CN111344130A - Method for manufacturing substrate for flexible device - Google Patents
Method for manufacturing substrate for flexible device Download PDFInfo
- Publication number
- CN111344130A CN111344130A CN201880036744.5A CN201880036744A CN111344130A CN 111344130 A CN111344130 A CN 111344130A CN 201880036744 A CN201880036744 A CN 201880036744A CN 111344130 A CN111344130 A CN 111344130A
- Authority
- CN
- China
- Prior art keywords
- release layer
- resin film
- forming
- heat
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/22—Making multilayered or multicoloured articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- C08G73/1039—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
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Moulding By Coating Moulds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The purpose of the present invention is to provide a method for forming a resin thin film laminate, which can obtain a plastic thin film having excellent properties as a base film of a flexible device substrate such as a flexible display substrate, which can be easily peeled from a glass carrier while maintaining excellent properties such as excellent heat resistance, low retardation, excellent flexibility, and further excellent transparency. A method for producing a resin film laminate, characterized in that a release layer is formed on a support base using a composition for forming a release layer containing a heat-resistant polymer and an organic solvent, then a resin film is formed on the release layer using a composition for forming a resin film containing a heat-resistant polymer and an organic solvent, and then the release layer and the resin film are integrated and peeled from the support base, characterized in that substantially only the composition for forming a resin film further contains silica particles having an average particle diameter of 100nm or less as calculated from a value of specific surface area measured by a nitrogen adsorption method.
Description
Technical Field
The present invention relates to a method for producing a resin thin film laminate which is a base film of a substrate for a flexible device, particularly a flexible printed circuit board such as a flexible display, and more particularly to a heat-resistant polymer laminate in which a transparent laminate is laminated on a support substrate.
Background
In recent years, with rapid progress in electronic devices such as liquid crystal displays and organic electroluminescence displays, thinning, weight reduction, and flexibility of devices have been required.
In these devices, various electronic components such as a thin film transistor and a transparent electrode are formed on a glass substrate, but it is expected that the device itself can be made thinner, lighter, and more flexible by replacing the glass material with a soft and lightweight resin material.
Polyimide has attracted attention as a candidate for such a resin material, and various reports have been made on polyimide films.
For example, patent document 1 relates to an invention relating to a polyimide useful as a plastic substrate for flexible displays and a precursor thereof, and reports that a polyimide obtained by reacting tetracarboxylic acids containing an alicyclic structure such as cyclohexylphenyltetracarboxylic acid with various diamines is excellent in transparency and heat resistance.
In addition, in patent document 2, the addition of a silica sol to polyimide improves the disadvantages of the conventional plastic substrate, which cannot satisfy the linear expansion coefficient, transparency, and low birefringence, and thus, the application to the plastic substrate for flexible displays is sufficiently expected.
On the other hand, in pursuit of the advantages of the plastic substrate, the workability and dimensional stability of the plastic substrate itself become problems. That is, if the plastic substrate is made thin in the form of a film, it is difficult to prevent the occurrence of wrinkles and cracks, and it is difficult to maintain the positional accuracy when the functional layers such as Thin Film Transistors (TFTs) and electrodes are formed in a stacked manner and the dimensional accuracy after the functional layers are formed. Therefore, non-patent document 1 proposes a method (a method called an EPLaR method (electron on Plastic by Laser Release) in which a predetermined functional layer is formed on a Plastic substrate that is applied to and adhered to glass, and then the Plastic substrate provided with the functional layer is forcibly separated from the glass by irradiating the glass with Laser light.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2008-231327
Patent document 2: international publication No. 2015/152178
Non-patent document
Non-patent document 1: "Flexible OLED display Made with the EPLaR Process", Proc. Eurodisplay' 07, pp.36-39(2007)
Disclosure of Invention
Problems to be solved by the invention
The technique described in non-patent document 1 uses glass as a support base material, and forms a functional layer on a plastic substrate fixed to the glass, thereby ensuring the operability and dimensional stability of the resin substrate. However, since the EPLaR method (laser lift-off method) is a method in which the interface between the resin substrate and the support base material is broken by laser irradiation when the resin substrate is separated from the support base material, there are problems such as damage to the functional layer (TFT and the like) around the irradiated portion due to the impact of the laser, a large damage to the resin substrate itself, and a decrease in transmittance, and the like, and the characteristics of the resin substrate and the functional layer formed thereon may be deteriorated.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a resin thin film laminate which is capable of obtaining a plastic thin film having excellent properties as a base film of a flexible device substrate such as a flexible display substrate without relying on the above-mentioned laser lift-off technique, and particularly to provide a method for producing a resin thin film laminate (substrate for a flexible device) which is capable of maintaining excellent properties such as excellent heat resistance, low retardation, excellent flexibility, and further excellent transparency, and also ensuring operability and dimensional stability.
Means for solving the problems
As a result of intensive studies to achieve the above object, the present inventors have found that a resin film laminate which is excellent in heat resistance, low in retardation, excellent in flexibility and further excellent in transparency and is easily peeled from a support base can be realized by providing a release layer between a heat-resistant polymer and the support base when forming a resin film in which silica is blended with the heat-resistant polymer to achieve both heat resistance and optical characteristics, and have completed the present invention.
That is, the present invention relates to a method for producing a resin thin film laminate, as a first aspect, characterized in that,
comprises the following steps:
a step of forming a release layer on a support substrate using a release layer-forming composition containing a heat-resistant polymer A and an organic solvent;
forming a resin film on the release layer using a resin film-forming composition containing a heat-resistant polymer B and an organic solvent; and
a step of peeling the peeling layer together with the resin film from the support base to obtain a resin film laminate,
the resin film-forming composition further contains silica particles having an average particle diameter of 100nm or less as calculated from a specific surface area value measured by a nitrogen adsorption method,
the composition for forming a release layer does not contain silica particles.
In a 2 nd aspect, the production method according to the 1 st aspect, wherein the heat-resistant polymer a and the heat-resistant polymer B are the same polymer.
In a 3 rd aspect, the present invention relates to the production method according to the 1 st aspect, wherein the heat-resistant polymer a and the heat-resistant polymer B are each independently selected from the group consisting of polyimide and polybenzo
Azole, polybenzobis
At least one polymer of oxazole, polybenzimidazole and polybenzothiazole.
A4 th aspect relates to the production method according to the 1 st aspect, wherein the heat-resistant polymer a and the heat-resistant polymer B are each independently a polyimide obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride with a diamine component containing a fluorine-containing aromatic diamine.
An aspect 5 relates to the production method according to aspect 4, wherein the alicyclic tetracarboxylic dianhydride comprises a tetracarboxylic dianhydride represented by the formula (C1).
[ in the formula, B1Represents a 4-valent group selected from the group consisting of the formulae (X-1) to (X-12).
(wherein R's each independently represents a hydrogen atom or a methyl group; and represents a bond.)
In view of the 6 th aspect, the production method according to the 4 th aspect, wherein the fluorine-containing aromatic diamine comprises a diamine represented by the formula (a 1).
H2N-B2-NH2(A1)
(in the formula, B2Represents a 2-valent group selected from the group consisting of formulas (Y-1) to (Y-34). )
(wherein, represents a bond.)
In view of 7, the production method according to view of 4, wherein the polyimide comprises a monomer unit represented by formula (1), a monomer unit represented by formula (2), or both of the monomer units.
An 8 th aspect of the present invention relates to the production method according to the 1 st aspect, wherein the resin film-forming composition is a resin composition having a mass ratio of 7: 3-3: the proportion of 7 includes the heat-resistant polymer B and the silica particles.
A 9 th aspect relates to the production method according to the 1 st aspect, wherein the silica particles have an average particle diameter of 60nm or less.
An aspect 10 relates to the production method according to aspect 1, wherein either the composition for forming a release layer or the composition for forming a resin film further contains a crosslinking agent.
An 11 th aspect of the present invention relates to the production method according to the 1 st aspect, wherein heat or ultraviolet rays are used for curing.
A 12 th aspect of the present invention relates to the production method according to the 1 st aspect, wherein the adhesiveness between the release layer and the resin film is 0 to 5% in the CCJ series (JIS5400) classification, and the adhesiveness between the support base and the release layer is 50% in the CCJ series (JIS5400) classification.
In a 13 th aspect, the method according to the 1 st aspect, wherein the release layer has a thickness of 100 μm to 1 nm.
As a 14 th aspect, the present invention relates to the manufacturing method according to the 1 st aspect, wherein the step of obtaining the resin thin film laminate is performed by a method selected from the group consisting of cutting with a knife, mechanical separation, and pulling.
A 15 th aspect relates to a flexible substrate produced by the production method according to any one of the 1 st to 14 th aspects.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the method for producing a resin thin film laminate of one aspect of the present invention, since the resin thin film laminate can be easily peeled from the support base, the resin thin film laminate can be easily produced with good reproducibility without impairing the properties such as low linear expansion coefficient, excellent heat resistance, low retardation, and excellent flexibility.
The resin thin film laminate thus obtained exhibits a low coefficient of linear expansion, high transparency (high light transmittance, low yellowness index), low retardation, and excellent flexibility, and therefore can be suitably used as a substrate for flexible devices, particularly flexible displays.
The method for producing a resin thin film laminate according to the present invention can sufficiently cope with the progress in the field of substrates for flexible devices, particularly substrates for flexible displays, which are required to have high flexibility, a low coefficient of linear expansion, high transparency (high light transmittance, low yellowness), low retardation, and other properties.
Drawings
Fig. 1 is a view showing stages of the manufacturing method of the present invention.
Fig. 2 is a schematic view (sectional view) of a laminate obtained by the production method of the present invention. G1 denotes a support substrate, L II denotes a release layer, L I denotes a resin film, and L IV denotes an electrode layer formed on the resin film.
Fig. 3 is a schematic view of a method for peeling the laminate obtained by the manufacturing method of the present invention from the support base material.
Fig. 4 is a view showing the structure of the release layer, the resin film and the intermediate layer in the laminate obtained by the production method of the present invention.
Fig. 5 is a sectional photograph (sectional TEM) of the laminate obtained in example a.
Fig. 6 is a photograph (cross-sectional TEM) of a cross-section of the laminate obtained in example a (a) and a composition (b) of each layer.
Fig. 7 shows raman IR spectra of the release layer, the resin thin film, and the interface thereof in the laminate obtained in example a.
Fig. 8 is a sectional photograph (sectional TEM) of the laminate obtained in example B.
Fig. 9 is a photograph (cross-sectional TEM) of a cross-section of the laminate obtained in example B (a) and a composition (B) of each layer.
Fig. 10 shows raman IR spectra of the release layer, the resin thin film, and the interface thereof in the laminate obtained in example B.
Detailed Description
The present invention will be described in detail below.
The method for producing a resin film laminate of the present invention is characterized in that, when a resin film laminate is obtained by forming a release layer on a support base using a release layer-forming composition containing a heat-resistant polymer A and an organic solvent, then forming a resin film on the release layer using a resin film-forming composition containing a heat-resistant polymer B and an organic solvent, and peeling the release layer together with the resin film (as one body) from the support base, substantially only the resin film-forming composition is further made to contain silica particles having an average particle diameter of 100nm or less as calculated from a specific surface area value measured by a nitrogen adsorption method. In order to exhibit the effects of the present invention, it is important that the silica particles are substantially contained only in the composition for forming a resin film and are substantially not contained in the composition for forming a release layer.
In the present invention, "substantially not containing" the silica particles means that the silica particles are not contained except for being unintentionally mixed in during the preparation of the composition, and even when the silica particles are mixed in, the content of the silica particles with respect to the heat-resistant polymer B in the release layer-forming composition is smaller than the content of the silica particles with respect to the heat-resistant polymer a in the resin film-forming composition. The content of the silica particles in the release layer-forming composition, assuming that the silica particles are mixed therein, is, specifically, preferably less than 5% of the content of the silica particles in the resin film-forming composition with respect to the heat-resistant polymer a.
Hereinafter, first, the release layer-forming composition and the resin film-forming composition used in the method for producing a resin film laminate will be described with respect to the respective components constituting them.
[ Heat-resistant polymers (A and B) ]
The release layer-forming composition and the resin film-forming composition used in the present invention each contain a heat-resistant polymer a and a heat-resistant polymer B.
In the present invention, the heat-resistant polymer a contained in the release layer-forming composition is preferably the same as the heat-resistant polymer B contained in the resin film-forming composition (hereinafter, the heat-resistant polymer a and the heat-resistant polymer B are collectively referred to as heat-resistant polymers).
As the heat-resistant polymer used in the present invention, one selected from the group consisting of polyimide and polybenzene is suitably used
Azole, polybenzobis
At least one of oxazole, polybenzimidazole and polybenzothiazole. Among these, polyimide is preferable, and particularly preferable is a specific polyimide described later, that is, a polyimide obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride with a diamine component containing a fluorine-containing aromatic diamine.
In the present specification, the heat-resistant polymer is a polymer having a weight loss of 5% or less at a temperature of 350 ℃ or higher.
[ polyimide ]
The polyimide suitably used in the present invention is a polyimide obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride with a diamine component containing a fluorine-containing aromatic diamine.
Among them, the alicyclic tetracarboxylic dianhydride preferably includes a tetracarboxylic dianhydride represented by the following formula (C1), and the fluorine-containing aromatic diamine preferably includes a diamine represented by the following formula (a 1).
[ in the formula, B1Represents a 4-valent group selected from the group consisting of the formulae (X-1) to (X-12).
(wherein R's each independently represents a hydrogen atom or a methyl group; and represents a bond.)
H2N-B2-NH2(A1)
(in the formula, B2Represents a 2-valent group selected from the group consisting of formulas (Y-1) to (Y-34). )
(wherein, represents a bond.)
In the tetracarboxylic dianhydride represented by the formula (C1), B in the formula is preferable1A compound represented by the formula (X-1), (X-4), (X-6) or (X-7).
Among the diamines represented by the above (A1), B in the formula is preferable2A compound represented by the formula (Y-12) or (Y-13).
As a suitable example, a polyimide obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride represented by the above formula (C1) with a diamine represented by the above formula (a1) contains a monomer unit represented by the below-described formula (2).
In order to obtain a resin thin film laminate having characteristics of low linear expansion coefficient, low retardation, and high transparency, which are the objects of the present invention, and excellent flexibility, an alicyclic tetracarboxylic dianhydride, for example, a tetracarboxylic dianhydride represented by the above formula (C1) is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly, a tetracarboxylic dianhydride represented by the above formula (C1) is preferable in terms of the total molar number of tetracarboxylic dianhydride components.
Similarly, in order to obtain the above-described characteristics of low linear expansion coefficient, low retardation, and high transparency, and a resin thin film laminate excellent in flexibility, the fluorinated aromatic diamine, for example, the diamine represented by the formula (a1), is preferably 90 mol% or more, and more preferably 95 mol% or more, based on the total number of moles of the diamine component. Further, the total (100 mol%) of the diamine component may be a diamine represented by the above formula (a 1).
As an example of a suitable embodiment, the polyimide used in the present invention contains a monomer unit represented by the following formula (1).
The monomer unit represented by the above formula (1) is preferably a monomer unit represented by the formula (1-1) or the formula (1-2), and more preferably a monomer unit represented by the formula (1-1).
According to a preferred embodiment of the present invention, the polyimide used in the present invention contains a monomer unit represented by formula (2). The polyimide used in the present invention may contain both the monomer unit represented by formula (1) and the monomer unit represented by formula (2).
The monomer unit represented by the above formula (2) is preferably a monomer unit represented by the formula (2-1) or the formula (2-2), and more preferably a monomer unit represented by the formula (2-1).
When the polyimide used in the present invention comprises a monomer unit represented by the above formula (1) and a monomer unit represented by the above formula (2), it is preferably a monomer unit represented by the formula (1) in terms of a molar ratio in the polyimide chain: a monomer unit represented by formula (2) ═ 10: 1-1: a ratio of 10 comprises, more preferably between 10: 1-3: the ratio of 1 includes.
The polyimide of the present invention may contain other monomer units in addition to monomer units derived from an alicyclic tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the above formula (C1) and a diamine component containing a diamine represented by the formula (a1), for example, monomer units represented by the above formulae (1) and (2). The content ratio of the other monomer unit is arbitrarily determined as long as the properties of the resin thin film laminate formed from the release layer-forming composition and the resin thin film-forming composition of the present invention are not impaired.
The ratio is preferably less than 20 mol%, more preferably less than 10 mol%, and still more preferably less than 5 mol% relative to the number of moles of a monomer unit derived from an alicyclic tetracarboxylic dianhydride component comprising a tetracarboxylic dianhydride represented by the above formula (C1) and a diamine component comprising a diamine represented by the formula (a1), for example, a monomer unit represented by the formula (1) or a monomer unit represented by the formula (2), or relative to the total number of moles of the monomer unit represented by the formula (1) and the monomer unit represented by the formula (2).
Examples of such other monomer units include, but are not limited to, monomer units having other polyimide structures as shown in formula (3).
In the formula (3), A represents a 4-valent organic group, preferably a 4-valent group represented by any one of the following formulae (A-1) to (A-4). In the formula (3), B represents a 2-valent organic group, preferably a 2-valent group represented by any one of the following formulae (B-1) to (B-11). In each formula, a represents a bond. In the formula (3), when A represents a 4-valent group represented by any one of the following formulae (A-1) to (A-4), B may be a 2-valent group represented by any one of the formulae (Y-1) to (Y-34). Alternatively, in formula (3), when B represents a 2-valent group represented by any one of formulae (B-1) to (B-11), A may be a 4-valent group represented by any one of formulae (X-1) to (X-12).
When the polyimide used in the present invention contains a monomer unit represented by formula (3), it may contain only a monomer unit in which a and B are composed of only one kind of group represented by the following formula, for example, or may contain two or more kinds of monomer units in which at least one of a and B is selected from two or more kinds of groups represented by the following formula. In the following formulae, a represents a bond.
In the polyimide used in the present invention, the monomer units are bonded in an arbitrary order.
As a suitable example, the polyimide having a monomer unit represented by the above formula (1) is obtained by polymerizing bicyclo [2,2,2] octane-2, 3,5, 6-tetracarboxylic dianhydride as a tetracarboxylic dianhydride component and a diamine represented by the following formula (4) as a diamine component in an organic solvent, and imidizing the obtained polyamic acid.
In the case where the polyimide used in the present invention has a monomer unit represented by the above formula (2), the polyimide is obtained by polymerizing 1,2,3, 4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride component and a diamine represented by the following formula (4) as a diamine component in an organic solvent and imidizing the obtained polyamic acid.
Further, in the case where the polyimide used in the present invention has a monomer unit represented by the above formula (2) in addition to the monomer unit represented by the above formula (1), the polyimide containing each of the monomer units represented by the above formulae (1) and (2) is obtained by polymerizing 1,2,3, 4-cyclobutanetetracarboxylic dianhydride in addition to the tetracarboxylic dianhydride as a tetracarboxylic dianhydride component and a diamine represented by the following formula (4) as a diamine component in an organic solvent, and imidizing the obtained polyamic acid.
Examples of the diamine represented by the above formula (4) include 2,2 ' -bis (trifluoromethyl) benzidine, 3 ' -bis (trifluoromethyl) benzidine, and 2,3 ' -bis (trifluoromethyl) benzidine.
Among these, from the viewpoint of making the linear expansion coefficient of the resin thin film laminate of the present invention lower and making the resin thin film laminate more transparent, 2 ' -bis (trifluoromethyl) benzidine represented by the following formula (4-1) or 3,3 ' -bis (trifluoromethyl) benzidine represented by the following formula (4-2) is preferably used as the diamine component, and 2,2 ' -bis (trifluoromethyl) benzidine is particularly preferably used.
Further, in the case where the polyimide used in the present invention has another monomer unit represented by the above formula (3) in addition to the above-mentioned monomer units derived from the alicyclic tetracarboxylic dianhydride component comprising a tetracarboxylic dianhydride represented by the formula (C1) and the diamine component comprising a diamine represented by the formula (A1), for example, the monomer unit represented by the above formula (1) and the monomer unit represented by the above formula (2), the polyimide containing each monomer unit represented by formula (1), formula (2) and formula (3) is obtained by polymerizing a tetracarboxylic dianhydride represented by formula (5) as a tetracarboxylic dianhydride component in addition to the 2 tetracarboxylic dianhydrides described above and a diamine represented by formula (6) as a diamine component in addition to the diamine represented by formula (4) described above in an organic solvent, and imidizing the obtained polyamic acid.
A in the above formula (5) and B in the formula (6) are the same as A and B in the above formula (3), respectively.
Specifically, examples of the tetracarboxylic acid dianhydride represented by the formula (5) include pyromellitic acid dianhydride, 3 ', 4,4 ' -biphenyltetracarboxylic acid dianhydride, 3 ', 4,4 ' -benzophenonetetracarboxylic acid dianhydride, 3 ', 4,4 ' -diphenylethertetracarboxylic acid dianhydride, 3 ', 4,4 ' -diphenylsulfonetetracarboxylic acid dianhydride, 4,4 ' - (hexafluoroisopropylidene) diphthalic acid dianhydride, 11-bis (trifluoromethyl) -1H-difurano [3, 4-b: 3 ', 4' -i ] xanthene-1, 3,7,9- (11H-tetraone), 6 '-bis (trifluoromethyl) - [5, 5' -diisobenzofuran ] -1,1 ', 3, 3' -tetraone, 4,6,10, 12-tetrafluorodifurano [3, 4-b: 3 ', 4' -i ] dibenzo [ b, e ] [1,4] dioxin-1, 3,7, 9-tetraone, 4, 8-bis (trifluoromethoxy) benzo [1, 2-c: 4,5-c '] difuran-1, 3,5, 7-tetraone, and aromatic tetracarboxylic acids such as N, N' - [2,2 '-bis (trifluoromethyl) biphenyl-4, 4' -diyl ] bis (1, 3-dioxo-1, 3-dihydroisobenzofuran-5-carboxamide); alicyclic tetracarboxylic acid dianhydrides such as 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3, 4-cyclohexane tetracarboxylic acid dianhydride, and 3, 4-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalene succinic acid dianhydride; and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3, 4-butanetetracarboxylic acid dianhydride, but are not limited thereto.
Among them, a tetracarboxylic dianhydride in which a in the formula (5) is a 4-valent group represented by any one of the formulae (a-1) to (a-4) is preferable, and examples thereof include 11, 11-bis (trifluoromethyl) -1H-difurano [3, 4-b: 3 ', 4' -i ] xanthene-1, 3,7,9- (11H-tetraone), 6 '-bis (trifluoromethyl) - [5, 5' -diisobenzofuran ] -1,1 ', 3, 3' -tetraone, 4,6,10, 12-tetrafluorodifurano [3, 4-b: 3 ', 4' -i ] dibenzo [ b, e ] [1,4] dioxin-1, 3,7, 9-tetraone, and 4, 8-bis (trifluoromethoxy) benzo [1, 2-c: 4, 5-c' ] difuran-1, 3,5, 7-tetraone as the preferred compound.
Further, examples of the diamine represented by the formula (6) include 2- (trifluoromethyl) benzene-1, 4-diamine, 5- (trifluoromethyl) benzene-1, 3-diamine, 5- (trifluoromethyl) benzene-1, 2-diamine, 2, 5-bis (trifluoromethyl) -benzene-1, 4-diamine, 2, 3-bis (trifluoromethyl) -benzene-1, 4-diamine, 2, 6-bis (trifluoromethyl) -benzene-1, 4-diamine, 3, 5-bis (trifluoromethyl) -benzene-1, 2-diamine, tetrakis (trifluoromethyl) -1, 4-phenylenediamine, 2- (trifluoromethyl) -1, 3-phenylenediamine, 4- (trifluoromethyl) -1, 3-phenylenediamine, 2-methoxy-1, 4-phenylenediamine, 2, 5-dimethoxy-1, 4-phenylenediamine, 2-hydroxy-1, 4-phenylenediamine, 2, 5-dihydroxy-1, 4-phenylenediamine, 2-fluorobenzene-1, 4-diamine, 2, 5-difluorobenzene-1, 4-diamine, 2-chlorobenzene-1, 4-diamine, 2, 5-dichlorobenzene-1, 4-diamine, 2,3,5, 6-tetrafluorobenzene-1, 4-diamine, 4 ' - (perfluoropropane-2, 2-diyl) diphenylamine, 4 ' -oxybis [3- (trifluoromethyl) aniline ], 1, 4-bis (4-aminophenoxy) benzene, 2, 5-dimethoxy-1, 4-phenylenediamine, 2, 5-difluorobenzene-1, 4-diamine, 2-dichloro-diamine, 4-difluorobenzene, 4 ' -oxybis (trifluoromethyl, 1,3 ' -bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, benzidine, 2-methylbenzidine, 3-methylbenzidine, 2- (trifluoromethyl) benzidine, 3- (trifluoromethyl) benzidine, 2 ' -dimethylbenzidine (m-tolidine), 3 ' -dimethylbenzidine (o-tolidine), 2,3 ' -dimethylbenzidine, 2 ' -dimethoxybenzidine, 3 ' -dimethoxybenzidine, 2 ' -dihydroxybenzidine, 3 ' -dihydroxybenzidine, 2 ' -difluorobenzidine, 3 ' -difluorobenzidine, 2,3 ' -dihydroxybenzidine, 2 ' -difluorobenzidine, 3 ' -difluorobenzidine, 2,3 ' -difluorobenzidine, 2 ' -dichlorobenzidine, 3 ' -dichlorobenzidine, 2,3 ' -dichlorobenzidine, 4 ' -diaminobenzanilide, 4-aminophenyl-4 ' -aminobenzoate, octafluorobenzidine, 2 ', 5,5 ' -tetramethylbenzidine, 3 ', 5,5 ' -tetramethylbenzidine, 2 ', 5,5 ' -tetrakis (trifluoromethyl) benzidine, 3 ', 5,5 ' -tetrakis (trifluoromethyl) benzidine, 2 ', 5,5 ' -tetrachlorobenzidine, 4 ' -bis (4-aminophenoxy) biphenyl, 4 ' -bis (3-aminophenoxy) biphenyl, 4 ' - { [3,3 "-bis (trifluoromethyl) - (1, 1': aromatic diamines such as 3 ', 1 "-terphenyl) -4, 4" -diyl ] -bis (oxy) } diphenylamine, 4' - { [ (perfluoropropane-2, 2-diyl) bis (4, 1-phenylene) ] bis (oxy) } diphenylamine, and 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5 (or 6) amine; 4,4 '-methylenebis (cyclohexylamine), 4' -methylenebis (3-methylcyclohexylamine), isophoronediamine, trans-1, 4-cyclohexanediamine, cis-1, 4-cyclohexanediamine, 2, 5-bis (aminomethyl) bicyclo [ 2.2.1 ] heptane, 2, 6-bis (aminomethyl) bicyclo [ 2.2.1 ] heptane, 3, 8-bis (aminomethyl) tricyclo [ 5.2.1.0 ] decane, 1, 3-diaminoadamantane, 2-bis (4-aminocyclohexyl) propane, 2-bis (4-aminocyclohexyl) hexafluoropropane, 1, 3-propanediamine, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, Aliphatic diamines such as 1, 7-heptanediamine, 1, 8-octanediamine and 1, 9-nonanediamine, but are not limited thereto.
Among them, preferred is an aromatic diamine in which B in the formula (6) is a 2-valent group represented by any one of the formulae (B-1) to (B-11), that is, 2 ' -bis (trifluoromethoxy) - (1,1 ' -biphenyl) -4,4 ' -diamine [ otherwise known as: 2,2 ' -dimethoxybenzidine ], 4 ' - (perfluoropropane-2, 2-diyl) diphenylamine, 2, 5-bis (trifluoromethyl) benzene-1, 4-diamine, 2-fluorobenzene-1, 4-diamine, 4 ' -oxybis [3- (trifluoromethyl) aniline ], 2 ', 3,3 ', 5,5 ', 6,6 ' -octafluoro [1,1 ' -biphenyl ] -4,4 ' -diamine [ otherwise known as: octafluorobenzidine ], 2,3,5, 6-tetrafluorobenzene-1, 4-diamine, 4 ' - { [3,3 ' -bis (trifluoromethyl) - (1,1 ': 3 ', 1 ' -terphenyl) -4,4 ' -diyl ] -bis (oxy) } diphenylamine, 4 ' - { [ (perfluoropropane-2, 2-diyl) bis (4, 1-phenylene) ] bis (oxy) } diphenylamine, and 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5 (or 6) amine are preferred diamines.
Synthesis of Polyamic acid
The polyimide used in the present invention is obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride represented by the above formula (C1) with a diamine component containing a fluorine-containing aromatic diamine represented by the above formula (a1) as described above.
Specifically, for example, as a suitable example, the polyamic acid is obtained by polymerizing a tetracarboxylic dianhydride component comprising bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride and, if necessary, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, and further, if necessary, a tetracarboxylic dianhydride represented by the above formula (5), and a diamine component comprising a diamine represented by the above formula (4) and, if necessary, a diamine component represented by the above formula (6) in an organic solvent, and imidizing the obtained polyamic acid.
The reaction of the above-mentioned components with the polyamic acid is advantageous in that it can be relatively easily carried out in an organic solvent and that by-products are not generated.
The addition ratio (molar ratio) of the diamine component in the reaction of the tetracarboxylic dianhydride component and the diamine component is appropriately set in consideration of the molecular weight of the polyamic acid, the polyimide obtained by the subsequent imidization, and the like, but the tetracarboxylic dianhydride component may be usually about 0.8 to 1.2, for example about 0.9 to 1.1, and preferably about 0.95 to 1.02, relative to the diamine component 1. Similarly to the ordinary polycondensation reaction, the molecular weight of the polyamic acid produced increases as the molar ratio is closer to 1.0.
The organic solvent used in the reaction of the tetracarboxylic dianhydride component and the diamine component is not particularly limited as long as it does not adversely affect the reaction and the resulting polyamide acid dissolves. Specific examples thereof are given below.
Examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, 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, 3-sec-butoxy-N, N-dimethylpropionamide, 3-tert-butoxy-N, N-dimethylpropionamide, N-ethylpropionamide, gamma-butyrolactone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyletherAlkyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, dipropyl ether, dihexyl ether, diisopropyl ether, methyl isobutyl ether, methyl ethyl isobutyl ether, methyl hexyl ether, dimethyl butyl ether, dimethyl isobutyl ether, dimethyl
Examples of the alkyl group include, but are not limited to, an alkane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, isopropyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination of 2 or more.
Further, even if the solvent is a solvent that does not dissolve the polyamic acid, the solvent may be mixed and used within a range that the produced polyamic acid does not precipitate. Further, since the water content in the organic solvent may inhibit the polymerization reaction and may hydrolyze the formed polyamic acid, it is preferable to use an organic solvent which is dehydrated and dried as much as possible.
Examples of the method of reacting the tetracarboxylic dianhydride component and the diamine component in the organic solvent include a method of stirring a dispersion or solution obtained by dispersing or dissolving the diamine component in the organic solvent, and adding the tetracarboxylic dianhydride component directly thereto, or adding a substance obtained by dispersing or dissolving the tetracarboxylic dianhydride component in the organic solvent, a method of adding the diamine component to a dispersion or solution obtained by dispersing or dissolving the tetracarboxylic dianhydride component in the organic solvent, and a method of alternately adding the tetracarboxylic dianhydride component and the diamine compound component, and the like, and any of these methods can be used.
In the case where the tetracarboxylic dianhydride component and/or the diamine component is composed of a plurality of compounds, the reaction may be carried out in a state of being mixed in advance, or the reaction may be carried out sequentially one by one, or the low-molecular-weight materials obtained by the reaction one by one may be further subjected to a mixing reaction to produce a high-molecular-weight material.
The temperature for the synthesis of the polyamic acid may be set as appropriate within a range from the melting point to the boiling point of the solvent used, and may be any temperature, for example, from-20 ℃ to 150 ℃, but is preferably from-5 ℃ to 150 ℃, usually from about 0 ℃ to 150 ℃, and preferably from about 0 ℃ to 140 ℃.
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 reaction may be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult, and therefore the total concentration of the tetracarboxylic dianhydride component and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 40% by mass. The reaction may be carried out at a high concentration at the initial stage of the reaction, and then an organic solvent may be added.
Imidization of polyamic acid
Examples of the method for imidizing the polyamic acid include thermal imidization in which a solution of the polyamic acid is directly heated, and imidization in which a catalyst is added to a solution of the polyamic acid.
The temperature for thermal imidization of the polyamic acid in the solution is preferably 100 to 400 ℃, more preferably 120 to 250 ℃, and is preferably carried out while excluding water produced by the imidization reaction from the system.
The chemical (catalytic) imidization of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyamic acid and stirring the inside of the system at a temperature of-20 to 250 ℃, preferably 0 to 180 ℃.
The amount of the basic catalyst is 0.5 to 30 mol times, preferably 1.5 to 20 mol times, and the amount of the acid anhydride is 1 to 50 mol times, preferably 2 to 30 mol times, of the amic acid group of the polyamic acid.
Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and 1-ethylpiperidine, and among them, pyridine and 1-ethylpiperidine are preferable because they have a suitable basic property for allowing the reaction to proceed.
The acid anhydride includes acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among these, acetic anhydride is preferable because purification after completion of the reaction is easy when acetic anhydride is used.
The imidization rate based on the catalyst imidization can be controlled by adjusting the amount of the catalyst and the reaction temperature, reaction time.
In the polyimide resin used in the present invention, the dehydration ring-closing ratio (imidization ratio) of the amic acid groups need not be 100%, and can be arbitrarily adjusted and used according to the application and purpose. Particularly preferably 50% or more.
In the present invention, the reaction solution may be filtered and the filtrate may be used as it is, or the composition for forming a release layer may be prepared by diluting or concentrating the filtrate, or the composition for forming a resin film may be prepared by further blending silica or the like described later therein. When the filtration is performed in this way, not only can the incorporation of impurities, which may cause deterioration in the heat resistance, flexibility, and linear expansion coefficient characteristics of the obtained resin film laminate, be reduced, but also the composition for forming a release layer and the composition for forming a resin film can be obtained efficiently.
The polyimide used in the present invention preferably has a weight average molecular weight (Mw) of 5,000 to 200,000 in terms of polystyrene by Gel Permeation Chromatography (GPC) in consideration of the strength of the resin thin film laminate, the workability in forming the resin thin film laminate, the uniformity of the resin thin film laminate, and the like.
Polymer recovery
When the polymer component is recovered from the reaction solution of the polyamic acid and the polyimide and used, the reaction solution may be put into a poor solvent to precipitate the polymer component. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in the poor solvent may be recovered by filtration, and then dried at normal temperature or under reduced pressure or by heating.
Further, if the operation of re-dissolving the polymer recovered by precipitation in an organic solvent and re-precipitating and recovering (re-precipitation recovery step) is repeated 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent in this case, if using more than 3 kinds of poor solvents such as alcohols, ketones, hydrocarbons, etc., the purification efficiency is further improved, so it is preferable.
The organic solvent for dissolving the resin component in the reprecipitation recovery step is not particularly limited. Specific examples thereof include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, γ -butyrolactone, 1, 3-dimethyl-imidazolidinone, dipentene, ethylpentyl ketone, methylnonyl ketone, methylethyl ketone, methylisopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, and 4-hydroxy-4-methyl-2-pentanone. These solvents may be used in combination of 2 or more.
[ silica ]
The silica (silica) used in the composition for forming a resin film of the present invention is not particularly limited, but is in the form of particles, and has an average particle diameter of, for example, 100nm or less, for example, 5nm to 100nm, 5nm to 60nm, preferably 5nm to 55nm, and from the viewpoint of obtaining a more transparent film with good reproducibility, is preferably 5nm to 50nm, more preferably 5nm to 45nm, even more preferably 5nm to 35nm, and even more preferably 5nm to 30 nm.
The average particle size of the silica particles in the present invention is an average particle size value calculated from a specific surface area value measured by a nitrogen adsorption method using the silica particles.
In particular, in the present invention, colloidal silica having the above-described average particle diameter value can be suitably used, and as the colloidal silica, a silica sol can be used. As the silica sol, an aqueous silica sol produced by a known method using a sodium silicate aqueous solution as a raw material, and an organic silica sol obtained by replacing water as a dispersion medium of the aqueous silica sol with an organic solvent can be used.
Further, a silica sol obtained by hydrolyzing and condensing an alkoxysilane such as methyl silicate or ethyl silicate in an organic solvent such as alcohol in the presence of a catalyst (for example, an alkali catalyst such as ammonia, an organic amine compound, or sodium hydroxide), or an organic silica sol obtained by replacing the solvent of the silica sol with another organic solvent may be used.
Among them, the present invention preferably uses an organic silica sol in which the dispersion medium is an organic solvent.
Examples of the organic solvent in the organic silica sol include lower alcohols such as methanol, ethanol, and isopropanol; linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide; cyclic amides such as N-methyl-2-pyrrolidone; ethers such as γ -butyrolactone; ethyl cellosolve, glycols such as ethylene glycol, acetonitrile, and the like. The substitution can be carried out by a usual method such as distillation or ultrafiltration.
The viscosity of the organic silica sol is about 0.6 mPas-100 mPas at 20 ℃.
Examples of the commercially available product of the organic silica sol include, for example, a product name of MA-ST-S (methanol-dispersed silica sol, manufactured by Nissan chemical industry Co., Ltd.), a product name of MT-ST (methanol-dispersed silica sol, manufactured by Nissan chemical industry Co., Ltd.), a product name of MA-ST-UP (methanol-dispersed silica sol, manufactured by Nissan chemical industry Co., Ltd.), a product name of MA-ST-M (methanol-dispersed silica sol, manufactured by Nissan chemical industry Co., Ltd.), a product name of MA-ST-L (methanol-dispersed silica sol, manufactured by Nissan chemical industry Co., Ltd.), a product name of IPA-ST-S (isopropyl alcohol-dispersed silica sol, manufactured by Nissan chemical industry Co., Ltd.), a product name of IPA-ST (isopropyl alcohol-dispersed silica sol, manufactured by Nissan chemical industry Co., Ltd.), the trade name IPA-ST-UP (isopropyl alcohol-dispersed silica sol manufactured by Nissan chemical industry Co., Ltd.), the trade name IPA-ST-L (isopropyl alcohol-dispersed silica sol manufactured by Nissan chemical industry Co., Ltd.), the trade name IPA-ST-ZL (isopropyl alcohol-dispersed silica sol manufactured by Nissan chemical industry Co., Ltd.), the trade name NPC-ST-30 (n-propyl cellosolve-dispersed silica sol manufactured by Nissan chemical industry Co., Ltd.), the trade name PGM-ST (1-methoxy-2-propanol-dispersed silica sol manufactured by Nissan chemical industry Co., Ltd.), the trade name DMAC-ST (dimethylacetamide-dispersed silica sol manufactured by Nissan chemical industry Co., Ltd.), the trade name XBA-ST (xylene/n-butanol mixed solvent-dispersed silica sol), manufactured by Nissan chemical industries, Ltd.), the trade name EAC-ST (Ethyl acetate dispersed silica sol manufactured by Nissan chemical industries, Ltd.), the trade name PMA-ST (propylene glycol monomethyl ether acetate dispersed silica sol manufactured by Nissan chemical industries, Ltd.), the trade name MEK-ST (methyl ethyl ketone dispersed silica sol manufactured by Nissan chemical industries, Ltd.), the trade name MEK-ST-UP (methyl ethyl ketone dispersed silica sol manufactured by Nissan chemical industries, Ltd.), the trade name MEK-ST-L (methyl ethyl ketone dispersed silica sol manufactured by Nissan chemical industries, Ltd.), and the trade name MIBK-ST (methyl isobutyl ketone dispersed silica sol manufactured by Nissan chemical industries, Ltd.), and the like, but are not limited thereto.
In the present invention, two or more kinds of silica such as those exemplified in the above products used as the organic silica sol may be used in combination.
[ crosslinking agent ]
The release layer-forming composition and the resin film-forming composition used in the present invention may further contain a crosslinking agent. In the case where a crosslinking agent is used in the present invention, it is preferable to blend only the release layer forming composition or the resin film forming composition, and it is preferable to blend only the crosslinking agent in the resin film forming composition.
The crosslinking agent used herein is a compound consisting of only hydrogen atoms, carbon atoms and oxygen atoms, or a compound consisting of only these atoms and nitrogen atoms, and is a crosslinking agent consisting of a compound having 2 or more groups selected from hydroxyl groups, epoxy groups and alkoxy groups having 1 to 5 carbon atoms and having a ring structure. By using such a crosslinking agent, a release layer-forming composition and a resin film-forming composition having further improved storage stability can be realized, while obtaining a resin film laminate suitable for a flexible device substrate having excellent solvent resistance with good reproducibility.
Among these, the total number of hydroxyl groups, epoxy groups, and alkoxy groups having 1 to 5 carbon atoms per compound in the crosslinking agent is preferably 3 or more from the viewpoint of achieving solvent resistance of the obtained resin thin film laminate with good reproducibility, and is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less from the viewpoint of achieving flexibility of the obtained resin thin film laminate with good reproducibility.
Specific examples of the ring structure of the crosslinking agent include aromatic rings such as benzene, heteroaromatic rings containing a nitrogen atom such as pyridine, pyrazine, pyrimidine, pyridazine and 1,3, 5-triazine, cycloalkane rings such as cyclopentane, cyclohexane and cycloheptane, and cyclic amines such as piperidine, piperazine, hexahydropyrimidine, hexahydropyridazine and hexahydro-1, 3, 5-triazine.
The number of ring structures per compound in the crosslinking agent is not particularly limited as long as 1 or more, and is preferably 1 or 2 from the viewpoint of ensuring solubility of the crosslinking agent in a solvent and obtaining a resin thin film laminate having high flatness.
When the number of the ring structures is 2 or more, the ring structures may be condensed with each other, or may be bonded to each other via a linking group such as an alkane-diyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a1, 3-propylene group, a propane-2, 2-diyl group, or the like.
The molecular weight of the crosslinking agent is not particularly limited as long as it has crosslinking ability and dissolves in the solvent used, but is preferably about 100 to 500, more preferably about 150 to 400, in consideration of solvent resistance of the resin thin film laminate obtained, solubility of the crosslinking agent itself in an organic solvent, availability, price, and the like.
The crosslinking agent may further have a group which a ketone group, an ester group (bond), or the like may be derived from a hydrogen atom, a carbon atom, a nitrogen atom, and an oxygen atom.
Preferable examples of the crosslinking agent include compounds represented by the following formulas (K1) to (K5), one preferable embodiment of the formula (K4) is a compound represented by the formula (K4-1), and one preferable embodiment of the formula (K5) is a compound represented by the formula (5-1).
In the above formula, each A1And A2Independently represents an alkane-diyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a1, 3-propylene group, a propane-2, 2-diyl group and the like, wherein A represents1Preferably methylene or ethylene, more preferably methylene, as A2Methylene and propane-2, 2-diyl are preferred.
Each X independently represents an alkoxy group having 1 to 5 carbon atoms such as a hydroxyl group, an epoxy group (oxa-cyclopropyl group), or a methoxy group, an ethoxy group, a 1-propyloxy group, an isopropyloxy group, a 1-butyloxy group, or a tert-butyloxy group.
Among them, in view of availability, price, and the like of the crosslinking agent, X is preferably an epoxy group in the formulae (K1) and (K5), an alkoxy group having 1 to 5 carbon atoms in the formulae (K2) and (K3), and a hydroxyl group in the formula (K4).
In the formula (K4), each n represents- (A) bonded to a benzene ring1The number of the groups-X) is an integer of 1 to 5 independently of one another, but is preferably 2 to 3, more preferably 3.
Among the compounds, each A is preferred1Preferably, each X is the same group throughout.
The compounds represented by the above formulae (K1) to (K5) can be obtained by reacting a skeleton compound such as an aryl compound, heteroaryl compound, or cyclic amine having the same ring structure as that of each of these compounds with an epoxyalkyl halogen compound, alkoxy halogen compound, or the like by a carbon-carbon coupling reaction or an N-alkylation reaction, or by hydrolyzing the alkoxy moiety of the product.
The crosslinking agent may be a commercially available one, or one synthesized by a known synthesis method.
Commercially available products include CYMEL (registered trademark) 300, CYMEL 301, CYMEL303 LF, CYMEL303ULF, CYMEL 304, CYMEL 350, CYMEL 3745, CYMEL XW3106, CYMEL MM-100, CYMEL 323, CYMEL 325, CYMEL 327, CYMEL 328, CYMEL 385, CYMEL 370, CYMEL 373, CYMEL 380, CYMEL1116, CYMEL 1130, CYMEL 1133, CYMEL 1141, CYMEL 1161, CYMEL 1168, CYMEL 3020, CYMEL202, CYMEL 203, CYMEL 1156, CYMEL MB-94, CYMEL MB-96, CYMEL MB-98, CYMEL 247-10, CYMEL 651, CYMEL 658, CYMEL 683, CYMEL 688 8, CYMEL 14, CYMEL MI-MI 65, CYMEL MI 80, CYMEL MI-MI 80, CYMEL MI-80, CYMEL IX-80, CYMEL-8, CYMEL-5, CYMEL-8, CYME, CYMEL U-227-8, CYMEL U-1050-10, CYMEL U-1052-8, CYMEL U-1054, CYMEL U-610, CYMEL U-640, CYMEL UB-24-BX, CYMEL UB-26-BX, CYMEL UB-90-BX, CYMEL UB-25-BE, CYMEL UB-30-B, CYMEL U-662, CYMEL U-663, CYMEL U-1051, CYMEL UI-19-I, CYMEL UI-19-IE, CYMEL UI-21-E, CYMEL UI-27-BE, CYMEL U-38-I, CYMEL UI-20-E, CYMEL659, CYMEL 1123, CYMEL 1125, CYMEL 5010, CYMEL 1170, CYMEL 1172, CYMEL U-38-I, CYMEL UI-20-E, CYMEL-659, CYMEL 1123, CYMEL 1125, CYMEL 5010, CYMEL NF2000, etc. (supra); TEPIC (registered trademark) V, TEPIC S, TEPIC HP, TEPIC L, TEPIC PAS, TEPIC VL, and TEPIC UC (manufactured by Nissan chemical industry Co., Ltd.), TM-BIP-A (manufactured by Asahi organic materials Co., Ltd.), 1,3,4, 6-tetrakis (methoxymethyl) glycoluril (hereinafter abbreviated as TMG) (manufactured by Tokyo Kasei Co., Ltd.), 4' -methylenebis (N, N-diglycidylaniline) (manufactured by Aldrich Co., Ltd.), HP-4032D, HP-7200L, HP-7200, HP-7200H, HP-7200HH, HP-7200HHH, HP-4700, HP-4770, HP-5000, HP-6000, HP-4710, EXA-4850-150, EXA-4850-1000, EXA-4816, and HP-820(DIC strain), TG-G (four kingdom Industrial Co., Ltd.), and the like.
Hereinafter, preferred specific examples of the crosslinking agent are mentioned, but the crosslinking agent is not limited thereto.
The amount of the crosslinking agent to be blended is appropriately determined depending on the kind of the crosslinking agent and the like, and therefore cannot be generally specified, but is usually 50 mass% or less, preferably 100 mass% or less, with respect to the mass of the polyimide contained in the composition for forming a release layer or the total mass of the polyimide and the silica contained in the composition for forming a resin thin film, from the viewpoint of securing flexibility and suppressing embrittlement of the obtained resin thin film laminate, and is 0.1 mass% or more, preferably 1 mass% or more, from the viewpoint of securing solvent resistance of the obtained resin thin film laminate.
[ organic solvent ]
The release layer-forming composition and the resin film-forming composition used in the present invention contain an organic solvent. The organic solvent is not particularly limited, and examples thereof include the same organic solvents as specific examples of the reaction solvent used in the preparation of the polyamic acid and the polyimide. More specifically, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, γ -butyrolactone, and the like can be given. The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Among them, if a resin thin film laminate having high flatness is obtained with good reproducibility, N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ -butyrolactone are preferable.
[ composition for Forming Release layer ]
The release layer-forming composition used in the present invention is a composition containing the heat-resistant polymer and an organic solvent, and optionally a crosslinking agent, and substantially contains no silicon dioxide as described above. The amount and viscosity of the solid content in the release layer-forming composition were determined in accordance with the following resin film-forming composition.
[ composition for Forming resin film ]
The resin film-forming composition used in the present invention is a composition containing the heat-resistant polymer, silica and an organic solvent, and may contain a crosslinking agent as needed. The composition for forming a resin film was uniform, and no phase separation was observed.
In the resin film-forming composition, the mixing ratio of the heat-resistant polymer to the silica is preferably, in terms of mass ratio, a heat-resistant polymer: silica 10: 1-1: 10, more preferably 8: 2-2: 8, for example 7: 3-3: 7.
the amount of the solid content in the resin film-forming composition is usually about 0.5 to 30% by mass, preferably about 5 to 25% by mass. If the solid content concentration is less than 0.5% by mass, the film forming efficiency in the production of the resin film is low, and the viscosity of the resin film-forming composition is low, so that it is difficult to obtain a coating film having a uniform surface. Further, if the solid content concentration exceeds 30 mass%, the viscosity of the resin film-forming composition becomes too high, and there is a possibility that the film-forming efficiency deteriorates and the surface uniformity of the coating film becomes poor. The solid content (solid content concentration) herein means the total mass of components other than the organic solvent, and is contained as a solid content in the weight of the monomer even in a liquid state.
The viscosity of the resin film-forming composition is appropriately set in consideration of the thickness of the resin film to be produced, and when the resin film having a thickness of about 5 to 50 μm is to be obtained with good reproducibility, the viscosity is usually about 500 to 50,000mPa · s, preferably about 1,000 to 20,000mPa · s, at 25 ℃.
< other ingredients >
In addition to the release layer-forming composition and the resin film-forming composition, various organic or inorganic low-molecular or high-molecular compounds may be blended to impart processing characteristics and various functionalities. For example, catalysts, defoaming agents, leveling agents, surfactants, dyes, plasticizers, fine particles, coupling agents, sensitizers, and the like may be used. For example, the catalyst may be added for the purpose of reducing the retardation and linear expansion coefficient of the resin thin film laminate.
The release layer-forming composition can be obtained by, for example, dissolving polyimide obtained by the above-described method as a heat-resistant polymer, a crosslinking agent if necessary, and other components (various organic or inorganic low-molecular or high-molecular compounds) if necessary in the organic solvent.
The resin film-forming composition can be obtained by dissolving, for example, polyimide and silica obtained by the above-described method as heat-resistant polymers, a crosslinking agent if necessary, and other components (various organic or inorganic low-molecular or high-molecular compounds) if necessary in the organic solvent. Alternatively, silica may be added to the reaction solution after preparation of the polyimide, and the organic solvent may be further added as necessary.
As described above, when the crosslinking agent is used in the present invention, the crosslinking agent is used in either the composition for forming a release layer or the composition for forming a resin film.
In the present invention, the resin contained in the composition for forming a release layer and the resin contained in the composition for forming a resin film are preferably the same as described above, from the viewpoint of not affecting the properties and the like. In addition, substantially only the resin film-forming composition further contains silica particles. When these suitable conditions are satisfied, the method for preparing each composition is not particularly limited. Therefore, in the method of the present invention, for example, after the release layer forming composition is prepared, the release layer forming composition and the resin film forming composition can be easily prepared by adding the silica particles to a part of the obtained release layer forming composition as described above and further adding an organic solvent as necessary, and they can be used in the method of the present invention.
< method for producing resin thin film laminate >
[ procedure for Forming Release layer ]
This step is a step of forming a release layer on a support base by using the composition for forming a release layer described above.
Specifically, by applying the release layer-forming composition to a support substrate and drying/heating the composition to remove the organic solvent, a release layer which can be easily peeled from the support substrate by at least one method selected from cutting with a knife, mechanical separation and simultaneous pulling and peeling while maintaining excellent properties such as excellent heat resistance, low retardation, excellent flexibility and further excellent transparency can be obtained, and a flexible device substrate can be obtained.
Examples of the support base include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metals, stainless steel (SUS), wood, paper, glass, silicon wafers, slates, and the like.
In particular, the support substrate to be used is preferably glass or a silicon wafer from the viewpoint that existing equipment can be used, and further preferably glass from the viewpoint that the resulting release layer exhibits good releasability. The linear expansion coefficient of the support substrate to be used is preferably 40 ppm/c or less, and more preferably 30 ppm/c or less, from the viewpoint of warpage of the support substrate after coating.
The method for applying the composition for forming a release layer to a support base is not particularly limited, and examples thereof include a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an ink jet method, a printing method (relief printing, gravure printing, offset printing, screen printing, etc.), and the like, and they can be used as appropriate according to the purpose.
The heating temperature is preferably 500 ℃ or lower, and more preferably 450 ℃ or lower. However, if the temperature exceeds 300 ℃, a problem of yellowing may occur, but even in this case, the ratio of the thickness of the release layer in the thickness of the entire resin thin film laminate obtained by the production method of the present invention is sufficiently small as described below, and therefore, the influence on the characteristics is small. In addition, when the release layer is coated with the resin film-forming composition, the proportion of the release layer dissolved in the resin film-forming composition decreases when the final firing temperature is high, and for example, the release layer is not easily dissolved when the firing temperature is 400 ℃.
In addition, considering the heat resistance and linear expansion coefficient characteristics of the release layer obtained, it is desirable that the applied release layer-forming composition is heated at 40 to 100 ℃ for 5 minutes to 2 hours, then the heating temperature is raised gradually, and finally heated at a temperature in the range of more than 175 to 450 ℃ for 30 minutes to 2 hours. In this way, by heating at a temperature of 2 or more stages, i.e., the stage of drying the solvent and the stage of promoting molecular orientation, the low thermal expansion characteristics can be expressed with better reproducibility.
It is particularly preferable that the composition for forming a release layer to be applied is heated at 40 to 100 ℃ for 5 minutes to 2 hours, then at more than 100 to 175 ℃ for 5 minutes to 2 hours, and then at a temperature in the range of more than 175 to 450 ℃ for 5 minutes to 2 hours.
Examples of the heating device include an electric hot plate and an oven. The heating atmosphere may be air or an inert gas such as nitrogen, or may be normal pressure or reduced pressure, or different pressures may be applied in each stage of heating.
In the present step, a fine structure (intermediate layer) may be formed on the surface of the release layer by a coating technique, in order to further improve the adhesion between the release layer and the resin film to be formed later. In this case, specifically, it is preferable to form a fine structure on the surface of the release layer before curing the release layer, for example, after applying the release layer forming composition or during the stepwise heating after applying the release layer forming composition.
The thickness of the release layer is appropriately determined in consideration of the type of flexible device in the range of about 1nm to 200 μm, but in order to exhibit the effects of the present invention, it is necessary to be at least larger than the diameter of the silicon dioxide particles. In particular, when the resin thin film laminate is used as a substrate for a flexible display, the thickness of the coating film before heating is adjusted to be generally about 10nm to 10 μm, preferably about 100nm to 5 μm, thereby forming a release layer having a desired thickness.
[ Process for Forming resin film ]
This step is a step of forming a resin film on the release layer by using the composition for forming a resin film of the present invention. This step can also be said to be a step of forming a resin thin film laminate including a release layer and a resin thin film formed thereon on a support base.
Specifically, the film-forming composition is applied to a release layer formed on the support substrate, and dried/heated to remove the organic solvent, whereby a resin film having high heat resistance, high transparency, appropriate flexibility, and an appropriate linear expansion coefficient and having a small retardation can be obtained.
In this step, a part of the release layer is dissolved by the organic solvent contained in the composition for forming a resin film, and the resin film and the release layer are adhered to each other, whereby the adhesion between the two layers is enhanced.
The method of applying the composition for forming a resin film on the release layer, the heating temperature, the tool used for heating, and the thickness of the resin film are set according to the conditions described in the step of forming the release layer.
In the resin film laminate formed on the support base in this manner, in order to realize easy peeling from the support base, it is preferable that the adhesion of the resin film to the peeling layer is larger than the adhesion of the peeling layer to the support base.
Specifically, the adhesiveness between the release layer and the resin film is preferably 0 to 1 (0 to 5% peelable) in the CCJ series (JIS5400) classification, and the adhesiveness between the support substrate and the release layer is preferably 5 (50% peelable) in the CCJ series (JIS5400) classification. The CCJ series is defined as a classification of 0 to 5, a classification of 0 means 0% of the area of the peelable square, a classification of 1 means 1 to 5% of the area of the peelable square, a classification of 2 means 6 to 10% of the area of the peelable square, a classification of 3 means 11 to 25% of the area of the peelable square, a classification of 4 means 26 to 50% of the area of the peelable square, and a classification of 5 means 50% or more of the area of the peelable square. In other words, it is preferable that the number of peeling of the resin film from the square of the peeling layer is classified into 0 to 2 and the number of peeling of the peeling layer from the square of the support substrate is classified into 5 under the conditions of the cross cut test according to JIS K5400.
[ Process for obtaining a resin thin film laminate ]
This step is a step of peeling the release layer together with the resin film from a support base to obtain a resin film laminate.
The method for peeling the resin thin film laminate formed in this manner from the support base is not particularly limited, and examples thereof include a method in which the resin thin film laminate is cooled together with the support base, a method in which a crack is introduced into the resin thin film laminate and the laminate is peeled, and a method in which the laminate is peeled by applying tension via a roller. In particular, as a method for peeling the resin thin film laminate from the support base material in the present invention, at least one method selected from cutting with a knife, mechanical separation, and pulling can be applied.
In this way, according to the method of the present invention, since the adhesiveness of the release layer to the resin film is stronger than the adhesiveness of the release layer to the support base, the release layer and the resin film can be easily peeled as one from the support base to obtain a resin film laminate.
In the present invention, the thickness of the resin thin film laminate can be appropriately determined in consideration of the type of the flexible device within a range of about 1 μm to 200 μm. The thickness of the release layer is preferably 1 to 35% relative to the thickness (100%) of the resin thin film laminate.
The resin thin film laminate obtained in a preferred embodiment of the present invention can realize high transparency with a light transmittance of 75% or more at a wavelength of 400 nm.
Further, the resin thin film laminate can have a low linear expansion coefficient of 60 ppm/DEG C or less, particularly 10 ppm/DEG C to 35 ppm/DEG C at 50 to 200 ℃, and can have a low linear expansion coefficient of 80 ppm/DEG C or less, particularly 15 ppm/DEG C to 55 ppm/DEG C at 200 to 250 ℃, for example, and is excellent in dimensional stability during heating.
In particular, the resin thin film laminate has a characteristic that the in-plane retardation R is expressed by the product of the birefringence (difference in refractive indices orthogonal to each other in the plane) and the film thickness (thickness of the laminate) when the wavelength of incident light is 590nm0And a thickness direction retardation R represented by an average value of 2 phase differences obtained by multiplying 2 birefringence values (differences between 2 in-plane refractive indices and the refractive index value in the thickness direction) when viewed from a cross section in the thickness direction by the film thickness (thickness of the laminate)thAre very small. When the average film thickness (average thickness of the laminate) of the resin thin-film laminate obtained by the production method of the present invention is 15 to 40 μm, the retardation R in the thickness directionthLess than 700nm, for example up to 660nm, for example from 10 to 660nm, in-plane retardation R0Less than 4, for example, 0.3 to 3.9, and the birefringence Δ n has a very low value of less than 0.02, for example, 0.0003 to 0.019.
Thus, the retardation of the resin thin film laminate obtained by the production method of the present invention can be reduced.
The resin thin film laminate obtained by the above-described production method of the present invention satisfies the respective conditions required as the base film of the flexible display substrate because of the above-described characteristics, and can be suitably used as the base film of the flexible display substrate. That is, the present invention is suitable as a method for manufacturing a substrate for a flexible device.
Fig. 1 shows an example of manufacturing a flexible device using the manufacturing method of the present invention.
As shown in fig. 1, first, a release layer is formed on a support base, and a resin film is formed on the release layer to prepare a resin film laminate. Then, after a functional layer is formed on the resin thin film laminate, these layers are peeled off together to obtain a flexible device.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.
The meanings of the shorthand symbols used in the following examples are as follows.
< acid dianhydride >
BODAxx: bicyclo [2,2,2] octane-2, 3,5, 6-tetracarboxylic dianhydride
CBDA: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride
< diamine >
TFMB: 2, 2' -bis (trifluoromethyl) benzidine
< organic solvent >
GBL: gamma-butyrolactone
In the examples, the apparatus and conditions used for preparation of the sample and analysis and evaluation of the physical properties were as follows.
1) Determination of number average molecular weight and weight average molecular weight
The number average molecular weight (hereinafter abbreviated as Mn) and the weight average molecular weight (hereinafter abbreviated as Mw) of the polymer were measured in the following manner: showdex GPC-101 manufactured by Showdex Denko K.K., column: KD803 and KD805, column temperature: 50 ℃, elution solvent: DMF, flow rate: 1.5 ml/min, standard curve: measured under standard polystyrene conditions.
2) Coefficient of linear expansion (CTE)
The film (or laminate) was cut into a size of 5mm in width and 16mm in length using a TMA Q400 manufactured by TA インスツルメンツ, and the film (or laminate) was first heated at 10 ℃/min from 50 ℃ to 350 ℃ (first heating), then cooled at 10 ℃/min to 50 ℃, and then heated at 10 ℃/min from 50 ℃ to 420 ℃ (second heating), and the linear expansion coefficient (CTE [ ppm/° c ]) at 50 ℃ to 200 ℃ of the second heating was measured. A load of 0.05N was applied throughout the first heating, cooling, and second heating.
3) 5% weight loss temperature (Td)5％)
5% weight loss temperature (Td)5％[℃]) The film (or laminate) was measured by heating about 5 to 10mg of the film (or laminate) from 50 ℃ to 800 ℃ at 10 ℃/min in nitrogen using TGA Q500 manufactured by TA インスツルメンツ.
4) Light transmittance (transparency) (T)308nm、T400nm、T550nm) And CIE b value (CIE b)*)
Light transmittance (T) at wavelengths of 308nm, 400nm and 550nm308nm，T400nm，T550nm[％]) And CIE b value (CIEb)*) The measurement was performed using a SA4000 spectrophotometer manufactured by Nippon Denshoku industries Co., Ltd. with the reference air at room temperature.
5) Delay (R)th，R0)
The thickness direction retardation (R) was measured at room temperature using KOBURA 2100ADH manufactured by prince measuring machineth) And in-plane retardation (R)0)。
The thickness direction retardation (R) isth) And in-plane retardation (R)0) Calculated by the following equation.
R0＝(Nx-Ny)×d＝ΔNxy×d
Rth＝[(Nx+Ny)/2-Nz]×d＝[(ΔNxz×d)+(ΔNyz×d)/2
Nx, Ny: in-plane orthogonal 2 indices of refraction (Nx > Ny, Nx also known as the slow axis, Ny also known as the fast axis)
Nz: refractive index in thickness (perpendicular) direction with respect to plane
d: film thickness (thickness of laminate)
Δ Nxy: in-plane 2 difference in refractive index (Nx-Ny) (birefringence)
Δ Nxz: difference between in-plane refractive index Nx and thickness-direction refractive index Nz (birefringence)
Δ Nyz: difference between in-plane refractive index Ny and thickness-direction refractive index Nz (birefringence)
6) Birefringence (DELTA n)
Using the thickness direction retardation (R) obtained by the above-mentioned < 5) retardation >th) The value of (d) is calculated by the following equation.
Δn＝[RthD (thickness of the film (thickness of the laminate))]/1000
7) Film thickness (thickness of laminate)
The thickness of the obtained resin thin film and the thickness of the resin thin film laminate were measured by a thickness meter manufactured by model テクロック (ltd.).
[1] Preparation examples
Preparation example 1: preparation of silica Sol (GBL-M)
A1000 mL round-bottom flask was charged with a methanol-dispersed silica sol prepared by Nissan chemical industries, Ltd: 350g of MA-ST-M (silica solid content concentration: 40.4% by mass) and 419g of γ -butyl lactone. Further, the flask was connected to a vacuum evaporator, the pressure in the flask was reduced, and the flask was immersed in a warm water bath at about 35 ℃ for 20 to 50 minutes to obtain about 560.3g (silica solid content concentration: 25.25 mass%) of a silica sol (GBL-M) in which the solvent was replaced with γ -butyl lactone from methanol.
[2] Synthesis example
Synthesis example 1: synthesis of polyimide A (PI-A)
Into a 250mL reaction three-necked flask equipped with an inlet/outlet for nitrogen gas, a mechanical stirrer and a cooler, 25.61g (0.08mol) of TFMB was charged. Then, 173.86g of GBL was added to the solution, and stirring was started. After complete dissolution of the diamine in the solvent, 10g (0.04mol) of BODAxx, 7.84g (0.04mol) of CBDA and 43.4g of GBL were added with stirring and heated to 140 ℃ under nitrogen. Then, 0.348g of 1-ethylpiperidine was added to the solution, and the mixture was heated at 180 ℃ for 7 hours under nitrogen. Finally, the heating was stopped, and the reaction solution was diluted up to 10% and kept stirring overnight. The polyimide reaction solution was added to 2000g of methanol and stirred for 30 minutes, and then the polyimide solid was filtered, thereby purifying the polyimide. The polyimide solid was stirred in 2000g of methanol for 30 minutes, and the polyimide solid was filtered. The purification step of stirring and filtering the polyimide solid was repeated 3 times. Methanol residue in the polyimide was removed by drying in a vacuum oven at 150 ℃ for 8 hours, and finally, 31.16g of dried polyimide a was obtained. The yield of the polyimide a (PI-a) was 74% (Mw: 169,802, Mn: 55,308).
[3] Composition for forming release layer, preparation of composition for forming resin thin film, and production of resin thin film laminate (1)
Example 1: formation of a Release layer
A release layer-forming composition was obtained by gradually pressure-filtering 1g of the polyimide (PI-A) of Synthesis example 1 dissolved in a GBL solvent so as to be 8 mass% through a1 μm filter at room temperature. Then, the composition was coated on a glass support substrate, and fired at a temperature of 50 ℃ for 30 minutes, 140 ℃ for 30 minutes, 200 ℃ for 60 minutes, and further fired at 300 ℃ for 60 minutes in an air atmosphere. In this way, a transparent polyimide film as a release layer was formed on the glass support substrate. The optical properties and thermal properties are shown in table 1.
Example 2: formation of a Release layer
A transparent polyimide film as a release layer was obtained on a glass support substrate in the same manner as in example 1 except that the release layer-forming composition prepared in example 1 was applied to a glass support substrate, and fired at 50 ℃ for 30 minutes, 140 ℃ for 30 minutes, 200 ℃ for 60 minutes, and then further fired at 400 ℃ for 60 minutes in an air atmosphere. The optical properties and thermal properties are shown in table 1.
Example 3: preparation of composition for Forming resin film
1g of the polyimide (PI-A) of Synthesis example 1 was dissolved in a GBL solvent so as to be 10 mass% and then the resultant solution was gradually subjected to pressure filtration through a 5 μm filter at room temperature. Then, the filtrate was added to silica sol (GBL-M) (SiO of 18 to 23nm dispersed in GBL at 25.25%)2Nanoparticles) 9.241g, and was mixed for 30 minutes, and then the mixture was left still overnight to obtain a composition for forming a resin film.
The resin film-forming composition was applied to a glass support substrate, and fired at a temperature of 50 ℃ for 30 minutes, 140 ℃ for 30 minutes and 200 ℃ for 60 minutes in an air atmosphere, and further fired at 280 ℃ for 60 minutes in a vacuum atmosphere of-99 kpa to obtain a resin film. The optical properties and thermal properties of the obtained resin film are shown in table 1.
Example A: production of resin thin film laminate A
The composition for forming a resin film prepared in example 3 was applied to the release layer obtained in example 1, and then fired at 50 ℃ for 30 minutes, 140 ℃ for 30 minutes, 200 ℃ for 60 minutes in an air atmosphere, and further fired at 280 ℃ for 60 minutes in a vacuum atmosphere of-99 kpa, to obtain a resin film (polyimide a/silica sol composite resin film).
Then, the release layer and the resin film formed on the glass support substrate were separated (peeled) from the glass support substrate by mechanical cutting, to obtain a resin film laminate a.
The optical properties and thermal properties of the resin thin film laminate a are shown in table 1.
Fig. 5 and 6 show cross-sectional views (cross-sectional TEM) of the resin thin film laminate a, and fig. 7 shows raman IR spectra of (a) the front surface (resin thin film side), (b) the interface between the release layer and the resin thin film, and (c) the back surface (release layer side) of the resin thin film laminate a. FIG. 6(a) is an enlarged view of the vicinity of "blend" in FIG. 5, and FIG. 6(b) shows the composition of each layer constituting the laminate, and [001 ]]Represents an intermediate layer, [002 ]]Indicating resin film (polyimide + SiO)2)，[003]Denotes a release layer (DBL).
According to the cross-sectional TEMs of fig. 5 and 6, formation of an intermediate layer was confirmed at the interface between the formed release layer and the resin thin film, and the thickness was about 300 nm.
As shown in the raman IR spectrum of fig. 7, the IR spectrum at the interface between the release layer (b) and the resin film and the IR spectrum at the back surface (c) almost match each other in shape, and the interface is derived from at least the release layer.
Example B: production of resin thin film laminate B
A resin thin film laminate B was obtained by the same procedure as in example a except that the composition for forming a resin thin film prepared in example 3 was applied to the release layer obtained in example 2.
Fig. 8 and 9 show cross-sectional views (cross-sectional TEM) of the resin thin film laminate B, and fig. 10 shows raman IR spectra of the resin thin film laminate B (a) on the front surface (resin thin film side), (B) at the interface between the release layer and the resin thin film, and (c) on the back surface (release layer side). FIG. 9(a) is an enlarged view of the vicinity of the interface in FIG. 8, and FIG. 9(b) shows the composition of each layer constituting the laminate, and [001 ]]Denotes a release layer (DBL) [002 ]]Indicating resin film (polyimide + SiO)2)。
According to the cross-sectional TEMs of fig. 8 and 9, the interface between the release layer and the resin film formed was clearly separated from example a, and the thickness of the intermediate layer in this case was about 1nm or less and very thin.
As shown in the raman IR spectrum of fig. 10, the shape of the IR spectrum at the interface between the release layer (b) and the resin film and the shape of the IR spectrum at the back surface (c) almost match, and the interface is derived from the release layer.
Schematic cross-sectional views of the resin thin-film laminates a and B obtained in the above-described examples are shown in fig. 2 and 3.
As shown in fig. 2, it was confirmed that the resin thin film laminates a and B had a laminated structure in the order of the release layer (L II), the intermediate layer (L III), and the resin thin film (polyimide a/silica sol composite resin film) (L I) on the support base (G1). Further, as shown in FIG. 3, by separating (peeling) these laminated structures from the supporting base material (G1), resin thin film laminates A and B were obtained. In fig. 2 and 3, the element layer such as an electrode is denoted by liv.
Here, the release layer (L II), the resin film (polyimide a/silica sol composite resin film) (L I), and the intermediate layer formed therebetween are considered to have a polymer network structure shown in fig. 4. This network means that 2 polymers and nano-silica are bonded to each other by van der waals force or hydrogen bond, whereby the adhesion between the resin film and the release layer becomes strong. The intermediate layer can be obtained not only from the release layer but also from the resin film. This is because the upper surface of the release layer can be partially dissolved by the solvent contained in the resin film forming composition at the time of forming the resin film. Further, the intermediate layer can be obtained by reacting (thermal imidization) the release layer with the resin film again.
[ Table 1]
TABLE 1
As shown in table 1, the resin thin film laminate a obtained by the production method of the present invention was confirmed to have a low coefficient of linear expansion [ ppm/° c ] (50 to 200 ℃), high light transmittance [% ] at 400nm and 550nm after curing, a small yellow color indicated by CIEb value, and a low retardation.
The resin thin film laminate a of the present invention obtained in the above-described embodiment has no cracks even when it is held by both hands and bent at an acute angle (about 30 degrees), and has high flexibility required for a flexible display substrate.
[4] Production of resin thin film laminate (2)
Using the above < example 1: release layer formation the release layer-forming composition prepared in > and < example 3: preparation of resin thin film-forming composition the resin thin film-forming composition prepared in (1) was prepared into a resin thin film laminate by the following procedure.
(a) Preparation of composition for Forming Release layer containing crosslinking agent
In the above < example 1: release layer formation > in the release layer-forming composition prepared in (1), CYMEL (registered trademark) 303 (manufactured by allnex) was mixed so that the mass of polyimide (PI-a) contained in the composition became 30phr, to prepare a cross-linker-mixed release layer-forming composition.
(b) Preparation of composition for Forming resin film containing crosslinking agent
In the above < example 3: preparation of composition for Forming resin film > in the composition for Forming resin film prepared in (1), CYMEL303 was mixed so that the total mass of the polyimide (PI-A) and the silica sol (GBL-M) contained in the composition became 30phr, to prepare a composition for Forming resin film containing a crosslinking agent.
(i) After a release layer is formed on a glass support substrate using the composition for forming a release layer, a resin film is formed on the release layer using the composition for forming a resin film.
(ii) After a release layer is formed on a glass support substrate using the composition for forming a release layer, a resin film is formed on the release layer using the composition for compounding a crosslinking agent and forming a resin film.
(iii) After a release layer is formed on a glass support substrate using the composition for forming a crosslinking agent-incorporating release layer, a resin film is formed on the release layer using the composition for forming a resin film.
(iv) After a release layer is formed on a glass support substrate using the composition for forming a crosslinking agent-incorporated/release layer, a resin film is formed on the release layer using the composition for forming a crosslinking agent-incorporated/resin film.
After the resin film was formed, the release layer was peeled together with the resin film from the glass support substrate by mechanical cutting, and the peelability was evaluated based on the following criteria.
< evaluation of peelability >
◎ -capable of being completely separated (peeled) from the glass support substrate (almost 100%)
△ difficulty in separating from the glass support base material (5 to 50%)
× inability to separate (< 5%) from glass support substrate
In all cases, the firing conditions were set to 120 ℃ for 20 minutes, 140 ℃ for 20 minutes, 200 ℃ for 30 minutes, and 250 ℃ for 60 minutes in an air atmosphere.
The obtained results are shown in table 2.
[ Table 2]
TABLE 2
As shown in table 2, when a crosslinking agent was added to either one of the composition for forming a release layer or the composition for forming a resin film, it was confirmed that the resin film laminate was easily released from the glass support substrate.
Claims (15)
1. A method for producing a resin thin film laminate, characterized in that,
comprises the following steps:
a step of forming a release layer on a support substrate using a release layer-forming composition containing a heat-resistant polymer A and an organic solvent;
forming a resin film on the release layer using a resin film-forming composition containing a heat-resistant polymer B and an organic solvent; and
a step of peeling the peeling layer together with the resin film from the support base to obtain a resin film laminate,
the resin film-forming composition further contains silica particles having an average particle diameter of 100nm or less as calculated from a specific surface area value measured by a nitrogen adsorption method,
the composition for forming a release layer does not contain silica particles.
2. The production method according to claim 1, wherein the heat-resistant polymer A and the heat-resistant polymer B are the same polymer.
3. The production method according to claim 1, wherein the heat-resistant polymer A and the heat-resistant polymer B are each independently selected from the group consisting of polyimide, polybenzo
Azole, polybenzobis
At least one polymer of oxazole, polybenzimidazole and polybenzothiazole.
4. The production method according to claim 1, wherein each of the heat-resistant polymer A and the heat-resistant polymer B is independently a polyimide obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride with a diamine component containing a fluorine-containing aromatic diamine.
5. The production method according to claim 4, wherein the alicyclic tetracarboxylic dianhydride comprises a tetracarboxylic dianhydride represented by the formula (C1),
in the formula, B1Represents a 4-valent group selected from the group consisting of the formulae (X-1) to (X-12),
wherein R's are each independently a hydrogen atom or a methyl group, and ＊ represents a bond.
6. The production method according to claim 4, wherein the fluorine-containing aromatic diamine comprises a diamine represented by the formula (A1),
H2N-B2-NH2(A1)
in the formula, B2Represents a 2-valent group selected from the group consisting of formulas (Y-1) to (Y-34),
wherein ＊ represents a bond.
7. The production method according to claim 4, wherein the polyimide comprises a monomer unit represented by formula (1), a monomer unit represented by formula (2), or both of the monomer units,
8. the production method according to claim 1, wherein the resin film-forming composition is mixed in a mass ratio of 7: 3-3: the ratio of 7 contains the heat-resistant polymer B and the silica particles.
9. The production method according to claim 1, wherein the silica particles have an average particle diameter of 60nm or less.
10. The production method according to claim 1, wherein either the release layer-forming composition or the resin film-forming composition further comprises a crosslinking agent.
11. The manufacturing method according to claim 1, wherein the curing uses heat or ultraviolet rays.
12. The production method according to claim 1, wherein the adhesiveness between the release layer and the resin film is 0 to 5% in the CCJ series (JIS5400) classification, and the adhesiveness between the support base material and the release layer is 50% or more in the CCJ series (JIS5400) classification.
13. The production method according to claim 1, wherein the release layer has a thickness of 100 μm to 1 nm.
14. The production method according to claim 1, wherein the step of obtaining the resin thin film laminate is performed by a method selected from the group consisting of cutting with a knife, mechanical separation, and pulling.
15. A flexible substrate produced by the production method according to any one of claims 1 to 14.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-113594 | 2017-06-08 | ||
| JP2017113594 | 2017-06-08 | ||
| PCT/JP2018/021885 WO2018225825A1 (en) | 2017-06-08 | 2018-06-07 | Method for producing substrate for flexible device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111344130A true CN111344130A (en) | 2020-06-26 |
| CN111344130B CN111344130B (en) | 2022-08-19 |
Family
ID=64565868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880036744.5A Active CN111344130B (en) | 2017-06-08 | 2018-06-07 | Method for manufacturing substrate for flexible device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7116366B2 (en) |
| KR (1) | KR102604658B1 (en) |
| CN (1) | CN111344130B (en) |
| TW (1) | TWI782037B (en) |
| WO (1) | WO2018225825A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109866437B (en) * | 2019-02-25 | 2021-04-20 | 山东非金属材料研究所 | Preparation method of thermosetting resin-based composite material of carbon fiber spreading cloth |
| CN112322035B (en) * | 2020-11-12 | 2021-06-08 | 华东理工大学 | Three-layer mesoporous hollow silica-fluorine-containing polybenzoxazole composite film and preparation method and application thereof |
| WO2023021899A1 (en) * | 2021-08-18 | 2023-02-23 | 東洋紡株式会社 | Transparent heat-resistant laminated film |
| WO2023149435A1 (en) * | 2022-02-03 | 2023-08-10 | 株式会社カネカ | Resin composition, molded object, and film |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010111853A (en) * | 2008-09-15 | 2010-05-20 | Ind Technol Res Inst | Release layer material, substrate structure including the same, and method for manufacturing substrate structure |
| JP4883432B2 (en) * | 2010-05-31 | 2012-02-22 | 東洋紡績株式会社 | Flexible metal-clad laminate |
| JP2012158149A (en) * | 2011-02-02 | 2012-08-23 | Kaneka Corp | Method of manufacturing polyimide based multilayer film |
| CN103171214A (en) * | 2011-12-26 | 2013-06-26 | 奇美实业股份有限公司 | Substrate structure with release layer and manufacturing method thereof |
| KR20140027264A (en) * | 2011-04-15 | 2014-03-06 | 도요보 가부시키가이샤 | Laminate, method for producing same, and method for producing device structure using same |
| CN103972141A (en) * | 2013-02-06 | 2014-08-06 | 财团法人工业技术研究院 | Film structure and manufacturing method of flexible electronic device |
| WO2015053132A1 (en) * | 2013-10-07 | 2015-04-16 | 東レ株式会社 | Element-processing layered structure, method for manufacturing element-processing layered structure, and method for manufacturing thin element using same |
| CN104854165A (en) * | 2013-03-18 | 2015-08-19 | 旭化成电子材料株式会社 | Resin precursor, resin composition containing said resin precursor, resin film, method for producing said resin film, laminate, and method for producing said laminate |
| CN105304469A (en) * | 2015-09-25 | 2016-02-03 | 京东方科技集团股份有限公司 | Polyimide substrate, preparation method of polyimide substrate and flexible displayer |
| JP2017047684A (en) * | 2015-08-31 | 2017-03-09 | 新日鉄住金化学株式会社 | Manufacturing method of polyimide substrate film with functional layer, long-sized polyimide substrate film with functional layer, long-sized polyimide laminate and long-sized polyimide laminate with functional layer |
| CN106541652A (en) * | 2015-09-23 | 2017-03-29 | 新日铁住金化学株式会社 | Polyimides laminate structure and its manufacture method and display device and touch screen |
| WO2017057741A1 (en) * | 2015-09-30 | 2017-04-06 | 日産化学工業株式会社 | Composition for forming resin thin film |
| CN106604816A (en) * | 2014-08-15 | 2017-04-26 | 电化株式会社 | Cover film and electronic component packaging employing same |
| CN106687541A (en) * | 2014-07-22 | 2017-05-17 | 布鲁尔科技公司 | Polyimides as laser release materials for 3-D IC applications |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2947684B2 (en) * | 1992-11-20 | 1999-09-13 | オルガノ株式会社 | Nitrogen removal equipment |
| JP2008231327A (en) | 2007-03-22 | 2008-10-02 | Ihara Chem Ind Co Ltd | Polyimide having high transparency and its manufacturing method |
| KR102345844B1 (en) | 2014-03-31 | 2021-12-31 | 닛산 가가쿠 가부시키가이샤 | Method for producing resin thin film, and composition for forming resin thin film |
| JP7063273B2 (en) * | 2016-12-27 | 2022-05-09 | 日産化学株式会社 | Composition for forming a substrate protective layer |
-
2018
- 2018-06-07 WO PCT/JP2018/021885 patent/WO2018225825A1/en active Application Filing
- 2018-06-07 JP JP2019523972A patent/JP7116366B2/en active Active
- 2018-06-07 CN CN201880036744.5A patent/CN111344130B/en active Active
- 2018-06-07 KR KR1020197038705A patent/KR102604658B1/en active IP Right Grant
- 2018-06-08 TW TW107119772A patent/TWI782037B/en active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010111853A (en) * | 2008-09-15 | 2010-05-20 | Ind Technol Res Inst | Release layer material, substrate structure including the same, and method for manufacturing substrate structure |
| JP4883432B2 (en) * | 2010-05-31 | 2012-02-22 | 東洋紡績株式会社 | Flexible metal-clad laminate |
| JP2012158149A (en) * | 2011-02-02 | 2012-08-23 | Kaneka Corp | Method of manufacturing polyimide based multilayer film |
| KR20140027264A (en) * | 2011-04-15 | 2014-03-06 | 도요보 가부시키가이샤 | Laminate, method for producing same, and method for producing device structure using same |
| CN103171214A (en) * | 2011-12-26 | 2013-06-26 | 奇美实业股份有限公司 | Substrate structure with release layer and manufacturing method thereof |
| CN103972141A (en) * | 2013-02-06 | 2014-08-06 | 财团法人工业技术研究院 | Film structure and manufacturing method of flexible electronic device |
| CN104854165A (en) * | 2013-03-18 | 2015-08-19 | 旭化成电子材料株式会社 | Resin precursor, resin composition containing said resin precursor, resin film, method for producing said resin film, laminate, and method for producing said laminate |
| WO2015053132A1 (en) * | 2013-10-07 | 2015-04-16 | 東レ株式会社 | Element-processing layered structure, method for manufacturing element-processing layered structure, and method for manufacturing thin element using same |
| CN106687541A (en) * | 2014-07-22 | 2017-05-17 | 布鲁尔科技公司 | Polyimides as laser release materials for 3-D IC applications |
| CN106604816A (en) * | 2014-08-15 | 2017-04-26 | 电化株式会社 | Cover film and electronic component packaging employing same |
| JP2017047684A (en) * | 2015-08-31 | 2017-03-09 | 新日鉄住金化学株式会社 | Manufacturing method of polyimide substrate film with functional layer, long-sized polyimide substrate film with functional layer, long-sized polyimide laminate and long-sized polyimide laminate with functional layer |
| CN106541652A (en) * | 2015-09-23 | 2017-03-29 | 新日铁住金化学株式会社 | Polyimides laminate structure and its manufacture method and display device and touch screen |
| CN105304469A (en) * | 2015-09-25 | 2016-02-03 | 京东方科技集团股份有限公司 | Polyimide substrate, preparation method of polyimide substrate and flexible displayer |
| WO2017057741A1 (en) * | 2015-09-30 | 2017-04-06 | 日産化学工業株式会社 | Composition for forming resin thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20200017433A (en) | 2020-02-18 |
| TWI782037B (en) | 2022-11-01 |
| KR102604658B1 (en) | 2023-11-21 |
| JPWO2018225825A1 (en) | 2020-05-21 |
| JP7116366B2 (en) | 2022-08-10 |
| CN111344130B (en) | 2022-08-19 |
| TW201919912A (en) | 2019-06-01 |
| WO2018225825A1 (en) | 2018-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI705993B (en) | Production method for resin thin film and composition for forming resin thin film | |
| CN108137924B (en) | Composition for forming resin film | |
| TWI742204B (en) | Composition for forming flexible device substrate | |
| CN111344130B (en) | Method for manufacturing substrate for flexible device | |
| TWI804564B (en) | Hybrid resin composition | |
| TWI758357B (en) | Composition for forming flexible device substrate | |
| CN108473764B (en) | Composition for forming flexible device substrate | |
| JP7054064B2 (en) | Composition for forming a flexible device substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |