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WO2018225825A1 - Procédé de fabrication de substrat pour dispositif flexible - Google Patents

Procédé de fabrication de substrat pour dispositif flexible Download PDF

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Publication number
WO2018225825A1
WO2018225825A1 PCT/JP2018/021885 JP2018021885W WO2018225825A1 WO 2018225825 A1 WO2018225825 A1 WO 2018225825A1 JP 2018021885 W JP2018021885 W JP 2018021885W WO 2018225825 A1 WO2018225825 A1 WO 2018225825A1
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WO
WIPO (PCT)
Prior art keywords
thin film
resin thin
release layer
forming
composition
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.)
Ceased
Application number
PCT/JP2018/021885
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English (en)
Japanese (ja)
Inventor
江原　和也
鎮嘉 葉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
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Nissan Chemical Corp
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Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to CN201880036744.5A priority Critical patent/CN111344130B/zh
Priority to KR1020197038705A priority patent/KR102604658B1/ko
Priority to JP2019523972A priority patent/JP7116366B2/ja
Publication of WO2018225825A1 publication Critical patent/WO2018225825A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing a resin thin film laminate used as a base film for flexible printed circuit boards, particularly flexible printed boards such as flexible displays, and more specifically, heat resistance obtained by laminating a transparent laminate on a support substrate.
  • the present invention relates to a polymer laminate.
  • Patent Document 1 relates to a polyimide useful as a plastic substrate for a flexible display and an invention related to a precursor thereof, and tetracarboxylic acids and various diamines containing an alicyclic structure such as cyclohexylphenyltetracarboxylic acid. It has been reported that the polyimide reacted with is excellent in transparency and heat resistance.
  • Patent Document 2 improves the compatibility of linear expansion coefficient, transparency, and low birefringence, which has been a drawback of conventional plastic substrates, by adding silica sol to polyimide. The application to can be expected.
  • Non-Patent Document 1 after a predetermined functional layer is formed on a plastic substrate that is applied and fixed on glass, a laser is irradiated from the glass side to force the plastic substrate provided with the functional layer from the glass.
  • a separation method a so-called laser lift-off process (a method called EPLaR method (Electronics-on-Plastic-by-Laser-Release) has been proposed.
  • Non-Patent Document 1 guarantees the handleability and dimensional stability of a resin substrate by forming a functional layer on a plastic substrate fixed to glass using glass as a supporting base material. It is.
  • this EPLaR method laser lift-off method
  • the interface between the resin substrate and the support base material is destroyed by laser irradiation when separating the resin substrate from the support base material.
  • the characteristics of the resin substrate and the functional layer formed thereon may be deteriorated, such as a problem that the functional layer (TFT or the like) is damaged or a problem that the resin substrate itself is greatly damaged and the transmittance is lowered.
  • the present invention has been made in view of such circumstances, and is a resin thin film that provides a plastic thin film having excellent performance as a base film of a flexible device substrate such as a flexible display substrate that does not depend on the laser lift-off technology described above.
  • Providing a manufacturing method for laminates, especially while maintaining excellent performance of excellent heat resistance, low retardation, excellent flexibility, and excellent transparency, as well as its handleability and dimensional stability It aims at providing the manufacturing method of the resin thin film laminated body (substrate for flexible devices) which can ensure.
  • the present inventors have found that when forming a resin thin film in which silicon dioxide is blended with a heat resistant polymer in order to achieve both heat resistance and optical properties, By providing a release layer in between, the resin thin film laminate can be easily peeled off from the support substrate while maintaining the characteristics of excellent heat resistance, low retardation, excellent flexibility, and excellent transparency.
  • the present invention has been completed.
  • the present invention provides, as a first aspect, a method for producing a resin thin film laminate, Forming a release layer on the support substrate using the release layer-forming composition containing the heat-resistant polymer A and an organic solvent; A step of forming a resin thin film on the release layer using a composition for forming a resin thin film containing the heat-resistant polymer B and an organic solvent; Peeling the support layer together with the release layer and the resin thin film to obtain a resin thin film laminate,
  • the resin thin film forming composition further includes silicon dioxide particles having an average particle diameter calculated from a specific surface area value measured by a nitrogen adsorption method of 100 nm or less, provided that The release layer-forming composition does not contain silicon dioxide particles, and relates to a production method.
  • the said heat resistant polymer A and the said heat resistant polymer B are related with the manufacturing method as described in a 1st viewpoint which is the same polymer.
  • the heat-resistant polymer A and the heat-resistant polymer B are each independently at least one polymer selected from polyimide, polybenzoxazole, polybenzobisoxazole, polybenzimidazole, and polybenzothiazole. The manufacturing method according to the first aspect.
  • the heat-resistant polymer A and the heat-resistant polymer B are each independently a diamine containing a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride and a fluorine-containing aromatic diamine. It is related with the manufacturing method as described in a 1st viewpoint which is a polyimide obtained by imidating the polyamic acid obtained by making a component react. As a 5th viewpoint, the said alicyclic tetracarboxylic dianhydride is related with the manufacturing method as described in a 4th viewpoint containing the tetracarboxylic dianhydride represented by Formula (C1).
  • B 1 represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12).
  • a plurality of R's independently represent a hydrogen atom or a methyl group, and * represents a bond.
  • the said fluorine-containing aromatic diamine is related with the manufacturing method as described in a 4th viewpoint containing the diamine represented by a formula (A1).
  • B 2 represents a divalent group selected from the group consisting of formulas (Y-1) to (Y-34)).
  • the said polyimide is related with the manufacturing method as described in a 4th viewpoint containing the monomer unit represented by Formula (1), the monomer unit represented by Formula (2), or the monomer unit of both.
  • the composition for forming a resin thin film includes the heat-resistant polymer B and the silicon dioxide particles in a mass ratio of 7: 3 to 3: 7. Regarding the method.
  • the said silicon dioxide particle is related with the manufacturing method as described in a 1st viewpoint which has an average particle diameter of 60 nm or less.
  • the present invention relates to the manufacturing method according to the first aspect, wherein either the release layer forming composition or the resin thin film forming composition further includes a crosslinking agent.
  • the present invention relates to the manufacturing method according to the first aspect, characterized in that the curing is by heat or ultraviolet rays.
  • the adhesiveness between the release layer and the resin thin film is peelable from 0 to 5% in the CCJ series (JIS5400) classification, and the adhesiveness between the support substrate and the release layer. It is related with the manufacturing method as described in the 1st viewpoint characterized by being able to peel 50% by CCJ series (JIS5400) classification.
  • the present invention relates to the manufacturing method according to the first aspect, wherein the release layer has a thickness of 100 ⁇ m to 1 nm.
  • the present invention relates to the manufacturing method according to the first aspect, wherein the step of obtaining the resin thin film laminate is performed using a method selected from cutting with a knife, mechanical separation, and peeling.
  • a 15th viewpoint it is related with the flexible substrate manufactured by the manufacturing method as described in any one among 1st viewpoint thru
  • the resin thin film laminate can be easily peeled from the support base, a low coefficient of linear expansion, excellent heat resistance, low retardation, and excellent flexibility
  • the resin thin film laminate can be easily produced with good reproducibility without impairing performance such as performance.
  • the obtained resin thin film laminate exhibits a low linear expansion coefficient, high transparency (high light transmittance, low yellowness), low retardation, and excellent flexibility, so that it is a flexible device, particularly a flexible display. It can be suitably used as a substrate.
  • Such a method for producing a resin thin film laminate according to the present invention is a flexile device that requires characteristics such as high flexibility, low linear expansion coefficient, high transparency (high light transmittance, low yellowness), low retardation, and the like.
  • the present invention can sufficiently cope with the progress in the field of industrial substrates, particularly flexible display substrates.
  • FIG. 1 represents a supporting substrate
  • L II represents a release layer
  • L I represents a resin thin film
  • L IV represents an electrode layer formed on the resin thin film.
  • FIG. 2 is a cross-sectional photograph (cross section TEM) of a laminate obtained in Example A.
  • FIG. 2 is a Raman IR spectrum of a release layer, a resin thin film, and an interface thereof in the laminate obtained in Example A.
  • FIG. 2 is a cross-sectional photograph (cross section TEM) of a laminate obtained in Example B.
  • FIG. It is a figure which shows the cross-sectional photograph (cross section TEM) (a) of the laminated body obtained in Example B, and the component composition (b) of each layer. It is a Raman IR spectrum of the release layer, the resin thin film, and the interface thereof in the laminate obtained in Example B.
  • a release layer is formed using a composition for forming a release layer containing a heat resistant polymer A and an organic solvent on a supporting substrate, and then the heat resistant polymer B and the organic solvent are formed.
  • a resin thin film is formed on the release layer using the composition for forming a resin thin film containing the resin, and the release layer and the resin thin film are peeled together (as an integral body) from the support substrate, and the resin thin film is laminated.
  • silicon dioxide particles having an average particle diameter of 100 nm or less calculated from the specific surface area value measured by the nitrogen adsorption method is substantially further contained only in the resin thin film forming composition. It is a method to do. In order to achieve the effect of the present invention, it is important that the silicon dioxide particles are substantially contained only in the resin thin film forming composition and not contained in the release layer forming composition. . In the present invention, the term “substantially does not contain” silicon dioxide particles means that the composition does not contain silicon dioxide particles except for random mixing in the preparation process of the composition.
  • the content with respect to the heat-resistant polymer B in the composition for forming a release layer is smaller than the content of silicon dioxide particles with respect to the heat-resistant polymer A in the composition for forming a resin thin film.
  • the content of silicon dioxide particles when silicon dioxide particles are mixed into the release layer forming composition is specifically 5% of the content of silicon dioxide particles with respect to the heat-resistant polymer A of the resin thin film forming composition. It is preferable that it is less than.
  • the composition for forming a release layer and the composition for forming a resin thin film used in the present invention include a heat resistant polymer A and a heat resistant polymer B, respectively.
  • the heat-resistant polymer A contained in the release layer-forming composition and the heat-resistant polymer B contained in the resin thin-film-forming composition are the same (hereinafter referred to as heat-resistant polymer A and heat-resistant polymer A).
  • the functional polymer B is collectively referred to as a heat resistant polymer).
  • the heat-resistant polymer used in the present invention at least one selected from polyimide, polybenzoxazole, polybenzobisoxazole, polybenzimidazole and polybenzothiazole is preferably used.
  • polyimide is preferable, and in particular, a specific polyimide described later, that is, a polyamic obtained by reacting a tetracarboxylic dianhydride component including an alicyclic tetracarboxylic dianhydride and a diamine component including a fluorine-containing aromatic diamine.
  • a polyimide obtained by imidizing an acid is preferred.
  • the heat-resistant polymer is a polymer having a weight loss of 5% or less at a temperature of 350 ° C. or higher.
  • the polyimide suitably used in the present invention imidizes polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride and a diamine component containing a fluorinated aromatic diamine. Is a polyimide obtained.
  • the alicyclic tetracarboxylic dianhydride includes a tetracarboxylic dianhydride represented by the following formula (C1)
  • the fluorine-containing aromatic diamine is represented by the following formula (A1). It is preferable that the diamine contains.
  • B 1 represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12). (In the formula, a plurality of R's independently represent a hydrogen atom or a methyl group, and * represents a bond.)
  • B 2 represents a divalent group selected from the group consisting of formulas (Y-1) to (Y-34)). (In the formula, * represents a bond.)
  • B 1 in the formula is represented by the formulas (X-1), (X-4), (X-6), (X-7). It is preferable that it is a compound.
  • B 2 in the formula is preferably a compound represented by the formula (Y-12) or (Y-13).
  • a polyimide obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride represented by the above formula (C1) and a diamine represented by the above formula (A1) is described below.
  • the monomer unit represented by Formula (2) is included.
  • the total number of moles of tetracarboxylic dianhydride component is The alicyclic tetracarboxylic dianhydride, for example, the tetracarboxylic dianhydride represented by the above formula (C1) is preferably 90 mol% or more, more preferably 95 mol% or more, In particular, it is optimal that all (100 mol%) is a tetracarboxylic dianhydride represented by the above formula (C1).
  • the fluorine-containing aromatic is used with respect to the total number of moles of the diamine component.
  • the diamine for example, the diamine represented by the formula (A1) is preferably 90 mol% or more, and more preferably 95 mol% or more.
  • the diamine represented by the said Formula (A1) may be sufficient as all (100 mol%) of a diamine component.
  • the polyimide used by this invention contains the monomer unit represented by following formula (1).
  • those represented by the formula (1-1) or the formula (1-2) are preferable, and those represented by the formula (1-1) are more preferable.
  • the polyimide used by this invention contains the monomer unit represented by Formula (2).
  • the polyimide used in the present invention may contain a monomer unit represented by the formula (1) and a monomer unit represented by the formula (2) at the same time.
  • the molar ratio in the polyimide chain is represented by the formula (1).
  • the monomer unit represented by the formula (2) is preferably contained at a ratio of 10: 1 to 1:10, more preferably 10: 1 to 3: 1.
  • the polyimide of the present invention includes an alicyclic tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the above formula (C1), a diamine component containing a diamine represented by the formula (A1), and In addition to monomer units derived from, for example, monomer units represented by the above formulas (1) and (2), other monomer units may be included.
  • the content ratio of the other monomer units 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 derived from the alicyclic tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the formula (C1) and the diamine component containing the diamine represented by the formula (A1).
  • the monomer unit represented by formula (1) or the number of moles of the monomer unit represented by formula (2), or the monomer unit represented by formula (1) and formula (2) Is preferably less than 20 mol%, more preferably less than 10 mol%, and even more preferably less than 5 mol%.
  • Examples of such other monomer units include, but are not limited to, monomer units having other polyimide structures represented by the formula (3).
  • A represents a tetravalent organic group, preferably a tetravalent group represented by any of the following formulas (A-1) to (A-4).
  • B represents a divalent organic group, preferably a divalent group represented by any of the following formulas (B-1) to (B-11).
  • * represents a bond.
  • B represents the above formulas (Y-1) to ( Y-34) may be a divalent group.
  • a and B include, for example, only a monomer unit composed of only one of the groups exemplified by the following formula. Alternatively, at least one of A and B may contain two or more monomer units selected from two or more groups exemplified below.
  • * represents a bond.
  • each monomer unit is bonded in an arbitrary order.
  • a polyimide having a monomer unit represented by the above formula (1) has bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic acid as a tetracarboxylic dianhydride component. It can be obtained by polymerizing a dianhydride and a diamine represented by the following formula (4) as a diamine component in an organic solvent and imidizing the resulting polyamic acid.
  • the polyimide used in the present invention has a monomer unit represented by the above formula (2), the polyimide may be 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride component.
  • the polyimide containing each monomer unit has 1,2,3,4-cyclobutanetetracarboxylic dianhydride and the following formula as a diamine component: It is obtained by polymerizing the diamine represented by (4) in an organic solvent and imidizing the resulting polyamic acid.
  • Examples of the diamine represented by the above formula (4) include 2,2′-bis (trifluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, and 2,3′-bis (trifluoromethyl).
  • Benzidine is mentioned.
  • the diamine component is represented by the following formula (4-1) from the viewpoint of lowering the linear expansion coefficient of the resin thin film laminate of the present invention and higher transparency of the resin thin film laminate.
  • 2,2′-bis (trifluoromethyl) benzidine or 3,3′-bis (trifluoromethyl) benzidine represented by the following formula (4-2) is preferably used, and in particular, 2,2′- Bis (trifluoromethyl) benzidine is preferably used.
  • the polyimide used by this invention contains the diamine represented by the alicyclic tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the above-mentioned formula (C1), and a formula (A1).
  • the monomer unit derived from the diamine component for example, the monomer unit represented by the above formula (1) and the monomer unit represented by the formula (2), other monomer units represented by the above formula (3)
  • the polyimide containing each monomer unit represented by Formula (1), Formula (2), and Formula (3) is one of the above-mentioned two types of tetracarboxylic dianhydrides as the tetracarboxylic dianhydride component.
  • a tetracarboxylic dianhydride represented by the following formula (5), a diamine represented by the following formula (6) as a diamine component, and a diamine represented by the following formula (6) in an organic solvent Polymer obtained by polymerization with Obtained by imidizing a click acid.
  • a in the above formula (5) and B in the formula (6) have the same meaning as A and B in the above formula (3), respectively.
  • tetracarboxylic dianhydride represented by the formula (5)
  • tetracarboxylic dianhydrides in which A in the formula (5) is a tetravalent group represented by any one of the above formulas (A-1) to (A-4) are preferable.
  • 4,8-bis (trifluoromethoxy) benzo [1,2-c: 4, 5-c ′] difuran-1,3,5,7-tetraone can be mentioned as
  • Examples of the diamine represented by the formula (6) include 2- (trifluoromethyl) benzene-1,4-diamine, 5- (trifluoromethyl) benzene-1,3-diamine, and 5- (trifluoromethyl).
  • aromatic diamines in which B in the formula (6) is a divalent group represented by any one of the formulas (B-1) to (B-11) are preferable, that is, 2,2 ′.
  • -Bis (trifluoromethoxy)-(1,1'-biphenyl) -4,4'-diamine [other name: 2,2'-dimethoxybenzidine], 4,4 '-(perfluoropropane-2,2- Diyl) dianiline, 2,5-bis (trifluoromethyl) benzene-1,4-diamine, 2- (trifluoromethyl) benzene-1,4-diamine, 2-fluorobenzene-1,4-diamine, 4, 4′-oxybis [3- (trifluoromethyl) aniline], 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octafluoro [1,1′-biphenyl] -4,4 ′ -Diamine [Alternative name:
  • the polyimide used in the present invention is represented by the tetracarboxylic dianhydride component including the alicyclic tetracarboxylic dianhydride represented by the above formula (C1) and the above formula (A1). It is obtained by imidizing a polyamic acid obtained by reacting a diamine component containing a fluorine-containing aromatic diamine.
  • the reaction from the two components to the polyamic acid is advantageous in that it can proceed relatively easily in an organic solvent and no by-product is formed.
  • the charging ratio (molar ratio) of the diamine component in the reaction between the tetracarboxylic dianhydride component and the diamine component is appropriately set in consideration of the molecular weight of the polyamic acid and the polyimide obtained by subsequent imidization.
  • the tetracarboxylic dianhydride component can usually be about 0.8 to 1.2, for example about 0.9 to 1.1, preferably about 0.1. It is about 95 to 1.02. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
  • the organic solvent used in the reaction between the tetracarboxylic dianhydride component and the diamine component is not particularly limited as long as it does not adversely affect the reaction and the produced polyamic acid dissolves. Specific examples are given below.
  • the solvent does not dissolve the polyamic acid, it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
  • water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
  • a dispersion or solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride is added here.
  • a method of adding a component as it is, or a method in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, or a dispersion or solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent.
  • Examples thereof include a method of adding a diamine component and a method of alternately adding a tetracarboxylic dianhydride component and a diamine compound component, and any of these methods may be used.
  • the tetracarboxylic dianhydride component and / or the diamine component are composed of a plurality of types of compounds, they may be reacted in a premixed state, individually individually, or further individually. Low molecular weight substances may be mixed and reacted to form high molecular weight substances.
  • the temperature at the time of synthesizing the polyamic acid may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, and can be selected, for example, from -20 ° C to 150 ° C. C. to 150.degree. C., usually about 0 to 150.degree. C., preferably about 0 to 140.degree.
  • the reaction time depends on the reaction temperature and the reactivity of the raw material, it cannot be defined unconditionally, but is usually about 1 to 100 hours.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult.
  • 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 initial stage of the reaction can be performed at a high concentration, and then an organic solvent can be added.
  • Examples of the method for imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
  • the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
  • the chemical (catalyst) imidization of polyamic acid is carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution, and igniting the system under a temperature condition of ⁇ 20 to 250 ° C., preferably 0 to 180 ° C. This can be done by stirring.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 1.5 to 20 mol times the amide acid group of the polyamic acid, and the amount of the acid anhydride is 1 to 50 mol of the amide acid group of the polyamic acid. Double, preferably 2 to 30 mole times.
  • Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and 1-ethylpiperidine. Among them, pyridine and 1-ethylpiperidine have an appropriate basicity for proceeding with the reaction. Therefore, it is preferable.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the dehydration cyclization rate (imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the use and purpose. Particularly preferably, it is 50% or more.
  • the filtrate after filtering the reaction solution, the filtrate may be used as it is, or may be diluted or concentrated to form a release layer forming composition, and further, silicon dioxide or the like described later is further blended therein to form a resin thin film.
  • a forming composition may be used.
  • the polyimide used in the present invention is a gel permeation chromatography (GPC) polystyrene in consideration of the strength of the resin thin film laminate, the workability when forming the resin thin film laminate, the uniformity of the resin thin film laminate, and the like.
  • the weight average molecular weight (Mw) in terms of conversion is preferably 5,000 to 200,000.
  • the reaction solution may be poured into a poor solvent and precipitated.
  • 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 a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
  • the organic solvent for dissolving the resin component in the reprecipitation collection step is not particularly limited. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2- Pyrrolidone, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Examples include ketones, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, and 4-hydroxy-4-methyl-2
  • Silicon dioxide (silica) used in the resin thin film forming composition of the present invention is not particularly limited, but silicon dioxide in the form of particles, for example, an average particle diameter of 100 nm or less, for example, 5 nm to 100 nm, 5 nm to 60 nm, preferably 5 nm to 55 nm. From the viewpoint of obtaining a highly transparent thin film with good reproducibility, it is preferably 5 nm to 50 nm, more preferably 5 nm to 45 nm, still more preferably 5 nm to 35 nm, and further preferably 5 nm to 30 nm.
  • the average particle diameter of silicon dioxide particles is an average particle diameter value calculated from specific surface area values measured by a nitrogen adsorption method using silicon dioxide particles.
  • colloidal silica having the above average particle size can be suitably used, and silica sol can be used as the colloidal silica.
  • silica sol there can be used an aqueous silica sol produced by a known method using a sodium silicate aqueous solution as a raw material, and an organosilica sol obtained by substituting water as a dispersion medium of the aqueous silica sol with an organic solvent.
  • alkoxysilanes such as methyl silicate and ethyl silicate are obtained by hydrolysis and condensation 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).
  • a silica sol obtained by replacing the silica sol with another organic solvent can be used.
  • the present invention preferably uses an organosilica sol whose dispersion medium is an organic solvent.
  • Examples of the organic solvent in the above-described organosilica sol include: lower alcohols such as methyl alcohol, ethyl alcohol and isopropanol; linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide; N-methyl-2- Examples include cyclic amides such as pyrrolidone; ethers such as ⁇ -butyrolactone; glycols such as ethyl cellosolve and ethylene glycol, acetonitrile, and the like. This substitution can be performed by a usual method such as a distillation method or an ultrafiltration method.
  • the viscosity of the organosilica sol is about 0.6 mPa ⁇ s to 100 mPa ⁇ s at 20 ° C.
  • organosilica sols examples include, for example, trade name MA-ST-S (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), trade name MT-ST (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.).
  • Product name XBA-ST xylene / n-butanol mixed solvent dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • product name EAC-ST ethyl acetate dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • product Name PMA-ST propylene glycol monomethyl ether acetate dispersed silica sol, Nissan Chemical Industries, Ltd.
  • Trade name MEK-ST methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • trade name MEK-ST-UP methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • trade name MEK-ST-L examples thereof include, but are not limited to, methyl ethyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd., and trade name MIBK-ST (methyl isobutyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries
  • the composition for forming a release layer and the composition for forming a resin thin film used in the present invention can further contain a crosslinking agent.
  • a crosslinking agent in the present invention, it is suitable to be blended only in either the release layer forming composition or the resin thin film forming composition, and among them, only in the resin thin film forming composition. It is preferable to blend a crosslinking agent.
  • the cross-linking agent used here is a compound composed only of hydrogen atoms, carbon atoms and oxygen atoms, or a compound composed only of these atoms and nitrogen atoms, and comprises a hydroxy group, an epoxy group and a carbon atom number of 1 to
  • a crosslinking agent comprising a compound having two or more groups selected from the group consisting of 5 alkoxy groups and having a ring structure.
  • the total number of hydroxy groups, epoxy groups and alkoxy groups having 1 to 5 carbon atoms per compound in the crosslinking agent is preferably from the viewpoint of realizing the solvent resistance of the resulting resin thin film laminate with good reproducibility. From the viewpoint of realizing the flexibility of the resulting resin thin film laminate with good reproducibility, it is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • ring structure of the crosslinking agent examples include aryl rings such as benzene, nitrogen-containing heteroaryl rings such as pyridine, pyrazine, pyrimidine, pyridazine, and 1,3,5-triazine, cyclopentane, cyclohexane, and cyclohexane.
  • cycloalkane rings such as heptane, cyclic amines such as piperidine, piperazine, hexahydropyrimidine, hexahydropyridazine, and hexahydro-1,3,5-triazine.
  • the number of ring structures per compound in the cross-linking agent is not particularly limited as long as it is 1 or more, but from the viewpoint of ensuring the solubility of the cross-linking agent in a solvent and obtaining a highly flat resin thin film laminate, 1 or 2 is preferred.
  • the ring structures may be condensed with each other, and an alkane having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a propane-2,2-diyl group, etc.
  • the ring structures may be bonded to each other through a linking group such as a diyl group.
  • the molecular weight of the crosslinking agent is not particularly limited as long as it has crosslinking ability and dissolves in the solvent to be used, but the solvent resistance of the resulting resin thin film laminate, the solubility of the crosslinking agent itself in an organic solvent, In consideration of availability, price, etc., it is preferably about 100 to 500, more preferably about 150 to 400.
  • the crosslinking agent may further have a group that can be derived from a hydrogen atom, a carbon atom, a nitrogen atom, and an oxygen atom, such as a ketone group or an ester group (bond).
  • Preferred examples of the crosslinking agent include compounds represented by the following formulas (K1) to (K5), and one preferred embodiment of the formula (K4) is a compound represented by the formula (K4-1).
  • a compound represented by the formula (5-1) can be exemplified.
  • each of A 1 and A 2 independently represents an alkane-diyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, and a propane-2,2-diyl group.
  • a 1 is preferably a methylene group or an ethylene group, more preferably a methylene group
  • a 2 is preferably a methylene group or a propane-2,2-diyl group.
  • Each X is independently of each other a hydroxy 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, a t-butyloxy group, etc.
  • X is preferably an epoxy group in the formulas (K1) and (K5), and has 1 to 5 carbon atoms in the formulas (K2) and (K3) in consideration of the availability, price, etc. of the crosslinking agent.
  • An alkoxy group is preferable, and a hydroxy group is preferable in the formula (K4).
  • each n represents the number of — (A 1 -X) groups bonded to the benzene ring and is an integer of 1 to 5 independently of each other, preferably 2 to 3, more preferably 3.
  • each A 1 is preferably the same group, and each X is preferably the same group.
  • the compounds represented by the above formulas (K1) to (K5) are skeleton compounds such as aryl compounds, heteroaryl compounds, and cyclic amines having the same ring structure as the ring structure in these compounds, epoxy alkyl halide compounds, It can be obtained by reacting an alkoxy halide compound or the like with a carbon-carbon coupling reaction or an N-alkylation reaction, or hydrolyzing the resulting alkoxy moiety.
  • a commercial item may be used for a crosslinking agent, and what was synthesize
  • combining method may be used for it.
  • Commercially available products include CYMEL (registered trademark) 300, 301, 303LF, 303ULF, 304, 350, 3745, XW3106, MM-100, 323, 325, 327, 328, Same 385, Same 370, Same 373, Same 380, Same 1116, Same 1130, Same 1133, Same 1141, Same 1161, Same 1168, Same 3020, Same 202, Same 203, Same 1156, Same MB-94, Same MB- 96, MB-98, 247-10, 651, 658, 683, 683, 688, 1158, MB-14, MI-12-I, MI-97-IX, U-65 UM-15, U-80, U-21-511, U-21-510, U-216-8, U-227-8, U-1050-10, U-1052 -8, the same
  • the amount of the crosslinking agent is appropriately determined according to the type of the crosslinking agent and the like, and thus cannot be defined unconditionally, but is usually based on the mass of the polyimide contained in the release layer forming composition or resin thin film formation. 50% by mass or less, preferably 100% by mass or less, from the viewpoint of ensuring the flexibility of the resulting resin thin film laminate and suppressing embrittlement relative to the total mass of the polyimide and silicon dioxide contained in the composition for use. From the viewpoint of ensuring the solvent resistance of the obtained resin thin film laminate, it is 0.1% by mass or more, preferably 1% by mass or more.
  • the composition for forming a release layer and the composition for forming a resin thin film used in the present invention contain an organic solvent.
  • This organic solvent is not specifically limited, For example, the thing similar to the specific example of the reaction solvent used at the time of preparation of the said polyamic acid and a polyimide is mentioned. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, ⁇ - Examples include butyrolactone.
  • an organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and ⁇ -butyrolactone are preferable in view of obtaining a highly flat resin thin film laminate with high reproducibility.
  • composition for forming a release layer used in the present invention is a composition containing the heat-resistant polymer and an organic solvent, and optionally containing a crosslinking agent, and substantially contains silicon dioxide as described above. It is something that does not.
  • the amount of solids and the viscosity in the composition for forming a release layer conform to the following composition for forming a resin thin film.
  • composition for resin thin film formation is a composition that contains the heat-resistant polymer, silicon dioxide, and an organic solvent, and may optionally contain a crosslinking agent.
  • the composition for forming a resin thin film is uniform and phase separation is not observed.
  • the solid content in the composition for forming a resin thin film is usually about 0.5 to 30% by mass, preferably about 5 to 25% by mass.
  • the solid content concentration means the total mass of components other than the organic solvent, and even a liquid monomer or the like is included in the weight as a solid content.
  • the viscosity of the composition for forming a resin thin film is appropriately set in consideration of the thickness of the resin thin film to be produced, etc.
  • the object is to obtain a resin thin film having a thickness of about 5 to 50 ⁇ m with good reproducibility.
  • the pressure is usually about 500 to 50,000 mPa ⁇ s at 25 ° C., preferably about 1,000 to 20,000 mPa ⁇ s.
  • various organic or inorganic low-molecular or high-molecular compounds may be blended in the release layer forming composition and the resin thin film forming composition in order to impart processing characteristics and various functionalities.
  • a catalyst an antifoaming agent, a leveling agent, a surfactant, a dye, a plasticizer, fine particles, a coupling agent, a sensitizer, and the like can be used.
  • the catalyst can be added for the purpose of reducing the retardation and linear expansion coefficient of the resin thin film laminate.
  • the release layer-forming composition is, for example, a polyimide obtained by the above-described method as a heat-resistant polymer, a crosslinking agent as necessary, and other components as necessary (various organic or inorganic low-molecular or high-molecular compounds ) Can be obtained by dissolving in the above-mentioned organic solvent.
  • the composition for forming a resin thin film includes, for example, a polyimide and silicon dioxide obtained by the above-described method as a heat-resistant polymer, a crosslinking agent as necessary, and other components as necessary (various organic or inorganic low molecules or Polymer compound) can be obtained by dissolving in the above-mentioned organic solvent.
  • silicon dioxide may be added to the reaction solution after the polyimide is prepared, and the organic solvent may be further added as desired.
  • a crosslinking agent is used in the present invention, it is used in either the release layer forming composition or the resin thin film forming composition.
  • the resin contained in the release layer forming composition and the resin contained in the resin thin film forming composition are the same as described above from the viewpoint of not affecting the characteristics and the like.
  • silicon dioxide particles are further contained only in the resin thin film forming composition.
  • the preparation method of each composition is not particularly limited. Therefore, in the method of the present invention, for example, after first preparing a release layer forming composition, silicon dioxide particles are added to a part of the obtained release layer forming composition as described above, and if desired, organic By further adding a solvent, a composition for forming a release layer and a composition for forming a resin thin film can be easily prepared, and these can be used in the method of the present invention.
  • This step is a step of forming a release layer on the supporting substrate using the above-described release layer forming composition. Specifically, by applying the release layer-forming composition on a support substrate, drying and heating to remove the organic solvent, it has excellent heat resistance, low retardation, excellent flexibility, and further transparency It is possible to obtain an exfoliation layer that can be easily exfoliated from a supporting substrate by at least one method selected from the group consisting of cutting with a knife, mechanical separation, and simultaneous peeling, while maintaining excellent performance of being excellent in properties. As a result, a flexible device substrate can be obtained.
  • the support substrate examples include plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, stainless steel (SUS), wood, Paper, glass, a silicon wafer, a slate, etc. are mentioned.
  • the supporting substrate to be applied is preferably glass or a silicon wafer, and since the resulting release layer exhibits good peelability, it should be glass. Further preferred.
  • a linear expansion coefficient of the support base material to apply from a viewpoint of the curvature of the support base material after coating, Preferably it is 40 ppm / degrees C or less, More preferably, it is 30 ppm / degrees C or less.
  • the method for applying the composition for forming the release layer on the support substrate 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, and a bar coating method. , Die coating method, ink jet method, printing method (letter plate, intaglio plate, planographic plate, screen printing, etc.) and the like, and these can be appropriately used according to the purpose.
  • the heating temperature is preferably 500 ° C. or lower, and more preferably 450 ° C. or lower.
  • the ratio of the thickness of the release layer to the entire thickness of the resin thin film laminate obtained by the production method of the present invention is as follows. Since it is sufficiently small as described in (1), the influence on the characteristics is small.
  • the resin thin film forming composition is applied onto the formed release layer, the higher the final firing temperature, the smaller the proportion of the release layer dissolved in the resin thin film forming composition.
  • the temperature is 400 ° C., the release layer is difficult to dissolve. As a result, the boundary between the release layer and the resin thin film becomes clear.
  • the applied release layer forming composition is heated at 40 ° C. to 100 ° C. for 5 minutes to 2 hours, and then the heating temperature is gradually increased. Finally, it is desirable to heat at a temperature in the range of more than 175 ° C. to 450 ° C. for 30 minutes to 2 hours.
  • the applied composition for forming a release layer is heated at 40 ° C. to 100 ° C. for 5 minutes to 2 hours, then at a temperature exceeding 100 ° C. to 175 ° C. for 5 minutes to 2 hours, and then within a range from 175 ° C. to 450 ° C. It is preferable to heat at the inner temperature for 5 minutes to 2 hours.
  • the appliance used for heating include a hot plate and an oven.
  • the heating atmosphere may be under air or under an inert gas such as nitrogen, and may be under normal pressure or under reduced pressure, and different pressures are applied at each stage of heating. May be.
  • a fine structure may be formed on the surface of the release layer by a coating technique from the viewpoint of further improving the adhesion between the release layer and the resin thin film formed thereafter.
  • a coating technique from the viewpoint of further improving the adhesion between the release layer and the resin thin film formed thereafter.
  • the thickness of the release layer is appropriately determined in consideration of the type of the flexible device within a range of about 1 nm to 200 ⁇ m. However, in order to achieve the effects of the present invention, it is at least thicker than the diameter of the silica particles. It is necessary. In particular, assuming that the resin thin film laminate is used as a substrate for a flexible display, it is usually about 10 nm to 10 ⁇ m, preferably about 100 nm to 5 ⁇ m, and the desired thickness can be adjusted by adjusting the thickness of the coating film before heating. A release layer is formed.
  • This step is a step of forming a resin thin film on the release layer using the resin thin film forming composition of the present invention described above.
  • This step can 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 supporting substrate.
  • the thin film-forming composition is applied onto the release layer formed on the support substrate, dried and heated to remove the organic solvent, thereby providing high heat resistance and high transparency.
  • a part of peeling layer is melt
  • the coating method of the composition for forming a resin thin film on the release layer, the heating temperature, the apparatus used for heating, and the thickness of the resin thin film conform to the respective conditions described in the formation process of the release layer.
  • the adhesion force of the resin thin film to the release layer is greater than the adhesion force of the release layer to the support substrate. Is preferably large.
  • the adhesion between the release layer and the resin thin film is 0 to 1 (0 to 5% peelable) according to the CCJ series (JIS5400) classification, and the support substrate and the release layer Is preferably 5 (50% or more peelable) in the CCJ series (JIS5400) classification.
  • the CCJ series is defined as a classification from 0 to 5, where 0 classification means that 0% of the square area can be removed, 1 classification means 1-5% of the square area, 2 classifications Is 6-10% of the square area, 3 is 11-25% of the square area, 4 is 26-50% of the square area, and 5 is 50% of the square area This means that each can be peeled off.
  • 0 classification means that 0% of the square area can be removed
  • 1 classification means 1-5% of the square area
  • 2 classifications Is 6-10% of the square area 3 is 11-25% of the square area
  • 4 is 26-50% of the square area
  • 5 50% of the square area
  • each can be peeled off.
  • the number of square peels of the resin thin film with respect to the release layer is class 0-2
  • the number of square peels of the release layer with respect to the support substrate is class 5 It is preferable that
  • Step of obtaining a resin thin film laminate In this step, the release layer and the resin thin film are peeled together from the support substrate to obtain a resin thin film laminate.
  • the method of peeling the resin thin film laminate formed in this way from the support substrate is not particularly limited.
  • the resin thin film laminate is cooled together with the support substrate, and the resin thin film laminate is cut and peeled off. And a method of peeling by applying tension through a roll.
  • a method for peeling the resin thin film laminate from the supporting substrate in the present invention at least one method selected from cutting with a knife, mechanical separation, and peeling can be applied.
  • the release layer and the resin thin film are integrated. It can be easily peeled off from the support base material to obtain a resin thin film laminate.
  • the thickness of the resin thin film laminate can be appropriately determined in consideration of the type of flexible device within the range of about 1 ⁇ m to 200 ⁇ m.
  • the thickness of the release layer relative to the thickness of the resin thin film laminate (100%) is preferably 1 to 35%.
  • the resin thin film laminate obtained in one preferred embodiment of the present invention can achieve high transparency with a light transmittance of 75% or more at a wavelength of 400 nm.
  • the resin thin film laminate can have a low coefficient of linear expansion of, for example, 60 ppm / ° C. or less, particularly 10 ppm / ° C. to 35 ppm / ° C. at 50 ° C. to 200 ° C., for example, at 200 ° C. to 250 ° C.
  • the linear expansion coefficient can be as low as 80 ppm / ° C. or less, particularly 15 ppm / ° C. to 55 ppm / ° C., and has excellent dimensional stability during heating.
  • the resin thin film laminate is represented by a product of birefringence (difference between two in-plane orthogonal refractive indexes) and a film thickness (thickness of the laminate) when the wavelength of incident light is 590 nm.
  • Resin thin film laminate obtained by the production method of the present invention when the average film thickness (average thickness of the laminate) of 15 [mu] m ⁇ 40 [mu] m, the retardation R th is less than 700nm in the thickness direction, for example 660nm or less, for example, 10nm ⁇ 660 nm, in-plane retardation R 0 is less than 4, eg 0.3 to 3.9, and birefringence ⁇ n is very low, eg less than 0.02, eg 0.0003 to 0.019 . Thus, retardation can be reduced in the resin thin film laminate obtained by the production method of the present invention.
  • the resin thin film laminate obtained by using the manufacturing method of the present invention described above has the above-mentioned characteristics, it satisfies each condition necessary as a base film of a flexible display substrate. Can be used particularly preferably. That is, the present invention is suitable as a method for manufacturing a flexible device substrate.
  • FIG. 1 An example of manufacturing a flexible device using the manufacturing method of the present invention is shown in FIG. As shown in FIG. 1, first, a release layer is formed on a support substrate, a resin thin film is formed on the release layer, and a resin thin film laminate is obtained. Then, after forming a functional layer on a resin thin film laminated body, these can be peeled together and a flexible device can be obtained.
  • the apparatus and conditions used for sample preparation and physical property analysis and evaluation are as follows. 1) Measurement 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 a polymer were measured by a device: Showdex GPC-101, manufactured by Showa Denko KK Column: KD803 and KD805, column temperature: 50 ° C., elution solvent: DMF, flow rate: 1.5 ml / min, calibration curve: standard polystyrene.
  • Mn number average molecular weight
  • Mw weight average molecular weight of a polymer were measured by a device: Showdex GPC-101, manufactured by Showa Denko KK Column: KD803 and KD805, column temperature: 50 ° C., elution solvent: DMF, flow rate: 1.5 ml / min, calibration curve: standard polystyrene.
  • Td 5% 5% weight loss temperature
  • the 5% weight loss temperature (Td 5% [° C.]) is TGA Q500 manufactured by TA Instruments, and the temperature is increased from about 5 to 10 mg of a thin film (or laminate) to 50 to 800 ° C. at 10 ° C./min in nitrogen. And obtained by measuring.
  • Preparation Example 1 Preparation of silica sol (GBL-M) In a 1000 mL round bottom flask, 350 g of methanol-dispersed silica sol manufactured by Nissan Chemical Industries, Ltd .: MA-ST-M (silica solid content concentration: 40.4) % By weight) and 419 g of ⁇ -butyllactone. Then, the flask was connected to a vacuum evaporator to reduce the pressure in the flask, and immersed in a warm water bath at about 35 ° C. for 20 to 50 minutes, so that silica sol (GBL-M) in which the solvent was substituted from methanol to ⁇ -butyllactone was reduced. 560.3 g was obtained (silica solid content concentration: 25.25% by mass).
  • Synthesis Example 1 Synthesis of Polyimide A (PI-A) In a 250 mL reaction three-necked flask equipped with a nitrogen inlet / outlet, a mechanical stirrer and a condenser, TFMB 25.61 g (0.08 mol) ) Thereafter, 173.86 g of GBL was added and stirring was started. Immediately after the diamine was completely dissolved in the solvent, 10 g (0.04 mol) of stirred BODAxx, 7.84 g (0.04 mol) of CBDA and 43.4 g of GBL were added and heated to 140 ° C. under nitrogen. .
  • Example 1 Formation of release layer At room temperature, 1 g of the polyimide (PI-A) of Synthesis Example 1 dissolved in GBL solvent so as to be 8% by mass was slowly filtered under pressure through a 1 ⁇ m filter, and the release layer A forming composition was obtained. Thereafter, the composition is coated on a glass support substrate, fired at 50 ° C. for 30 minutes, 140 ° C. for 30 minutes, and 200 ° C. for 60 minutes, and further fired at 300 ° C. for 60 minutes. did. Thus, a transparent polyimide film as a release layer was formed on the glass supporting substrate. The optical and thermal properties are shown in Table 1.
  • Example 2 Formation of Release Layer Using the release layer forming composition prepared in Example 1, this was coated on a glass support substrate, and in an air atmosphere at a temperature of 50 ° C for 30 minutes, at 140 ° C for 30 minutes and A transparent polyimide film as a release layer was obtained on a glass supporting substrate in the same manner as in Example 1 except that baking was performed at 200 ° C. for 60 minutes and then baking was further performed at 400 ° C. for 60 minutes.
  • the optical and thermal properties are shown in Table 1.
  • Example 3 Preparation of composition for resin thin film formation
  • PI-A polyimide
  • GBL-M silica sol
  • Example A Production of Resin Thin Film Laminate A
  • the resin thin film-forming composition prepared in Example 3 was coated on the release layer obtained in Example 1, and 140 minutes at a temperature of 50 ° C. for 30 minutes in an air atmosphere. C. for 30 minutes at 200.degree. C. for 60 minutes at 200.degree. C. and in a vacuum atmosphere of -99 kpa for 60 minutes at 280.degree. C. to obtain a resin thin film (polyimide A / silica sol composite resin thin film).
  • the peeling layer and resin thin film which were formed on the glass support base material were isolate
  • Table 1 shows the optical and thermal characteristics of the resin thin film laminate A.
  • FIGS. 5 and 6 are cross-sectional views (cross section TEM) of the resin thin film laminate A
  • FIG. 7 is a (a) surface (resin thin film side) of the resin thin film laminate A, and (b) an interface between the release layer and the resin thin film.
  • FIG. 6A is an enlarged view of the vicinity of “mixing” in FIG. 5, and FIG. 6B shows the component composition of each layer constituting the laminate, in which [001] is an intermediate layer, [ 002] indicates a resin thin film (polyimide + SiO 2 ), and [003] indicates a release layer (DBL).
  • [001] is an intermediate layer
  • [ 002] indicates a resin thin film (polyimide + SiO 2 )
  • [003] indicates a release layer (DBL).
  • Example B Production of Resin Thin Film Laminate B
  • Resin thin film laminate B was prepared in the same manner as in Example A except that the resin thin film forming composition prepared in Example 3 was coated on the release layer obtained in Example 2.
  • a thin film laminate B was obtained.
  • FIG. 8 and FIG. 9 are cross-sectional views (cross section TEM) of the resin thin film laminate B
  • FIG. 10 is the resin thin film laminate B (a) surface (resin thin film side), (b) the interface between the release layer and the resin thin film, And (c) The Raman IR spectrum of the back surface (peeling layer side) is shown, respectively.
  • FIG. 9 (a) is an enlarged view of the vicinity of the interface in FIG. 8, and FIG. 9 (b) shows the component composition of each layer constituting the laminate, where [001] is a release layer (DBL), [002] indicates a resin thin film (polyimide + SiO 2 ).
  • DBL release layer
  • [002] indicates a resin thin film (polyimide + SiO 2 ).
  • the interface between the formed release layer and the resin thin film is clearly separated compared to Example A, and the thickness of the intermediate layer in this case is very thin, about 1 nm or less. Met. Also, as shown in the Raman IR spectrum of FIG. 10, (b) the IR spectrum at the interface between the release layer and the resin thin film is almost identical to the (c) IR spectrum on the back surface, and the interface is considered to originate from the release layer. As a result.
  • FIG.2 and FIG.3 The cross-sectional schematic diagram of the resin thin film laminated bodies A and B obtained in the said Example is shown in FIG.2 and FIG.3.
  • the resin thin film laminates A and B are formed on the supporting base (G1) with a release layer (L II), an intermediate layer (L III), a resin thin film (polyimide A / silica sol composite resin thin film) ( It was confirmed to have a laminated structure in the order of LI).
  • resin thin film laminated body A and B were obtained by isolate
  • the release layer (L II), the resin thin film (polyimide A / silica sol composite resin thin film) (LI), and the intermediate layer formed between them each have a polymer network structure shown in FIG. It is thought that.
  • This network means that two polymers and nanosilica are bonded to each other by van der Waals force or hydrogen bond, thereby increasing the adhesive force between the resin thin film and the release layer.
  • the intermediate layer can be obtained not only from the release layer but also from a resin thin film. This is because when the resin thin film is formed, the upper surface of the release layer can be partially dissolved by the solvent contained in the resin thin film forming composition. And thereby, an intermediate
  • the resin thin film laminate A obtained by the production method of the present invention has a low coefficient of linear expansion [ppm / ° C.] (50 to 200 ° C.) and transmits light at 400 nm and 550 nm after curing. It was confirmed that the rate [%] was high, the yellowness represented by the CIE b * value was small, and the retardation was suppressed to a low value.
  • the resin thin film laminate A of the present invention obtained in the above examples does not break even when held with both hands and bent at an acute angle (about 30 degrees), and has high flexibility required for a flexible display substrate.
  • a composition for forming a release layer containing a crosslinking agent was prepared by mixing at 30 phr with respect to the mass of polyimide (PI-A) contained in the product.
  • CYMEL 303 is added to a polyimide ( PI-A) and silica sol (GBL-M) were mixed at 30 phr with respect to the total mass to prepare a composition for forming a resin thin film forming a crosslinking agent.
  • the firing conditions were 120 ° C. for 20 minutes, 140 ° C. for 20 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 60 minutes in an air atmosphere.
  • the obtained results are shown in Table 2.

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  • 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)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention a pour objet de fournir un procédé de formation de stratifié de film mince en résine qui permet d'obtenir un film mince de plastique, lequel film mince de plastique tout en préservant d'excellentes performances telles qu'une excellente résistance à la chaleur, un faible retard optique et une excellente souplesse, présente d'excellentes performances en tant que film de base pour un substrat de dispositif flexible tel qu'un écran flexible, ou similaire, permettant un retrait aisé d'un support de verre. Plus précisément, l'invention concerne un procédé de fabrication de stratifié de film mince en résine qui est caractéristique en ce qu'après formation sur un substrat de support d'une couche de retrait à l'aide d'une composition pour formation de couche de rertrait comprenant un polymère résistant à la chaleur et un solvant organique, un film mince en résine est formé sur cette couche de retrait à l'aide d'une composition pour formation de film mince en résine comprenant un polymère résistant à la chaleur et un solvant organique, puis la couche de retrait et le film mince en résine sont retirés ensemble du substrat de support. Le procédé de l'invention est également caractéristique en ce que de manière pratique des particules de dioxyde de silicium présentant un diamètre particulaire moyen inférieur ou égal à 100mm calculé à partir d'une surface spécifique mesurée selon une technique d'adsorption de nitrogène, sont également comprises exclusivement dans la composition pour formation de film mince en résine.
PCT/JP2018/021885 2017-06-08 2018-06-07 Procédé de fabrication de substrat pour dispositif flexible Ceased WO2018225825A1 (fr)

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CN201880036744.5A CN111344130B (zh) 2017-06-08 2018-06-07 柔性器件用基板的制造方法
KR1020197038705A KR102604658B1 (ko) 2017-06-08 2018-06-07 플렉서블 디바이스용 기판의 제조방법
JP2019523972A JP7116366B2 (ja) 2017-06-08 2018-06-07 フレキシブルデバイス用基板の製造方法

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CN112322035A (zh) * 2020-11-12 2021-02-05 华东理工大学 一种三层介孔空心二氧化硅-含氟聚苯并二噁唑复合薄膜及其制备方法和应用
WO2023021899A1 (fr) * 2021-08-18 2023-02-23 東洋紡株式会社 Film stratifié transparent résistant à la chaleur
WO2023149435A1 (fr) * 2022-02-03 2023-08-10 株式会社カネカ Composition de résine, objet moulé et film

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KR102676871B1 (ko) * 2022-01-28 2024-06-21 대구가톨릭대학교산학협력단 신규한 디아민계 화합물, 이의 제조 방법, 폴리아마이드계 화합물, 폴리벤조옥사졸 필름 및 플렉서블 디바이스

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CN111344130A (zh) 2020-06-26
TWI782037B (zh) 2022-11-01
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JPWO2018225825A1 (ja) 2020-05-21
JP7116366B2 (ja) 2022-08-10
TW201919912A (zh) 2019-06-01
KR102604658B1 (ko) 2023-11-21

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