WO2019139167A1 - ハイブリッド樹脂組成物 - Google Patents
ハイブリッド樹脂組成物 Download PDFInfo
- Publication number
- WO2019139167A1 WO2019139167A1 PCT/JP2019/000933 JP2019000933W WO2019139167A1 WO 2019139167 A1 WO2019139167 A1 WO 2019139167A1 JP 2019000933 W JP2019000933 W JP 2019000933W WO 2019139167 A1 WO2019139167 A1 WO 2019139167A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- organic
- resin composition
- group
- inorganic hybrid
- Prior art date
Links
- 0 CC(*)C(C(*)C(C1)C2)C1C2(CCC12C(C3)C(*)C(*C(C(*)C4C5)C5CC4(CCCC45C(C6)C(*)C(*)C6C4)C5=O)C3C1)C2=O Chemical compound CC(*)C(C(*)C(C1)C2)C1C2(CCC12C(C3)C(*)C(*C(C(*)C4C5)C5CC4(CCCC45C(C6)C(*)C(*)C6C4)C5=O)C3C1)C2=O 0.000 description 25
- OIMPBYNCDBZTDO-UHFFFAOYSA-N Cc(cc1)c(C(F)(F)F)cc1-c(cc1C(F)(F)F)ccc1N(C(C(C1C(N2C)=O)C3C1C2=O)=O)C3=O Chemical compound Cc(cc1)c(C(F)(F)F)cc1-c(cc1C(F)(F)F)ccc1N(C(C(C1C(N2C)=O)C3C1C2=O)=O)C3=O OIMPBYNCDBZTDO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—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 hybrid resin composition, and more specifically, a flexible device such as a flexible display capable of forming a film that can be peeled off by a mechanical peeling method from a peeling layer formed on a carrier substrate, in particular.
- the present invention relates to a composition that can be suitably used to form a substrate.
- Patent Document 1 relates to an invention relating to a polyimide useful as a plastic substrate for a flexible display, and a precursor thereof, wherein a reaction between a tetracarboxylic acid containing an alicyclic structure such as cyclohexylphenyltetracarboxylic acid and various diamines It is reported that the prepared polyimide is excellent in transparency and heat resistance.
- Patent Document 2 the addition of silica sol to polyimide improves the coexistence of the coefficient of linear expansion, the transparency, and the low birefringence, which is a defect of the conventional plastic substrate, and is a plastic substrate for a flexible display. It can be expected to be applied to
- Non-Patent Document 1 after a predetermined functional layer is formed on a plastic substrate applied and fixed on glass, a laser is irradiated from the glass side to force the plastic substrate provided with the functional layer from glass.
- a separation method a method called a so-called laser lift-off process (EPLaR method (Electronics on Plastic by Laser Release) has been proposed.
- Non-Patent Document 1 secures 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 substrate. It is.
- this EPLaR method laser lift-off method
- the impact of the laser light causes the periphery of the irradiated portion
- the characteristics of the resin substrate and the functional layer formed on the resin substrate may be deteriorated, such as the problem that the functional layer (such as TFT) is damaged or the resin substrate itself is largely damaged and the transmittance is reduced.
- the present invention has been made in view of such circumstances, and does not rely on the above-described laser lift-off technology, and provides a resin composition which provides a plastic thin film having excellent performance as a base film of a flexible device substrate such as a flexible display substrate. It is possible to secure the handling property and the dimensional stability while maintaining the excellent performance of providing the product, in particular, excellent heat resistance, low retardation, excellent flexibility, and excellent transparency. It is an object of the present invention to provide a resin composition that provides a flexible device substrate that can be peeled off from a supporting substrate or a peeling layer by mechanical peeling, and a flexible device substrate obtained therefrom.
- the present inventors have found that a resin composition in which a silica sol modified with a specific siloxane is blended with a heat resistant polymer adopted to achieve both heat resistance and optical properties. It is found that it is possible to form a thin film which is easy to peel from a supporting substrate or the like while maintaining the features of excellent heat resistance, low retardation, excellent flexibility and excellent transparency, and complete the present invention.
- this invention relates to the organic-inorganic hybrid resin composition characterized by including following (A) component, (B) component, and (C) component as a 1st viewpoint.
- Component (A) The fine particle surface is modified with an alkoxysilane compound having two aromatic groups having 6 to 18 carbon atoms or one aromatic group having 7 to 18 carbon atoms, and the average particle size is 1 nm to 100 nm inorganic particles
- Component (B) polyimide having fluorine
- (C) component organic solvent.
- a second aspect relates to the organic-inorganic hybrid resin composition according to the first aspect, wherein the alkoxysilane compound in the component (A) is a compound represented by the following formula (S1).
- R 1 and R 2 are each independently an alkyl group having 1 to 3 carbon atoms
- W is an integer of 1 to 3
- Z 1 represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms
- m represents an integer of 0 to 5, provided that m is 2 or more
- Z 1 may be the same or different groups.
- the present invention relates to, as a third aspect, the organic-inorganic hybrid resin composition according to the first aspect or the second aspect, wherein m is 0 in the above formula.
- a polyamic acid which is a reaction product of a tetracarboxylic acid dianhydride component and a diamine component containing a fluorine-containing aromatic diamine represented by the following formula (A1):
- the organic-inorganic hybrid resin composition according to any one of the first to third aspects, which is an imidized compound of the present invention.
- a fifth aspect relates to the organic-inorganic hybrid resin composition according to the fourth aspect, wherein the tetracarboxylic acid dianhydride component includes an alicyclic tetracarboxylic acid dianhydride represented by the following 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 each independently represent a hydrogen atom or a methyl group, and * represents a bond).
- a sixth aspect relates to the organic-inorganic hybrid resin composition according to any one of the first to fifth aspects, wherein the inorganic fine particles of the component (A) are silicon dioxide particles.
- the mass ratio of the component (A) to the component (B) is 5: 5 to 9: 1 in (A) :( B).
- the present invention relates to the organic-inorganic hybrid resin composition described in Item.
- the inorganic fine particle of the component (A) is an inorganic fine particle having an average particle diameter of 1 nm to 60 nm.
- a light transmittance of 80% or more at 400 nm formed from the organic-inorganic hybrid resin composition according to any one of the first to ninth aspects is transparent and has a haze of 2% or less It is about the resin thin film which it has.
- the present invention relates to a flexible device substrate made of the resin thin film according to the tenth aspect.
- a method of manufacturing a flexible device substrate a) forming a release layer on a supporting substrate; b) forming a resin thin film to be a substrate for a flexible device comprising the organic-inorganic hybrid resin composition according to any one of the first to ninth aspects on the release layer; and c) the resin thin film Peeling off the release layer to obtain a substrate for a flexible device; On the way, including.
- a resin thin film having low coefficient of linear expansion, excellent heat resistance, low retardation, and excellent flexibility can be formed. It is possible to form a resin thin film which is easy to peel off from the supporting substrate without losing its strength.
- the resin thin film formed from the organic-inorganic hybrid resin composition of the present invention exhibits high heat resistance, low coefficient of linear expansion, high transparency (high light transmittance, low yellowness), low retardation, and further flexibility. Also, since it is excellent, it can be suitably used as a base film of a flexible device, particularly a flexible display substrate.
- the organic-inorganic hybrid resin composition according to the present invention and the resin thin film formed therefrom have characteristics such as high flexibility, low coefficient of linear expansion, high transparency (high light transmittance, low yellowness), low retardation and the like. Can be sufficiently addressed in the field of substrates for flexible devices, in particular substrates for flexible displays, which are required.
- the organic-inorganic hybrid resin composition of the present invention comprises (A) component: inorganic fine particles modified with a specific alkoxysilane, (B) component: the following specific polyimide, and (C) component: an organic solvent, if desired It contains a crosslinking agent and other components.
- the component (A) is an inorganic fine particle in which the surface of the fine particle is modified with a specific alkoxysilane described later.
- the average particle diameter of the inorganic fine particles can be appropriately selected according to the purpose and the like. Among them, the average particle size is preferably 1 nm to 100 nm, more preferably 1 nm to 60 nm, or 9 nm to 60 nm, and particularly preferably 9 nm to 45 nm, from the viewpoint of obtaining a highly transparent thin film.
- the average particle size of the inorganic fine particles is an average particle size calculated from the specific surface area value measured by the nitrogen adsorption method using the inorganic fine particles.
- silica (silicon dioxide) particles for example, colloidal silica having the above-mentioned average particle diameter
- silica sol can be used as the colloidal silica.
- 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 replacing water which is a dispersion medium of the aqueous silica sol with an organic solvent can be used.
- alkoxysilane such as methyl silicate and ethyl silicate is obtained by hydrolysis and condensation in the presence of a catalyst (for example, an ammonia, an organic amine compound, an alkali catalyst such as sodium hydroxide) in an organic solvent such as alcohol.
- a catalyst for example, an ammonia, an organic amine compound, an alkali catalyst such as sodium hydroxide
- an organosilica sol obtained by solvent-substituting the silica sol with another organic solvent.
- Examples of the organic solvent in the above organosilica sol include lower alcohols such as methyl alcohol, ethyl alcohol and isopropanol; linear amides such as N, N-dimethylformamide, N, N-dimethylacetamide; N-methyl-2- Cyclic amides such as pyrrolidone; ethers such as ⁇ -butyrolactone; glycols such as ethyl cellosolve and ethylene glycol; and acetonitrile.
- the substitution of water, which is the dispersion medium of the aqueous silica sol, and the substitution with another target organic solvent can be carried out by a conventional method such as distillation or ultrafiltration.
- the viscosity of the above organosilica sol is about 0.6 mPa ⁇ s to 100 mPa ⁇ s at 20 ° C.
- Examples of commercially available products of the above organosilica sol include, for example, trade name MA-ST-S (methanol dispersed silica sol, Nissan Chemical Industries, Ltd. (currently Nissan Chemical Co., Ltd., same hereafter), trade name MT-ST. (Methanol dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), trade name MA-ST-UP (methanol dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), trade name MA-ST-M (methanol dispersed silica sol, Nissan Chemical Industries, Ltd.
- Trade name MA-ST-L methanol dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
- Trade name IPA-ST-S isopropanol dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
- trade name IPA-ST isopropanol dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
- trade name IPA-ST-UP isopropanol dispersed silica sol, Nissan Chemical Industries, Ltd.
- IPA-ST-L isopropanol dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
- trade name IPA-ST-ZL isopropanol dispersed silica sol, manufactured by Nissan Chemical Industries Ltd.
- trade name NPC -ST-30 n-propyl cellosolve dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
- trade name PGM-ST (1-methoxy-2-propanol dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
- DMAC- ST dimethyl acetamide dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
- trade name XBA-ST xylene / n-butanol mixed solvent dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
- trade name XBA-ST xylene / n-butanol mixed solvent dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
- trade name XBA-ST xylene /
- silicon dioxide for example, silicon dioxide as mentioned in the above-mentioned product used as an organosilica sol may be used as a mixture of two or more.
- the alkoxysilane compound (hereinafter referred to as a specific alkoxysilane) used for the modification of the inorganic fine particles is an alkoxysilane compound having two aromatic groups of 6 to 18 carbon atoms, or 7 to 18 carbon atoms. And an alkoxysilane compound having one aromatic group.
- a specific alkoxysilane used for the modification of the inorganic fine particles
- an alkoxysilane compound having one aromatic group is an alkoxysilane compound having two aromatic groups of 6 to 18 carbon atoms, or 7 to 18 carbon atoms.
- an alkoxysilane compound having one aromatic group As said C6-C18 aromatic group, a phenyl group and the below-mentioned C7-C18 aromatic group are mentioned.
- the aromatic group having 7 to 18 carbon atoms include a group having 2 to 3 benzene rings, and a group having 2 to 4 condensed benzene rings.
- an alkoxysilane having a biphenyl group as an aromatic group having 7 to 18 carbon atoms and having a structure represented by the following formula (S1) is preferable.
- R 1 and R 2 are each independently an alkyl group having 1 to 3 carbon atoms
- W is an integer of 1 to 3
- Z 1 represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms
- m represents an integer of 0 to 5, provided that m is 2 or more
- Z 1 may be the same or different groups.
- alkoxysilanes in which m is 0 (biphenyl group is not substituted) are preferable.
- alkoxysilane compound represented by the above formula (S1) examples include 4-biphenyltrimethoxysilane, 4-biphenyltriethoxysilane, 3-biphenyltrimethoxysilane, 3-biphenyltriethoxysilane and the like.
- the inorganic fine particles having the surface modified with the specific alkoxysilane can be prepared by bringing the specific alkoxysilane into contact with the silica particles.
- the specific alkoxysilane for example, the silanol group or alkoxysilyl group in the specific alkoxysilane condenses and bonds with the hydroxy group present on the surface of the silica particle, and the surface is modified with the specific alkoxysilane It is believed that the formed silica particles are formed.
- the mixing of the colloidal solution and the specific alkoxysilane solution may be performed at normal temperature or may be performed while heating. From the viewpoint of reaction efficiency, mixing is preferably performed while heating.
- the heating temperature can be appropriately selected according to the solvent and the like. The heating temperature can be, for example, 60 ° C. or higher, and is preferably the reflux temperature of the solvent.
- the mixing ratio of the specific alkoxysilane and the silica particles can be appropriately selected according to the purpose and the like.
- the mass ratio of silica particles to specific alkoxysilane is preferably 70/30 to 99/1, more preferably 70/30 to 90/10, and 80 / More preferably, it is 20 to 90/10.
- the mass number of the silica particles is calculated using the composition formula of the silica particles as SiO 2 .
- the polyimide preferably used in the present invention is a polyimide having fluorine, and more specifically, a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride component with a diamine component containing a fluorine-containing aromatic diamine ( It is a polyimide (imidized) obtained by imidating a reaction product).
- the said fluorine-containing aromatic diamine is what contains the diamine represented by a following formula (A1).
- B 2 represents a divalent group selected from the group consisting of formulas (Y-1) to (Y-34).
- * represents a bond.
- the alicyclic tetracarboxylic acid dianhydride component it is preferable to use an alicyclic tetracarboxylic acid dianhydride from the viewpoint of transparency and solubility in a solvent.
- the alicyclic tetracarboxylic acid dianhydride preferably includes a tetracarboxylic acid dianhydride represented by the following formula (C1).
- B 1 represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12).
- R's each independently represent a hydrogen atom or a methyl group, and * represents a bond).
- B 1 in the formula is represented by the formulas (X-1), (X-4), (X-6) and (X-7) It is preferred that the compound be Further, among the diamines represented by the above (A1), it is preferable that B 2 in the formula is a compound represented by the formulas (Y-12) and (Y-13).
- B 2 in the formula is a compound represented by the formulas (Y-12) and (Y-13).
- a polyimide obtained by imidating a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride represented by the above formula (C1) with a diamine represented by the above formula (A1) is described later. Containing the monomer unit represented by Formula (2).
- the alicyclic tetracarboxylic acid dianhydride for example, the tetracarboxylic acid dianhydride represented by the above formula (C1) is preferably 90% by mol or more, and more preferably 95% by mol or more, relative to the number of moles. Is more preferable, and in particular, it is optimal that all (100 mol%) be the tetracarboxylic acid dianhydride represented by the above formula (C1).
- a resin thin film (substrate for flexible devices) having the above-mentioned characteristics of low linear expansion coefficient, low retardation and high transparency and excellent in flexibility, relative to the total number of moles of the diamine component, It is preferable that it is 90 mol% or more, and, as for fluorine-containing aromatic diamine, for example, diamine represented by Formula (A1), it is more preferable that it is 95 mol% or more. In addition, all (100 mol%) of the diamine component may be a diamine represented by the above formula (A1).
- the polyimide used in the present invention contains a monomer unit represented by the following formula (1).
- the polyimide used in the present invention contains a monomer unit represented by the formula (2).
- the polyimide used in the present invention may simultaneously contain the monomer unit represented by Formula (1) and the monomer unit represented by Formula (2).
- the polyimide used in the present invention contains the monomer unit represented by the formula (1) and the monomer unit represented by the formula (2), the molar ratio in the polyimide chain is represented by the formula (1)
- Monomer unit: monomer unit represented by the formula (2) 10: 1 to 1:10 is preferable, more preferably 8: 2 to 2: 8 is preferable, 6: 6 More preferably, the ratio is 4 to 4: 6.
- the polyimide of the present invention comprises an alicyclic tetracarboxylic acid dianhydride component containing tetracarboxylic acid dianhydride represented by the above formula (C1), and a diamine component containing a diamine represented by the formula (A1)
- C1 tetracarboxylic acid dianhydride
- A1 diamine component containing a diamine represented by the formula (A1)
- other monomer units may be contained.
- the content ratio of this other monomer unit is arbitrarily determined as long as the characteristics of the resin thin film formed from the organic-inorganic hybrid resin composition of the present invention are not impaired.
- the ratio is derived from an alicyclic tetracarboxylic acid dianhydride component containing tetracarboxylic acid dianhydride represented by the above-mentioned formula (C1) and a diamine component containing a diamine represented by the formula (A1)
- C1 alicyclic tetracarboxylic acid dianhydride component containing tetracarboxylic acid dianhydride represented by the above-mentioned formula (C1) and a diamine component containing a diamine represented by the formula (A1)
- the number of moles of the monomer unit represented by for example, the monomer unit represented by the formula (1) or the monomer unit represented by the formula (2), or the monomer unit represented by the formula (1) and the formula (2)
- Less than 20 mol% is preferable, less than 10 mol% is more preferable, and it is still more preferable that it is less than 5 mol% with respect to the total number of moles of the monomer unit represented by
- Examples of such other monomer units include, but not limited to, monomer units having other polyimide structures represented by Formula (3).
- A represents a tetravalent organic group, preferably a tetravalent group represented by any one of the following formulas (A-1) to (A-4).
- B represents a divalent organic group, preferably a divalent group represented by any one of formulas (B-1) to (B-11).
- * represents a bond.
- A represents a tetravalent group represented by any one of the following formulas (A-1) to (A-4)
- B is a group of the above-mentioned formulas (Y-1) to (Y) It may be a divalent group represented by any of Y-34).
- B represents a divalent group represented by any one of the following formulas (B-1) to (B-11)
- A is a group of the above-mentioned formulas (X-1) to (X) It may be a tetravalent group represented by any of -12).
- a and B contain, for example, only a monomer unit composed of only one of the groups exemplified by the following formulas. Or at least one of A and B may contain two or more types of monomer units selected from the two or more types of groups exemplified below.
- each monomer unit is bonded in an arbitrary order.
- a polyimide having a monomer unit represented by the above formula (1) can be used as a tetracarboxylic acid dianhydride component as a bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic acid It is 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 obtained polyamic acid.
- this polyimide is 1,2,3,4- cyclobutane tetracarboxylic dianhydride as a tetracarboxylic dianhydride component.
- a diamine represented by the following formula (4) as a diamine component are polymerized in an organic solvent to obtain an obtained polyamic acid by imidization.
- the polyimide used in the present invention has the monomer unit represented by the above formula (2) in addition to the monomer unit represented by the above formula (1), it is represented by the formula (1) and the formula (2)
- the polyimide containing each monomer unit has, in addition to the above-mentioned tetracarboxylic acid dianhydride as the tetracarboxylic acid dianhydride component, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and the following formula as the diamine component: It is obtained by polymerizing the diamine represented by (4) in an organic solvent, and imidizing the obtained polyamic acid.
- the diamine component from the viewpoint of making the coefficient of linear expansion of the resin thin film (substrate for flexible device) of the present invention lower and making the transparency of the resin thin film (substrate for flexible device) higher, Using 2,2′-bis (trifluoromethyl) benzidine represented by formula (4-1) or 3,3′-bis (trifluoromethyl) benzidine represented by the following formula (4-2) In particular, it is preferable to use 2,2′-bis (trifluoromethyl) benzidine.
- the polyimide used in the present invention contains an alicyclic tetracarboxylic acid dianhydride component including the tetracarboxylic acid dianhydride represented by the above-mentioned formula (C1), and a diamine represented by the formula (A1)
- the polyimide containing each monomer unit represented by Formula (1), Formula (2), and Formula (3) is a tetracarboxylic acid dianhydride component of the above-mentioned 2 types of tetracarboxylic acid dianhydride
- tetracarboxylic acid dianhydride represented by the formula (5)
- Examples include, but are not limited to, aliphatic tetracarboxylic acid dianhydrides.
- tetracarboxylic acid dianhydrides in which A in the formula (5) is a tetravalent group represented by any of the above formulas (A-1) to (A-4) are preferable, ie, 11 , 11-Bis (trifluoromethyl) -1H-difluoro [3,4-b: 3 ', 4'-i] xanthene-1,3,7,9- (11H-tetraone), 6,6'-bis (Trifluoromethyl)-[5,5'-biisobenzofuran] -1,1 ', 3,3'-tetraone, 4,6,10,12-tetrafluorodifuro [3,4-b: 3' , 4'-i] dibenzo [b, e] [1,4] dioxin-1,3,7,9-tetraone, and 4,8-bis (trifluo
- diamine represented by the formula (6) for example, 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-phenyne Diamine,
- aromatic diamines in which B in the formula (6) is a divalent group represented by any of the above formulas (B-1) to (B-11) are preferable, ie, 2,2 ′.
- -Bis (trifluoromethoxy)-(1,1'-biphenyl) -4,4'-diamine [another 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 [another name: o
- the polyimide used in the present invention is, in a preferred embodiment, as described above, a tetracarboxylic acid dianhydride component containing an alicyclic tetracarboxylic acid dianhydride represented by the above formula (C1), and the above formula (A1) It is obtained by imidating the polyamic acid obtained by making it react with the diamine component containing the fluorine-containing aromatic diamine represented by these.
- An acid dianhydride further optionally a tetracarboxylic acid dianhydride component consisting of a tetracarboxylic acid dihydrate represented by the above formula (5), a diamine represented by the above formula (4), and optionally the above formula ( It is obtained by polymerizing the diamine component which consists of a diamine component represented by 6) in an organic solvent, and imidating the polyamic acid obtained.
- the reaction from the above two components to the polyamic acid is advantageous in that it can proceed relatively easily in an organic solvent, and no by-products are formed.
- the preparation ratio (molar ratio) of the diamine component in the reaction of the tetracarboxylic acid dianhydride component and the diamine component is appropriately set in consideration of the molecular weight of the polyamic acid and the polyimide obtained by imidization thereafter.
- the amount of the tetracarboxylic acid dianhydride component can be generally 0.8 to 1.2 or so, for example, about 0.9 to 1.1, preferably 0. It is about 95 to 1.02. Similar to a normal polycondensation reaction, the molecular weight of the formed polyamic acid increases as the molar ratio approaches 1.0.
- the organic solvent used in the reaction of the tetracarboxylic acid dianhydride component and the diamine component is not particularly limited as long as it does not adversely affect the reaction and the generated polyamic acid dissolves.
- the specific example is given below.
- tetracarboxylic acid dianhydride component As a method of reacting the above-mentioned tetracarboxylic acid dianhydride component and the diamine component in an organic solvent, a dispersion or solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and tetracarboxylic acid dianhydride is used here.
- the component is added as it is, or a method in which the tetracarboxylic acid component is dispersed or dissolved in an organic solvent is added, conversely, in a dispersion or solution in which the tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent
- a method of adding a diamine component and a method of alternately adding a tetracarboxylic acid dianhydride component and a diamine compound component, and the like, and any of these methods may be used.
- tetracarboxylic acid dianhydride component and / or the diamine component consist of a plurality of compounds, they may be reacted in a mixed state in advance, may be reacted separately one after another, and are further reacted individually
- the low molecular weight products may be mixed and reacted to form high molecular weight products.
- the temperature at the time of the above-mentioned polyamic acid synthesis may be appropriately set in the range from the melting point to the boiling point of the above-mentioned solvent used, for example, any temperature of -20 ° C to 150 ° C can be selected.
- C. to 150.degree. C. usually about 0 to 150.degree. C., preferably about 0 to 140.degree.
- the reaction time can not be generally defined because it depends on the reaction temperature and the reactivity of the raw material, but it is usually about 1 to 100 hours.
- the reaction can be carried out at any concentration, but when the concentration is too low, it becomes difficult to obtain a polymer of high molecular weight, and when the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult Therefore, the total concentration in the reaction solution of the tetracarboxylic acid dianhydride component and the diamine component is preferably 1 to 50% by mass, more preferably 5 to 40% by mass.
- the initial stage of the reaction may be carried out at a high concentration, and then an organic solvent may be added.
- Examples of the method for imidizing polyamic acid include thermal imidization in which a solution of polyamic acid is heated as it is, and catalytic imidization in which a catalyst is added to a solution of polyamic acid.
- the temperature for thermally imidizing the polyamic acid in a solution is 100.degree. C. to 400.degree. C., preferably 120.degree. C. to 250.degree. C., and it is preferable to carry out while removing water generated by the imidization reaction out of the system.
- a basic catalyst and an acid anhydride are added to a solution of polyamic acid, and the temperature in the system is changed at -20 to 250 ° C, preferably 0 to 180 ° C. It can be carried out by stirring.
- the amount of the basic catalyst is 0.5 to 30 moles, preferably 1.5 to 20 moles, of the amic acid group of the polyamic acid, and the amount of the acid anhydride is 1 to 50 moles of the amic acid group of the polyamic acid Times, preferably 2 to 30 times mole.
- the basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine or 1-ethylpiperidine.
- pyridine and 1-ethylpiperidine have an appropriate basicity to proceed the reaction. So preferred.
- the imidation ratio by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.
- the dehydration ring closure ratio (imidization ratio) of the amic acid group does not necessarily have to be 100%, and can be adjusted and used arbitrarily according to the application and purpose. Particularly preferably, it is 50% or more.
- the reaction solution for imidation described above can be used as it is for preparation of the organic-inorganic hybrid resin composition without passing through the polymer recovery step described later, in which case the reaction solution is filtered and then
- the filtrate itself or one obtained by diluting or concentrating the filtrate is preferably used for the organic-inorganic hybrid resin composition.
- the polyimide used in the present invention forms a resin thin film made of an organic-inorganic hybrid resin composition on the strength of a resin thin film (organic-inorganic hybrid resin thin film) obtained from the organic-inorganic hybrid resin composition and a supporting substrate.
- Mw weight average molecular weight
- GPC gel permeation chromatography
- the reaction solution is put 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, isopropanol, water and the like.
- the polymer precipitated by being introduced into a poor solvent and recovered by filtration can be dried by heating at normal temperature or under normal pressure or reduced pressure.
- impurities in the polymer can be reduced. It is preferable to use three or more types of poor solvents such as alcohols, ketones, and hydrocarbons as the poor solvent in this case, because the efficiency of purification is further increased.
- the organic solvent in which the resin component is dissolved in the reprecipitation recovery step is not particularly limited. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, and tetra Methyl 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 ketone, cyclohexanone, ethylene carbonate And propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-p
- the organic-inorganic hybrid resin composition of the present invention can contain other inorganic fine particles other than the above-mentioned inorganic fine particles, that is, other inorganic fine particles which have not been modified with a specific alkoxysilane compound.
- the content of the other inorganic fine particles not modified with the specific alkoxysilane compound is based on the total of the inorganic fine particles which is the component (A) of the present application and the other inorganic fine particles not modified with the specific alkoxysilane compound.
- the content is 50% by mass to 0% by mass, preferably 20% by mass to 0% by mass.
- the organic-inorganic hybrid resin composition of the present invention can further contain a crosslinking agent.
- the crosslinking agent used here is a compound composed of only a hydrogen atom, a carbon atom and an oxygen atom or a compound composed of only a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom, and is a hydroxy group
- a crosslinking agent comprising a compound having two or more groups selected from the group consisting of an epoxy group and an alkoxy group having 1 to 5 carbon atoms, and having a ring structure.
- an organic-inorganic hybrid resin composition is obtained which not only gives a resin thin film excellent in solvent resistance and suitable for a substrate for flexible devices with good reproducibility, but also has improved storage stability. can do.
- the total number of hydroxy group, epoxy group and alkoxy group having 1 to 5 carbon atoms per compound in the crosslinking agent is preferably 3 or more from the viewpoint of achieving the solvent resistance of the obtained resin thin film with good reproducibility. It is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less, from the viewpoint of realizing the flexibility of the obtained resin thin film with good reproducibility.
- ring structure possessed by the crosslinking agent examples include an aryl ring such as benzene, a nitrogen-containing heteroaryl ring such as pyridine, pyrazine, pyrimidine, pyridazine and 1,3,5-triazine, cyclopentane, cyclohexane, cycloheptane and the like
- 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 it is 1 or more, but from the viewpoint of securing the solubility of the crosslinking agent in the solvent and obtaining a highly flat resin film, 1 or 2 is preferable.
- the ring structures may be fused to each other, and an alkane having 1 to 5 carbon atoms, such as methylene, ethylene, trimethylene, propane-2,2-diyl, etc.
- the ring structures may be linked via a linking group such as a diyl group.
- the molecular weight of the crosslinking agent is not particularly limited as long as it has a crosslinking ability and dissolves in the solvent used, but the solvent resistance of the resin thin film obtained, the solubility of the crosslinking agent itself in an organic solvent, and the availability thereof In consideration of the properties and the price, it is preferably about 100 to 500, and more preferably about 150 to 400.
- the crosslinking agent may further have a group derivable from a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom, such as a ketone group and an ester group (bond).
- Preferred examples of the crosslinking agent include compounds represented by any of the following formulas (K1) to (K5), and one preferable embodiment of formula (K4) is a compound represented by formula (K4-1)
- the compound represented by the formula (5-1) is exemplified as one of the preferred embodiments of the formula (K5).
- each of A 1 and A 2 independently represents an alkanediyl group having 1 to 5 carbon atoms, such as methylene group, ethylene group, trimethylene group or propane-2,2-diyl group, Among them, as A 1 , a methylene group and an ethylene group are preferable, and a methylene group is more preferable. As A 2 , a methylene group and a propane-2,2-diyl group are preferable.
- each X independently of each other is a hydroxy group, an epoxy group (oxa-cyclopropyl group), or a methoxy group, an ethoxy group, a 1-propyloxy group, an isopropyloxy group, It represents an alkoxy group having 1 to 5 carbon atoms such as 1-butyloxy group and t-butyloxy group.
- 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 and cost of the crosslinking agent.
- An alkoxy group is preferred, and in formula (K4), a hydroxy group is preferred.
- each n represents the number of-(A 1 -X) groups bonded to a benzene ring, and independently of each other is an integer of 1 to 5, preferably 2 to 3, more preferably It is three.
- 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 a skeleton compound such as an aryl compound having the same ring structure as the ring structure in each of the compounds, a heteroaryl compound, a cyclic amine and the like, an epoxyalkyl halide compound It can be obtained by reacting an alkoxyhalide compound or the like by a carbon-carbon coupling reaction or an N-alkylation reaction, or hydrolyzing an alkoxy moiety of the resultant product.
- a commercial item may be used for a crosslinking agent, and what was synthesize
- Commercially available products are CYMEL (registered trademark) 300, 301, 303 LF, 303 ULF, 304, 350, 3745, XW 3106, MM-100, 323, 325, 327, 328, The same 385, 370, 373, 380, 1116, 1130, 1133, 1141, 1161, 1168, 3020, 202, 203, 1156, MB-94, MB- 96, MB-98, 247-10, 651, 658, 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, same -1054, U-610, U-640, UB-24-BX, UB
- TEPIC registered trademark
- V, S, HP, etc. L PAS
- VL UC
- TM-BIP-A Alkyo Chemical Industry Co., Ltd.
- TMG Tokyo Chemical Industry Co., Ltd.
- crosslinking agent examples include but the invention is not limited thereto.
- the compounding quantity of a crosslinking agent is suitably decided according to the kind etc. of a crosslinking agent, although it can not generally prescribe, it is usually obtained with respect to the mass of the said polyimide or with respect to the total mass of the said polyimide and the said inorganic fine particle. Or less, preferably 100% by mass or less from the viewpoint of securing the flexibility of the resin thin film and suppressing the embrittlement, and 0.1% by mass from the viewpoint of securing the solvent resistance of the obtained resin thin film
- the above content is preferably 1% by mass or more.
- the organic-inorganic hybrid resin composition of the present invention includes an organic solvent in addition to the polyimide, the inorganic fine particles whose surface is modified with a specific alkoxysilane, any other inorganic fine particles and a crosslinking agent.
- the organic solvent is not particularly limited, and examples thereof include the same ones as the specific examples of the reaction solvent used in the preparation of the polyamic acid and the polyimide. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, ⁇ - Butyrolactone etc. are mentioned.
- an organic solvent may be used individually by 1 type, and may be used combining 2 or more types.
- N, N-dimethylacetamide, N-methyl-2-pyrrolidone and ⁇ -butyrolactone are preferable in consideration of obtaining a resin thin film having high flatness with good reproducibility.
- Organic-inorganic hybrid resin composition The present invention comprises (A) inorganic fine particles whose surface is modified with a specific alkoxysilane, (B) the aforementioned polyimide, and (C) an organic solvent, and optionally containing other inorganic fine particles such as silicon dioxide, a crosslinking agent, etc.
- Organic-inorganic hybrid resin composition Here, the organic-inorganic hybrid resin composition of the present invention is homogeneous, and no phase separation is observed.
- the blending ratio of (A) inorganic fine particles whose surface is modified with a specific alkoxysilane, and (B) the above-mentioned polyimide is the mass ratio of (A) inorganic fine particles:
- the polyimide is preferably 10: 1 to 1:10, more preferably 8: 2 to 2: 8, for example 7: 3 to 3: 7, or 5: 5 to 9: 1. .
- the above mass ratio can be considered as the mass of the (A) inorganic fine particles including the other inorganic fine particles.
- the content of the other inorganic fine particles not modified with the specific alkoxysilane compound is the total of the inorganic fine particles which is the component (A) of the present application and the other inorganic fine particles not modified with the specific alkoxysilane compound.
- the content is 50% by mass to 0% by mass, preferably 20% by mass to 0% by mass.
- the solid amount in the organic-inorganic hybrid resin composition of the present invention is usually in the range of 0.5 to 30% by mass, but preferably 5% to 20% by mass from the viewpoint of film uniformity. It is.
- solid content means the remaining component except a solvent from all the components which comprise an organic inorganic hybrid resin composition.
- the viscosity of the organic-inorganic hybrid resin composition is appropriately determined in consideration of the coating method to be used, the thickness of the resin thin film to be produced, etc., but is usually 1 to 50,000 mPa ⁇ s at 25 ° C.
- the organic-inorganic hybrid resin composition of the present invention may further contain various organic or inorganic low-molecular or high-molecular compounds in order to impart processing characteristics and various functions.
- a catalyst an antifoamer, a leveling agent, a surfactant, a dye, a plasticizer, fine particles, a coupling agent, a sensitizer and the like can be used.
- a catalyst may be added for the purpose of reducing the retardation and linear expansion coefficient of the resin thin film.
- the organic-inorganic hybrid resin composition of the present invention includes the polyimide obtained by the above-mentioned method, inorganic fine particles whose surface is modified with the above-mentioned specific alkoxysilane compound, and, if desired, other inorganic fine particles such as silicon dioxide, crosslinking agents, etc.
- inorganic fine particles whose surface is modified with the above-mentioned specific alkoxysilane compound or a solution thereof is added, and further, if desired, silicon dioxide, crosslinking It is good also as adding an agent etc. and further adding the said organic solvent if desired.
- the organic-inorganic hybrid resin composition of the present invention described above is applied to a base material, dried and heated to remove the organic solvent, excellent in heat resistance, low in retardation, and excellent in flexibility, and further It is also possible to obtain resin thin films that are excellent in transparency (high light transmittance: for example, light transmittance at 400 nm, low yellowness: for example, 2% or less, light transmittance at 400 nm), and maintain these excellent performances.
- resin thin film useful as a flexible device substrate which can be peeled off from the release layer by mechanical peeling.
- a resin thin film formed from the organic-inorganic hybrid resin composition and a substrate for a flexible device that is, inorganic fine particles whose surface is modified with the above-mentioned polyimide and the above-mentioned specific alkoxysilane compound, and, optionally, inorganic fine particles such as silicon dioxide, crosslinked
- the substrate for a flexible device containing an agent etc. that is, the substrate for a flexible device comprising the cured product of the organic-inorganic hybrid resin composition of the present invention is also an object of the present invention.
- the substrate to be applied is preferably glass or silicon wafer from the viewpoint of being able to utilize existing equipment, and the substrate for a flexible device to be obtained has good releasability It is more preferable that it is glass from showing.
- the linear expansion coefficient of the substrate to be applied is preferably 40 ppm / ° C. or less, more preferably 30 ppm / ° C. or less, from the viewpoint of warpage of the substrate after coating.
- Known methods may be used to form the release layer on the substrate. That is, after a known release layer-forming composition containing an aromatic polyimide, polybenzoxazole or the like is applied onto a substrate, the substrate is fired by a known method such that the temperature reaches over 450 ° C.
- a release layer can be formed thereon. They apply, for example, the composition and release layer described as a release layer-forming composition and release layer in WO 2017/204178, WO 2017/204182, WO 2017/204186, etc. It is possible.
- the method of applying the organic-inorganic hybrid resin composition to the base material or to the release layer formed on the base material is not particularly limited, and examples thereof include cast coating, spin coating, blade coating, A dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, a printing method (a relief printing plate, intaglio printing plate, lithography, screen printing, etc.), etc. may be mentioned, and these can be used appropriately according to the purpose.
- the heating temperature is preferably 350 ° C. or less. If the temperature exceeds 350 ° C., the resulting resin thin film may become brittle, and in particular, a resin thin film suitable for display substrate applications may not be obtained.
- the heating temperature is raised stepwise after heating the applied organic-inorganic hybrid resin composition at 40 ° C. to 100 ° C. for 5 minutes to 2 hours Finally, it is desirable to heat at a temperature of more than 175.degree. C. to 350.degree. C. for 30 minutes to 2 hours. As described above, the low thermal expansion characteristics can be developed with higher reproducibility by heating at two or more temperatures of the step of drying the solvent and the step of promoting molecular orientation.
- the coated organic-inorganic hybrid resin composition is heated at 40 ° C. to 100 ° C. for 5 minutes to 2 hours, it is heated at 100 ° C. to 175 ° C. for 5 minutes to 2 hours, and then at 175 ° C. to 350 ° C. It is preferable to heat for 2 minutes.
- the apparatus used for heating includes, for example, a hot plate, an oven, and the like.
- 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 may be applied at each stage of heating. May be
- the thickness of the resin thin film is appropriately determined in consideration of the type of flexible device within the range of about 1 to 200 ⁇ m, but is usually 1 to 60 ⁇ m in particular when it is assumed to be used as a substrate for a flexible display.
- the thickness is preferably about 5 to 50 ⁇ m, and the thickness of the coating before heating is adjusted to form a resin thin film of a desired thickness.
- the resin thin film according to a preferred embodiment of the present invention thus obtained has a light transmittance of 80% or more at 400 nm, a high transparency of 90% or more at a wavelength of 550 nm, and a transparency of 2% or less A low yellowness of a haze value of preferably 1.5% or less can be achieved.
- the resin thin film can have, for example, a linear expansion coefficient at 50 ° C. to 200 ° C. of 25 ppm / ° C. or less, in particular, a low value of 5 ppm / ° C. to 25 ppm / ° C. It is.
- the resin thin film has birefringence when the wavelength of incident light is 590 nm, that is, two birefringence (two in-plane refractive indices and refractive index in the thickness direction) when viewed from the cross section in the thickness direction.
- the thickness direction retardation R th represented as an average value of two retardations obtained by multiplying the film thickness by each of the respective film thickness differences is small.
- the resin thin film described above has the above-mentioned characteristics, it satisfies each condition necessary as a base film of a flexible device substrate, and can be suitably used particularly as a base film of a flexible device, particularly a substrate of a flexible display. it can.
- Another aspect of the present invention provides a method of manufacturing a flexible device substrate.
- the method is a) forming a release layer on a supporting substrate such as a glass substrate; b) forming a resin thin film to be a substrate for a flexible device using the organic-inorganic hybrid resin composition of the present invention on the peeling layer; and c) peeling the resin thin film from the peeling layer, a substrate for a flexible device Obtaining a process;
- the substrate for a flexible device can be obtained by As shown in FIG. 1, the step c) is a step of peeling the resin thin film at the interface between the peeling layer (De-Bonding Layer) and the resin thin film (PI / silica film) to be a flexible device substrate.
- the release layer can be formed from a known release layer-forming composition containing the above-mentioned aromatic polyimide, polybenzoxazole or the like.
- devices and conditions used for sample preparation and analysis and evaluation of physical properties are as follows.
- the number average molecular weight of the polymer (hereinafter, abbreviated as Mn) and the weight average molecular weight (hereinafter, abbreviated as Mw) are as follows: Device: Showdex GPC-101, manufactured by Showa Denko KK Column: Measured under the conditions of KD 803 and KD 805, column temperature: 50 ° C., elution solvent: DMF, flow rate: 1.0 ml / min, calibration curve: standard polystyrene. 2) Film Thickness The film thickness of the obtained resin thin film was measured by a thickness gauge manufactured by Tek Co., Ltd.
- CTE Coefficient of linear expansion
- a thin film is cut into a size of 5 mm wide and 16 mm long using TA Instruments TMA Q400, first heated at 10 ° C./min and heated to 50 to 350 ° C. (first heating), then 10 ° C.
- load 0.05N was added through 1st heating, cooling, and 2nd heating.
- Td 5% Thermal decomposition temperature 5% weight loss temperature
- Td 5% [° C] The 5% weight loss temperature (Td 5% [° C]) should be measured using a TA Instruments TGA Q500 with a thin film of approximately 5 to 10 mg in nitrogen heated to 50 to 800 ° C at 10 ° C / min. I asked for.
- the thickness direction retardation (R th ) is calculated by the following equation.
- Nz refractive index in the direction of thickness (perpendicular) to the surface d: film thickness
- ⁇ Nxy difference between two refractive indexes in the plane (Nx-Ny) (birefringence)
- ⁇ Nxz difference between in-plane refractive index Nx and thickness-direction refractive index Nz (birefringence)
- ⁇ Nyz Difference between in-plane refractive index Ny and thickness-direction refractive index Nz (birefringence)
- Synthesis Example 1 Synthesis of polyimide A (PI-A), and preparation of 7 wt% solution 25.6 g (0.08 mol) of TFMB were placed in a 250 mL reaction three-necked flask fitted with a nitrogen inlet / outlet, mechanical stirrer and condenser. After that, 173 g of GBL was added and stirring was started. Immediately after the diamine is completely dissolved in the solvent, 10.0 g (0.04 mol) of stirred BODAxx, 7.84 g (0.04 mol) of CBDA and 43.4 g of GBL are added and stirred at 140 ° C. under nitrogen. Heated.
- PI-A polyimide A
- PI-B 7 wt% polyimide GBL solution
- Preparation Example 1 Preparation of Solution Containing Specific Alkoxysilane-Modified Silica Particles (Si-1) In a 500 mL reaction three-necked flask equipped with a nitrogen inlet / outlet and condenser, Quortron PL-1- 200 g (13.3%) of IPA (Sakai Chemical Industry Co., Ltd., registered trademark, particle diameter (specific surface area conversion) 10 to 15 nm, dispersion medium isopropanol) and 1.644 g of 4-biphenyltrimethoxysilane were added. Then, it heated at 100 degreeC under nitrogen atmosphere for 17 hours.
- IPA Silicon Organic solvent
- Preparation Example 2 Preparation of Solution Containing Specific Alkoxysilane-Modified Silica Particles (Si-2) In a 100 mL three-necked reaction flask equipped with a nitrogen inlet / outlet and condenser, quartron PL-1-IPA 50 g (13.3%) of particle diameter (specific surface area conversion) 10 to 15 nm, dispersion medium isopropanol), and 0.206 g of 4-biphenyltrimethoxysilane were added. Then, it heated at 100 degreeC under nitrogen atmosphere for 22 hours.
- Preparation Example 3 Preparation of Alkoxysilane-Modified Silica Particle-Containing Solution (Si-3) In a 500 mL reaction three-necked flask fitted with a nitrogen inlet / outlet and condenser, Quortron PL-1-IPA 200 g (13.3%) of a particle size (specific surface area conversion) of 10 to 15 nm, dispersion medium isopropanol, and 1.13 g of phenyltrimethoxysilane were added. Then, it heated at 100 degreeC under nitrogen atmosphere for 17 hours.
- Preparation Example 4 Preparation of Silica Particle-Containing Solution (Si-4) Qutron L-1-IPA (manufactured by Sakai Chemical Industry Co., Ltd., registered trademark, particle diameter (specific surface area conversion) 10 to 15 nm, dispersion medium) in a 500 mL recovery flask 200 g (13.3%) of isopropanol) and 79.8 g of GBL were added, and the isopropanol was evaporated under reduced pressure with an evaporator to obtain a GBL sol solution (Si-4) of the alkoxysilane unmodified silica particles. When 1 g of this solution was heated at 200 ° C. for 2 hours on an aluminum cup and the concentration was calculated from the remaining amount, the concentration was 35 wt%.
- Example 2 A varnish (organic-inorganic hybrid resin composition) was prepared in the same manner as in Example 1 except that 4.66 g of a specific alkoxysilane-modified silica particle-containing solution (Si-2) was used instead of the above (Si-1). The resultant was coated on a release layer to form a film, and a transparent PI film L2 was obtained. L2 could be easily peeled off from the peeling layer as L1.
- the optical and thermal properties of L2 are shown in Table 1.
- Example 3 3.00 g of a specific alkoxysilane-modified silica particle-containing solution (Si-1) and 0.46 g of GBL were added to 10 g of a 7 wt% polyimide GBL solution (PI-B) obtained in Synthesis Example 1 and stirred at room temperature for 3 days did. Then, it filtered with a 0.45 micron propylene filter, and the target varnish (organic-inorganic hybrid resin composition) was obtained. The resulting varnish was coated on the release layer with a bar coater (gap 250 microns) and heated at 100 ° C. for 1 hour using a hot plate. The heating temperature was raised to 350 ° C.
- PI-B polyimide GBL solution
- L3 (10 ° C./min) in a nitrogen atmosphere in a vacuum gas displacement furnace KDF-900GL (manufactured by Denken), and further heated at 350 ° C. for 30 minutes to obtain a transparent PI film L3.
- L3 could be easily peeled off from the peeling layer as shown in FIG.
- the optical and thermal properties of L3 are shown in Table 1.
- Comparative example 4 10 g of the 7 wt% polyimide GBL solution (PI-B) obtained in Synthesis Example 1 was coated on a release layer plate with a bar coater (gap 500 microns), and heated at 100 ° C. for 1 hour using a hot plate. Further, the film was heated on a hot plate at 280 ° C. for 30 minutes to obtain a transparent PI film HL4. HL4 could be peeled off from the peeling layer as shown in FIG. The optical and thermal properties of HL4 are shown in Table 1.
- the films L1 to L3 obtained in the examples were easily peeled from the release layer to exhibit self-supporting properties, and exhibited excellent optical properties and low CTE.
- Comparative Examples 1 to 3 a self-supporting film could not be obtained.
- Comparative Example 4 in which the self-supporting film was obtained, the retardation value was high, the light transmittance was low compared to the example, and the yellowness represented by the CIE b * value was high. The results show a higher CTE.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Theoretical Computer Science (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Liquid Crystal (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
これらのデバイスにおいては、ガラス基板上に様々な電子素子、例えば、薄膜トランジスタや透明電極等が形成されているが、このガラス材料を柔軟かつ軽量な樹脂材料に替えることで、デバイス自体の薄型化や軽量化、フレキシブル化を図ることが期待される。
このような樹脂材料の候補としては、ポリイミドが注目されており、ポリイミド膜に関する種々の報告がなされている。
(A)成分:炭素原子数6乃至18の芳香族基を2つ有するか又は炭素原子数7乃至18の芳香族基を1つ有するアルコキシシラン化合物で微粒子表面を修飾した、平均粒子径1nm乃至100nmの無機微粒子、
(B)成分:フッ素を有するポリイミド、
(C)成分:有機溶媒。
第2観点として、前記(A)成分におけるアルコキシシラン化合物が、下記式(S1)で表される化合物である、第1観点に記載の有機無機ハイブリッド樹脂組成物に関する。
R1とR2はそれぞれ独立して、炭素原子数1~3のアルキル基であり、
Wは1~3の整数であり、
Yは0~2の整数であり、且つ、W+Y=3であり、
Z1はハロゲン原子、炭素原子数1~10のアルキル基及び炭素原子数1~10のアルコキシ基からなる群から選ばれる基を表し、mは0乃至5の整数を表し、但しmが2以上の整数の場合、Z1は同一または相異なる基であってよい。)
第3観点として、前記式中、mが0である、第1観点または第2観点に記載の有機無機ハイブリッド樹脂組成物に関する。
第4観点として、前記(B)成分のポリイミドが、テトラカルボン酸二無水物成分と、下記式(A1)で表される含フッ素芳香族ジアミンを含むジアミン成分との反応生成物であるポリアミック酸のイミド化物である、第1観点乃至第3観点のいずれか一項に記載の有機無機ハイブリッド樹脂組成物に関する。
第5観点として、前記テトラカルボン酸二無水物成分が、下記式(C1)で表される脂環式テトラカルボン酸二無水物を含む、第4観点に記載の有機無機ハイブリッド樹脂組成物に関する。
第6観点として、前記(A)成分の無機微粒子が二酸化ケイ素粒子である、第1観点乃至第5観点のいずれか一項に記載の有機無機ハイブリッド樹脂組成物に関する。
第7観点として、前記(A)成分と(B)成分の質量比が、(A):(B)にて5:5~9:1である、第1観点乃至第6観点のいずれか一項に記載の有機無機ハイブリッド樹脂組成物に関する。
第8観点として、前記(A)成分の無機微粒子が、1nm乃至60nmの平均粒子径を有する無機微粒子である、第1観点乃至第7観点のいずれか一項に記載の有機無機ハイブリッド樹脂組成物に関する。
第9観点として、前記(C)成分が、エステル系溶媒であることを特徴とする、請求項1乃至第8観点のいずれか一項に記載の有機無機ハイブリッド樹脂組成物に関する。
第10観点として、第1観点乃至第9観点のいずれか一項に記載の有機無機ハイブリッド樹脂組成物から形成される400nmにおける光透過率80%以上で透明であり、なおかつ2%以下のヘイズを持つ樹脂薄膜に関する。
第11観点として、第10観点に記載の樹脂薄膜からなるフレキシブルデバイス用基板に関する。
第12観点として、フレキシブルデバイス用基板の製造方法であって、
a)支持基材上に剥離層を形成する工程;
b)該剥離層上に、第1観点乃至第9観点のいずれか一項に記載の有機無機ハイブリッド樹脂組成物からなるフレキシブルデバイス用基板となる樹脂薄膜を形成する工程;及び
c)前記樹脂薄膜を剥離層から剥離し、フレキシブルデバイス用基板を得る工程;
を含む、方法に関する。
そして本発明の有機無機ハイブリッド樹脂組成物から形成された樹脂薄膜は、高い耐熱性、低線膨張係数、高い透明性(高い光線透過率、低い黄色度)、低いリタデーションを示し、さらに柔軟性にも優れることから、フレキシブルデバイス、特にフレキシブルディスプレイ基板のベースフィルムとして好適に用いることができる。
このような本発明に係る有機無機ハイブリッド樹脂組成物及びそれから形成される樹脂薄膜は、高い柔軟性、低い線膨張係数、高い透明性(高い光線透過率、低い黄色度)、低いリタデーション等の特性が求められるフレキシルデバイス用基板、特にフレキシブルディスプレイ用基板の分野における進展に十分対応し得るものである。
本発明の有機無機ハイブリッド樹脂組成物は、(A)成分:特定のアルコキシシランで修飾した無機微粒子、(B)成分:下記特定のポリイミド、及び(C)成分:有機溶媒を含有し、所望により架橋剤及びその他成分を含有する。
(A)成分は、後述する特定のアルコキシシランで微粒子表面を修飾した無機微粒子である。該無機微粒子は目的等に応じてその平均粒子径を適宜選択できる。中でも平均粒子径は、より高透明な薄膜を得る観点から、1nm~100nmであることが好ましく、例えば1nm~60nm、あるいは9nm~60nmであることが更に好ましく、9nm~45nmであることが特に好ましい。
本発明において無機微粒子の平均粒子径とは、無機微粒子を用いて窒素吸着法により測定された比表面積値から算出される平均粒子径値である。
また、メチルシリケートやエチルシリケート等のアルコキシシランを、アルコール等の有機溶媒中で触媒(例えば、アンモニア、有機アミン化合物、水酸化ナトリウム等のアルカリ触媒)の存在下において加水分解し、縮合して得られるシリカゾル、又はそのシリカゾルを他の有機溶媒に溶媒置換したオルガノシリカゾルも用いることができる。
これらの中でも本発明は分散媒が有機溶媒であるオルガノシリカゾルを用いることが好ましい。
水性シリカゾルの分散媒である水の置換や、目的とする別の有機溶媒への置換は、蒸留法、限外濾過法等による通常の方法により行うことができる。
上記のオルガノシリカゾルの粘度は、20℃で、0.6mPa・s~100mPa・s程度である。
本発明において二酸化ケイ素、例えばオルガノシリカゾルとして使用される上記製品に挙げたような二酸化ケイ素は、二種以上を混合して用いてもよい。
本発明において、無機微粒子の修飾に用いるアルコキシシラン化合物(以下、特定アルコキシシランと称する)は、炭素原子数6乃至18の芳香族基を2つ有するアルコキシシラン化合物、又は、炭素原子数7乃至18の芳香族基を1つ有するアルコキシシラン化合物である。
上記炭素原子数6乃至18の芳香族基としては、フェニル基、及び、後述の炭素原子数7乃至18の芳香族基が挙げられる。炭素原子数7乃至18の芳香族基としては、ベンゼン環を2つ乃至3つ有する基、及び、縮環したベンゼン環を2つ乃至4つ有する基などが挙げられる。中でも、炭素原子数7乃至18の芳香族基としてビフェニル基を有する、下記式(S1)で表される構造を有するアルコキシシランが好ましい。
R1とR2はそれぞれ独立して、炭素原子数1~3のアルキル基であり、
Wは1~3の整数であり、
Yは0~2の整数であり、且つ、W+Y=3であり、
Z1はハロゲン原子、炭素原子数1~10のアルキル基及び炭素原子数1~10のアルコキシ基からなる群から選ばれる基を表し、mは0乃至5の整数を表し、但しmが2以上の整数の場合、Z1は同一または相異なる基であってよい。
中でもmが0である(ビフェニル基が置換されていない)アルコキシシランが好ましい。
具体的には、例えば、シリカ粒子のコロイド溶液と、予め準備した特定アルコキシシラン溶液とを混合することで、特定アルコキシシランで表面を修飾したシリカ粒子を調製することができる。コロイド溶液と特定アルコキシシラン溶液の混合は常温で行ってもよく、加熱しながら行ってもよい。反応効率の観点から、混合は加熱しながら行うことが好ましい。混合を加熱しながら行う場合、その加熱温度は溶媒等に応じて適宜選択することができる。加熱温度は例えば、60℃以上とすることができ、溶媒の還流温度であることが好ましい。
本発明において好適に用いられるポリイミドはフッ素を有するポリイミドであって、より具体的には、テトラカルボン酸二無水物成分と含フッ素芳香族ジアミンを含むジアミン成分とを反応させて得られるポリアミック酸(反応生成物)をイミド化して得られるポリイミド(イミド化物)である。
中でも、前記含フッ素芳香族ジアミンが、下記式(A1)で表されるジアミンを含むものであることが好ましい。
中でも、前記脂環式テトラカルボン酸二無水物が、下記式(C1)で表されるテトラカルボン酸二無水物を含むものであることが好ましい。
また上記(A1)で表されるジアミンの中でも、式中のB2が式(Y-12)、(Y-13)で表される化合物であることが好ましい。
好適な例として、上記式(C1)で表されるテトラカルボン酸二無水物と上記式(A1)で表されるジアミンとを反応させて得られるポリアミック酸をイミド化して得られるポリイミドは、後述する式(2)で表されるモノマー単位を含む。
また同様に、上記低線膨張係数、低リタデーション及び高透明性の特性を有し、柔軟性に優れる樹脂薄膜(フレキシブルデバイス用基板)を得るためには、ジアミン成分の全モル数に対して、含フッ素芳香族ジアミン、例えば式(A1)で表されるジアミンが90モル%以上であることが好ましく、95モル%以上であることがより好ましい。またジアミン成分の全て(100モル%)が上記式(A1)で表されるジアミンであってもよい。
その割合は、前述の式(C1)で表されるテトラカルボン酸二無水物を含む脂環式テトラカルボン酸二無水物成分と、式(A1)で表されるジアミンを含むジアミン成分とから誘導されるモノマー単位、例えば式(1)で表されるモノマー単位又は式(2)で表されるモノマー単位のモル数に対して、或いは式(1)で表されるモノマー単位及び式(2)で表されるモノマー単位の総モル数に対して、20モル%未満が好ましく、10モル%未満がより好ましく、5モル%未満であることがより一層好ましい。
また本発明で使用するポリイミドが、上記式(2)で表されるモノマー単位を有する場合、該ポリイミドは、テトラカルボン酸二無水物成分として1,2,3,4-シクロブタンテトラカルボン酸二無水物と、ジアミン成分として下記式(4)で表されるジアミンとを有機溶媒中で重合させ、得られるポリアミック酸をイミド化することにより得られる。
さらに本発明で使用するポリイミドが、上記式(1)で表されるモノマー単位に加え、上記式(2)で表されるモノマー単位を有する場合、式(1)及び式(2)で表される各モノマー単位を含有するポリイミドは、テトラカルボン酸二無水物成分として上記テトラカルボン酸二無水物の他、1,2,3,4-シクロブタンテトラカルボン酸二無水物と、ジアミン成分として下記式(4)で表されるジアミンとを有機溶媒中で重合させ、得られるポリアミック酸をイミド化することにより得られる。
中でも、ジアミン成分としては、本発明の樹脂薄膜(フレキシブルデバイス用基板)が具える線膨張係数をより低く、そして樹脂薄膜(フレキシブルデバイス用基板)の透明性をより高いものとする観点から、下記式(4-1)で表される2,2’-ビス(トリフルオロメチル)ベンジジン又は下記式(4-2)で表される3,3’-ビス(トリフルオロメチル)ベンジジンを用いることが好ましく、特に2,2’-ビス(トリフルオロメチル)ベンジジンを用いることが好ましい。
これらの中でも、式(5)中のAが前記式(A-1)~(A-4)のいずれかで表される4価の基であるテトラカルボン酸二無水物が好ましく、すなわち、11,11-ビス(トリフルオロメチル)-1H-ジフルオロ[3,4-b:3’,4’-i]キサンテン-1,3,7,9-(11H-テトラオン)、6,6’-ビス(トリフルオロメチル)-[5,5’-ビイソベンゾフラン]-1,1’,3,3’-テトラオン、4,6,10,12-テトラフルオロジフロ[3,4-b:3’,4’-i]ジベンゾ[b,e][1,4]ジオキシン-1,3,7,9-テトラオン、及び4,8-ビス(トリフルオロメトキシ)ベンゾ[1,2-c:4,5-c’]ジフラン-1,3,5,7-テトラオンを好ましい化合物として挙げることができる。
これらの中でも、式(6)中のBが前記式(B-1)~(B-11)のいずれかで表される2価の基である芳香族ジアミンが好ましく、すなわち、2,2’-ビス(トリフロオロメトキシ)-(1,1’-ビフェニル)-4,4’-ジアミン[別称:2,2’-ジメトキシベンジジン]、4,4’-(パーフルオロプロパン-2,2-ジイル)ジアニリン、2,5-ビス(トリフルオロメチル)ベンゼン-1,4-ジアミン、2-(トリフルオロメチル)ベンゼン-1,4-ジアミン、2-フルオロベンゼン-1,4-ジアミン、4,4’-オキシビス[3-(トリフルオロメチル)アニリン]、2,2’,3,3’,5,5’,6,6’-オクタフルオロ[1,1’-ビフェニル]-4,4’-ジアミン[別称:オクタフルオロベンジジン]、2,3,5,6-テトラフルオロベンゼン-1,4-ジアミン、4,4’-{[3,3”-ビス(トリフルオロメチル)-(1,1’:3’,1”-ターフェニル)-4,4”-ジイル]-ビス(オキシ)}ジアニリン、4,4’-{[(パーフルオロプロパン-2,2-ジイル)ビス(4,1-フェニレン)]ビス(オキシ)}ジアニリン、及び1-(4-アミノフェニル)-2,3-ジヒドロ-1,3,3-トリメチル-1H-インデン-5(または6)アミンを好ましいジアミンとして挙げることができる。
本発明で使用するポリイミドは、好ましい態様において、前述したように、上記式(C1)で表される脂環式テトラカルボン酸二無水物を含むテトラカルボン酸二無水物成分と、上記式(A1)で表される含フッ素芳香族ジアミンを含むジアミン成分とを反応させて得られるポリアミック酸をイミド化して得られる。
具体的には、例えば好適な一例として、ビシクロ[2.2.2]オクタン-2,3,5,6-テトラカルボン酸二無水物、そして場合により1,2,3,4-シクロブタンテトラカルボン酸二無水物、さらに所望により上記式(5)で表されるテトラカルボン酸二水物からなるテトラカルボン酸二無水物成分と、上記式(4)で表されるジアミン及び所望により上記式(6)で表されるジアミン成分からなるジアミン成分とを有機溶媒中で重合させ、得られるポリアミック酸をイミド化することにより得られる。
上記二成分からポリアミック酸への反応は、有機溶媒中で比較的容易に進行させることができ、かつ副生成物が生成しない点で有利である。
例えば、m-クレゾール、2-ピロリドン、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、N-ビニル-2-ピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、3-メトキシ-N,N-ジメチルプロピルアミド、3-エトキシ-N,N-ジメチルプロピルアミド、3-プロポキシ-N,N-ジメチルプロピルアミド、3-イソプロポキシ-N,N-ジメチルプロピルアミド、3-ブトキシ-N,N-ジメチルプロピルアミド、3-sec-ブトキシ-N,N-ジメチルプロピルアミド、3-tert-ブトキシ-N,N-ジメチルプロピルアミド、γ-ブチロラクトン、N-メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、イソプロピルアルコール、メトキシメチルペンタノール、ジペンテン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、メチルセロソルブ、エチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール-tert-ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、3-メチル-3-メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、3-メチル-3-メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、ジプロピルエーテル、ジヘキシルエーテル、ジオキサン、n-へキサン、n-ペンタン、n-オクタン、ジエチルエーテル、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸n-ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸イソプロピル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸、3-メトキシプロピオン酸、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチル、ジグライム、及び4-ヒドロキシ-4-メチル-2-ペンタノン等が挙げられるがこれらに限定されない。これらは単独で又は2種以上を組み合わせて使用してもよい。
さらに、ポリアミック酸を溶解させない溶媒であっても、生成したポリアミック酸が析出しない範囲で、上記溶媒に混合して使用してもよい。また、有機溶媒中の水分は重合反応を阻害し、さらには生成したポリアミック酸を加水分解させる原因となるので、有機溶媒はなるべく脱水乾燥させたものを用いることが好ましい。
また、テトラカルボン酸二無水物成分及び/又はジアミン成分が複数種の化合物からなる場合は、あらかじめ混合した状態で反応させてもよく、個別に順次反応させてもよく、さらに個別に反応させた低分子量体を混合反応させ高分子量体としてもよい。
反応時間は、反応温度や原料物質の反応性に依存するため一概に規定できないが、通常1~100時間程度である。
また、反応は任意の濃度で行うことができるが、濃度が低すぎると高分子量の重合体を得ることが難しくなり、濃度が高すぎると反応液の粘性が高くなり過ぎて均一な撹拌が困難となるので、テトラカルボン酸二無水物成分とジアミン成分との反応溶液中での合計濃度が、好ましくは1~50質量%、より好ましくは5~40質量%である。反応初期は高濃度で行い、その後、有機溶媒を追加することもできる。
ポリアミック酸をイミド化させる方法としては、ポリアミック酸の溶液をそのまま加熱する熱イミド化、ポリアミック酸の溶液に触媒を添加する触媒イミド化が挙げられる。
ポリアミック酸を溶液中で熱イミド化させる場合の温度は、100℃~400℃、好ましくは120℃~250℃であり、イミド化反応により生成する水を系外に除きながら行う方が好ましい。
塩基性触媒の量はポリアミック酸のアミド酸基の0.5~30モル倍、好ましくは1.5~20モル倍であり、酸無水物の量はポリアミック酸のアミド酸基の1~50モル倍、好ましくは2~30モル倍である。
触媒イミド化によるイミド化率は、触媒量と反応温度、反応時間を調節することにより制御することができる。
ポリアミック酸及びポリイミドの反応溶液からポリマー成分を回収し、これをポリイミドの調製、さらには、有機無機ハイブリッド樹脂組成物の調製に用いる場合には、反応溶液を貧溶媒に投入して沈殿させればよい。沈殿に用いる貧溶媒としてはメタノール、アセトン、ヘキサン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン、イソプロパノール、水などを挙げることができる。貧溶媒に投入して沈殿させたポリマーは濾過により回収した後、常圧あるいは減圧下で、常温あるいは加熱して乾燥することができる。
また、沈殿回収したポリマーを、有機溶媒に再溶解させ、再沈殿回収する操作を2から10回繰り返すと、ポリマー中の不純物を少なくすることができる。この際の貧溶媒として例えばアルコール類、ケトン類、炭化水素など3種類以上の貧溶媒を用いると、より一層精製の効率が上がるので好ましい。
本発明の有機無機ハイブリッド樹脂組成物には、上述の無機微粒子以外のその他の無機微粒子、すなわち、特定アルコキシシラン化合物で修飾していないその他の無機微粒子を含むことができる。その際の、特定アルコキシシラン化合物で修飾していないその他無機微粒子の含有量は、本願の(A)成分である無機微粒子と、特定アルコキシシラン化合物で修飾していないその他無機微粒子との合計に基づいて、50質量%~0質量%、好ましくは20質量%~0質量%である。
本発明の有機無機ハイブリッド樹脂組成物には、さらに架橋剤を含むことができる。ここで使用する架橋剤は、水素原子、炭素原子、及び酸素原子のみから構成される化合物であるか又は水素原子、炭素原子、窒素原子および酸素原子のみから構成される化合物であって、ヒドロキシ基、エポキシ基および炭素原子数1~5のアルコキシ基からなる群から選ばれる基を2つ以上有し、且つ、環構造を有する化合物からなる架橋剤である。このような架橋剤を用いることで、耐溶剤性に優れる、フレキシブルデバイス用基板に好適な樹脂薄膜を再現性よく与えるだけでなく、保存安定性がより改善された有機無機ハイブリッド樹脂組成物を実現することができる。
中でも、架橋剤における一化合物あたりのヒドロキシ基、エポキシ基および炭素原子数1~5のアルコキシ基の合計数は、得られる樹脂薄膜の耐溶剤性を再現性よく実現する観点から、好ましくは3以上であり、得られる樹脂薄膜の柔軟性を再現性よく実現する観点から、好ましく10以下、より好ましくは8以下、より一層好ましくは6以下である。
なお、環構造が2以上存在する場合、環構造同士が縮合していてもよく、メチレン基、エチレン基、トリメチレン基、プロパン-2,2-ジイル基等の炭素原子数1~5のアルカン-ジイル基等の連結基を介して環構造同士が結合していてもよい。
中でも、架橋剤の入手容易性、価格等を考慮すると、Xは、式(K1)および(K5)においてはエポキシ基が好ましく、式(K2)および(K3)においては炭素原子数1~5のアルコキシ基が好ましく、式(K4)においてはヒドロキシ基が好ましい。
市販品としては、CYMEL(登録商標)300、同301、同303LF,同303ULF、同304、同350、同3745、同XW3106、同MM-100、同323、同325、同327、同328、同385、同370、同373、同380、同1116、同1130、同1133、同1141、同1161、同1168、同3020、同202、同203、同1156、同MB-94、同MB-96、同MB-98、同247-10、同651、同658、同683、同688、同1158、同MB-14、同MI-12-I、同MI-97-IX、同U-65、同UM-15、同U―80、同U-21-511、同U-21-510、同U-216-8、同U-227-8、同U-1050-10、同U-1052-8、同U-1054、同U-610、同U-640、同UB-24-BX、同UB-26-BX、同UB-90-BX、同UB-25-BE、同UB-30-B、同U-662、同U-663、同U-1051、同UI-19-I、同UI-19-IE、同UI-21-E、同UI-27-EI、同U-38-I、同UI-20-E同659、同1123、同1125、同5010、同1170、同1172、同NF3041、同NF2000等(以上、allnex社製);TEPIC(登録商標)V、同S、同HP、同L、同PAS、同VL、同UC(以上、日産化学工業(株)製)、TM-BIP-A(旭有機材工業(株)製)、1,3,4,6-テトラキス(メトキシメチル)グリコールウリル(以下、TMGと略す)(東京化成工業(株)製)、4,4’-メチレンビス(N,N-ジグリシジルアニリン)(Aldrich社製)、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、HP-820(DIC(株))、TG-G(四国化成工業(株))等が挙げられる。
本発明の有機無機ハイブリッド樹脂組成物は、前記ポリイミド、特定のアルコキシシランで表面を修飾した無機微粒子、任意のその他無機微粒子及び架橋剤等に加えて、有機溶媒を含む。該有機溶媒は、特に限定されるものではなく、例えば、上記ポリアミック酸及びポリイミドの調製時に用いた反応溶媒の具体例と同様のものが挙げられる。より具体的には、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、N-エチル-2-ピロリドン、γ-ブチロラクトンなどが挙げられる。なお、有機溶媒は、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。
これらの中でも、平坦性の高い樹脂薄膜を再現性よく得ることを考慮すると、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、γ-ブチロラクトンが好ましい。
本発明は、(A)特定のアルコキシシランで表面を修飾した無機微粒子、(B)前記ポリイミド、及び(C)有機溶媒を含み、所望により二酸化ケイ素等のその他の無機微粒子、架橋剤等を含有する有機無機ハイブリッド樹脂組成物である。ここで本発明の有機無機ハイブリッド樹脂組成物は、均一なものであって、相分離は認められないものである。
本発明の有機無機ハイブリッド樹脂組成物において、(A)特定のアルコキシシランで表面を修飾した無機微粒子と、(B)前記ポリイミドの配合比は、質量比で、(A)無機微粒子:(B)ポリイミド=10:1~1:10であることが好ましく、より好ましくは8:2~2:8、例えば7:3~3:7であり、あるいは5:5~9:1とすることができる。なお、特定アルコキシシラン化合物で修飾していないその他の無機微粒子が含まれる場合、上記の質量比は、(A)無機微粒子の質量にその他の無機微粒子を含めたものとして考慮することができるが、前述したように、特定アルコキシシラン化合物で修飾していないその他無機微粒子の含有量は、本願の(A)成分である無機微粒子と、特定アルコキシシラン化合物で修飾していないその他無機微粒子との合計に基づいて、50質量%~0質量%、好ましくは20質量%~0質量%である。
また本発明の有機無機ハイブリッド樹脂組成物中の固形量は、通常0.5~30質量%の範囲内であるが、膜の均一性の観点から、好ましくは5質量%以上、20質量%以下である。なお、固形分とは、有機無機ハイブリッド樹脂組成物を構成する全成分から溶媒を除いた残りの成分を意味する。
なお、有機無機ハイブリッド樹脂組成物の粘度は、用いる塗布法、作製する樹脂薄膜の厚み等を勘案して適宜決定されるものではあるが、通常25℃で1~50,000mPa・sである。
本発明の有機無機ハイブリッド樹脂組成物は、上述の方法で得られたポリイミド、前述の特定アルコキシシラン化合物で表面を修飾した無機微粒子、そして所望により二酸化ケイ素等のその他無機微粒子、架橋剤等を上述の有機溶媒に溶解して得ることができるし、ポリイミドの調製後の反応溶液に、前述の特定アルコキシシラン化合物で表面を修飾した無機微粒子またはその溶液を添加し、さらに、所望により二酸化ケイ素、架橋剤等を添加し、所望により前記有機溶媒を更に加えたものとしてもよい。
以上説明した本発明の有機無機ハイブリッド樹脂組成物は、これを基材に塗布して、乾燥・加熱することで有機溶媒を除去し、耐熱性に優れ、リタデーションが低く、柔軟性に優れ、さらに透明性にも優れる(高い光線透過率:例えば400nmにおける光透過率80%以上、低い黄色度:例えば2%以下のヘイズ値)樹脂薄膜を得ることができ、またこれらの優れた性能を維持するとともに、剥離層から機械的剥離により剥離可能な、フレキシブルデバイス用基板として有用な樹脂薄膜を得ることができる。
そして上記有機無機ハイブリッド樹脂組成物から形成される樹脂薄膜、並びにフレキシブルデバイス用基板、すなわち上記ポリイミド及び前述の特定アルコキシシラン化合物で表面を修飾した無機微粒子と、所望により二酸化ケイ素等の無機微粒子、架橋剤等を含有するフレキシブルデバイス用基板、すなわち、本発明の有機無機ハイブリッド樹脂組成物の硬化物からなるフレキシブルデバイス用基板も本発明の対象である。
特に、フレキシブルデバイス用基板として適用する際、既存設備を利用することができるという観点から、適用する基材がガラス、シリコンウェハであることが好ましく、また得られるフレキシブルデバイス用基板が良好な剥離性を示すことからガラスであることがさらに好ましい。なお、適用する基材の線膨張係数としては塗工後の基材の反りの観点から、好ましくは40ppm/℃以下、より好ましくは、30ppm/℃以下である。
また、得られる樹脂薄膜の耐熱性と線膨張係数特性を考慮すると、塗布した有機無機ハイブリッド樹脂組成物を40℃~100℃で5分間~2時間加熱した後に、そのまま段階的に加熱温度を上昇させ、最終的に175℃超~350℃で30分~2時間加熱することが望ましい。このように、溶媒を乾燥させる段階と分子配向を促進する段階の2段階以上の温度で加熱することにより、より再現性よく低熱膨張特性を発現させることができる。
特に、塗布した有機無機ハイブリッド樹脂組成物は、40℃~100℃で5分間~2時間加熱した後に、100℃超~175℃で5分間~2時間、次いで、175℃超~350℃で5分~2時間加熱することが好ましい。
加熱に用いる器具は、例えばホットプレート、オーブン等が挙げられる。加熱雰囲気は、空気下であっても窒素等の不活性ガス下であってもよく、また、常圧下であっても減圧下であってもよく、また加熱の各段階において異なる圧力を適用してもよい。
なおこのようにして形成された樹脂薄膜を基材から剥離する方法としては特に限定はなく、該樹脂薄膜を基材ごと冷却し、薄膜に切れ目を入れ剥離する方法やロールを介して張力を与えて剥離する方法等が挙げられる。
更に、該樹脂薄膜は、例えば50℃乃至200℃における線膨張係数が25ppm/℃以下、特に5ppm/℃乃至25ppm/℃という低い値を有することができ、加熱時の寸法安定性に優れたものである。
また該樹脂薄膜は、入射光の波長を590nmとした場合における複屈折、すなわち、厚さ方向の断面からみたときの2つの複屈折(面内の2つの屈折率と厚さ方向の屈折率との夫々の差)にそれぞれ膜厚を掛けて得られる2つの位相差の平均値として表される厚さ方向リタデーションRthが小さいことを特長とする。
該方法は、
a)ガラス基板等の支持基材上に剥離層を形成する工程;
b)該剥離層上に、本発明の有機無機ハイブリッド樹脂組成物を用いてフレキシブルデバイス用基板となる樹脂薄膜を形成する工程;及び
c)前記樹脂薄膜を剥離層から剥離し、フレキシブルデバイス用基板を得る工程;
を有することにより、フレキシブルデバイス用基板を得ることができる。
図1に示すように、上記c)工程は、剥離層(De-Bonding Layer)とフレキシブルデバイス基板となる樹脂薄膜(PI/シリカフィルム)との界面において、上記樹脂薄膜を剥離する工程である。
上記剥離層は、上述の芳香族ポリイミドやポリベンゾオキサゾール等を含有する公知の剥離層形成組成物より形成可能である。
<酸二無水物>
BODAxx:ビシクロ[2,2,2]オクタン-2,3,5,6-テトラカルボン酸二無水物
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物
PMDA:ピロメリット酸二無水物
<ジアミン>
TFMB:2,2’-ビス(トリフルオロメチル)ベンジジン
p-PDA:p-フェニレンジアミン
<有機溶媒>
GBL:γ-ブチロラクトン
NMP:N-メチル-2-ピロリドン
1)数平均分子量及び重量平均分子量の測定
ポリマーの数平均分子量(以下、Mnと略す)と重量平均分子量(以下、Mwと略す)は、装置:昭和電工(株)製、Showdex GPC-101、カラム:KD803およびKD805、カラム温度:50℃、溶出溶媒:DMF、流量:1.0ml/分、検量線:標準ポリスチレン、の条件にて測定した。
2)膜厚
得られた樹脂薄膜の膜厚は、(株)テクロック製 シックネスゲージにて測定した。
3)線膨張係数(CTE)
TAインスツルメンツ社製 TMA Q400を用いて、薄膜を幅5mm、長さ16mmのサイズにカットし、まず10℃/minで昇温して50乃至350℃まで加熱(第一加熱)し、次いで10℃/minで降温して50℃まで冷却した後に、10℃/minで昇温して50乃至420℃まで加熱(第二加熱)した際の、第二加熱の50℃乃至200℃における線膨張係数(CTE[ppm/℃])の値を測定することで求めた。なお、第一加熱、冷却および第二加熱を通じて、荷重0.05Nを加えた。
4)熱分解温度5%重量減少温度(Td5%)
5%重量減少温度(Td5%[℃])は、TAインスツルメンツ社製 TGA Q500を用い、窒素中、薄膜約5乃至10mgを50乃至800℃まで10℃/minで昇温して測定することで求めた。
5)光線透過率(透明性)(T400nm、T550nm)及びCIE b値(CIE b*)
波長400nm及び550nmの光線透過率(T400nm、T550nm[%])及びCIE b値(CIE b*)は、日本電色工業(株)製 SA4000スペクトロメーターを用いて、室温にて、リファレンスを空気として、測定を行った。
6)リタデーション(Rth)
厚さ方向リタデーション(Rth)を、王子計測機器(株)製、KOBURA 2100ADHを用いて、室温にて測定した。
なお、厚さ方向リタデーション(Rth)は以下の式にて算出される。
Rth=[(Nx+Ny)/2-Nz]×d=[(ΔNxz×d)+(ΔNyz×d)/2
Nx、Ny:面内の直交する2つの屈折率(Nx>Ny、Nxを遅相軸、Nyを進相軸とも称する)
Nz:面に対して厚さ(垂直)方向の屈折率
d:膜厚
ΔNxy:面内の2つの屈折率の差(Nx-Ny)(複屈折)
ΔNxz:面内の屈折率Nxと厚さ方向の屈折率Nzの差(複屈折)
ΔNyz:面内の屈折率Nyと厚さ方向の屈折率Nzの差(複屈折)
7)ポリイミドはアドヴァンテック社製のDrv 320真空オーブンにて乾燥させた。
合成例1:ポリイミドA(PI-A)の合成、及び7wt%溶液の調製
p-PDA 1.02g(9.5mmol)をNMP 26.4gに溶解させた。得られた溶液に、PMDA 2.58g(11.8mmol)を加え、窒素雰囲気下、23℃で24時間反応させた。その後、アニリン 0.44g(4.7mmol)を添加し、更に24時間反応させた。得られたポリマーのMwは31,500、分子量分布3.2であった。この溶液にNMP23gを添加し、室温で24時間撹拌し、剥離層用ワニス(DBL-1)を得た。
調製例1:特定アルコキシシラン修飾シリカ粒子含有溶液(Si-1)の調製
窒素の注入口/排出口と冷却器を取り付けた500mLの反応三口フラスコ内に、クォートロンPL-1-IPA(扶桑化学工業株式会社製、登録商標、粒子径(比表面積換算)10~15nm、分散媒イソプロパノール)200g(13.3%)と、4-ビフェニルトリメトキシシラン1.644gを入れた。その後、窒素雰囲気下、100℃で17時間加熱した。反応終了後、GBL79.8gを入れ、エバポレータでイソプロパノールの減圧留去を行い、特定アルコキシシランで修飾されたシリカ粒子のGBLゾル溶液(Si-1)を得た。この溶液1gをアルミカップ上で200℃2時間加熱し、残量から濃度を算出したところ、濃度は35wt%であった
窒素の注入口/排出口と冷却器を取り付けた100mLの反応三口フラスコ内に、クォートロンPL-1-IPA(扶桑化学工業株式会社製、登録商標、粒子径(比表面積換算)10~15nm、分散媒イソプロパノール)50g(13.3%)と、4-ビフェニルトリメトキシシラン0.206gを入れた。その後、窒素雰囲気下、100℃で22時間加熱した。反応終了後、GBL19.9gを入れ、エバポレータでイソプロパノールの減圧留去を行い、特定アルコキシシランで修飾されたシリカ粒子のGBLゾル溶液(Si-2)を得た。この溶液1gをアルミカップ上で200℃2時間加熱し、残量から濃度を算出したところ、濃度は35wt%であった。
窒素の注入口/排出口と冷却器を取り付けた500mLの反応三口フラスコ内に、クォートロンPL-1-IPA(扶桑化学工業株式会社製、登録商標、粒子径(比表面積換算)10~15nm、分散媒イソプロパノール)200g(13.3%)と、フェニルトリメトキシシラン1.13gを入れた。その後、窒素雰囲気下、100℃で17時間加熱した。反応終了後、GBL79.8gを入れ、エバポレータでイソプロパノールの減圧留去を行い、アルコキシシランで修飾されたシリカ粒子のGBLゾル溶液(Si-3)を得た。この溶液1gをアルミカップ上で200℃2時間加熱し、残量から濃度を算出したところ、濃度は35wt%であった。
500mLのナスフラスコにクォートロンPL-1-IPA(扶桑化学工業株式会社製、登録商標、粒子径(比表面積換算)10~15nm、分散媒イソプロパノール)200g(13.3%)と、GBL79.8gを入れ、エバポレータでイソプロパノールの減圧留去を行い、アルコキシシラン非修飾のシリカ粒子のGBLゾル溶液(Si-4)を得た。この溶液1gをアルミカップ上で200℃2時間加熱し、残量から濃度を算出したところ、濃度は35wt%であった。
スピンコータ(条件:回転数3,000rpmで約30秒)を用いて、合成例2で得られた剥離層用ワニス(DBL-1)を、ガラス基体としての100mm×100mmガラス基板(以下同様)の上に塗布した。
そして、得られた塗膜を、ホットプレートを用いて80℃で10分間加熱し、その後、オーブンを用いて、300℃で30分間加熱し、加熱温度を500℃まで昇温(10℃/分)し、さらに500℃で10分間加熱し、ガラス基板上に厚さ約0.1μmの剥離層を形成した。なお、昇温の間、膜付き基板をオーブンから取り出すことはせず、オーブン内で加熱した。
実施例1
合成例1で得られた7wt%のポリイミドGBL溶液(PI-B)10gに、特定アルコキシシラン修飾シリカ粒子含有溶液(Si-1)4.66g、GBL3.27gを添加し、室温で3日間撹拌した。その後、0.45ミクロンのプロピレンフィルターでろ過し、目的のワニス(有機無機ハイブリッド樹脂組成物)を得た。得られたワニスを剥離層上にバーコーター(ギャップ250ミクロン)で塗布し、ホットプレートを用いて100℃で1時間加熱した。更に、ホットプレートにて280℃で30分間加熱し、透明PIフィルムLIを得た。L1は、図1に示すように剥離層から容易に剥離することができた。L1の光学的及び熱的特性を表1に示す。
上記(Si-1)の代わりに、特定アルコキシシラン修飾シリカ粒子含有溶液(Si-2)4.66gを使用した以外は、実施例1と同様の方法でワニス(有機無機ハイブリッド樹脂組成物)を得、これを剥離層上に塗布してフィルム化し、透明PIフィルムL2を得た。L2はL1同様に、剥離層から容易に剥離することができた。L2の光学的及び熱的特性を表1に示す。
合成例1で得られた7wt%のポリイミドGBL溶液(PI-B)10gに、特定アルコキシシラン修飾シリカ粒子含有溶液(Si-1)3.00g、GBL0.46gを添加し、室温で3日間撹拌した。その後、0.45ミクロンのプロピレンフィルターでろ過し、目的のワニス(有機無機ハイブリッド樹脂組成物)を得た。得られたワニスを剥離層上にバーコーター(ギャップ250ミクロン)で塗布し、ホットプレートを用いて100℃で1時間加熱した。真空ガス置換炉KDF-900GL(デンケン製)で窒素雰囲気下、加熱温度を350℃まで昇温(10℃/分)し、さらに350℃で30分間加熱し、透明PIフィルムL3を得た。L3は、図1に示すように剥離層から容易に剥離することができた。L3の光学的及び熱的特性を表1に示す。
合成例1で得られた7wt%のポリイミドGBL溶液(PI-B)10gに、アルコキシシラン修飾シリカ粒子含有溶液(Si-3)4.66g、GBL3.27gを添加し、室温で3日間撹拌した。その後、0.45ミクロンのプロピレンフィルターでろ過し、目的のワニスを得た。得られたワニスを剥離層上にバーコーター(ギャップ250ミクロン)で塗布し、ホットプレートを用いて100℃で1時間加熱した。しかし、加熱乾燥時にワニスが収縮し、フィルムを得ることができなかった。
合成例1で得られた7wt%のポリイミドGBL溶液(PI-B)10gに、シリカ粒子含有溶液(Si-4)4.66g、GBL3.27gを添加し、室温で3日間撹拌した。その後、0.45ミクロンのプロピレンフィルターでろ過し、目的のワニスを得た。得られたワニスを無アルカリガラス基板上にバーコーター(ギャップ250ミクロン)で塗布し、ホットプレートを用いて100℃で1時間加熱した。更に、ホットプレートにて280℃で30分間加熱し、透明PIフィルムHL2を得た。このフィルムを図1と同様に剥離を試みたが、全く剥がれず、クラックが生じた。
合成例1で得られた7wt%のポリイミドGBL溶液(PI-B)10gに、シリカ粒子含有溶液(Si-4)4.66g、GBL3.27gを添加し、室温で3日間撹拌した。その後、0.45ミクロンのプロピレンフィルターでろ過し、目的のワニスを得た。得られたワニスを剥離層板上にバーコーター(ギャップ250ミクロン)で塗布し、ホットプレートを用いて100℃で1時間加熱した。更に、ホットプレートにて280℃で30分間加熱し、透明PIフィルムHL3を得た。このフィルムを図1と同様に剥離を試みたが、全く剥がれず、クラックが生じた。
合成例1で得られた7wt%のポリイミドGBL溶液(PI-B)10gを剥離層板上にバーコーター(ギャップ500ミクロン)で塗布し、ホットプレートを用いて100℃で1時間加熱した。更に、ホットプレートにて280℃で30分間加熱し、透明PIフィルムHL4を得た。HL4は、図1に示すように剥離層から剥離することができた。HL4の光学的及び熱的特性を表1に示す。
Claims (12)
- 下記(A)成分、(B)成分及び(C)成分を含むことを特徴とする有機無機ハイブリッド樹脂組成物。
(A)成分:炭素原子数6乃至18の芳香族基を2つ有するか又は炭素原子数7乃至18の芳香族基を1つ有するアルコキシシラン化合物で微粒子表面を修飾した、平均粒子径1nm乃至100nmの無機微粒子、
(B)成分:フッ素を有するポリイミド、
(C)成分:有機溶媒。 - 前記式中、mが0である、請求項1または2に記載の有機無機ハイブリッド樹脂組成物。
- 前記(A)成分の無機微粒子が二酸化ケイ素粒子である、請求項1乃至5のいずれか一項に記載の有機無機ハイブリッド樹脂組成物。
- 前記(A)成分と(B)成分の質量比が、(A):(B)にて5:5~9:1である、請求項1乃至6のいずれか一項に記載の有機無機ハイブリッド樹脂組成物。
- 前記(A)成分の無機微粒子が、1nm乃至60nmの平均粒子径を有する無機微粒子である、請求項1乃至7のいずれか一項に記載の有機無機ハイブリッド樹脂組成物。
- 前記(C)成分が、エステル系溶媒であることを特徴とする、請求項1乃至8のいずれか一項に記載の有機無機ハイブリッド樹脂組成物。
- 請求項1乃至9のいずれか一項に記載の有機無機ハイブリッド樹脂組成物から形成される400nmにおける光透過率80%以上で透明であり、なおかつ2%以下のヘイズを持つ樹脂薄膜。
- 請求項10に記載の樹脂薄膜からなるフレキシブルデバイス用基板。
- フレキシブルデバイス用基板の製造方法であって、
a)支持基材上に剥離層を形成する工程;
b)該剥離層上に、請求項1乃至9のいずれか一項に記載の有機無機ハイブリッド樹脂組成物からなるフレキシブルデバイス用基板となる樹脂薄膜を形成する工程;及び
c)前記樹脂薄膜を剥離層から剥離し、フレキシブルデバイス用基板を得る工程;
を含む、方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019564775A JP7231887B2 (ja) | 2018-01-15 | 2019-01-15 | ハイブリッド樹脂組成物 |
CN201980008617.9A CN111699218B (zh) | 2018-01-15 | 2019-01-15 | 杂化树脂组合物 |
KR1020207020651A KR20200103734A (ko) | 2018-01-15 | 2019-01-15 | 하이브리드 수지조성물 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018004427 | 2018-01-15 | ||
JP2018-004427 | 2018-01-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019139167A1 true WO2019139167A1 (ja) | 2019-07-18 |
Family
ID=67218335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/000933 WO2019139167A1 (ja) | 2018-01-15 | 2019-01-15 | ハイブリッド樹脂組成物 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP7231887B2 (ja) |
KR (1) | KR20200103734A (ja) |
CN (1) | CN111699218B (ja) |
TW (1) | TWI804564B (ja) |
WO (1) | WO2019139167A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7131728B1 (ja) | 2022-03-30 | 2022-09-06 | 日産化学株式会社 | 蒸着マスク |
KR20240009968A (ko) | 2021-05-20 | 2024-01-23 | 사카모토 야쿠힌고교 가부시키가이샤 | 유리 성분 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6746025B1 (ja) * | 2020-03-31 | 2020-08-26 | 株式会社アドマテックス | 表面改質粒子材料及びスラリー組成物 |
KR102245533B1 (ko) * | 2020-11-02 | 2021-04-28 | 주식회사 지게차코리아 | 운송수단용 림 및 이의 제조방법 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008239959A (ja) * | 2007-03-01 | 2008-10-09 | Mitsubishi Gas Chem Co Inc | ポリイミド樹脂組成物 |
JP2010280807A (ja) * | 2009-06-04 | 2010-12-16 | Nitto Denko Corp | ポリイミド樹脂用組成物 |
US20110091732A1 (en) * | 2009-10-15 | 2011-04-21 | Industrial Technology Research Institute | Polyamic acid resin composition and polyimide film prepared therefrom |
JP2011521866A (ja) * | 2008-04-18 | 2011-07-28 | ナノレジンス アーゲー | 表面修飾二酸化ケイ素粒子 |
WO2013008437A1 (ja) * | 2011-07-08 | 2013-01-17 | 三井化学株式会社 | ポリイミド樹脂組成物およびそれを含む積層体 |
JP2017520662A (ja) * | 2014-06-30 | 2017-07-27 | コーロン インダストリーズ インク | 表面改質複合シリカ粒子及びこれを含むポリイミドフィルム |
WO2017170385A1 (ja) * | 2016-03-31 | 2017-10-05 | 日産化学工業株式会社 | 被膜形成用組成物及びその製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008231327A (ja) | 2007-03-22 | 2008-10-02 | Ihara Chem Ind Co Ltd | 高透明性を有するポリイミドおよびその製造方法 |
WO2009096050A1 (ja) * | 2008-01-28 | 2009-08-06 | Toray Industries, Inc. | シロキサン系樹脂組成物 |
JP6631804B2 (ja) | 2014-03-31 | 2020-01-15 | 日産化学株式会社 | 樹脂薄膜の製造方法および樹脂薄膜形成用組成物 |
-
2019
- 2019-01-15 CN CN201980008617.9A patent/CN111699218B/zh active Active
- 2019-01-15 TW TW108101509A patent/TWI804564B/zh active
- 2019-01-15 KR KR1020207020651A patent/KR20200103734A/ko not_active Application Discontinuation
- 2019-01-15 JP JP2019564775A patent/JP7231887B2/ja active Active
- 2019-01-15 WO PCT/JP2019/000933 patent/WO2019139167A1/ja active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008239959A (ja) * | 2007-03-01 | 2008-10-09 | Mitsubishi Gas Chem Co Inc | ポリイミド樹脂組成物 |
JP2011521866A (ja) * | 2008-04-18 | 2011-07-28 | ナノレジンス アーゲー | 表面修飾二酸化ケイ素粒子 |
JP2010280807A (ja) * | 2009-06-04 | 2010-12-16 | Nitto Denko Corp | ポリイミド樹脂用組成物 |
US20110091732A1 (en) * | 2009-10-15 | 2011-04-21 | Industrial Technology Research Institute | Polyamic acid resin composition and polyimide film prepared therefrom |
WO2013008437A1 (ja) * | 2011-07-08 | 2013-01-17 | 三井化学株式会社 | ポリイミド樹脂組成物およびそれを含む積層体 |
JP2017520662A (ja) * | 2014-06-30 | 2017-07-27 | コーロン インダストリーズ インク | 表面改質複合シリカ粒子及びこれを含むポリイミドフィルム |
WO2017170385A1 (ja) * | 2016-03-31 | 2017-10-05 | 日産化学工業株式会社 | 被膜形成用組成物及びその製造方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20240009968A (ko) | 2021-05-20 | 2024-01-23 | 사카모토 야쿠힌고교 가부시키가이샤 | 유리 성분 |
JP7131728B1 (ja) | 2022-03-30 | 2022-09-06 | 日産化学株式会社 | 蒸着マスク |
WO2023190861A1 (ja) * | 2022-03-30 | 2023-10-05 | 日産化学株式会社 | 蒸着マスク |
JP2023149108A (ja) * | 2022-03-30 | 2023-10-13 | 日産化学株式会社 | 蒸着マスク |
Also Published As
Publication number | Publication date |
---|---|
JP7231887B2 (ja) | 2023-03-02 |
CN111699218B (zh) | 2023-05-26 |
TW201940570A (zh) | 2019-10-16 |
KR20200103734A (ko) | 2020-09-02 |
TWI804564B (zh) | 2023-06-11 |
JPWO2019139167A1 (ja) | 2021-01-28 |
CN111699218A (zh) | 2020-09-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6631804B2 (ja) | 樹脂薄膜の製造方法および樹脂薄膜形成用組成物 | |
TWI742204B (zh) | 可撓性元件基板形成用組成物 | |
WO2019139167A1 (ja) | ハイブリッド樹脂組成物 | |
KR102599925B1 (ko) | 수지박막형성용 조성물 | |
JP7116366B2 (ja) | フレキシブルデバイス用基板の製造方法 | |
TWI758357B (zh) | 可撓性元件基板形成用組成物 | |
JP6905213B2 (ja) | フレキシブルデバイス基板形成用組成物 | |
WO2019009259A1 (ja) | フレキシブルデバイス基板形成用組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19738831 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2019564775 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20207020651 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19738831 Country of ref document: EP Kind code of ref document: A1 |