WO2014142170A1 - Composition de résine pour substrats d'affichage, film mince en résine pour substrats d'affichage, et procédé de production dudit film mince en résine pour substrats d'affichage - Google Patents
Composition de résine pour substrats d'affichage, film mince en résine pour substrats d'affichage, et procédé de production dudit film mince en résine pour substrats d'affichage Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a resin composition for display substrate, a resin thin film for display substrate, and a method for producing a resin thin film for display substrate.
- polyimide resins which are known to be easy to manufacture and have high heat resistance, are attracting attention as display substrate materials that replace glass.
- polyimide in order to use polyimide as a display substrate material, it is necessary to have a linear expansion coefficient as small as glass (about 5 to 15 ppm / K), but many polyimides are about 60 to 80 ppm / K. Most polyimides are not suitable for display substrate materials.
- an active matrix driving panel is used for a high-definition display, and in order to form an active matrix layer including a thin film active element in addition to a matrix-like pixel electrode, not only high-temperature processing at 200 ° C. or more, Accurate alignment is also essential.
- polyimide is inferior to glass in terms of linear expansion characteristics (linear expansion coefficient), it shrinks or expands more than a glass substrate at high temperatures. Therefore, when polyimide is used as a substrate material, It is often difficult to maintain high dimensional stability. Therefore, more appropriate molecular design is required in order to make use of the heat resistance of polyimide and realize suitable linear expansion characteristics.
- the polyimide produced using the former biphenyltetracarboxylic dianhydride has a problem that the linear expansion coefficient becomes high in the high temperature region (250 ° C. to 400 ° C.) required for the production process, and the latter pyromellitic acid.
- anhydride is used, there is a problem that the flexibility of the resulting polyimide is lowered in combination with p-phenylenediamine, which is a versatile diamine.
- the polyamic acid obtained from a versatile diamine and a versatile acid dianhydride and suitable for the production of a polyimide film having properties necessary for a display substrate, and a resin composition containing the polyamic acid are specific. Was not known.
- the present invention has been made in view of such circumstances, and is obtained from a versatile diamine and a versatile acid dianhydride, and has high heat resistance and moderate flexibility that can withstand the display manufacturing process. It aims at providing the resin composition for display substrates which can form the resin thin film which has the property and a moderate linear expansion coefficient, especially a moderate linear expansion coefficient in 400 degreeC vicinity.
- flexibility here means self-supporting property and the high softness
- the appropriate linear expansion coefficient means, for example, when the substrate is glass, a linear expansion coefficient (about 5 to 15 ppm / K) that is equal to or lower than that of the glass of the substrate.
- a resin thin film having high heat resistance, appropriate flexibility, and appropriate linear expansion coefficient required for a display substrate can be obtained by a composition containing polyamic acid derived from bis (4-aminophenoxy) biphenyl.
- the headline and the present invention were completed.
- a resin composition for a display substrate comprising a polyamic acid having a weight average molecular weight of 5000 or more and containing at least 50 mol% of the three structural units represented by the formula (1-1),
- Ar 1 represents a divalent group represented by any one of formulas (2) to (4)
- Ar 2 represents a divalent group represented by formula (5)
- Ar 2 3 represents a divalent group represented by the formula (6)
- Ar 4 represents a tetravalent group represented by the formula (7) or (8)
- Ar 5 represents a divalent group represented by any one of the formulas (2) to (6), and Ar 4 represents the formula (7) or (8).
- R 1 to R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- Z is represented by the formula (17) or (18).
- Q represents the number of Z bonded to the benzene ring, and represents an integer of 1 to 3.
- R 5 to R 8 each independently represent a hydrogen atom or an aryl group having 6 to 20 carbon atoms.)] ⁇ 3.
- a resin thin film for a display substrate produced by sequentially heating at 375 ° C. to 450 ° C. for 30 minutes to 4 hours for 5 minutes to 2 hours, 5.
- An image display device comprising 3 or 4 resin thin films for display substrates, 6).
- a method for producing a resin thin film for a display substrate comprising using the resin composition for a display substrate according to 1 or 2, 7). 1 or 2 of the resin composition for display substrate is applied on a base material, and the temperature is from 50 ° C. to 100 ° C. for 5 minutes to 2 hours, from 100 ° C. to 200 ° C.
- a method for producing a resin thin film for a display substrate comprising heating for 5 minutes to 2 hours at 375 ° C. to 450 ° C. for 30 minutes to 4 hours, 8).
- 3 or 4 method for producing an image display device comprising using a resin thin film for a display substrate, 9.
- Ar 1 represents a divalent group represented by any one of formulas (2) to (4)
- Ar 2 represents a divalent group represented by formula (5)
- Ar 2 3 represents a divalent group represented by the formula (6)
- Ar 4 represents a tetravalent group represented by the formula (7) or (8)
- R 1 to R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- Z is represented by the formula (17) or (18).
- Q represents the number of Z bonded to the benzene ring, and represents an integer of 1 to 3.
- R 5 to R 8 each independently represent a hydrogen atom or an aryl group having 6 to 20 carbon atoms.)] ⁇ I will provide a.
- the resin composition for display substrates of the present invention can be produced from a versatile acid dianhydride and a versatile diamine, and by using this, high heat resistance and appropriate flexibility can be achieved by a wet process.
- a resin thin film having an appropriate linear expansion coefficient, particularly an appropriate linear expansion coefficient in the vicinity of 400 ° C. can be obtained in a large area with good reproducibility. Therefore, by using the resin composition for a display substrate of the present invention, it is possible not only to reduce the weight and size of the display but also to reduce the cost of the display by reducing raw material costs and improving manufacturing efficiency. Become.
- the resin composition for a display substrate of the present invention contains a polyamic acid having a weight average molecular weight of 5000 or more and containing at least 50 mol% of the three types of structural units represented by the formula (1-1).
- Ar 1 represents a divalent group represented by any one of the formulas (2) to (4), and Ar 2 represents a divalent group represented by the formula (5).
- Ar 3 represents a divalent group represented by the formula (6).
- Ar 1 is preferably a group represented by the formula (2) or (3), and a group represented by the formula (2) is Is optimal.
- Ar 4 represents a tetravalent group represented by the formula (7) or (8).
- the group represented by the formula (7) is optimal as Ar 4 .
- a resin thin film having higher heat resistance can be obtained with good reproducibility by using a polyamic acid represented by the formula (1-2) having an unsaturated bond at both ends.
- a polyamic acid represented by the formula (1-2) having an unsaturated bond at both ends.
- X 1 represents a monovalent group represented by formula (9) or (10)
- X 2 represents a monovalent group represented by formula (11) or (12). Represents a group.
- X 1 and X 2 are arbitrarily bonded to three structural units independently represented by the formula (1-1).
- Ar 5 represents a divalent group represented by any one of the formulas (2) to (6), and Ar 4 has the same meaning as described above.
- Y 1 represents a divalent group represented by any of formulas (13) to (15), and Y 2 represents a monovalent group represented by formula (16). Represents a group of
- Z represents a monovalent group represented by formula (17) or (18).
- R 5 to R 8 each independently represent a hydrogen atom or an aryl group having 6 to 20 carbon atoms.
- the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3 -Phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
- R 5 to R 8 are preferably a hydrogen atom or an aryl group having 14 or less carbon atoms, more preferably a hydrogen atom or an aryl group having 10 or less carbon atoms, in consideration of increasing the solubility of the polyamic acid in an organic solvent.
- a hydrogen atom or a phenyl group is even more preferable.
- one of R 5 to R 7 is preferably a hydrogen atom, and more preferably two are hydrogen atoms.
- q represents the number of Z bonded to the benzene ring, is an integer of 1 to 3, and is preferably 1 or 2, for example. When q is 2 or more, the plurality of Zs may all be the same or different.
- R 1 to R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- the alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic.
- R 1 to R 4 are preferably a hydrogen atom or an alkyl group having 10 or less carbon atoms, more preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, in consideration of increasing the solubility of the polyamic acid in an organic solvent.
- a hydrogen atom or a methyl group is even more preferable.
- each of R 1 and R 2 and R 3 and R 4 is preferably a hydrogen atom.
- the polyamic acid containing the three structural units represented by the formula (1-1) and the polyamic acid represented by the formula (1-2) are represented by the formula (a).
- 3 units of the structural unit, the structural unit represented by the formula (b) and the structural unit represented by the formula (c) are contained in a total of 50 mol% or more in the polymer chain, and these structural units are in any order ( It means a polyamic acid bonded with other structural units between these units). Therefore, in the present specification, in order to clarify the meaning, in the claims of the present application, each structural unit in the formulas (1-1) and (1-2) is different from the repeating unit, and the bonding hand penetrates the parenthesis. There is no description.
- Such other structural units include 2-methyl-1,4-phenylenediamine, 5-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, benzidine, 2,2 '-Dimethylbenzidine, 3,3'-dimethylbenzidine, 2,3'-dimethylbenzidine, 4,4'-diphenyl ether, 4,4'-diaminobenzanilide, 5-amino-2- (3-aminophenyl)- Diamines such as 1H-benzimidazole, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic acid Acid dianhydrides such as anhydrides, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, Reacted include the
- the polyamic acid used in the present invention comprises at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, and still more preferably three types of structural units represented by the formula (1-1). It contains at least 80 mol%, more preferably at least 90 mol%.
- the polyamic acid used in the present invention may contain other structural units in addition to the three structural units represented by the formula (1-1) (structural units represented by the formulas (a) to (c)).
- the content of such structural units should be less than 50 mol%, preferably less than 40 mol%, more preferably less than 30 mol%, and less than 20 mol%. Is more preferable, and it is further more preferable that it is less than 10 mol%.
- the polyamic acid containing the three structural units represented by the formula (1-1) includes a diamine represented by the formulas (19) to (21), an acid dianhydride represented by the formula (22), Can be obtained by reacting.
- diamines represented by the formulas (19) to (21) and the acid dianhydride represented by the formula (22) commercially available products may be used, or those synthesized by known methods may be used.
- examples of the diamine represented by the formula (19) include p-phenylenediamine, m-phenylenediamine, and o-phenylenediamine.
- Examples of the acid dianhydride represented by the formula (22) include 1,2,3,4-benzenetetracarboxylic dianhydride or 1,2,4,5-benzenetetracarboxylic dianhydride (pyromellitic acid). Anhydride).
- the polyamic acid represented by the formula (1-2) of the present invention includes a diamine represented by the formulas (19) to (21), an acid dianhydride represented by the formula (22), a formula ( It can be obtained by reacting the acid anhydride represented by any one of 23) to (25) and / or the amine represented by the formula (26).
- the acid anhydrides represented by the formulas (23) to (25) and the amine represented by the formula (26) commercially available products may be used, or those synthesized by known methods may be used.
- the acid anhydride represented by the formula (23) include 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 4-phenylethynylphthalic anhydride, and 4-ethynylphthalic anhydride. It is not limited to.
- Examples of the acid anhydride represented by the formula (24) include 5-norbornene-2,3-dicarboxylic acid anhydride and methyl-5-norbornene-2,3-dicarboxylic acid anhydride, but are not limited thereto. I don't mean.
- Examples of the acid anhydride represented by the formula (25) include, but are not limited to, maleic anhydride and citraconic anhydride.
- Examples of the amine represented by the formula (26) include 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline and the like, but are not limited thereto.
- a diamine represented by formulas (19) to (21) and an amine represented by formula (26) (hereinafter referred to as amine component), an acid dianhydride represented by formula (22) and
- the charging ratio (molar ratio) of the acid anhydrides represented by formulas (23) to (25) (hereinafter referred to as acid anhydride component) is appropriately set in consideration of the molecular weight of the polyamic acid and the like.
- the acid anhydride component can generally be about 0.6 to 1.4, preferably about 0.8 to 1.2.
- the charging ratio (molar ratio) of various diamines represented by the formulas (19) to (21) is represented by the number of moles (m 2 ) of the diamine represented by the formula (20) and the formula (21).
- the above reaction is preferably carried out in a solvent.
- a solvent various solvents can be used as long as they do not adversely affect the reaction. Specific examples include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide.
- the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, and is usually about 0 to 100 ° C. However, it prevents imidation of the resulting polyamic acid and maintains a high content of polyamic acid units. Therefore, it is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and still more preferably about 0 to 50 ° C.
- the reaction time depends on the reaction temperature and the reactivity of the raw material, it cannot be defined unconditionally, but is usually about 1 to 100 hours.
- the reaction solution containing the target polyamic acid can be obtained by the method described above.
- the filtrate is used as it is, or diluted or concentrated, and used as a resin composition (varnish) for a display substrate.
- a resin composition varnish
- the solvent used for dilution and concentration is not particularly limited, and examples thereof include those similar to the specific examples of the reaction solvent in the above reaction, and these may be used alone or in combination of two or more. .
- N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2- Preference is given to imidazolidinone, N-ethyl-2-pyrrolidone and ⁇ -butyrolactone.
- a varnish obtained by dissolving or dispersing the isolated polyamic acid in a solvent is used as a resin composition for a display substrate. You may use as a thing. In this case, it is preferable that the polyamic acid is dissolved in a solvent in consideration of obtaining a highly flat resin thin film with good reproducibility.
- the solvent used for dissolution and dispersion is not particularly limited, and examples thereof include the same specific examples of the reaction solvent for the above reaction, and these may be used alone or in combination of two or more. .
- the concentration of the polyamic acid with respect to the total mass of the varnish is appropriately set in consideration of the thickness of the thin film to be produced, the varnish viscosity, etc., but is usually about 0.5 to 30% by mass, preferably about 5 to 25% by mass. is there.
- the viscosity of the varnish is appropriately set in consideration of the thickness of the thin film to be produced.
- the purpose is to obtain a resin thin film having a thickness of about 5 to 50 ⁇ m with good reproducibility, it is usually 25
- the temperature is about 500 to 50,000 mPa ⁇ s, preferably about 1,000 to 20,000 mPa ⁇ s at ° C.
- the resin composition for a display substrate of the present invention can also contain a crosslinking agent (hereinafter also referred to as a crosslinkable compound).
- a crosslinking agent hereinafter also referred to as a crosslinkable compound.
- the content of the crosslinking agent is usually about 20 parts by mass or less with respect to 100 parts by mass of the polyamic acid.
- crosslinkable compound examples include Epolide GT-401, Epolide GT-403, Epolide GT-301, Epolide GT-302, Celoxide 2021, and Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.).
- Epoxy compounds having a cyclohexene structure bisphenol A type epoxy compounds such as Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, manufactured by Japan Epoxy Resins Co., Ltd.); Bisphenol F type epoxy compound such as 807 (manufactured by Japan Epoxy Resin Co., Ltd.); Epicoat 152, Epicoat 154 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPP 201, EPPN202 (above, Nippon Kayaku Co., Ltd.) and other phenol novolak type epoxy compounds; ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (above, Nippon Kayaku) Yakuhin Co., Ltd.), Crecoat novolak type epoxy compounds such as Epicote 180S75 (Japan Epoxy Resin Co., Ltd.); Naphthalene type epoxy compounds such as V8000
- benzoguanamine derivative or glycoluril having a group in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group or both, an average of 3.7 methoxymethyl groups are substituted per triazine ring.
- MX-750 MW-30 substituted with an average of 5.8 methoxymethyl groups per triazine ring (above, manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350 Methoxymethylated melamine such as Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712 and the like; Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254 and the like, methoxymethylated butoxymethylated Me Min; butoxymethylated melamines such as Cymel 506 and Cymel 508; carboxyl group-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141; methoxymethylated ethoxymethylated benzoguanamines such as Cymel 1123; Methoxymethylated butoxymethylated benzoguanamine; butoxymethylated benzoguanamine such as Cymel 1128; carboxyl-containing meth
- a resin thin film made of polyimide having high heat resistance, appropriate flexibility, and appropriate linear expansion coefficient is obtained.
- the substrate include plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate
- the glass substrate is optimal because the resulting resin thin film exhibits good releasability.
- the coating method is not particularly limited, but for example, cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, printing method (letter plate) , Intaglio, lithographic, screen printing, etc.).
- the heating temperature is preferably 450 ° C. or lower. If it exceeds 450 ° C., the resulting resin thin film becomes brittle, and a resin thin film suitable for display substrate use may not be obtained.
- the applied resin composition is heated at 50 ° C. to 100 ° C. for 5 minutes to 2 hours, and then the heating temperature is gradually increased. Finally, it is desirable to heat at over 375 ° C. to 450 ° C. for 30 minutes to 4 hours. In particular, the applied resin composition is heated at 50 ° C. to 100 ° C. for 5 minutes to 2 hours, then over 100 ° C. to 200 ° C. for 5 minutes to 2 hours, and then over 200 ° C.
- Heating is preferably performed for a period of time, and finally from 375 ° C. to 450 ° C. for 30 minutes to 4 hours.
- the appliance used for heating include a hot plate and an oven.
- the heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.
- the thickness of the resin thin film is usually about 1 to 60 ⁇ m, preferably about 5 to 50 ⁇ m, particularly when used as a substrate for a flexible display.
- the thickness of the coating film before heating is adjusted to obtain a resin having a desired thickness. A thin film is formed.
- the resin thin film described above satisfies each required performance required as a base film of a flexible display substrate, it is optimal for use as a base film of a flexible display substrate.
- the weight molecular weight (Mw) and molecular weight distribution were measured using a GPC apparatus manufactured by JASCO Corporation (column: Shodex SB803HQ and SB804HQ; elution solvent: dimethylformamide; flow rate: 0.9 mL / min; column temperature: 40 ° C .; Mw : Polystyrene conversion value) (hereinafter the same).
- Example 2 0.493 g (0.0046 mol) of PDA, 0.206 g (0.00059 mol) of FDA and 0.218 g (0.00059 mol) of BAPB were dissolved in 22.8 g of NMP, and 1.29 g of PMDA (0.0059 mol) After stirring at 23 ° C. for 1 hour under a nitrogen atmosphere, 0.0416 g (0.00036 mol) of 4EA was added, and the mixture was further reacted for 23 hours. The obtained polymer had Mw of 123,500 and a molecular weight distribution of 2.3. This solution was used as a resin composition for display substrates.
- Example 4 PDA 0.601 g (0.0056 mol), FDA 0.258 g (0.00074 mol) and BAPB 0.273 g (0.00074 mol) were dissolved in NMP 22.3 g, and PMDA 1.62 g (0.0074 mol) ) And then reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 147,800 and molecular weight distribution was 2.5. This solution was used as a resin composition for display substrates.
- Example 5 0.636 g (0.0059 mol) of PDA, 0.273 g (0.00078 mol) of FDA and 0.289 g (0.00078 mol) of BAPB were dissolved in 22.0 g of NMP to obtain 1.71 g (0.0078 mol) of PMDA. After stirring at 23 ° C. for 1 hour under a nitrogen atmosphere, 4919 0.0919 g (0.00078 mol) was added, and the mixture was further reacted for 23 hours. The obtained polymer had Mw of 128,700 and a molecular weight distribution of 2.4. This solution was used as a resin composition for display substrates.
- Example 7 PDA 0.760 g (0.0070 mol), FDA 0.306 g (0.00089 mol) and BAPB 0.324 g (0.00089 mol) were dissolved in 21.8 g of NMP, and PMDA 1.86 g (0.0085 mol) ) And then reacted at 23 ° C. for 24 hours under a nitrogen atmosphere.
- the obtained polymer had Mw of 65,300 and a molecular weight distribution of 3.1. This solution was used as a resin composition for display substrates.
- Example 8 0.601 g (0.0056 mol) of PDA, 0.242 g (0.00070 mol) of FDA and 0.256 g (0.00070 mol) of BAPB were dissolved in 22.4 g of NMP, and 1.50 g of PMDA (0.0069 mol) After stirring at 23 ° C. for 1 hour under a nitrogen atmosphere, 0.0239 g (0.00014 mol) of 4EPA was added, and the reaction was further continued for 23 hours. The obtained polymer had an Mw of 87,400 and a molecular weight distribution of 1.9. This solution was used as a resin composition for display substrates.
- Example 9 PDA 0.591 g (0.0055 mol), FDA 0.238 g (0.00068 mol) and BAPB 0.252 g (0.00068 mol) were dissolved in NMP 22.4 g, PMDA 1.47 g (0.0068 mol) After stirring at 23 ° C. for 1 hour under a nitrogen atmosphere, 0.0705 g (0.00041 mol) of 4EPA was added and the reaction was further continued for 23 hours.
- the obtained polymer had Mw of 78,100 and a molecular weight distribution of 2.1. This solution was used as a resin composition for display substrates.
- Example 11 Preparation of resin thin film for display substrate (preparation of polyimide film) ⁇ Example 11>
- the resin composition for a display substrate obtained in Example 1 was applied onto a glass substrate with a doctor blade, and was 120 ° C for 30 minutes, then 150 ° C for 30 minutes, then 180 ° C for 30 minutes in the air. Baking was performed, followed by baking at 210 ° C. for 30 minutes, subsequently at 240 ° C. for 30 minutes, subsequently at 300 ° C. for 20 minutes, and subsequently at 400 ° C. for 60 minutes in a nitrogen atmosphere to prepare a resin thin film.
- Examples 12 to 20 and Comparative Example 2> Instead of using the resin composition for display substrates obtained in Examples 2 to 10 and the resin composition obtained in Comparative Example 1 in place of the resin composition for display substrates obtained in Example 1, respectively. A resin thin film was produced in the same manner as in Example 11.
- the film thickness of the resin thin film was measured using a micrometer manufactured by Mitutoyo Corporation.
- ⁇ Heat resistance evaluation> The 5% mass reduction temperature (Td 5% (° C.)) of the resin thin film was measured. The measurement was performed using TG / DTA2000SA manufactured by Bruker AXS Co., Ltd. (temperature increase rate: from 50 ° C. to 800 ° C. at 10 ° C. per minute).
- the linear expansion coefficient of the resin thin film was measured. The measurement was performed using TMA-60 (manufactured by Shimadzu Corporation) (temperature increase rate: 50 ° C. to 400 ° C. at 10 ° C./min). The coefficient indicates an average value in each temperature region on the low temperature (100 ° C. to 250 ° C.) side and the high temperature (250 ° C. to 400 ° C.) side.
- the heat resistance and flexibility were similar to those of the resin thin film of the example, but the peelability from the glass substrate was poor, and the high temperature region (250 ° C.
- the linear expansion coefficient at ⁇ 400 ° C. was as high as 22 ppm.
- the resin thin films of Examples 11 to 20 not only have excellent releasability from the glass substrate, but also have high heat resistance and appropriate flexibility, and are appropriate in both low temperature and high temperature ranges. It had a linear expansion coefficient.
- a resin thin film In order to use a resin thin film as a display substrate, high heat resistance, appropriate flexibility, and appropriate linear expansion coefficient are required.
- a resin thin film is produced by applying a resin composition on a substrate and heating, and an active matrix layer is formed on the resin thin film without peeling off the resin thin film formed on the substrate. Etc. are sequentially formed, and finally the resin thin film is peeled off from the substrate. Therefore, it is preferable that the resin thin film for a substrate has good peelability from the substrate.
- the resin thin film obtained from the resin composition of the present invention not only has high heat resistance, appropriate flexibility and appropriate linear expansion coefficient, but also exhibits good peelability from the substrate. It can be seen that it is particularly suitable for display substrate applications.
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Abstract
Le problème décrit par la présente invention est de pourvoir à une composition de résine pour substrats d'affichage, qui est obtenue à partir d'une diamine à caractère général et d'un dianhydride d'acide à caractère général, et qui est capable de former un film mince en résine ayant une résistance élevée à la chaleur, une flexibilité adéquate et un coefficient de dilatation linéaire approprié capable de supporter le procédé de production d'un affichage. La solution selon l'invention porte sur une composition de résine pour substrats d'affichage, qui contient un acide polyamique comprenant au moins 50 % en moles de trois types de motifs structuraux représentés par la formule (1-1) au total, et qui a un poids moléculaire moyen en poids de 5 000 ou plus. (Dans la formule, Ar1 représente un groupe divalent représenté par une des formules (2)-(4); Ar2 représente un groupe divalent représenté par la formule (5); Ar3 représente un groupe divalent représenté par la formule (6); Ar4 représente un groupe tétravalent représenté par la formule (7) ou (8); chacun des n1-n3 représente le nombre de chaque motif structural; et n1/(n2 + n3) = 2,0-9,0 et n2/n3 = 0,1-10 sont satisfaits).
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JP2009155433A (ja) * | 2007-12-26 | 2009-07-16 | Mitsui Chemicals Inc | ポリイミドおよびポリアミド酸 |
WO2013133168A1 (fr) * | 2012-03-05 | 2013-09-12 | 日産化学工業株式会社 | Poly(acide amique) et polyimide |
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JP2009155433A (ja) * | 2007-12-26 | 2009-07-16 | Mitsui Chemicals Inc | ポリイミドおよびポリアミド酸 |
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JP2021507952A (ja) * | 2018-09-27 | 2021-02-25 | エルジー・ケム・リミテッド | ポリイミド前駆体溶液及びそれを用いるポリイミドフィルム |
JP7480461B2 (ja) | 2018-09-27 | 2024-05-10 | エルジー・ケム・リミテッド | ポリイミド前駆体溶液及びそれを用いるポリイミドフィルム |
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