Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
  • H10K77/10—Substrates, e.g. flexible substrates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
  • H05B33/14—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
  • H10K59/12—Active-matrix OLED [AMOLED] displays

Definitions

• the present invention relates to a laminate and a method for manufacturing the laminate.
• polyimide resin Since polyimide resin has excellent mechanical properties and heat resistance, various uses are being considered in fields such as electrical and electronic parts. For example, it is desired to replace glass substrates used in image display devices such as liquid crystal displays and OLED displays with polyimide film substrates, and polyimide resins that satisfy the performance as optical materials are being developed. Since polyimide resin has the above-mentioned excellent properties, development of a laminate in which an insulating film and a conductive film are laminated on a polyimide film is underway as an electronic device such as a touch sensor or an OLED.
• Patent Document 1 discloses, for the purpose of reducing delamination during the manufacturing process, a step of preparing a support substrate made of glass, a step of forming a first inorganic film containing silicon on one surface of the support substrate, A method for manufacturing an intermediate material for an electronic device is disclosed, which includes the steps of forming a polyimide film containing fluorine on a first inorganic film, and forming a second inorganic film containing silicon on the polyimide film.
• Polyimide resins have excellent properties as described above, but recently they are required to have even more heat resistance.
• TFT device type low temperature polysilicon TFT
• the process temperature exceeds 400° C.
• the polyimide substrate is required to have heat resistance to withstand high temperatures.
• display technology has led to the development of new forms of displays. For example, in transparent displays, displays using UDC (under display camera) technology, etc., substrates are required to have a low degree of yellowness.
• aromatic polyimide resins that do not have substituents which are conventional general-purpose polyimides, have excellent heat resistance that can withstand high temperatures, but they have the problem of high yellowness, and they also have substituents on the aromatic rings.
• polyimide having the above-mentioned polyimide easily yellowed. Therefore, a laminate containing polyimide that has heat resistance and low yellowness has been desired.
• the present invention has been made in view of these circumstances, and an object of the present invention is to provide a laminate for manufacturing TFT substrates that has excellent heat resistance, low yellowness, and small change in yellowness after heat treatment. and a manufacturing method.
• the present inventors have discovered that the above problem can be solved by a laminate in which a glass substrate, an inorganic film, and a specific polyimide resin are laminated, and have completed the invention.
• the present invention relates to the following [1] to [9].
• a supporting base material made of glass a first inorganic film laminated on the supporting base material, a polyimide resin laminated on the first inorganic film, and a polyimide resin laminated on the polyimide resin.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• Y 1 is a single bond
• R 1 and R 2 each independently represent a methyl group, a fluoro group, or a trifluoromethyl group.
• h and i are integers of 0 to 4, and at least One is an integer from 1 to 4.
• X 2 includes a tetravalent group represented by the following general formula (3), Y 2 is a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene (M is at least one selected from the group consisting of groups.
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, p is an integer of 1 to 4, and k is 1 or 2.
• [2] The laminate according to [1], wherein the first inorganic film has a thickness of 1 to 1,000 nm, and the second inorganic film has a thickness of 1 to 1,000 nm.
• [3] The laminate according to [1] or [2], wherein at least one of the first inorganic film and the second inorganic film contains silicon.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• Y 1 is a single bond
• R 1 and R 2 each independently represent a methyl group, a fluoro group, or a trifluoromethyl group.
• h and i are integers of 0 to 4, and at least One is an integer from 1 to 4.
• X 2 includes a tetravalent group represented by the following general formula (3), Y 2 is a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene (M is at least one selected from the group consisting of groups.
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, p is an integer of 1 to 4, and k is 1 or 2.
• a method for producing a laminate comprising the step of laminating a second inorganic film, wherein the polyimide resin precursor has a structural unit of the following general formula (4) or a structural unit of the following general formula (5). Production method.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• Y 1 is a single bond
• R 1 and R 2 each independently represent a methyl group, a fluoro group, or a trifluoromethyl group.
• R 3 and R 4 each independently represent a hydrogen atom.
• h and i are integers of 0 to 4, and at least one is an integer of 1 to 4.
• X 2 includes a tetravalent group represented by the following general formula (3)
• Y 2 is a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene
• R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• a TFT functional layer is laminated on the second inorganic film in the laminate according to any one of [1] to [4] above, and the first inorganic film is formed of a polyimide resin.
• a method for manufacturing a laminate for a TFT substrate that is peeled off from an interface. [8] A laminate for a TFT substrate obtained by the manufacturing method described in [7] above. [9] An electronic device containing the TFT substrate laminate according to [8] above.
• the present invention it is possible to provide a laminate and a manufacturing method for manufacturing a TFT substrate, which has excellent heat resistance, low yellowness, and also has a small change in yellowness after heat treatment.
• the laminate of the present invention includes a supporting base material made of glass, a first inorganic film laminated on the supporting base material, a polyimide resin laminated on the first inorganic film, and a polyimide resin laminated on the polyimide resin.
• the transition temperature is 400°C or higher.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• Y 1 is a single bond
• R 1 and R 2 each independently represent a methyl group, a fluoro group, or a trifluoromethyl group.
• h and i are integers of 0 to 4, and at least One is an integer from 1 to 4.
• X 2 includes a tetravalent group represented by the following general formula (3), Y 2 is a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene (M is 0, 1 or 2.)
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, p is an integer of 1 to 4, and k is 1 or 2.
• the polyimide resin contained in the laminate of the present invention has a structural unit represented by the following general formula (1) or a structural unit represented by the following general formula (2), and has a glass transition temperature of 400°C or higher.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• Y 1 is a single bond
• fluorenylidene R 1 and R 2 each independently represent a methyl group, a fluoro group, or a trifluoromethyl group.
• h and i are integers of 0 to 4, and at least One is an integer from 1 to 4.
• n is 0, 1 or 2.
• X 2 includes a tetravalent group represented by the following general formula (3), Y 2 is a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene (M is at least one selected from the group consisting of groups.
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, p is an integer of 1 to 4, and k is 1 or 2.
• a polyimide resin having a structural unit of the general formula (1) and a glass transition temperature of 400°C or higher will be referred to as a polyimide resin (1)
• a polyimide resin having a structural unit of the general formula (2) and a glass transition temperature of 400°C or higher A polyimide resin having a temperature of 400° C. or higher is referred to as polyimide resin (2).
• polyimide resin (1) is more preferable.
• the glass transition temperature of the polyimide resin contained in the laminate of the present invention is 400°C or higher.
• the glass transition temperature of the polyimide resin contained in the laminate of the present invention is preferably 410°C or higher, more preferably 420°C or higher, still more preferably 430°C or higher, even more preferably 440°C or higher.
• the temperature is even more preferably 450°C or higher.
• the laminate of the present invention has excellent heat resistance and is useful as a laminate for manufacturing TFT substrates.
• the laminate of the present invention is excellent as a laminate for manufacturing TFT substrates, and the obtained laminate has excellent properties such as excellent heat resistance, low yellowness, and small change in yellowness after heat treatment.
• the reason for this is not clear, but it is thought to be as follows.
• Polyimides using acid dianhydrides and diamines having substituents such as fluoro groups, trifluoromethyl groups, and methyl groups on aromatic rings are known as polyimides with low yellowness.
• Polyimides with substituents such as fluoro groups, trifluoromethyl groups, and methyl groups may be exposed to trace amounts of outgassing generated from the glass supporting base material when held at high temperatures of 400°C or higher, or due to the contact between the polyimide and the supporting base material.
• the laminate of the present invention contains a polyimide resin with excellent heat resistance and a glass transition temperature of 400°C or higher, and furthermore, the first inorganic film has a supporting base when maintained at a high temperature of 400°C or higher.
• the polyimide resin (1) has a structural unit represented by the following general formula (1), and has a glass transition temperature of 400°C or higher.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring structure
• Y 1 is a single bond
• R 1 and R 2 each independently represent a methyl group, a fluoro group, or a trifluoromethyl group.
• h and i are integers of 0 to 4, and at least One is an integer from 1 to 4.
• n is 0, 1 or 2.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring.
• X 1 is obtained by removing two dicarboxylic anhydride moieties (four carboxy group moieties) from tetracarboxylic dianhydride, which is the raw material for structural unit A1 derived from tetracarboxylic dianhydride, which will be described later. is preferred.
• X 1 preferably includes a tetravalent group having an aromatic ring, more preferably consists of a tetravalent group having an aromatic ring, and X 1 is a tetravalent group having an aromatic ring. It is even more preferable to consist of only one.
• X 1 in the formula (1) is more preferably a tetravalent group represented by formula (3), a tetravalent group represented by formula (6), or a tetravalent group represented by formula (7).
• at least one selected from the group consisting of a tetravalent group represented by formula (8), a tetravalent group represented by formula (9), and a tetravalent group represented by formula (10) More preferably, a tetravalent group represented by formula (3), a tetravalent group represented by formula (6), a tetravalent group represented by formula (7), a tetravalent group represented by formula (8), and a tetravalent group represented by formula (10), more preferably a tetravalent group represented by formula (3), Contains at least one selected from the group consisting of a tetravalent group represented by formula (6), a tetravalent group represented by formula (7), and a tetravalent group represented by formula (8) , more preferably
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, p is an integer of 1 to 4, and k is 1 or 2.
• X 1 contains a tetravalent group represented by formula (7), the resulting laminate has excellent heat resistance.
• each R is independently a methyl group or a trifluoromethyl group, preferably a methyl group.
• p is an integer from 1 to 4, preferably p is 3.
• k is 1 or 2, preferably k is 2.
• the tetravalent group represented by formula (3) is preferably a tetravalent group represented by formula (31), and from the viewpoint of heat resistance and yellowness reduction, it is more preferably represented by formula (32). It is a tetravalent group represented by (In formula (31), each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, and p is an integer of 1 to 4.)
• Y 1 is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene groups, preferably a single bond, -COO-, -OCO-, and fluorenylidene groups. It is at least one selected from the group consisting of groups, and is more preferably a single bond. A plurality of Y 1 's may be the same or different.
• R 1 and R 2 each independently represent a methyl group, a fluoro group or a trifluoromethyl group, preferably a trifluoromethyl group.
• h and i are integers from 0 to 4, and at least one is an integer from 1 to 4.
• At least one of h and i is an integer from 1 to 4. That is, when n is 1, at least one of h and i is an integer from 1 to 4. When n is 2, at least one of h and the plurality of i's is an integer of 1 to 4. h and i are preferably 0 or 1, more preferably 1. n is 0, 1 or 2, preferably 1.
• the polyimide resin (1) may have a structural unit represented by the following general formula (11), and from the viewpoint of further increasing heat resistance, the polyimide resin (1) may have a structural unit represented by the following general formula (11). It is preferable that you do so.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring structure
• Y 3 is a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene (at least one selected from the group consisting of groups; q is 0, 1 or 2)
• X 1 is the same as in the formula (1), and is a tetravalent group having an alicyclic structure or an aromatic ring.
• X 1 is obtained by removing two dicarboxylic acid anhydride moieties (four carboxy group moieties) from tetracarboxylic dianhydride, which is the raw material for structural unit A1 derived from tetracarboxylic dianhydride, which will be described later. is preferred.
• Y 3 is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene groups, preferably a single bond, -COO-, -OCO-, and fluorenylidene groups.
• the group is at least one selected from the group consisting of groups, from the viewpoint of heat resistance, more preferably -COO- and -OCO-, and from the viewpoint of suppressing yellowing, more preferably a fluorenylidene group.
• a plurality of Y 3 may be the same or different.
• q is 0, 1 or 2, preferably 1.
• the molar ratio [(1):(11)] of the structural unit of formula (1) to the structural unit of formula (11) is preferably 20:
• the ratio is 80 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 80:20, even more preferably 50:50 to 80, from the viewpoint of suppressing yellowing. :20, more preferably 50:50 to 70:30. Further, from the viewpoint of heat resistance, the ratio is more preferably 20:80 to 70:30, even more preferably 20:80 to 50:50, and even more preferably 30:70 to 50:50.
• the polyimide (1) has a structural unit A1 derived from a tetracarboxylic dianhydride and a structural unit B1 derived from a diamine.
• the structural unit A1 is a structural unit derived from a tetracarboxylic dianhydride, and is not particularly limited as long as it is a structural unit derived from a tetracarboxylic dianhydride, but is preferably an aromatic tetracarboxylic dianhydride. and at least one selected from the group consisting of alicyclic tetracarboxylic dianhydride, more preferably a structural unit derived from aromatic tetracarboxylic dianhydride.
• aromatic tetracarboxylic dianhydrides that provide structural units derived from aromatic tetracarboxylic dianhydrides include biphenyltetracarboxylic dianhydride (BPDA), 9,9-bis(3,4-dicarboxyphenyl) ) Fluorenedioic anhydride (BPAF), pyromellitic dianhydride, 3,3',4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-diphenylsulfone tetra Carboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride and a compound represented by the following formula (a4).
• BPDA biphenyltetracarboxylic dianhydride
• BPAF 9,9
• the structural unit A1 preferably includes a structural unit (A11) derived from a compound represented by the following formula (a1), a structural unit (A12) derived from a compound represented by the following formula (a2), and a structural unit (A12) derived from the following formula (a4).
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, p is an integer of 1 to 4, and k is 1 or 2.
• the compound represented by formula (a1) is biphenyltetracarboxylic dianhydride (BPDA), and a specific example thereof is 3,3',4,4'-biphenyl represented by the following formula (a1s).
• BPDA biphenyltetracarboxylic dianhydride
• a1s 3,3',4,4'-biphenyl represented by the following formula (a1s).
• a1i examples include 2,2',3,3'-biphenyltetracarboxylic dianhydride (i-BPDA).
• s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by the following formula (a1s) is preferred.
• the compound represented by formula (a2) is 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF).
• each R is independently a methyl group or a trifluoromethyl group, preferably a methyl group.
• p is an integer from 1 to 4, preferably p is 3. That is, the structural unit (A14) derived from the compound represented by the formula (a4) above is the structural unit (A141) derived from the compound represented by the following formula (a41) from the viewpoint of heat resistance and yellowness reduction. It is preferable to contain a structural unit (A142) derived from a compound represented by the following formula (a42).
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, and p is an integer of 1 to 4.
• Examples of the alicyclic tetracarboxylic dianhydride that provides a structural unit derived from alicyclic tetracarboxylic dianhydride include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3, 4-Cyclobutanetetracarboxylic dianhydride, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (CpODA), bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BODA), decahydro-1,4:5,8-dimethanonaphthalene -2,3,6,7-tetracarboxylic dianhydride (DNDA), dicyclohexyltetracarboxylic dianhydride, 5,5'-(1,4-phenylene
• the structural unit A1 is preferably a structural unit (A13) derived from a compound represented by the following formula (a3), a structural unit (A15) derived from a compound represented by the following formula (a5), and a structural unit (A15) derived from a compound represented by the following formula (a5).
• the structural unit A1 may include structural units other than the structural unit derived from aromatic tetracarboxylic dianhydride and the structural unit derived from alicyclic tetracarboxylic dianhydride.
• Tetracarboxylic dianhydrides that provide such structural units include, but are not particularly limited to, aliphatic tetracarboxylic dianhydrides.
• Examples of the aliphatic tetracarboxylic dianhydride that provides structural units derived from aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride and the like.
• the number of structural units optionally included in the structural unit A1 may be one, or two or more.
• aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings
• alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more alicyclic rings.
• aliphatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing the above and not containing an aromatic ring
• aliphatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing neither an aromatic ring nor an alicyclic ring.
• the structural unit B1 is a structural unit derived from a diamine, and is not particularly limited as long as it is a structural unit derived from a diamine, but preferably includes a structural unit derived from an aromatic diamine, and more preferably contains a structural unit derived from an aromatic diamine. It is a structural unit derived from
• aromatic diamines that provide structural units derived from aromatic diamines include 2,2'-bis(trifluoromethyl)benzidine (TFMB), 4-aminophenyl-4-aminobenzoate (4-BAAB), and 1,4 -Bis(4-aminobenzoyloxy)benzene (ABHQ), bis(4-aminophenyl) terephthalate (APTP), 9,9-bis(4-aminophenyl)fluorene (BAFL), 3,5-diaminobenzoic acid ( 3,5-DABA), 1,4-phenylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-dimethylbiphenyl- 4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4-bis[2-(4-aminophenyl)-2-propyl]
• the compound represented by the following formula (b11), the compound represented by the following formula (b12), and the compound represented by the following formula (b13) at least one selected from the group consisting of a compound represented by the following formula (b2) and a compound represented by the following formula (b3), more preferably a compound represented by the following formula (b11), a compound represented by the following formula At least one selected from the group consisting of a compound represented by (b12), a compound represented by the following formula (b13), and a compound represented by the following formula (b2), more preferably a compound represented by the following formula (b11).
• the structural unit B1 is preferably a structural unit (B111) derived from a compound represented by the following formula (b11), or a compound represented by the following formula (b12).
• the structural unit B1 may include two or more types of structural units derived from aromatic diamines. When two or more types are included, it is even more preferable that a structural unit (B111) derived from a compound represented by the following formula (b11) and a structural unit (B12) derived from a compound represented by the following formula (b2) or Contains a structural unit (B13) derived from a compound represented by the following formula (b3), more preferably a structural unit (B111) derived from a compound represented by the following formula (b11) and the following formula (b2). Contains a structural unit (B12) derived from the represented compound.
• the compound represented by formula (b11) is 2,2'-bis(trifluoromethyl)benzidine (TFMB).
• the compound represented by formula (b12) is 2,2''-Bis(trifluoromethyl)[1,1':4',1''-terphenyl]-4,4''-diamine.
• the compound represented by formula (b13) is 2,2',5',2''-Tetra(trifluoromethyl)-[1,1':4',1''-terphenyl]-4,4''- It is diamine.
• the compound represented by formula (b2) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
• the compound represented by formula (b3) is 9,9-bis(4-aminophenyl)fluorene (BAFL).
• the structural unit B1 may include structural units other than those derived from aromatic diamine. Such structural units include, but are not particularly limited to, structural units derived from alicyclic diamines and structural units derived from aliphatic diamines. Examples of the alicyclic diamine that provides a structural unit derived from an alicyclic diamine include 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane. Examples of aliphatic diamines that provide structural units derived from aliphatic diamines include ethylene diamine and hexamethylene diamine. The number of structural units optionally included in the structural unit B1 may be one, or two or more.
• aromatic diamine means a diamine containing one or more aromatic rings
• alicyclic diamine means a diamine containing one or more alicyclic rings and no aromatic ring
• Group diamine means a diamine containing neither aromatic ring nor alicyclic ring.
• the polyimide resin (2) has a structural unit represented by the following general formula (2), and has a glass transition temperature of 400°C or higher.
• X 2 includes a tetravalent group represented by the following general formula (3)
• Y 2 is a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene (M is 0, 1 or 2.
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, p is an integer of 1 to 4, and k is 1 or 2.
• X 2 includes a tetravalent group represented by the general formula (3).
• X 2 is obtained by removing two dicarboxylic anhydride moieties (four carboxy group moieties) from tetracarboxylic dianhydride, which is the raw material for structural unit A2 derived from tetracarboxylic dianhydride, which will be described later. is preferred.
• each R is independently a methyl group or a trifluoromethyl group, preferably a methyl group.
• p is an integer from 1 to 4, preferably p is 3.
• k is 1 or 2, preferably k is 2.
• the tetravalent group represented by formula (3) is preferably a tetravalent group represented by formula (31), and from the viewpoint of heat resistance and yellowness reduction, it is more preferably represented by formula (32). It is a tetravalent group represented by (In formula (31), each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, and p is an integer of 1 to 4.)
• Y 2 is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene group, preferably selected from the group consisting of -COO- and -OCO- At least one A plurality of Y 2 may be the same or different.
• m is 0, 1 or 2, preferably 1.
• the polyimide (2) has a structural unit A2 derived from a tetracarboxylic dianhydride and a structural unit B2 derived from a diamine.
• the structural unit A2 is a structural unit derived from a tetracarboxylic dianhydride, and includes a structural unit (A21) derived from a compound represented by the following formula (a4).
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, p is an integer of 1 to 4, and k is 1 or 2.
• each R is independently a methyl group or a trifluoromethyl group, preferably a methyl group.
• p is an integer from 1 to 4, preferably p is 3. That is, from the viewpoint of heat resistance and yellowness reduction, the structural unit (A21) derived from the compound represented by the formula (a4) is the structural unit (A211) derived from the compound represented by the following formula (a41). It is preferable to include a structural unit (A212) derived from a compound represented by the following formula (a42).
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, and p is an integer of 1 to 4.
• the structural unit A2 may include structural units other than aromatic tetracarboxylic dianhydride.
• the tetracarboxylic dianhydride that provides such a structural unit is not particularly limited, but aromatic tetracarboxylic dianhydrides other than the structural unit (A21) derived from the compound represented by formula (a4) above may be used. Examples include structural units derived from alicyclic tetracarboxylic dianhydrides, structural units derived from alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides.
• the group tetracarboxylic dianhydride is the same as that explained in (constituent unit A1) in the polyimide resin (1).
• the number of structural units optionally included in the structural unit A2 may be one, or two or more.
• the structural unit B2 is a structural unit derived from a diamine, and is not particularly limited as long as it is a structural unit derived from a diamine, but preferably includes a structural unit derived from an aromatic diamine, and more preferably contains a structural unit derived from an aromatic diamine. It is a structural unit derived from
• aromatic diamines that provide structural units derived from aromatic diamines include 2,2'-bis(trifluoromethyl)benzidine (TFMB), 4-aminophenyl-4-aminobenzoate (4-BAAB), and 1,4 -Bis(4-aminobenzoyloxy)benzene (ABHQ), bis(4-aminophenyl) terephthalate (APTP), 9,9-bis(4-aminophenyl)fluorene (BAFL), 3,5-diaminobenzoic acid ( 3,5-DABA), 1,4-phenylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-dimethylbiphenyl- 4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4-bis[2-(4-aminophenyl)-2-propyl]
• the structural unit B2 preferably includes a structural unit (B21) derived from a compound represented by the following formula (b2).
• the compound represented by formula (b2) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
• the structural unit B2 may include structural units other than those derived from aromatic diamine.
• Diamines that provide such structural units include, but are not particularly limited to, alicyclic diamines and aliphatic diamines.
• Examples of the alicyclic diamine that provides a structural unit derived from an alicyclic diamine include 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane.
• Examples of aliphatic diamines that provide structural units derived from aliphatic diamines include ethylene diamine and hexamethylene diamine.
• the number of structural units optionally included in the structural unit B2 may be one, or two or more.
• the polyimide resin may be manufactured by any method, it is preferably manufactured by the following method.
• the polyimide resin may be obtained by directly obtaining polyimide by polymerizing diamine (hereinafter also referred to as diamine component) and tetracarboxylic dianhydride (hereinafter also referred to as tetracarboxylic acid component);
• a polyamic acid or an imide-amic acid copolymer, which is a precursor of a polyimide resin may be obtained by polymerizing the product, and then imidized to obtain a polyimide resin when producing a laminate.
• an imide-amic acid copolymer that is a polyimide resin precursor, a method for producing polyamic acid, and a method for producing a polyimide resin that directly obtains a polyimide resin will be described.
• Step 1 A step of reacting a tetracarboxylic dianhydride and a diamine in the presence of a solvent to obtain an imide oligomer.
• Step 2 The imide oligomer obtained in Step 1, and at least one of the tetracarboxylic dianhydride and the diamine.
• Step 1 is a step in which the tetracarboxylic dianhydride constituting the imide portion and the diamine are reacted in the presence of a solvent to obtain an imide oligomer.
• the amount of diamine relative to the tetracarboxylic dianhydride is preferably 1.01 to 2 mol, more preferably 1.05 to 1.9 mol, and 1.1 to 1.7 mol. It is even more preferable that there be.
• the imidization reaction it is preferable to use a Dean-Stark apparatus or the like to conduct the reaction while removing water generated during production. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
• imidization catalysts include base catalysts and acid catalysts.
• Base catalysts include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N
• organic base catalysts such as -dimethylaniline and N,N-diethylaniline
• inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate.
• examples of acid catalysts include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc. can be mentioned.
• the above imidization catalysts may be used alone or in combination of two or more.
• base catalysts are preferred, organic base catalysts are more preferred, one or more selected from triethylamine and triethylenediamine are still more preferred, and triethylamine is even more preferred.
• the temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°C from the viewpoint of reaction rate and suppression of gelation and the like. Further, the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
• a solution containing an imide oligomer dissolved in a solvent is obtained.
• the solution containing the imide oligomer obtained in Step 1 contains at least a portion of the components used as the tetracarboxylic dianhydride and diamine in Step 1 as unreacted monomers to the extent that the effects of the present invention are not impaired. You can leave it there.
• Step 2 is a step in which the imide oligomer obtained in Step 1 and at least one of a tetracarboxylic dianhydride and a diamine are mixed and polymerized.
• the diamine component relative to the tetracarboxylic acid component in Steps 1 and 2 as a whole is preferably 0.9 to 1.1 mol.
• step 2 the method for polymerizing the imide oligomer, tetracarboxylic dianhydride, and diamine obtained in step 1 is not particularly limited, and any known method can be used.
• a specific reaction method (1) an imide oligomer and at least one of a tetracarboxylic dianhydride and a diamine are charged into a reactor and heated at a temperature of 0 to 120°C, preferably 5 to 80°C for 1 to 72 hours.
• the concentration of the copolymer in the resulting solution is usually 1 to 50% by weight, preferably 3 to 35% by weight, and more preferably 5 to 30% by weight.
• Method for producing polyamic acid which is a polyimide resin precursor
• a preferred method for producing the polyimide resin precursor is to react a tetracarboxylic dianhydride and a diamine in the presence of a solvent to obtain a polyamic acid.
• a solvent for polymerizing tetracarboxylic dianhydride and diamine, and any known method can be used.
• a specific reaction method includes a method in which a solution containing a diamine and a solvent and a tetracarboxylic dianhydride are charged into a reactor and stirred at a temperature of 0 to 120°C, preferably 5 to 80°C for 1 to 72 hours. can be mentioned.
• the amount of diamine component relative to the tetracarboxylic acid component is preferably 0.9 to 1.1 mol.
• the concentration of polyamic acid in the resulting solution is usually 1 to 50% by weight, preferably 3 to 35% by weight, and more preferably 5 to 30% by weight.
• a preferred manufacturing method for directly obtaining a polyimide resin is a method in which a tetracarboxylic dianhydride and a diamine are reacted in the presence of a solvent to obtain a polyimide resin.
• a specific reaction method is as follows: (1) A solution containing a diamine and a solvent and a tetracarboxylic dianhydride are charged into a reactor, stirred at 10 to 110°C for 0.5 to 30 hours as necessary, and then (2) A method in which a solution containing a diamine and a solvent and tetracarboxylic dianhydride are charged into a reactor, and the temperature is immediately raised to carry out an imidization reaction. .
• the imidization reaction it is preferable to use a Dean-Stark apparatus or the like to conduct the reaction while removing water generated during production. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
• imidization catalysts include base catalysts and acid catalysts.
• Base catalysts include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N
• organic base catalysts such as -dimethylaniline and N,N-diethylaniline
• inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate.
• examples of acid catalysts include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc. can be mentioned.
• the above imidization catalysts may be used alone or in combination of two or more.
• base catalysts are preferred, organic base catalysts are more preferred, one or more selected from triethylamine and triethylenediamine are still more preferred, and triethylamine is even more preferred.
• the temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°C from the viewpoint of reaction rate and suppression of gelation and the like. Further, the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
• the concentration of polyimide in the resulting solution is usually in the range of 1 to 50% by weight, preferably in the range of 3 to 35% by weight, and more preferably in the range of 5 to 30% by weight.
• the tetracarboxylic dianhydride used as a raw material in the production method is the tetracarboxylic dianhydride described in the structural unit A1 of the polyimide resin (1), and the tetracarboxylic dianhydride described in the structural unit A2 of the polyimide resin (2).
• it is a tetracarboxylic dianhydride.
• the tetracarboxylic dianhydride include acid dianhydrides, but are not limited thereto, and derivatives thereof may be used as long as they provide the structural unit A1 or the structural unit A2.
• Such derivatives include tetracarboxylic acids (free acids) and alkyl esters of the tetracarboxylic acids. Among these, acid dianhydrides are preferred.
• the diamine used as a raw material in the production method is preferably the diamine described in the structural unit B1 of the polyimide resin (1) and the diamine described in the structural unit B2 of the polyimide resin (2).
• the diamine include diamine, but the diamine is not limited thereto, and derivatives thereof may be used as long as they provide the structural unit B in the polymer. Examples of such derivatives include diisocyanates corresponding to diamines. Among these, diamines are preferred.
• Terminal sealing agent Furthermore, in addition to the above-mentioned tetracarboxylic acid component and diamine component, a terminal capping agent may be used in the production of the polymer.
• the terminal capping agent is preferably used in step 2 in the production of the imide-amic acid copolymer.
• monoamines or dicarboxylic acids are preferable.
• the amount of the terminal capping agent to be introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, per 1 mol of the tetracarboxylic acid component.
• Examples of monoamine terminal capping agents include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3- Ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, etc. are recommended. Among these, benzylamine and aniline can be preferably used.
• dicarboxylic acid terminal capping agent dicarboxylic acids are preferred, and a portion thereof may be ring-closed.
• phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1 , 2-dicarboxylic acid, etc. are recommended.
• phthalic acid and phthalic anhydride can be preferably used.
• the solvent used in the method for producing a polymer may be any solvent as long as it can dissolve the produced polymer. Examples include aprotic solvents, phenolic solvents, ether solvents, carbonate solvents, and the like.
• the aprotic solvent include amide solvents such as cyclic amides and chain amides, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, and ester solvents containing cyclic esters.
• the solvent preferably contains at least one selected from the group consisting of a cyclic amide, a chain amide, and a cyclic ester, and more preferably a cyclic amide.
• the cyclic amide include N-methylpyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, and the like, with N-methylpyrrolidone being preferred.
• Examples of the chain amide include N,N-dimethylformamide, N,N-dimethylacetamide, and tetramethylurea.
• Examples of the cyclic ester include ⁇ -butyrolactone and ⁇ -valerolactone.
• Other ester solvents include acetic acid (2-methoxy-1-methylethyl) and the like.
• Examples of the phosphorus-containing amide solvent include hexamethylphosphoric amide, hexamethylphosphine triamide, and the like.
• Examples of the sulfur-containing solvent include dimethylsulfone, dimethylsulfoxide, and sulfolane.
• Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, and the like.
• phenolic solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4 -xylenol, 3,5-xylenol, etc.
• ether solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, and bis[2-(2-methoxyethoxy)ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
• carbonate solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, and the like.
• it preferably contains at least one selected from the group consisting of cyclic amides, chain amides, and cyclic esters, more preferably contains cyclic amides, and still more preferably contains N-methylpyrrolidone.
• the above solvents may be used alone or in combination of two or more.
• the polyimide resin precursor used as a raw material for the polyimide resin is as shown below. That is, the polyimide resin precursor preferably has a structural unit represented by the following general formula (4) or a structural unit represented by the following general formula (5).
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• Y 1 is a single bond
• R 1 and R 2 each independently represent a methyl group, a fluoro group, or a trifluoromethyl group.
• R 3 and R 4 each independently represent a hydrogen atom.
• X 2 includes a tetravalent group represented by the following general formula (3)
• Y 2 is a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene
• R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• m is 0, 1 or 2)
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group
• p is an integer of 1 to 4
• k is 1 or 2.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring.
• X 1 is obtained by removing two dicarboxylic acid anhydride moieties (four carboxy group moieties) from tetracarboxylic dianhydride, which is the raw material for structural unit A1 derived from tetracarboxylic dianhydride, which will be described later. is preferred.
• X 1 preferably includes a tetravalent group having an aromatic ring, more preferably consists of a tetravalent group having an aromatic ring, and X 1 is a tetravalent group having an aromatic ring. It is even more preferable to consist of only one.
• X 1 in the formula (4) is more preferably a tetravalent group represented by formula (3), a tetravalent group represented by formula (6), or a tetravalent group represented by formula (7).
• at least one selected from the group consisting of a tetravalent group represented by formula (8), a tetravalent group represented by formula (9), and a tetravalent group represented by formula (10) More preferably, a tetravalent group represented by formula (3), a tetravalent group represented by formula (6), a tetravalent group represented by formula (7), a tetravalent group represented by formula (8), and a tetravalent group represented by formula (10), more preferably a tetravalent group represented by formula (3), Contains at least one selected from the group consisting of a tetravalent group represented by formula (6), a tetravalent group represented by formula (7), and a tetravalent group represented by formula (8) , more
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, p is an integer of 1 to 4, and k is 1 or 2.
• X 1 contains a tetravalent group represented by formula (7), the resulting laminate has excellent heat resistance.
• each R is independently a methyl group or a trifluoromethyl group, preferably a methyl group.
• p is an integer from 1 to 4, preferably p is 3.
• k is 1 or 2, preferably k is 2.
• the tetravalent group represented by formula (3) is preferably a tetravalent group represented by formula (31), and from the viewpoint of heat resistance and yellowness reduction, it is more preferably represented by formula (32). It is a tetravalent group represented by (In formula (31), each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, and p is an integer of 1 to 4.)
• Y 1 is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene groups, preferably a single bond, -COO-, -OCO-, and fluorenylidene groups. It is at least one selected from the group consisting of groups, and is more preferably a single bond.
• a plurality of Y 1 's may be the same or different.
• R 1 and R 2 each independently represent a methyl group, a fluoro group or a trifluoromethyl group, preferably a trifluoromethyl group.
• R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• h and i are integers from 0 to 4, and at least one is an integer from 1 to 4. At least one of h and i is an integer from 1 to 4. That is, when n is 1, at least one of h and i is an integer from 1 to 4. When n is 2, at least one of h and the plurality of i's is an integer of 1 to 4.
• h and i are preferably 0 or 1, more preferably 1.
• n is 0, 1 or 2, preferably 1.
• X 2 includes a tetravalent group represented by the general formula (3).
• X 2 is obtained by removing two dicarboxylic anhydride moieties (four carboxy group moieties) from the tetracarboxylic dianhydride that is the raw material for the structural unit A2 derived from the above-mentioned tetracarboxylic dianhydride. is preferred.
• R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• each R is independently a methyl group or a trifluoromethyl group, preferably a methyl group.
• p is an integer from 1 to 4, preferably p is 3.
• k is 1 or 2, preferably k is 2.
• the tetravalent group represented by formula (3) is preferably a tetravalent group represented by formula (31), and from the viewpoint of heat resistance and yellowness reduction, it is more preferably represented by formula (32). It is a tetravalent group represented by (In formula (31), each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, and p is an integer of 1 to 4.)
• Y 2 is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene group, preferably selected from the group consisting of -COO- and -OCO- At least one A plurality of Y 2 may be the same or different.
• m is 0, 1 or 2, preferably 1.
• the polyimide resin precursor having the structural unit of formula (4) has a structural unit A1 derived from tetracarboxylic dianhydride and a structural unit B1 derived from diamine, which are the structural units of polyimide (1) described above. is preferable, and more preferable structural units are also as described above.
• the polyimide resin precursor having the structural unit of formula (5) has structural unit A2 derived from tetracarboxylic dianhydride and structural unit B2 derived from diamine, which are the structural units of polyimide (2) described above. is preferable, and more preferable structural units are also as described above.
• the polyimide resin precursor may be an imide-amic acid copolymer, and in the case of an imide-amic acid copolymer, the polyimide portion is the polyimide resin (1) or the polyimide resin (2). ) preferably has the same structural unit as the polyimide resin (1), and preferably has the same structural unit as the polyimide resin (1).
• a preferable imide-amic acid copolymer has the same structural unit of the general formula (1) as the polyimide resin (1).
• the polyamic acid moiety may have a structural unit represented by the following general formula (12), and from the viewpoint of further increasing heat resistance, the imide-amic acid copolymer may have a structural unit represented by the following general formula (12).
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring structure
• R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or Represents an alkylsilyl group having 3 to 9 carbon atoms.
• Y 3 is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene group.
• q is 0, 1 or 2)
• X 1 is the same as in the above formula (1), and is a tetravalent group having an alicyclic structure or an aromatic ring.
• X 1 is obtained by removing two dicarboxylic anhydride moieties (four carboxy group moieties) from the tetracarboxylic dianhydride that is the raw material for the structural unit A1 derived from the above-mentioned tetracarboxylic dianhydride. is preferred.
• R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• Y 3 is each independently at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene group, preferably a single bond, -COO-, At least one selected from the group consisting of -OCO- and fluorenylidene groups, from the viewpoint of heat resistance, -COO- and -OCO-, and from the viewpoint of suppressing yellowing, more preferably fluorenylidene groups.
• a plurality of Y 3 may be the same or different.
• q is 0, 1 or 2, preferably 1.
• the molar ratio of the structural unit of formula (1) to the structural unit of formula (12) [(1):(12) ] is preferably 20:80 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 80:20 from the viewpoint of suppressing yellowing, and even more
• the ratio is preferably 50:50 to 80:20, and even more preferably 50:50 to 70:30. Further, from the viewpoint of heat resistance, the ratio is more preferably 20:80 to 70:30, even more preferably 20:80 to 50:50, and even more preferably 30:70 to 50:50.
• a varnish containing a polyimide resin precursor and an organic solvent is applied to a supporting base material made of glass and a first inorganic film laminated on the supporting base material, and then heated at 400°C or higher. It is preferable to obtain it by a manufacturing method including a step of. Next, the varnish used for manufacturing the laminate will be explained.
• the varnish contains the polyimide resin and an organic solvent, or contains a polyimide resin precursor and an organic solvent.
• the solvent may be any solvent as long as it dissolves the polyimide resin or polyimide resin precursor, and is not particularly limited.
• the above-mentioned compounds may be used alone or in a mixture of two or more as solvents used for producing the polyimide resin or polyimide resin precursor. It is preferable to use it.
• it preferably contains at least one selected from the group consisting of cyclic amides, chain amides, and cyclic esters, more preferably contains cyclic amides, and still more preferably contains N-methylpyrrolidone.
• the varnish may be the polyimide resin solution or polyimide resin precursor solution obtained by the above-mentioned method for producing a polyimide resin or polyimide resin precursor, or may be a solution with a solvent added thereto, or may be prepared by adding a solvent, etc. It may also be possible to reduce the amount of solvent.
• the varnish can further contain an imidization catalyst and a dehydration catalyst from the viewpoint of efficiently progressing imidization of the amic acid moiety.
• the imidization catalyst may be any imidization catalyst having a boiling point of 40° C. or higher and 180° C. or lower, and amine compounds having a boiling point of 180° C. or lower are preferred. If the imidization catalyst has a boiling point of 180° C. or lower, there is no risk that the polyimide film obtained during drying at high temperature after forming the laminate will be colored and the appearance will be impaired. Moreover, if the imidization catalyst has a boiling point of 40° C.
• An amine compound suitably used as an imidization catalyst includes pyridine or picoline.
• the above imidization catalysts may be used alone or in combination of two or more.
• the dehydration catalyst include acid anhydrides such as acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride; carbodiimide compounds such as dicyclohexylcarbodiimide; and the like. These may be used alone or in combination of two or more.
• the varnish preferably contains 3 to 40% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass of polyimide resin or polyimide resin precursor.
• the viscosity of the varnish is preferably 1 to 200 Pa ⁇ s, more preferably 2 to 20 Pa ⁇ s.
• the viscosity of the varnish is a value measured at 25°C using an E-type viscometer.
• the varnish may contain inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, antifoaming agents, optical brighteners, crosslinking agents, etc. within the range that does not impair the required properties of the polyimide film. It may also contain various additives such as a polymerization initiator, a photosensitive agent, and the like.
• the supporting base material used in the laminate of the present invention is made of glass.
• the type of glass is not particularly limited, and non-alkali glass (borosilicate glass), alkali glass, soda glass, non-fluorescent glass, phosphate glass, boric acid glass, quartz, etc. can be used.
• the top surface of the glass substrate has high flatness. Specifically, the surface roughness Rmax is preferably 10 ⁇ m or less, and more preferably 1 ⁇ m or less.
• a first inorganic film is laminated on a supporting base material made of glass, a polyimide resin is laminated on the first inorganic membrane, and a second inorganic membrane is laminated on the polyimide resin. be done. Further, a TFT functional layer is laminated on the second inorganic film in the laminate thus obtained, the first inorganic film is peeled off from the interface with the polyimide resin, and the second inorganic film is separated from the polyimide resin.
• a laminate for a TFT substrate (second laminate) in which an inorganic film and a TFT functional layer are laminated is also manufactured.
• the TFT substrate laminate is used as a TFT substrate and is included in an electronic device. That is, the laminate of the present invention (the first laminate) is used as a laminate of raw materials for a TFT substrate.
• At least one of the first inorganic film and the second inorganic film preferably contains silicon, and at least one of the first inorganic film and the second inorganic film contains silicon oxide, More preferably, at least one selected from silicon nitride and amorphous silicon is included, and at least one of the first inorganic film and the second inorganic film is selected from silicon oxide, silicon nitride, and amorphous silicon. It is more preferable that at least one of the first inorganic film and the second inorganic film is made of at least one selected from silicon oxide and amorphous silicon. .
• both the first inorganic film and the second inorganic film contain silicon, and the first inorganic film and the second inorganic film are made of silicon oxide, silicon nitride, or amorphous silicon. It is more preferable that the first inorganic film and the second inorganic film contain at least one selected from silicon oxide, silicon nitride, and amorphous silicon. It is even more preferable that the first inorganic film and the second inorganic film are made of at least one selected from silicon oxide and amorphous silicon.
• the first inorganic film and the second inorganic film are insulating films. That is, the second inorganic film functions as an insulating film and a barrier film between the polyimide film and the TFT functional layer in the TFT substrate laminate described later, and also functions as a buffer film.
• the thickness of the first inorganic film is preferably 1 to 1,000 nm, more preferably 1 to 400 nm, still more preferably 10 to 300 nm, even more preferably 20 to 200 nm.
• the thickness of the second inorganic film is preferably 1 to 1,000 nm, more preferably 1 to 400 nm, still more preferably 10 to 300 nm, even more preferably 20 to 200 nm.
• the laminate of the present invention may be obtained by any manufacturing method as long as it has the above structure, but it is preferably manufactured by the following method. Specifically, examples include a method of manufacturing using a varnish containing the polyimide resin, and a method of manufacturing using the polyimide resin precursor.
• a method for manufacturing a laminate using a varnish containing a polyimide resin includes applying a varnish containing a polyimide resin and an organic solvent to a supporting base material made of glass and a first inorganic film laminated on the supporting base material, A method for producing a laminate comprising a step of heating at 400° C.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• Y 1 is a single bond
• R 1 and R 2 each independently represent a methyl group, a fluoro group, or a trifluoromethyl group.
• h and i are integers of 0 to 4, and at least One is an integer from 1 to 4.
• X 2 includes a tetravalent group represented by the following general formula (3), Y 2 is a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene (M is at least one selected from the group consisting of groups. m is 0, 1 or 2.)
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group, p is an integer of 1 to 4, and k is 1 or 2.
• a method for manufacturing a laminate using a varnish containing a polyimide resin precursor includes applying a polyimide resin precursor and an organic solvent to a supporting base material made of glass and a first inorganic film laminated on the supporting base material.
• a method for producing a laminate comprising applying a varnish containing varnish and heating at 400°C or higher, and laminating a second inorganic film, wherein the polyimide resin precursor has a structural unit represented by the following general formula (4). Or it has a structural unit of the following general formula (5).
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• Y 1 is a single bond
• R 1 and R 2 each independently represent a methyl group, a fluoro group, or a trifluoromethyl group.
• R 3 and R 4 each independently represent a hydrogen atom.
• h and i are integers of 0 to 4, and at least one is an integer of 1 to 4.
• X 2 includes a tetravalent group represented by the following general formula (3)
• Y 2 is a single bond, -NHCO-, -CONH-, -COO-, -OCO-, and fluorenylidene
• R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• m is 0, 1 or 2)
• each R is independently a methyl group, a fluoro group, or a trifluoromethyl group
• p is an integer of 1 to 4
• k is 1 or 2.
• All of the above manufacturing methods include the step of applying varnish to a supporting base material made of glass and a first inorganic film laminated on the supporting base material, and heating it at 400° C. or higher.
• the varnish used in the step is the one described in the above section [Varnish], and the preferred varnish is also the same.
• the polyimide resin and polyimide resin precursor are also those explained in the above-mentioned [polyimide resin] and [polyimide resin precursor] sections, and preferred polyimide resins and polyimide resin precursors are also the same.
• a varnish containing a polyimide resin or a polyimide resin precursor and an organic solvent is applied to a supporting base material made of glass and a first inorganic film laminated on the supporting base material, and heated at 400°C or higher. It has a heating step.
• a preliminary laminate (according to the present invention) consisting of a supporting base material made of glass, a first inorganic film laminated on the supporting base material, and a polyimide resin laminated on the first inorganic film is obtained.
• a laminate which is a raw material for a laminate is obtained.
• the laminate of the present invention is obtained by laminating a second inorganic film on the polyimide resin of the preliminary laminate.
• the heating temperature is preferably 400°C or higher, more preferably 400 to 500°C.
• the heating time is usually 1 minute to 6 hours, preferably 5 minutes to 2 hours, more preferably 15 minutes to 1 hour.
• Examples of the heating atmosphere include air gas, nitrogen gas, oxygen gas, hydrogen gas, nitrogen/hydrogen mixed gas, etc., but in order to suppress coloring of the obtained polyimide resin, nitrogen gas with an oxygen concentration of 100 ppm or less, hydrogen concentration A nitrogen/hydrogen mixed gas containing 0.5% or less is preferred.
• the second inorganic film may be laminated by any method, but it is preferably laminated by sputtering, CVD film formation, or vacuum evaporation.
• a laminate for a TFT substrate (polyimide resin/second inorganic film/TFT functional layer) contained in an electronic device is also included in the present invention.
• the TFT substrate laminate is included in an electronic device as a TFT substrate.
• a TFT functional layer is laminated on the second inorganic film in the laminate (first laminate), and the first inorganic film is formed at an interface with a polyimide resin. It can be manufactured by peeling it off from the substrate.
• the laminate for a TFT substrate is the laminate described above (first laminate), that is, a laminate including a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film, and the laminate includes the above-mentioned laminate in the laminate. It can be manufactured by a method in which a TFT functional layer is laminated on a second inorganic film, and the first inorganic film is peeled off from the interface with the polyimide resin.
• the polyimide resin contained in the laminate has a structural unit represented by the following general formula (1) or a structural unit represented by the following general formula (2), and has a glass transition temperature of 400°C or higher.
• the method for manufacturing the first laminate is as described above.
• a TFT functional layer is laminated on the second inorganic film in the first laminate (a laminate consisting of a support base material, a first inorganic film, a polyimide resin, and a second inorganic film).
• the second inorganic film functions as an insulating film and a barrier film between the polyimide film and the TFT functional layer in the TFT substrate laminate, and serves as a buffer when forming the TFT functional layer. Functions as a membrane.
• the TFT functional layer is not particularly limited as long as it is a functional layer that can express the functions of the electronic device containing the TFT substrate laminate, but examples include amorphous silicon, indium gallium zinc oxide (IGZO), and low temperature polyester.
• the layer uses at least one semiconductor selected from the group consisting of silicon (LTPS).
• LTPS silicon
• the method for manufacturing the TFT functional layer is not particularly limited, an example will be shown below.
• a film of metal or the like is formed by sputtering, vapor deposition, CVD, printing, etc., and after coating with a resist and a photomask, exposure is performed, and further etching is performed to form electrodes and metal wiring.
• a TFT functional layer can be obtained by laminating one or more insulating films, semiconductor films, further electrodes, and metal wiring thereon, and finally forming a protective layer.
• Preferred specific examples of metals used for the electrodes and metal wiring include molybdenum, aluminum, and the like.
• ITO indium tin oxide
• the electronic device of the present invention includes the TFT substrate laminate described above. That is, a TFT functional layer is laminated on the second inorganic film in the first laminate (a laminate including a support base material, a first inorganic film, a polyimide resin, and a second inorganic film), and
• the present invention includes a laminate for a TFT substrate obtained by a manufacturing method in which one inorganic film is peeled from an interface with a polyimide resin.
• the TFT substrate laminate obtained by laminating a TFT functional layer on a film made of polyimide resin and an insulating film can be used for various purposes, such as liquid crystal display panels, OLEDs, quantum dot LED panels, and mini LED display panels. , used as a substrate for electronic devices for display devices such as micro LED display panels.
• film thickness of post-baked polyimide film was measured using a digital gauge SA-S110/03N manufactured by Citizen Fine Device Co., Ltd.
• Tg Glass transition temperature of polyimide film after post-baking Using a thermomechanical analyzer "TMA 7100C” manufactured by Hitachi High-Tech Science Co., Ltd., sample size 4 mm x 20 mm, tensile mode, load 50 mN, temperature increase rate 10 ° C / min from 40 ° C to 500 ° C The temperature was raised and TMA measurement was performed, and the point where the inflection point of elongation was observed was determined as the glass transition temperature (Tg) by extrapolation.
• TMA 7100C thermomechanical analyzer
• tetracarboxylic acid component and diamine component used in Examples and Comparative Examples, and their abbreviations are as follows.
• ⁇ Tetracarboxylic acid component> CpODA: norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (represented by formula (a3)) compound)
• s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation, compound represented by formula (a1s))
• BPAF 9,9-bis(3,4-dicarboxyphenyl)fluorenic acid anhydride (manufactured by JFE Chemical Co., Ltd.; compound represented by formula (a2))
• TMPBP-TME 2,2',3,3',5,5'-hexamethyl[1,1'-bipheny
• NMP N-methyl-2-pyrrolidone (manufactured by Tokyo Pure Chemical Industries, Ltd.)
• GBL ⁇ -butyrolactone (manufactured by Mitsubishi Chemical Corporation)
• TEA Triethylamine (manufactured by Kanto Kagaku Co., Ltd.)
• Example 1 Manufacture of polyimide varnish
• BAFL 13.938 g (0.040 mol) was placed in a 1 L 5-necked round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap.
• 19.214 g (0.060 mol) of TFMB and 126.903 g of GBL were added, and the system was stirred at a rotational speed of 200 rpm under a nitrogen atmosphere at a system temperature of 70° C. to obtain a solution.
• a SiO 2 film with a thickness of 300 ⁇ was formed as a first inorganic film on a supporting base material which was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick) by sputtering.
• the above-mentioned polyimide varnish was applied to the surface on which the first inorganic film of the supporting base material made of glass on which the SiO 2 film was laminated as the first inorganic film was applied, and the polyimide varnish was kept on a hot plate at 80° C. for 20 minutes.
• a laminate (supporting base material/first inorganic film/polyimide resin/second inorganic film) was manufactured by simulating the manufacturing process of a display for an image display device. Specifically, a second inorganic film was applied to the polyimide resin side of the three-layer preliminary laminate (supporting base material/first inorganic film/polyimide resin) obtained by the above method by sputtering.
• a 300 ⁇ SiO 2 film was formed, and a laminate consisting of a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film (supporting base material/first inorganic film/polyimide resin/second inorganic film) was formed. membrane) was obtained.
• Example 2 In Example 1, the laminate (supporting base material/first inorganic film/polyimide resin/second An inorganic film) and a polyimide film (post-baked polyimide film) were obtained. Table 1 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate.
• a-Si amorphous silicon
• Comparative example 1 In Example 1, the laminate (supporting base material/polyimide resin/second inorganic film) and polyimide film (after post-baking) were prepared in the same manner as in Example 1, except that the first inorganic film was not laminated. Polyimide film) was obtained. Table 1 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate. Note that the supporting base material is a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick).
• Example 3 Manufacture of polyimide varnish
• BAFL 13.938 g (0.040 mol) was placed in a 1 L 5-necked round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap.
• 19.214 g (0.060 mol) of TFMB and 93.686 g of GBL were added, and the system was stirred at a rotational speed of 200 rpm under a nitrogen atmosphere at a system temperature of 70° C. to obtain a solution.
• a SiO 2 film with a thickness of 300 ⁇ was formed as a first inorganic film on a supporting base material which was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick) by sputtering.
• the above-mentioned polyimide varnish was applied to the surface on which the first inorganic film of the supporting base material made of glass on which the SiO 2 film was laminated as the first inorganic film was applied, and the polyimide varnish was kept on a hot plate at 80° C. for 20 minutes.
• a laminate (supporting base material/first inorganic film/polyimide resin/second inorganic film) was manufactured by simulating the manufacturing process of a display for an image display device. Specifically, a second inorganic film was applied to the polyimide resin side of the three-layer preliminary laminate (supporting base material/first inorganic film/polyimide resin) obtained by the above method by sputtering.
• a 300 ⁇ SiO 2 film was formed, and a laminate consisting of a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film (supporting base material/first inorganic film/polyimide resin/second inorganic film) was formed. membrane) was obtained.
• Comparative example 2 In Example 3, the laminate (supporting base material/polyimide resin/second inorganic film) and polyimide film (after post-baking) were prepared in the same manner as in Example 3, except that the first inorganic film was not laminated. Polyimide film) was obtained. Table 1 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate. Note that the supporting base material is a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick).
• Example 4 Manufacture of polyamic acid varnish 22.825 g (0.100 mol) of 4-BAAB was placed in a 1 L 5-necked round-bottomed flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a Dean Stark fitted with a cooling tube, a thermometer, and a glass end cap. ), 383.95.975 g of NMP was added, and the system was stirred at a rotational speed of 200 rpm under a nitrogen atmosphere at a system temperature of 70° C. to obtain a solution.
• a SiO 2 film with a thickness of 300 ⁇ was formed as a first inorganic film on a supporting base material which was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick) by sputtering.
• the above-mentioned polyimide varnish was applied to the surface on which the first inorganic film of the supporting base material made of glass on which the SiO 2 film was laminated as the first inorganic film was applied, and the polyimide varnish was kept on a hot plate at 80° C. for 20 minutes. Thereafter, the temperature was raised to 400°C at a temperature increase rate of 5°C/min in a nitrogen atmosphere, and the solvent was evaporated by heating at 400°C in a hot air dryer for 30 minutes.
• a three-layer preliminary laminate (supporting base material/first inorganic membrane/polyimide resin) was obtained.
• a laminate (supporting base material/first inorganic film/polyimide resin/second inorganic film) was manufactured by simulating the manufacturing process of a display for an image display device.
• a second inorganic film was applied to the polyimide resin side of the three-layer preliminary laminate (supporting base material/first inorganic film/polyimide resin) obtained by the above method by sputtering.
• a 300 ⁇ SiO 2 film was formed, and a laminate consisting of a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film (supporting base material/first inorganic film/polyimide resin/second inorganic film) was formed. membrane) was obtained.
• Example 5 In Example 4, the laminate (supporting base material/first inorganic film/polyimide resin/second An inorganic film) and a polyimide film (post-baked polyimide film) were obtained. Table 2 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate. Furthermore, as the first inorganic film, an amorphous silicon (a-Si) film with a thickness of 200 ⁇ was formed by CVD on a supporting base material that was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick). It was filmed.
• a-Si amorphous silicon
• Example 4 the laminate (supporting base material/polyimide resin/second inorganic film) and polyimide film (after post-baking) were prepared in the same manner as in Example 4, except that the first inorganic film was not laminated. Polyimide film) was obtained. Table 2 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate.
• the supporting base material is a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick).
• Example 6 Manufacture of polyamic acid varnish
• Diamine (b12) 18.260 g (0.080 g mol), 6.416 g (0.020 mol) of TFMB, and 392.291 g of NMP were added, and the mixture was stirred at a rotation speed of 200 rpm at a system temperature of 70° C. under a nitrogen atmosphere to obtain a solution.
• 61.859 g (0.100 mol) of TMPBP-TME and 98.073 g of NMP were added all at once, and the mixture was stirred for 5 hours while being maintained at 70° C. using a mantle heater. Thereafter, 288.449 g of NMP was added, and the mixture was further stirred for about 1 hour to be homogenized to obtain a polyamic acid varnish with a solid content concentration of 10% by mass.
• a SiO 2 film with a thickness of 300 ⁇ was formed as a first inorganic film on a supporting base material which was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick) by sputtering.
• the polyimide varnish was applied to the surface on which the first inorganic film of the supporting base material made of glass was laminated with the SiO 2 film as the first inorganic film, and was kept on a hot plate at 80°C for 20 minutes. Thereafter, the temperature was raised to 400°C at a temperature increase rate of 5°C/min in a nitrogen atmosphere, and the solvent was evaporated by heating at 400°C in a hot air dryer for 30 minutes.
• a three-layer preliminary laminate (supporting base material/first inorganic membrane/polyimide resin) was obtained.
• a laminate (supporting base material/first inorganic film/polyimide resin/second inorganic film) was manufactured by simulating the manufacturing process of a display for an image display device.
• a second inorganic film was applied to the polyimide resin side of the three-layer preliminary laminate (supporting base material/first inorganic film/polyimide resin) obtained by the above method by sputtering.
• a 300 ⁇ SiO 2 film was formed, and a laminate consisting of a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film (supporting base material/first inorganic film/polyimide resin/second inorganic film) was formed. membrane) was obtained.
• Example 6 Comparative example 4 In Example 6, the laminate (supporting base material/polyimide resin/second inorganic film) and polyimide film (after post-baking) were prepared in the same manner as in Example 6, except that the first inorganic film was not laminated. Polyimide film) was obtained. Table 2 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate. Note that the supporting base material is a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick).
• Example 7 Manufacture of imide-amic acid copolymer varnish
• 9.607 g (0.030 mol) of TFMB was placed in a 1 L 5-necked round-bottomed flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap.
• 46.380 g of NMP were added, and the system was stirred at a rotational speed of 200 rpm under a nitrogen atmosphere at a system temperature of 70° C. to obtain a solution.
• a SiO 2 film with a thickness of 300 ⁇ was formed as a first inorganic film on a supporting base material which was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick) by sputtering.
• the above-mentioned polyimide varnish was applied to the surface on which the first inorganic film of the supporting base material made of glass on which the SiO 2 film was laminated as the first inorganic film was applied, and the polyimide varnish was kept on a hot plate at 80° C. for 20 minutes.
• the temperature was raised to 430°C at a temperature increase rate of 5°C/min in a nitrogen atmosphere, and heated at 430°C for 60 minutes in a hot air dryer to evaporate the solvent and thermally imidize the supporting base material, the first A three-layer preliminary laminate (supporting base material/first inorganic membrane/polyimide resin) consisting of an inorganic membrane and a polyimide resin was obtained.
• a laminate supporting base material/first inorganic film/polyimide resin/second inorganic film
• a second inorganic film was applied to the polyimide resin side of the three-layer preliminary laminate (supporting base material/first inorganic film/polyimide resin) obtained by the above method by sputtering.
• a 300 ⁇ SiO 2 film was formed, and a laminate consisting of a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film (supporting base material/first inorganic film/polyimide resin/second inorganic film) was formed. membrane) was obtained.
• Example 8 In Example 7, the laminate (supporting base material/first inorganic film/polyimide resin/second An inorganic film) and a polyimide film (post-baked polyimide film) were obtained. Table 3 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate.
• a-Si amorphous silicon
• Example 7 Comparative example 5 In Example 7, the laminate (supporting base material/polyimide resin/second inorganic film) and polyimide film (after post-baking) were prepared in the same manner as in Example 7, except that the first inorganic film was not laminated. Polyimide film) was obtained. Table 3 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate. Note that the supporting base material is a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick).
• Example 9 Manufacture of imide-amic acid copolymer varnish 12.829 g (0.040 mol) of TFMB was placed in a 1 L 5-necked round-bottomed flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. and 85.061 g of NMP were added and stirred at a rotational speed of 200 rpm at a system temperature of 70° C. and a nitrogen atmosphere to obtain a solution.
• a SiO 2 film with a thickness of 300 ⁇ was formed as a first inorganic film on a supporting base material which was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick) by sputtering.
• the above-mentioned polyimide varnish was applied to the surface on which the first inorganic film of the supporting base material made of glass on which the SiO 2 film was laminated as the first inorganic film was applied, and the polyimide varnish was kept on a hot plate at 80° C. for 20 minutes.
• the temperature was raised to 430°C at a temperature increase rate of 5°C/min in a nitrogen atmosphere, and heated at 430°C for 60 minutes in a hot air dryer to evaporate the solvent and thermally imidize the supporting base material, the first A three-layer preliminary laminate (supporting base material/first inorganic membrane/polyimide resin) consisting of an inorganic membrane and a polyimide resin was obtained.
• a laminate supporting base material/first inorganic film/polyimide resin/second inorganic film
• a second inorganic film was applied to the polyimide resin side of the three-layer preliminary laminate (supporting base material/first inorganic film/polyimide resin) obtained by the above method by sputtering.
• a 300 ⁇ SiO 2 film was formed, and a laminate consisting of a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film (supporting base material/first inorganic film/polyimide resin/second inorganic film) was formed. membrane) was obtained.
• Example 9 the laminate (supporting base material/polyimide resin/second inorganic film) and polyimide film (after post-baking) were prepared in the same manner as in Example 9, except that the first inorganic film was not laminated. Polyimide film) was obtained. Table 3 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate.
• the supporting base material is a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick).
• Example 10 Manufacture of imide-amic acid copolymer varnish 12.829 g (0.040 mol) of TFMB was placed in a 1 L 5-necked round-bottomed flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. and 78.938 g of NMP were added and stirred at a rotational speed of 200 rpm at a system temperature of 70° C. and a nitrogen atmosphere to obtain a solution.
• a SiO 2 film with a thickness of 300 ⁇ was formed as a first inorganic film on a supporting base material which was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick) by sputtering.
• the polyimide varnish was applied to the surface on which the first inorganic film of the supporting base material made of glass was laminated with the SiO 2 film as the first inorganic film, and was kept on a hot plate at 80°C for 20 minutes.
• the temperature was raised to 400°C at a temperature increase rate of 5°C/min in a nitrogen atmosphere, and heated at 400°C for 60 minutes in a hot air dryer to evaporate the solvent and thermally imidize the supporting base material, the first A three-layer preliminary laminate (supporting base material/first inorganic membrane/polyimide resin) consisting of an inorganic membrane and a polyimide resin was obtained.
• a laminate supporting base material/first inorganic film/polyimide resin/second inorganic film
• a second inorganic film was applied to the polyimide resin side of the three-layer preliminary laminate (supporting base material/first inorganic film/polyimide resin) obtained by the above method by sputtering.
• a 300 ⁇ SiO 2 film was formed, and a laminate consisting of a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film (supporting base material/first inorganic film/polyimide resin/second inorganic film) was formed. membrane) was obtained.
• Comparative example 7 In Example 10, the laminate (supporting base material/polyimide resin/second inorganic film) and polyimide film (after post-baking) were prepared in the same manner as in Example 10, except that the first inorganic film was not laminated. Polyimide film) was obtained. Table 3 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate. Note that the supporting base material is a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick).
• Example 11 Manufacture of polyamic acid varnish
• 29.422 g (0.100 mol) of s-BPDA and 78.037 g of NMP were added all at once, and the mixture was stirred for 5 hours while being maintained at 70° C. using a mantle heater. Thereafter, 229.520 g of NMP was added, and the mixture was further stirred for about 1 hour for homogenization to obtain a polyamic acid varnish with a solid content concentration of 10% by mass.
• a SiO 2 film with a thickness of 300 ⁇ was formed as a first inorganic film on a supporting base material which was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick) by sputtering.
• the polyimide varnish was applied to the surface on which the first inorganic film of the supporting base material made of glass was laminated with the SiO 2 film as the first inorganic film, and was kept on a hot plate at 80°C for 20 minutes. Thereafter, the temperature was raised to 430°C at a temperature increase rate of 5°C/min in a nitrogen atmosphere, and the solvent was evaporated by heating at 430°C in a hot air dryer for 60 minutes.
• a three-layer preliminary laminate (supporting base material/first inorganic membrane/polyimide resin) was obtained.
• a laminate (supporting base material/first inorganic film/polyimide resin/second inorganic film) was manufactured by simulating the manufacturing process of a display for an image display device.
• a second inorganic film was applied to the polyimide resin side of the three-layer preliminary laminate (supporting base material/first inorganic film/polyimide resin) obtained by the above method by sputtering.
• a 300 ⁇ SiO 2 film was formed, and a laminate consisting of a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film (supporting base material/first inorganic film/polyimide resin/second inorganic film) was formed. membrane) was obtained.
• Comparative example 8 In Example 11, the laminate (supporting base material/polyimide resin/second inorganic film) and polyimide film (after post-baking) were prepared in the same manner as in Example 11, except that the first inorganic film was not laminated. Polyimide film) was obtained. Table 4 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate. Note that the supporting base material is a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick).
• Example 12 Manufacture of polyamic acid varnish
• Diamine (B13) 46.333 g (0.100 mol) and 85.856 g of NMP were added, and the system was stirred at a rotational speed of 200 rpm at a system temperature of 70° C. and a nitrogen atmosphere to obtain a solution.
• 29.422 g (0.100 mol) of s-BPDA and 85.856 g of NMP were added all at once, and the mixture was stirred for 5 hours while being maintained at 70° C. using a mantle heater. Thereafter, 152.517 g of NMP was added, and the mixture was further stirred for about 1 hour for homogenization to obtain a polyamic acid varnish with a solid content concentration of 10% by mass.
• a SiO 2 film with a thickness of 300 ⁇ was formed as a first inorganic film on a supporting base material which was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick) by sputtering.
• the above-mentioned polyimide varnish was applied to the surface on which the first inorganic film of the supporting base material made of glass on which the SiO 2 film was laminated as the first inorganic film was applied, and the polyimide varnish was kept on a hot plate at 80° C. for 20 minutes.
• a three-layer preliminary laminate (supporting base material/first inorganic membrane/polyimide resin) was obtained.
• a laminate (supporting base material/first inorganic film/polyimide resin/second inorganic film) was manufactured by simulating the manufacturing process of a display for an image display device. Specifically, a second inorganic film was applied to the polyimide resin side of the three-layer preliminary laminate (supporting base material/first inorganic film/polyimide resin) obtained by the above method by sputtering.
• a 300 ⁇ SiO 2 film was formed, and a laminate consisting of a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film (supporting base material/first inorganic film/polyimide resin/second inorganic film) was formed. membrane) was obtained.
• Example 12 the laminate (supporting base material/polyimide resin/second inorganic film) and polyimide film (after post-baking) were prepared in the same manner as in Example 12, except that the first inorganic film was not laminated. Polyimide film) was obtained. Table 4 shows the physical properties and evaluation results of the polyimide film (post-baked polyimide film) and the evaluation results of the laminate.
• the supporting base material is a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick).
• Comparative example 10 Manufacture of polyamic acid varnish 32.024 g (0.100 mol) of TFMB was placed in a 1 L 5-neck round bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. and 196.627 g of NMP were added, and the system was stirred at a rotation speed of 200 rpm under a nitrogen atmosphere at a system temperature of 50° C. to obtain a solution. To this solution, 29.422 g (0.100 mol) of s-BPDA and 49.157 g of NMP were added all at once, and the mixture was stirred for 5 hours while being maintained at 50° C. using a mantle heater. Thereafter, 307.230 g of NMP was added, and the mixture was further stirred for about 1 hour to be homogenized to obtain a polyamic acid varnish with a solid content concentration of 10% by mass.
• a SiO 2 film with a thickness of 300 ⁇ was formed as a first inorganic film on a supporting base material which was a glass substrate (AN-100, manufactured by AGC Corporation, 0.7 mm thick) by sputtering.
• the polyimide varnish was applied to the surface on which the first inorganic film of the supporting base material made of glass was laminated with the SiO 2 film as the first inorganic film, and was kept on a hot plate at 80°C for 20 minutes.
• the temperature was raised to 400°C at a temperature increase rate of 5°C/min in a nitrogen atmosphere, and heated at 400°C for 60 minutes in a hot air dryer to evaporate the solvent and thermally imidize the supporting base material, the first A three-layer preliminary laminate (supporting base material/first inorganic membrane/polyimide resin) consisting of an inorganic membrane and a polyimide resin was obtained.
• a laminate supporting base material/first inorganic film/polyimide resin/second inorganic film
• a second inorganic film was applied to the polyimide resin side of the three-layer preliminary laminate (supporting base material/first inorganic film/polyimide resin) obtained by the above method by sputtering.
• a 300 ⁇ SiO 2 film was formed, and a laminate consisting of a supporting base material, a first inorganic film, a polyimide resin, and a second inorganic film (supporting base material/first inorganic film/polyimide resin/second inorganic film) was formed. membrane) was obtained.
• the laminate of the present invention has excellent heat resistance and low yellowness, and furthermore, the change in yellowness after heat treatment is small. Since the laminate of the present invention has the above-mentioned excellent properties, it is useful as a laminate for manufacturing TFT substrates.

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