,
9.8A method for manufacturing a flexible electronic device, wherein the resin substrate is a polyimide resin substrate,
10. a method for producing a resin substrate with a protective layer, characterized in that a substrate protective layer-forming composition of any one of 1 to 5 is applied to a substrate, fired at a maximum temperature of 500 ℃ or higher to form a substrate protective layer, then a resin substrate-forming composition is applied to the substrate protective layer, fired at a maximum temperature of 500 ℃ or higher to form a resin substrate, and then the resin substrate is peeled off from the substrate together with the substrate protective layer,
the method of 11.10, wherein said resin substrate is a polyimide resin substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
By using the composition for forming a substrate protective layer of the present invention, a substrate protective layer having an appropriate adhesiveness to a base, an appropriate peelability, and an excellent adhesiveness to a resin substrate can be obtained with good reproducibility. Therefore, by using the composition for forming a substrate protective layer of the present invention, the resin substrate and the substrate protective layer can be separated from the base together with the circuit and the like without damaging the resin substrate formed on the base and the circuit and the like provided thereon in the production process of the flexible electronic device. Therefore, the composition for forming a protective layer on a substrate of the present invention can facilitate the reuse of a base, and can contribute to simplification of the manufacturing process of a flexible electronic device provided with a resin substrate, improvement of the yield thereof, and the like.
Detailed Description
The present invention will be described in more detail below.
The composition for forming a protective layer on a substrate of the present invention comprises a polyamic acid and an organic solvent. Here, the substrate protective layer in the present invention is a layer provided for a predetermined purpose directly above the glass substrate, and a typical example thereof is a layer provided between the substrate and a resin substrate of a flexible electronic device made of a resin such as polyimide in a process for manufacturing the flexible electronic device, in order to fix the resin substrate in a predetermined process. The substrate protective layer is different from the conventional release layer in that it is peeled from the base together with the resin substrate after the electronic circuit and the like are formed on the resin substrate.
The diamine component and the acid dianhydride component used in the production of the polyamic acid are not particularly limited as long as they give a polyimide film having the property of peeling from the substrate together with the resin substrate after the above-described production process, that is, the property of being easily peelable from the substrate and having adhesion to the resin substrate, and in view of sufficiently exhibiting the properties of easy peeling from the substrate and adhesion to the resin substrate, a polyamic acid obtained by reacting a diamine component containing an aromatic diamine and an acid dianhydride component containing an aromatic tetracarboxylic dianhydride is preferable, and a polyamic acid represented by the following formula (1) and obtained using a biphenyltetracarboxylic dianhydride and an aromatic diamine having a fluorine atom is particularly preferable.
[ solution 6]
Figure BDA0002107328430000061
In the formula (1), X represents an aromatic group derived from biphenyltetracarboxylic acid represented by the following formula (2), and Y represents a 2-valent fluorine atom-containing aromatic group derived from an aromatic diamine having a fluorine atom.
n represents a natural number, preferably an integer of 2 or more.
[ solution 7]
Figure BDA0002107328430000062
Examples of the biphenyltetracarboxylic dianhydride which imparts the 2-valent group derived from biphenyltetracarboxylic acid represented by the above formula (2) include biphenyltetracarboxylic dianhydrides represented by the following formulae (C1) to (C3). In the present invention, particularly, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride represented by the formula (C1) is preferable. The compounds (C1) to (C3) may be used alone or in combination of 2 or more.
[ solution 8]
Figure BDA0002107328430000071
In the present invention, other tetracarboxylic dianhydrides can be used in addition to the above-mentioned biphenyltetracarboxylic acid.
Specific examples thereof include pyromellitic dianhydride, benzene-1, 2,3, 4-tetracarboxylic dianhydride, naphthalene-1, 2,5, 6-tetracarboxylic dianhydride, naphthalene-1, 2,6, 7-tetracarboxylic dianhydride, naphthalene-1, 2,7, 8-tetracarboxylic dianhydride, naphthalene-2, 3,5, 6-tetracarboxylic dianhydride, naphthalene-2, 3,6, 7-tetracarboxylic dianhydride, naphthalene-1, 4, 5, 8-tetracarboxylic dianhydride, anthracene-1, 2,3, 4-tetracarboxylic dianhydride, anthracene-1, 2,5, 6-tetracarboxylic dianhydride, anthracene-1, 2,6, 7-tetracarboxylic dianhydride, anthracene-1, 2,7, 8-tetracarboxylic dianhydride, Anthracene-2, 3,6, 7-tetracarboxylic dianhydride, phenanthrene-1, 2,3, 4-tetracarboxylic dianhydride, phenanthrene-1, 2,5, 6-tetracarboxylic dianhydride, phenanthrene-1, 2,6, 7-tetracarboxylic dianhydride, phenanthrene-1, 2,7, 8-tetracarboxylic dianhydride, phenanthrene-1, 2, 9, 10-tetracarboxylic dianhydride, phenanthrene-2, 3,5, 6-tetracarboxylic dianhydride, phenanthrene-2, 3,6, 7-tetracarboxylic dianhydride, phenanthrene-2, 3, 9, 10-tetracarboxylic dianhydride, phenanthrene-3, 4, 5, 6-tetracarboxylic dianhydride, phenanthrene-3, 4, 9, 10-tetracarboxylic dianhydride, and the like, which can be used alone or in combination of 2 or more.
In the polyamic acid used in the present invention, the amount of biphenyltetracarboxylic dianhydride in the tetracarboxylic acid component is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and most preferably 100 mol%, in view of both the above-described easy releasability from the substrate and adhesion to the resin substrate.
On the other hand, specific examples of the aromatic diamine having a fluorine atom to which the above-mentioned Y is added include 5-trifluoromethylbenzene-1, 3-diamine, 5-trifluoromethylbenzene-1, 2-diamine, 3, 5-bis (trifluoromethyl) benzene-1, 2-diamine, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl (2, 2 '-bis (trifluoromethyl) benzidine), 3, 3' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (3, 3' -bis (trifluoromethyl) benzidine), 2-bis (3-aminophenyl) -1, 1, 1,3, 3, 3-hexafluoropropane, 2-bis (4-aminophenyl) -1, 1, 1,3, 3, 3-hexafluoropropane, 3,3 '-bis (trifluoromethyl) biphenyl-4, 4' -diamine, 3,3 ', 5, 5' -tetrafluorobiphenyl-4, 4 '-diamine, 4' -diaminooctafluorobiphenyl and the like, and they may be used alone or in combination of 2 or more.
Of these, in view of both the above-mentioned easy releasability from the substrate and the adhesion to the resin substrate, 2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl (2, 2 ' -bis (trifluoromethyl) benzidine) and 3,3 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl (3, 3 ' -bis (trifluoromethyl) benzidine) are preferable, and 2,2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl (2, 2 ' -bis (trifluoromethyl) benzidine) is more preferable.
Therefore, preferred examples of Y in formula (1) include 2-valent aromatic groups represented by formulas (3) and (4).
[ solution 9]
Figure BDA0002107328430000081
[ solution 10]
Figure BDA0002107328430000082
In the present invention, other diamines may be used in addition to the aromatic diamine having a fluorine atom.
Specific examples thereof include 1-membered diamines having 1 benzene nucleus, such as 1, 4-diaminobenzene (p-phenylenediamine), 1, 3-diaminobenzene (m-phenylenediamine), 1, 2-diaminobenzene (o-phenylenediamine), 2, 4-diaminotoluene, 2, 5-diaminotoluene, 2, 6-diaminotoluene, 4, 6-dimethyl-m-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, 2, 6-dimethyl-p-phenylenediamine, 2,4, 6-trimethyl-1, 3-phenylenediamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine; 1, 2-naphthalenediamine, 1, 3-naphthalenediamine, 1, 4-naphthalenediamine, 1, 5-naphthalenediamine, 1, 6-naphthalenediamine, 1, 7-naphthalenediamine, 1, 8-naphthalenediamine, 2, 3-naphthalenediamine, 2, 6-naphthalenediamine, 4 '-biphenyldiamine, 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 3' -dicarboxy-4, 4 '-diaminodiphenylmethane, 3', 5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane, 4 '-diamino-N-benzanilide, 3' -dichlorobenzidine, 3 '-dimethylbenzidine, 2' -dimethylbenzidine, Diamines having 2 benzene nuclei, such as 3,3 '-diaminodiphenylmethane, 3, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylmethane, 2-bis (3-aminophenyl) propane, 2-bis (4-aminophenyl) propane, 3' -diaminodiphenylsulfoxide, 3,4 '-diaminodiphenylsulfoxide, 4' -diaminodiphenylsulfoxide, 2- (3-aminophenyl) -5-aminobenzimidazole, and 2- (4-aminophenyl) -5-aminobenzoxazole; 1, 5-diaminoanthracene, 2, 6-diaminoanthracene, 9, 10-diaminoanthracene, 1, 8-diaminophenanthrene, 2, 7-diaminophenanthrene, 3, 6-diaminophenanthrene, 9, 10-diaminophenanthrene, 1, 3-bis (3-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 1, 4-bis (3-aminophenyl) benzene, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (3-aminophenyl sulfide) benzene, 1, 3-bis (4-aminophenyl sulfide) benzene, 1, 4-bis (4-aminophenyl sulfide) benzene, 1, 3-bis (3-aminophenyl sulfone) benzene, 1, 3-bis (4-aminophenyl sulfone) benzene, 1, diamines having 3 benzene nuclei, such as 4-bis (4-aminophenylsulfone) benzene, 1, 3-bis [2- (4-aminophenyl) isopropyl ] benzene, 1, 4-bis [2- (3-aminophenyl) isopropyl ] benzene, 1, 4-bis [2- (4-aminophenyl) isopropyl ] benzene, 4 "-diamino-p-terphenyl, 4" -diamino-m-terphenyl, and the like, may be used alone or in combination of 2 or more.
In the polyamic acid used in the present invention, the amount of the aromatic diamine having a fluorine atom in the diamine component is preferably 70 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more, further preferably 95 mol% or more, and most preferably 100 mol%, from the viewpoint of the above-mentioned easy releasability from the substrate and adhesion to the resin substrate.
The polyamic acid contained in the composition for forming a protective layer for a substrate of the present invention can be obtained by reacting the diamine component and the tetracarboxylic dianhydride component described above in an organic solvent.
The organic solvent used in the reaction is not particularly limited as long as it does not adversely affect the reaction, and specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-propoxy-N, N-dimethylpropionamide, 3-isopropoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-isopropyloxy-N, N-dimethylpropionamide, N-butyloxy-N, N-dimethylpropionamide, and the like, 3-sec-butoxy-N, N-dimethylpropionamide, 3-tert-butoxy-N, N-dimethylpropionamide, γ -butyrolactone, etc. As the organic solvent, 1 kind can be used alone or 2 or more kinds can be used in combination.
The feed ratio (molar ratio) of the diamine component to the tetracarboxylic dianhydride component is not generally specified because it is appropriately determined in consideration of the target molecular weight, molecular weight distribution, kind of diamine, kind of tetracarboxylic dianhydride, and the like, and the diamine component is about 0.7 to 1.3, preferably about 0.8 to 1.2, and more preferably about 0.9 to 1.1 relative to the tetracarboxylic dianhydride component 1.
The reaction temperature is suitably set in a range from the melting point to the boiling point of the solvent used, and is usually about 0 to 100 ℃, and is preferably about 0 to 70 ℃, more preferably about 0 to 60 ℃, and further preferably about 0 to 50 ℃ in order to prevent imidization of the solution of the polyamic acid obtained and maintain a high content of the polyamic acid unit.
The reaction time depends on the reaction temperature and the reactivity of the raw material, and therefore cannot be generally specified, but is usually about 1 to 100 hours.
The weight average molecular weight of the polyamic acid thus obtained is usually about 5,000 to 500,000, and from the viewpoint of improving the function of the obtained film as a substrate protective layer, it is preferably about 10,000 to 200,000, and more preferably about 30,000 to 150,000. In the present invention, the weight average molecular weight is a polystyrene equivalent value measured by Gel Permeation Chromatography (GPC).
Note that, in the case of the polyamic acid used in the present invention, one or both of polymer chain ends thereof may be further reacted with an amine having an anchor group or an acid anhydride having an anchor group.
Examples of such an anchor group include a carboxylic acid group, a silyl group (for example, an alkylsilyl group, an alkoxysilyl group, a vinylsilyl group, an allylsilyl group, etc.), a vinyl group, a maleimido group, a phenolic hydroxyl group, etc., and among them, a carboxylic acid group and a silyl group (particularly, a silyl group in which 1 or more groups selected from an alkoxy group, a vinyl group, and an allyl group are bonded to a silicon atom) are preferable.
Further, a spacer group having 1 to about 10 carbon atoms such as an alkyl group or an aryl group having carbon atoms which does not significantly reduce releasability or heat resistance may be present between the polyamic acid obtained from the diamine component and the tetracarboxylic dianhydride component and the anchor group.
Specific examples of the amine having an anchor group include 4-aminophenoxytrimethylsilane, 4-aminophenoxydimethylvinylsilane, 4-aminophenoxymethyldiethylsilane, 4-aminophenoxytrivinylsilane, 4-aminophenoxydimethylallylsilane, 4-aminophenoxymethyldiallylsilane, 4-aminophenoxytriallylsilane, 4-aminophenoxydimethylphenylsilane, 4-aminophenoxymethyldiphenylsilane, 4-aminophenoxytriphenylsilane, 4-aminophenoxytrimethoxysilane, 4-aminophenoxydimethoxyvinylsilane, 4-aminophenoxymethoxydivinylsilane, 4-aminophenoxytrivinylsilane, 4-aminophenoxydimethylvinylsilane, 4-aminophenoxyethylvinylsilane, 4-aminophenoxydimethylvinylsilane, and the like, 4-aminophenoxy dimethoxyallylsilane, 4-aminophenoxy methoxydiallylsilane, 4-aminophenoxy dimethoxyphenylsilane, 4-aminophenoxy methoxydiphenylsilane, 4-aminophenoxy triethoxysilane, 4-aminophenoxy diethoxyvinylsilane, 4-aminophenoxy ethoxy divinylsilane, 4-aminophenoxy trivinylsilane, 4-aminophenoxy diethoxyallylsilane, 4-aminophenoxy ethoxy diallylsilane, 4-aminophenoxy diethoxyphenylsilane, 4-aminophenoxy ethoxy diphenylsilane, 3-aminophenoxy trimethylsilane, 3-aminophenoxy dimethylvinylsilane, 3-aminophenoxy methyl divinylsilane, 4-aminophenoxy methoxy dimethoxyallylsilane, 4-aminophenoxy diethoxylsilane, 4-aminophenoxy diethoxylsilylsilane, 3-aminophenoxy trimethylsilane, 3-aminophenoxy dimethylvinylsilane, 3-aminophenoxy methyl divinylsilane, 4-aminophenoxy methyl diphenylsilane, 4-aminophenoxy diethoxysilane, 4-phenoxyamino diethoxysilane, 4-phenoxysilane, 4-aminophenoxy diethoxylsilane, 4-amino diethoxysilane, 4-phenoxysilane, 4-aminophenoxy diethoxylsilane, 4-ethoxyvinylsilane, 4-aminophenoxy diethoxysilane, 4-phenoxysilane, 4-phenoxymethyldimethylsilane, and a mixture, 2-aminophenoxytrivinylsilane, 2-aminophenoxytrimethylsilane, 2-aminophenoxydimethylvinylsilane, 2-aminophenoxymethyldiethylvinylsilane, 2-aminophenoxytrivinylsilane, 3-aminopropyltriethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-aminophenoxyethyltrimethoxysilane, N-aminophenoxytrimethylsilane, N-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-triethoxysilane, N-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-trimethoxysilane, N-aminopropyltrimethoxysilane, N-3-ethoxycarbonyl-3-trimethoxysilane, N-aminopropyl-trimethoxysilane, N-3-trimethoxysilane, N-ethoxycarbonyl-3-aminopropyl-3-trimethoxysilane, N-3-aminopropyl-ethoxycarbonyl-2-amino-trimethoxysilane, N-amino-3-trimethoxysilane, N-2-amino-propyltrimethoxysilane, or a-2-amino-propyl-3-2-or a-amino-propyl-or a mixture thereof, or a mixture of, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 2-aminophenol, 3-aminophenol, 4-aminophenol and the like, but are not limited thereto.
Specific examples of the acid anhydride having an anchor group include trimellitic anhydride, vinyl maleic anhydride, 4-vinylnaphthalene-1, 2-dicarboxylic anhydride, maleic anhydride, 2, 3-dimethylmaleic anhydride, 4-hydroxyphthalic anhydride, and 3-hydroxyphthalic anhydride, but are not limited thereto.
The amount of the amine having an anchor group and the acid anhydride having an anchor group is about 0.01 to 0.6, preferably about 0.05 to 0.4, and more preferably about 0.1 to 0.2 in terms of a molar ratio relative to the tetracarboxylic dianhydride component 1, or about 0.01 to 0.52, preferably about 0.05 to 0.32, and more preferably about 0.1 to 0.2 in terms of a molar ratio relative to the diamine component 1.
The composition for forming a protective layer on a substrate of the present invention contains an organic solvent in addition to the polyamic acid described above. The organic solvent is not particularly limited, and is preferably selected from the following solvents.
[ solution 11]
Figure BDA0002107328430000121
(in the formula, R1～R8Independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R9And R10Independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms, b and m represent a natural number)
b and m are natural numbers, preferably 1 to 3, and more preferably 1 or 2.
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group and the like. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable.
Examples of the acyl group having 1 to 10 carbon atoms include an alkanoyl group having 1 to 8 carbon atoms (e.g., formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, pivaloyl group, etc.), a cycloalkylcarbonyl group having 3 to 6 carbon atoms (e.g., cyclopropylcarbonyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, etc.), a benzoyl group, and the like, and preferably an acetyl group.
Among them, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, and γ -butyrolactone are preferable, and N-methyl-2-pyrrolidone is more preferable, because polyamic acid is well dissolved and a composition having high uniformity can be easily prepared.
The solvent which does not dissolve the polyamic acid even when used alone can be used for the preparation of the composition as long as the polyamic acid is not precipitated. In particular, solvents having a low surface tension, such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and isoamyl lactate, can be suitably mixed. It is known that the coating film uniformity is improved when the coating is applied to a substrate, and the coating film can be preferably used in the present invention.
The method for producing the composition for forming a substrate protective layer of the present invention is optional. Preferred examples of the production method include: a method of filtering the reaction solution containing the objective polyamic acid obtained by the above-described method. In this case, the filtrate may be diluted or concentrated as necessary for the purpose of adjusting the concentration or the like. By adopting such a method, it is possible to reduce the mixing of impurities that may cause deterioration in adhesion, peeling property, and the like of the substrate protective layer produced from the obtained composition, and to efficiently obtain the composition for forming the substrate protective layer. The solvent used for dilution is not particularly limited, and specific examples thereof include the same solvents as those of the reaction solvent of the above reaction. As the solvent for dilution, 1 kind can be used alone or 2 or more kinds can be used in combination.
The concentration of the polyamic acid in the composition for forming a substrate protective layer of the present invention is suitably set in consideration of the thickness of the substrate protective layer to be produced, the viscosity of the composition, and the like, and is usually about 1 to 30 mass%, and preferably about 1 to 20 mass%. By setting the concentration to such a value, a substrate protective layer having a thickness of about 0.05 to 5 μm can be obtained with good reproducibility. The concentration of the polyamic acid can be adjusted by adjusting the amounts of the diamine and the tetracarboxylic dianhydride used as the raw materials of the polyamic acid, adjusting the amounts of the isolated polyamic acid when dissolved in a solvent, and the like.
The viscosity of the composition for forming a substrate protective layer of the present invention is suitably set in consideration of the thickness of the substrate protective layer to be produced, and in particular, when a film having a thickness of about 0.05 to 5 μm is to be obtained with good reproducibility, the viscosity is usually about 10 to 10,000mPa · s, preferably about 20 to 5,000mPa · s, at 25 ℃.
The viscosity can be measured at a temperature of 25 ℃ of the composition using a commercially available viscometer for measuring the viscosity of a liquid, for example, according to the procedure described in JIS K7117-2. Preferably, as the viscometer, can use the conical flat (cone plate type) rotation viscometer, preferably in the same type of viscometer using 1 degrees 34' × R24 as standard conical rotor composition temperature 25 ℃ under the conditions of measurement. An example of such a rotational viscometer is TVE-25L manufactured by Toyobo industries, Ltd.
The composition for forming a protective layer on a substrate of the present invention may contain a crosslinking agent or the like in addition to the polyamic acid and the organic solvent, for example, to improve the film strength.
After the composition for forming a release layer described above is applied to a substrate, a resin substrate protective layer made of a polyimide film having easy releasability from the substrate and excellent adhesion to a resin substrate can be obtained by thermal imidization of a polyamic acid by a firing method including a step of firing at a maximum temperature of 500 ℃.
In the present invention, the maximum temperature at the time of firing is not particularly limited as long as it is within a range of 500 ℃ or more and a heat-resistant temperature of polyimide or less. The upper limit is usually about 550 ℃, preferably about 520 ℃, and more preferably about 510 ℃. By setting the heating temperature in the above range, the imidization reaction can be sufficiently performed while preventing the resultant film from becoming brittle.
The heating time varies depending on the heating temperature, and therefore cannot be generally specified, but is usually 5 minutes to 5 hours. The imidization ratio may be in the range of 50 to 100%.
The temperature at the time of firing may include a step of firing at a temperature lower than the above range as long as the maximum temperature is within the above range.
As a preferred example of the heating method in the present invention, the following method can be mentioned: after heating at 50-150 ℃, the heating temperature is directly raised in stages, and finally the heating is carried out at 500 ℃ or higher. In particular, as a more preferable example of the heating method, the following method can be mentioned: heating at 50-100 deg.C, at more than 100 deg.C and less than 500 deg.C, and at more than 500 deg.C. Further, as another more preferable example of the heating method, the following method can be mentioned: heating at 50-100 deg.C, heating at 200-300 deg.C, heating at more than 300 deg.C and less than 500 deg.C, and finally heating at 500-510 deg.C.
In addition, as a preferable example of the heating method in consideration of the firing time, the following method can be mentioned: after heating at 50-150 ℃ for 1 min-2 h, the heating temperature is directly raised in stages, and finally heating at 500 ℃ or higher is carried out for 30 min-4 h. Particularly, as a more preferable example of the heating method, heating at 50 to 100 ℃ for 1 minute to 2 hours, heating at more than 100 ℃ and less than 500 ℃ for 5 minutes to 2 hours, and heating at 500 ℃ or more for 30 minutes to 4 hours can be cited. Further, as another more preferable example of the heating method, the following method can be mentioned: heating at 50-100 ℃ for 1 min-2 h, heating at 200-300 ℃ for 5 min-2 h, heating at more than 300 ℃ and less than 500 ℃ for 5 min-2 h, and finally heating at 500-510 ℃ for 1 min-2 h.
When the substrate protective layer of the present invention is formed on a base, the substrate protective layer may be formed on a part of the surface of the base or may be formed on the entire surface. Examples of the form of forming the substrate protective layer on the partial surface of the base include a form of forming the substrate protective layer only in a predetermined range on the surface of the base, and a form of forming the substrate protective layer in a pattern such as a dot pattern, a line pattern, a space pattern, or the like on the entire surface of the base. In the present invention, the base means a member to be used for the production of a flexible electronic device or the like, on the surface of which the composition for forming a protective layer for a substrate of the present invention is applied.
Examples of the substrate (base material) include glass, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metals (silicon wafer, etc.), wood, paper, slate, etc., and particularly, glass is preferable in view of the sufficient adhesion of the substrate protective layer of the present invention thereto. The surface of the substrate may be made of a single material or 2 or more materials. As a form in which the substrate surface is made of 2 or more kinds of materials, there is a form in which a certain range of the substrate surface is made of a certain material and the remaining surface is made of another material; a pattern in which a certain material exists in other materials in a dot pattern, a line pattern, a space pattern, or the like over the entire surface of the substrate.
The method for applying the composition for forming a protective layer on a substrate of the present invention to a substrate is not particularly limited, and examples thereof include a casting method, a spin coating method, a doctor blade method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an ink jet method, and a printing method (relief printing, gravure printing, offset printing, screen printing, etc.).
Examples of the heating tool include a hot plate and an oven. The heating atmosphere may be air or an inert gas, or may be normal pressure or reduced pressure.
The thickness of the substrate protective layer is usually about 0.01 to 50 μm, and preferably about 0.05 to 20 μm from the viewpoint of productivity. The desired thickness is achieved by adjusting the thickness of the coating film before heating.
The substrate protective layer described above has appropriate adhesion to a base, particularly a glass base, appropriate peelability, and excellent adhesion to a resin substrate. Therefore, the substrate protective layer of the present invention can be suitably used for: in a process for manufacturing a flexible electronic device, a resin substrate of the device is peeled from a base body together with a circuit or the like formed on the resin substrate without damaging the resin substrate.
The resin substrate formed on the substrate protective layer is not particularly limited, and a resin substrate having a 1% weight loss temperature of 500 ℃ or higher in thermogravimetric analysis is preferable from the viewpoint of heat resistance.
Examples of such a resin substrate include a resin substrate using a wholly aromatic polymer such as wholly aromatic polyimide, polybenzoxazole, polybenzothiazole, or polybenzimidazole. Further, a mixed film in which a silica sol, a titania sol, or the like is added to the polymer may be used.
An example of a method for manufacturing a flexible electronic device using the substrate protective layer of the present invention will be described below.
The substrate protective layer is formed on the glass substrate by the above-mentioned method using the composition for forming a substrate protective layer of the present invention. A resin substrate-forming solution for forming a resin substrate is applied to the substrate protective layer, and the coating film is baked, thereby forming a resin substrate fixed to a glass base via the substrate protective layer of the present invention.
The baking temperature of the coating film is appropriately set according to the kind of resin, and in the present invention, the maximum temperature at the time of baking is preferably 500 ℃. The upper limit is usually about 550 ℃, preferably about 520 ℃, and more preferably about 510 ℃.
By setting the maximum temperature at the time of firing in the production of the resin substrate within this range, the releasability between the protective layer as a base and the base, and the appropriate adhesion and releasability between the substrate protective layer and the resin substrate can be further improved.
In this case, the firing step may be included at a temperature lower than the maximum temperature as long as the maximum temperature is within the above range.
As a preferred example of the heating method in the production of the resin substrate, the following method can be mentioned: after heating at 50-150 ℃, the heating temperature is directly raised in stages, and finally the heating is carried out at 500 ℃ or higher. In particular, as a more preferable example of the heating method, the following method can be mentioned: heating at 50-100 deg.C, at more than 100 deg.C and less than 500 deg.C, and at more than 500 deg.C. Further, as another more preferable example of the heating method, the following method can be mentioned: heating at 50-100 deg.C, heating at more than 100 deg.C and below 200 deg.C, heating at more than 200 deg.C and below 300 deg.C, heating at more than 300 deg.C and below 500 deg.C, and finally heating at 500-510 deg.C.
In addition, as a preferable example of the heating method in consideration of the firing time, the following method can be mentioned: after heating at 50-150 ℃ for 1 min-2 h, the heating temperature is directly raised in stages, and finally heating is carried out at 500 ℃ or higher for 30 min-4 h. Particularly, as a more preferable example of the heating method, heating at 50 to 100 ℃ for 1 minute to 2 hours, heating at more than 100 ℃ and less than 500 ℃ for 5 minutes to 2 hours, and heating at 500 ℃ or more for 30 minutes to 4 hours can be cited. Further, as another more preferable example of the heating method, the following method can be mentioned: heating at 50-100 ℃ for 1 min-2 h, heating at more than 100 ℃ and below 200 ℃ for 5 min-2 h, heating at more than 200 ℃ and below 300 ℃ for 5 min-2 h, heating at more than 300 ℃ and below 500 ℃ for 5 min-2 h, and finally heating at 500-510 ℃ for 30 min-4 h.
Next, a desired circuit is formed on the resin substrate fixed to the base body via the substrate protective layer of the present invention, and then, for example, the resin substrate is cut along the substrate protective layer, and the resin substrate and the substrate protective layer are peeled from the base body together with the circuit, thereby separating the resin substrate and the substrate protective layer from the base body. At this time, a part of the base body may be cut together with the substrate protective layer.
In addition, japanese patent application laid-open No. 2013-147599 reports that the laser lift-off method (LLO method) used in the manufacture of high-brightness LEDs, three-dimensional semiconductor packages, and the like has been applied to the manufacture of flexible displays. The LLO method is characterized in that light having a specific wavelength, for example, light having a wavelength of 308nm is irradiated from the glass substrate side from the side opposite to the side on which the circuit and the like are formed. The irradiated light passes through the glass substrate, and only the polymer (polyimide) in the vicinity of the glass substrate absorbs the light to evaporate (sublimate). As a result, the substrate protective layer can be selectively peeled off from the glass base without affecting circuits and the like provided on the resin substrate, which determine the performance of the display.
The composition for forming a substrate protective layer of the present invention has a characteristic of sufficiently absorbing light having a specific wavelength (for example, 308nm) to which the LLO method can be applied, and thus can be used as a sacrificial layer of the LLO method. Therefore, in the present invention, after a desired circuit is formed on a resin substrate fixed to a glass substrate via a substrate protective layer formed using a composition, and 308nm light is irradiated by an LLO method, only the substrate protective layer absorbs the light and evaporates (sublimes). Thus, the substrate protective layer is sacrificial (functions as a sacrificial layer), and the resin substrate can be selectively peeled from the glass base.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
[1] Abbreviations for the Compounds
p-PDA: p-phenylenediamine
TFMB: 2, 2' -bis (trifluoromethyl) benzidine
BPDA: 3,3 ', 4, 4' -Biphenyltetracarboxylic dianhydride
And (3) PMDA: pyromellitic dianhydride
CBDA: 1,2, 3, 4-cyclobutanetetracarboxylic dianhydride
NMP: n-methyl-2-pyrrolidone
BCS: butyl cellosolve
PGME: propylene glycol monomethyl ether
[2] Method for measuring weight average molecular weight and molecular weight distribution
For the measurement of the weight average molecular weight (hereinafter abbreviated as Mw) and the molecular weight distribution of the polymer, GPC apparatus manufactured by Nippon spectral Co., Ltd. (columns: KD801 and KD805 manufactured by Shodex; eluent: dimethylformamide/LiBr. H)2O(29.6mM)/H3PO4(29.6mM)/THF (0.1 wt%); flow rate: 1.0 mL/min; column temperature: 40 ℃; mw: standard polystyrene conversion).
[3] Synthesis of polymers
The polyamic acid was synthesized by the following method.
The polymer is not isolated from the obtained reaction solution containing the polymer, but the reaction solution is diluted as described later, thereby preparing a composition for forming a resin substrate or a composition for forming a substrate protective layer.
Synthesis example S1 Synthesis of Polyamic acid (S1)
p-PDA3.176g (0.02937 mol) was dissolved in NMP88.2g, BPDA8.624g (0.02931 mol) was added thereto, and then the mixture was reacted at 23 ℃ for 24 hours under a nitrogen atmosphere. The Mw of the resulting polymer was 107300, with a molecular weight distribution of 4.6.
< Synthesis example Synthesis of polyamic acid (L1) L1
TFMB23.7g (74.2mmol) was dissolved in NMP352 g. To the resulting solution was added BPDA24.2g (82.5mmol), and the mixture was reacted under a nitrogen atmosphere at 23 ℃ for 24 hours. The Mw of the resulting polymer was 76400 with a molecular weight distribution of 2.2. The resulting solution was soluble in PGME.
< Synthesis example Synthesis of polyamic acid (L2) L2
TFMB9.89g (30.9mmol) was dissolved in PGME380 g. To the resulting solution, 10.0g (34.3mmol) of BPDA was added, and the mixture was reacted at 50 ℃ for 72 hours under a nitrogen atmosphere. The Mw of the resulting polymer was 76400 with a molecular weight distribution of 2.2.
< comparative Synthesis example Synthesis of polyamic acid HL1 (HL1)
TFMB2.73g (8.53mmol) was dissolved in NMP38.5g. To the resulting solution was added PMDA2.06g (9.47mmol), and the mixture was reacted at 23 ℃ for 24 hours under a nitrogen atmosphere. The Mw of the resulting polymer was 76400 with a molecular weight distribution of 2.2. The resulting solution was soluble in PGME.
< comparative Synthesis example Synthesis of polyamic acid HL2 (HL2)
TFMB2.86g (8.91mmol) was dissolved in NMP35.2g. To the resulting solution, CBDA1.94g (9.91mmol) was added, and the mixture was reacted under a nitrogen atmosphere at 23 ℃ for 24 hours. The Mw of the resulting polymer was 69200, with a molecular weight distribution of 2.2. The resulting solution was soluble in PGME.
[4] Preparation of composition for Forming resin substrate
[ preparation example 1]
The reaction solution obtained in synthesis example S1 was used as it was as a resin substrate-forming composition.
[5] Preparation of composition for Forming protective layer of substrate
[ example 1-1]
BCS and NMP were added to the reaction solution obtained in Synthesis example L1, and diluted so that the polymer concentration became 5 wt% and BCS became 20 mass%, to obtain a composition for forming a substrate protective layer.
[ examples 1-2]
The reaction solution obtained in synthesis example L2 was used as it was as a composition for forming a substrate protective layer.
Comparative examples 1 to 1
BCS and NMP were added to the reaction solution obtained in comparative Synthesis example HL1, and diluted so that the polymer concentration became 5 wt% and the BCS became 20 mass%, to obtain a composition for forming a substrate protective layer.
Comparative examples 1 and 2
BCS and NMP were added to the reaction solution obtained in comparative Synthesis example HL2, and diluted so that the polymer concentration became 5 wt% and the BCS became 20 mass%, to obtain a composition for forming a substrate protective layer.
[6] Substrate protective layer and production of resin substrate
[ example 2-1]
The composition for forming a substrate protective layer obtained in example 1-1 was applied onto a 100mm × 100mm glass substrate (the same applies below) as a glass substrate using a spin coater (conditions: rotation speed 3000rpm, about 30 seconds).
Then, the obtained coating film was heated at 80 ℃ for 10 minutes using a hot plate, then heated at 300 ℃ for 30 minutes and at 400 ℃ for 30 minutes using an oven, and further heated at 500 ℃ for 10 minutes, to form a substrate protective layer having a thickness of about 0.1 μm on a glass substrate, thereby obtaining a glass substrate with a substrate protective layer. The rate of temperature increase between the respective heating temperatures was set to 5 ℃/min, and during the temperature increase, the substrate with the film was heated in the oven without being taken out of the oven.
The resin substrate-forming composition was applied to the substrate protective layer (resin film) on the glass substrate obtained above using a bar coater (gap: 250 μm). Then, the obtained coating film was heated at 80 ℃ for 40 minutes using a hot plate, and then heated at 140 ℃, 210 ℃, 300 ℃ and 400 ℃ for 30 minutes using an oven, respectively, and further heated at 500 ℃ for 60 minutes, to form a polyimide resin substrate having a thickness of about 10 μm on the substrate protective layer, thereby obtaining a glass substrate with a resin substrate/substrate protective layer. The rate of temperature increase between the respective heating temperatures was set to 2 ℃/min, and during the temperature increase, the substrate with the film was heated in the oven without being taken out of the oven.
[ examples 2-2]
A substrate protective layer and a polyimide resin substrate were formed in the same manner as in example 2-1, except that the composition for forming a substrate protective layer obtained in example 1-2 was used in place of the composition for forming a substrate protective layer obtained in example 1-1, to obtain a glass substrate with a substrate protective layer and a glass substrate with a resin substrate/substrate protective layer.
Comparative examples 2-1 to 2-2
A substrate protective layer and a polyimide resin substrate were formed in the same manner as in example 2-1, except that the composition for forming a substrate protective layer obtained in comparative example 1-1 to 1-2 was used instead of the composition for forming a substrate protective layer obtained in example 1-1, to obtain a glass substrate with a substrate protective layer and a glass substrate with a resin substrate/substrate protective layer.
[7] Evaluation of peelability
The resin substrate and the substrate protective layer of the glass substrate with the resin substrate/substrate protective layer obtained in examples 2-1 to 2-2 and comparative examples 2-1 to 2-2 were cut into long strips having a width of 2cm and a length of 5cm using a cutting tool. Then, an adhesive tape was attached to the end of the cut resin substrate to obtain a test piece. The test piece was subjected to a peeling test using a push-pull tester manufactured by (ltd) アトニック so that the peeling angle became 170 °, and the peeling property was evaluated based on the following criteria. The results are shown in Table 1.
< evaluation Standard of peelability of glass substrate and substrate protective layer >
O: the substrate protective layer was completely peeled off from the glass base.
And (delta): the resin substrate can be peeled off, but a part of the substrate protective layer remains on the glass base.
X: the resin substrate and the substrate protective layer cannot be peeled off from the glass base.
The surface of the glass surface of the peeled portion was cut with a cutting tool, and the residual film property was evaluated based on the following criteria. The results are shown in Table 1.
< evaluation Standard of residual film Property of substrate protective layer on glass substrate >
O: the substrate protective layer does not remain.
And (delta): a portion of the substrate protective layer remains.
X: the substrate protection layer remains.
And (2) preparing: the resin substrate was not peeled off, and thus it was not evaluated.
[ Table 1]
Figure BDA0002107328430000221
As shown in table 1, it can be confirmed that: the substrate protective layers of examples 2-1 to 2-2 were easily peeled off together with the resin substrate, and the substrate protective layers were not left on the glass substrate. On the other hand, the resin substrates of comparative examples 2-1 to 2-2 were firmly adhered to the glass substrate via the substrate protective layer and could not be peeled from the glass substrate.
[9] Physical Properties of resin film
The mechanical properties of the resin substrate obtained in example 2-1 were measured. For comparison, a resin substrate was used which was prepared by directly applying and baking the resin substrate-forming composition S1 on a base without forming a substrate protective layer. At this time, a resin substrate was formed in the same manner as in example 2-1, except that the base was changed from a glass substrate to a silicon substrate. The obtained resin film was designated as SF 1.
< coefficient of linear expansion >
From the film obtained above, a long test piece of 20mm × 5mm was prepared, and the linear expansion coefficient from 50 ℃ to 500 ℃ was measured using TMA-4000SA (manufactured by ブルカー & エイエックスエス). The results are shown in table 2.
< weight reduction >
A long test piece of 20 mm. times.3 mm was prepared from the film obtained above, and the temperature at which 1% weight loss was observed was determined by measuring the weight loss from 50 ℃ to 600 ℃ using TGA-DTA-2000SR (manufactured by ブルカー & エイエックスエス Co.). The results are shown in table 2.
[ Table 2]
Figure BDA0002107328430000231
As shown in table 2, no difference in mechanical properties was observed between the resin substrates with the substrate protective layer produced in the examples and the resin substrates produced without the substrate protective layer. From the above results, it was confirmed that: the substrate protective layer does not affect the mechanical properties of the resin substrate to be produced.

Claims (7)

1. A method for producing a resin substrate with a protective layer, characterized in that a substrate protective layer-forming composition comprising a polyamic acid represented by the following formula (1) and an organic solvent is applied to a substrate, and fired to form a substrate protective layer, the firing comprising a step of firing at 500 ℃ or higher, then a resin substrate-forming composition is applied to the substrate protective layer, and fired to form a resin substrate, the firing comprising a step of firing at 500 ℃ or higher, and then the resin substrate is peeled from the substrate together with the substrate protective layer,
Figure FDA0003368814360000011
wherein X represents an aromatic group represented by the following formula (2), Y represents an aromatic group having a valence of 2 and a fluorine atom, n represents a positive integer,
Figure FDA0003368814360000012
2. the method for producing a resin substrate with a protective layer according to claim 1, wherein Y is an aromatic group represented by the following formula (3),
Figure FDA0003368814360000013
3. the method for producing a resin substrate with a protective layer according to claim 1 or 2, wherein Y is an aromatic group represented by the following formula (4),
Figure FDA0003368814360000014
4. the method for manufacturing a resin substrate with a protective layer according to claim 1 or 2, wherein the organic solvent is at least one selected from organic solvents having a structure represented by the following formulae (S1) to (S7),
Figure FDA0003368814360000021
in the formula, R1～R8Independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R9And R10Independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms, and b and n represent a positive integer.
5. The production method according to claim 1 or 2, wherein the resin substrate is a polyimide resin substrate.
6. A method of manufacturing a flexible electronic device, comprising:
a step of applying a composition for forming a substrate protective layer, which comprises a polyamic acid represented by the following formula (1) and an organic solvent, onto a substrate, and firing the composition to form a substrate protective layer having releasability from the substrate, wherein the firing comprises a step of firing the composition at 500 ℃ or higher;
a step of forming a resin substrate by applying a resin substrate-forming composition onto the substrate protective layer and baking the composition, wherein the baking step includes a step of baking at 500 ℃ or higher;
a step of manufacturing an electronic component on the resin substrate; and
a step of peeling the electronic component together with the substrate protective layer and the resin substrate from the base body,
Figure FDA0003368814360000022
wherein X represents an aromatic group represented by the following formula (2), Y represents an aromatic group having a valence of 2 and a fluorine atom, n represents a positive integer,
Figure FDA0003368814360000023
7. the method of manufacturing a flexible electronic device according to claim 6, wherein the resin substrate is a polyimide resin substrate.
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