WO2018070398A1 - Résine polyimide transparente, composition de résine polyimide transparente, film de résine polyimide transparente, composition absorbant les infrarouges, filtre bloquant les infrarouges et procédé de production pour un film de résine polyimide transparent - Google Patents

Résine polyimide transparente, composition de résine polyimide transparente, film de résine polyimide transparente, composition absorbant les infrarouges, filtre bloquant les infrarouges et procédé de production pour un film de résine polyimide transparent Download PDF

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WO2018070398A1
WO2018070398A1 PCT/JP2017/036735 JP2017036735W WO2018070398A1 WO 2018070398 A1 WO2018070398 A1 WO 2018070398A1 JP 2017036735 W JP2017036735 W JP 2017036735W WO 2018070398 A1 WO2018070398 A1 WO 2018070398A1
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polyimide resin
group
transparent polyimide
film
ring
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PCT/JP2017/036735
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English (en)
Japanese (ja)
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一成 中原
悠太郎 堀江
福坂　潔
康敏 伊藤
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コニカミノルタ株式会社
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Priority to JP2018545010A priority Critical patent/JP7036021B2/ja
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
    • F21V9/04—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters for filtering out infrared radiation

Definitions

  • the present invention relates to a transparent polyimide resin, a transparent polyimide resin composition, a transparent polyimide resin film, an infrared absorbing composition, an infrared cut filter, and a method for producing a transparent polyimide resin film. More specifically, the transparency of the film is good and the mechanical strength is improved. It is related with the transparent polyimide resin etc. which were excellent in.
  • a transparent substrate used for the outermost surface of the display is required to have strong mechanical strength and chemical stability such as scratch resistance, flexibility, impact resistance, and light resistance.
  • EL organic electroluminescence
  • foldable displays have been developed, and such displays are required to be transparent and have excellent bending resistance.
  • transparent and flexible printed boards are required to have high mechanical strength (bending strength, elastic modulus, etc.) and heat resistance.
  • high durability is required for in-vehicle films.
  • a transparent film with high mechanical strength and high heat resistance is expected in many fields.
  • Polyimide has been developed as a glass replacement film in recent years due to its high mechanical strength and heat resistance.
  • the polymer terminal has a large molecular mobility and affects the melting point, glass transition point, and thermal decomposition temperature.
  • the mobility at the molecular end is suppressed by the ⁇ - ⁇ interaction between the aromatic skeletons to improve the thermal decomposition temperature (non- (See Patent Document 1).
  • it is effective to reduce the mobility of the entire polymer chain, so it is necessary to suppress not only the mobility of the polymer end but also the mobility of the main chain .
  • Patent Document 2 describes that during polyimide synthesis, the amount of carboxylic dianhydride units is increased and polymerized, and the terminal is made carboxylic anhydride to suppress coloring.
  • the elastic modulus of the transparent polyimide having a carboxylic anhydride terminal described in this document is described as 1.0 to 3.0 GPa, which is insufficient for the required mechanical strength. If the terminal is a carboxylic acid anhydride, coloring by the amine can be suppressed, but since the carboxylic acid anhydride decomposes into a dicarboxylic acid structure, the terminal mobility is improved, and the elastic modulus and heat resistance are improved. It is not considered.
  • Patent Document 3 it is described that phthalic anhydride is modified at the amine terminal of a transparent polyimide.
  • this patent document has no description about the effect of terminal modification on mechanical strength, and the mechanical strength and heat resistance required by the polyimide terminal-modified with phthalic anhydride described in Examples could not be imparted.
  • the present invention has been made in view of the above-mentioned problems and situations, and a problem to be solved is to provide a transparent polyimide resin having good transparency and excellent mechanical strength (bending resistance, elastic modulus, etc.). Moreover, it is providing the transparent polyimide resin composition using a polyimide resin, a transparent polyimide resin film, an infrared rays absorption composition, and an infrared cut filter. Furthermore, it is providing the manufacturing method of a transparent polyimide resin film.
  • the transparent polyimide resin having aromaticity at the terminal has excellent solubility in a solvent (hereinafter also referred to as “re-solubility”) and is easy to produce a film by a solution casting method, and thus is excellent in productivity. I found.
  • the said polyimide has the structure represented by following General formula (1) or General formula (2),
  • the transparent polyimide resin as described in any one of 1st term
  • a and R each independently represents an aromatic ring, an aromatic heterocyclic ring, an aliphatic hydrocarbon group having 2 to 39 carbon atoms, or an alicyclic hydrocarbon group having 2 to 39 carbon atoms
  • a and R may be —O—, —SO 2 —, —CO—, —CH 2 —, —C (CH 3 ) 2 —, —OSi (CH 3 ) 2 —,
  • an alicyclic hydrocarbon group may be linked, provided that at least one aromatic moiety is present in the structure represented by A or R.
  • R 1 to R 8 are each independently a polyimide. Represents a terminal group, provided that at least one of R 1 to R 4 and at least one of R 5 to R 8 are N Two end groups having one or more aromatic rings having an ICS value in the range of -15.0 to -8.0, or two aromatic rings having an NICS value in the range of -15.0 to -7.0. It is a terminal group having two or more.
  • said A represents the following structure, The polyimide resin of Claim 5 characterized by the above-mentioned. [The above structure is bonded to N in the general formula (1) and the general formula (2) in the * part. ]
  • said R represents the following structure, The polyimide resin of Claim 5 or 6 characterized by the above-mentioned. [The above structure is bonded to the carbonyl group in the imide group at the * moiety. ]
  • a transparent polyimide resin composition comprising the transparent polyimide resin according to any one of items 1 to 7.
  • a transparent polyimide resin film comprising the transparent polyimide resin according to any one of items 1 to 7.
  • An infrared ray absorbing composition comprising the transparent polyimide resin according to any one of items 1 to 7.
  • An infrared cut filter comprising the transparent polyimide resin according to any one of items 1 to 7.
  • the manufacturing method of the transparent polyimide resin film characterized by including a process.
  • the above-mentioned means of the present invention can provide a transparent polyimide resin having good transparency and excellent mechanical strength.
  • the transparent polyimide resin composition using a transparent polyimide resin, a transparent polyimide resin film, an infrared rays absorption composition, and an infrared cut filter can be provided.
  • the manufacturing method of the said transparent polyimide resin film excellent in productivity can be provided.
  • the transparent polyimide is produced by a method of suppressing the generation of a CT complex by making the structure of the polyimide donor site and acceptor site orthogonal, a method of introducing an alicyclic monomer, a method of using a fluorine-based monomer, etc.
  • a method of introducing an alicyclic monomer a method of using a fluorine-based monomer, etc.
  • the transparent polyimide that can use these interactions is a polyimide containing an aromatic moiety in the main chain, and it was thought that the mechanical strength could be improved by introducing a substituent having a specific aromaticity at the terminal. .
  • the present inventors examined the end of the transparent polyimide in accordance with the above idea, and introduced a specific aromatic substituent having no crosslinking group at the end of the transparent polyimide containing an aromatic skeleton in the main chain. As a result, a transparent polyimide resin having high mechanical strength could be obtained.
  • polyimide refers to a compound having a polyimide structure
  • polyimide resin refers to a resin containing the polyimide
  • polyimide resin film refers to a film made from the polyimide resin
  • the transparent polyimide resin of the present invention has a terminal group having an aromatic ring having a NICS value in the range of -15.0 to -8.0 at least one end of the polyimide, and a NICS value of -15.0 to It has any group of terminal groups having two or more aromatic rings in the range of ⁇ 7.0. This feature is a technical feature common to the claimed invention.
  • the polyimide is a polymer of an aromatic dicarboxylic acid anhydride and an aromatic diamine having a sterically hindered group at the ortho position of the amino group, a transparent polyimide resin, and a transparent It is preferable from the viewpoint of excellent transparency of the polyimide resin film.
  • the polyimide is preferably a polymer of an alicyclic dicarboxylic acid anhydride and an aromatic diamine from the viewpoint of excellent transparency of the transparent polyimide resin and the transparent polyimide resin film.
  • the terminal group is preferably a terminal group having one or more aromatic rings having a NICS value in the range of ⁇ 14.0 to ⁇ 10.0 from the viewpoint of excellent mechanical strength of the transparent polyimide resin film. .
  • the polyimide has a structure represented by the general formula (1) or the general formula (2) from the viewpoint of excellent re-solubility, and production by a solution casting method is possible, thereby improving productivity. Excellent.
  • This effect is an effect that cannot be obtained with a polyimide resin having a crosslinkable group at the end of the polyimide.
  • the transparent polyimide resin composition of the present invention preferably contains the transparent polyimide resin of the present invention from the viewpoint of excellent transparency, mechanical strength, and heat resistance.
  • the transparent polyimide resin film of the present invention preferably contains the transparent polyimide resin of the present invention from the viewpoint of excellent mechanical strength, heat resistance, and productivity of the transparent polyimide resin film.
  • the method for producing the transparent polyimide resin film of the present invention includes a step of preparing a dope obtained by dissolving the transparent polyimide resin of the present invention in an organic solvent, and casting the dope on a support to form a film. It is preferable from a viewpoint which is excellent in productivity of a transparent polyimide resin film to include a process.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the transparent polyimide resin of the present invention is a transparent polyimide resin containing a polyimide having an aromatic moiety, and has a NICS value in the range of ⁇ 15.0 to ⁇ 8.0 at at least one of the ends of the polyimide. It has a terminal group having an aromatic ring and any group of terminal groups having two or more aromatic rings having a NICS value in the range of -15.0 to -7.0.
  • the conventional transparent polyimide resin (for example, the transparent polyimide resin described in Patent Document 2) has a benzene ring at the terminal, and does not correspond to the terminal group having a specific NICS value according to the present invention.
  • the polyimide according to the present invention is a compound containing an imide bond in a repeating unit, and is preferably formed from diamine or a derivative thereof and an acid anhydride or a derivative thereof.
  • the polyimide according to the present invention is characterized in that it includes a structure that suppresses the CT complex between and within the polyimide. Thereby, coloring is improved and transparency is improved.
  • an aromatic diamine having an electron-withdrawing group an aromatic diamine having a sterically hindered group at the ortho position, a monomer having a highly sterically hindered group, an alicyclic ring It is necessary to use a formula monomer or the like.
  • the polyimide according to the present invention is characterized by having an aromatic moiety in the main chain in order to provide desired performance.
  • the aromatic part should just be introduce
  • the polyimide according to the present invention is preferably a polymer of an aromatic dicarboxylic acid anhydride and an aromatic diamine having a sterically hindered group at the ortho position of the amino group.
  • the polyimide is preferably a polymer of an alicyclic dicarboxylic acid anhydride and an aromatic amine.
  • the terminal of the polyimide according to the present invention is substituted with a structure containing an aromatic ring having a NICS value of -15.0 to -8.0, or two or more aromatic rings having a NICS value of -15.0 to -7.0 are present. It is characterized by being substituted with the structure it contains. This suppresses the mobility of the resin by forming ⁇ - ⁇ interaction or CH- ⁇ interaction between the resin ends or the aromatic moiety contained in the main chain described above, so that the mechanical strength and heat resistance are reduced. improves.
  • the polyimide according to the present invention is substituted with a structure containing an aromatic ring having a NICS value of -15.0 to -8.0 on at least one of the terminals, or an aromatic ring having a NICS value of -15.0 to -7.0. As long as it is substituted with a structure containing 2 or more, and it is preferable that both ends are substituted.
  • the molecular weight of the polyimide in the present invention is preferably in the range of 30,000 to 500,000, more preferably in the range of 50,000 to 300,000, and in the range of 70,000 to 250,000. It is particularly preferred. If the molecular weight is 30,000 or more, the mechanical strength as a polymer is improved, and if it is 500,000 or less, the viscosity becomes an appropriate viscosity, so that the productivity of polyimide and polyimide film is excellent.
  • Polyimide having a structure represented by General Formula (1) or General Formula (2)> As the polyimide that can be used in the present invention, a polyimide having a repeating unit represented by the general formula (1) or the general formula (2) and a terminal structure is particularly preferable.
  • a and R each independently represents an aromatic ring, an aromatic heterocyclic ring, an aliphatic hydrocarbon group having 2 to 39 carbon atoms, or an alicyclic hydrocarbon group having 2 to 39 carbon atoms
  • a and R may be —O—, —SO 2 —, —CO—, —CH 2 —, —C (CH 3 ) 2 —, —OSi (CH 3 ) 2 —,
  • an alicyclic hydrocarbon group may be linked, provided that at least one aromatic moiety is present in the structure represented by A or R.
  • R 1 to R 8 are each independently a polyimide. Represents a terminal group, provided that at least one of R 1 to R 4 and at least one of R 5 to R 8 are N Two end groups having one or more aromatic rings having an ICS value in the range of -15.0 to -8.0, or two aromatic rings having an NICS value in the range of -15.0 to -7.0. It is a terminal group having two or more.)
  • the A or R has at least one aromatic moiety in the structure, and has a partial structure that suppresses the intermolecular or intramolecular CT described above.
  • the polyimide resin can be made transparent by having a partial structure that suppresses intermolecular or intramolecular CT in the structure represented by A or R.
  • “having two or more aromatic rings” means that there are two or more 5-membered rings or 6-membered rings, and the condensed ring counts each ring individually. Therefore, in the present invention, the naphthalene ring is “two aromatic rings”.
  • aromatic hydrocarbon ring represented by A and R for example, benzene ring, biphenyl ring, naphthalene ring, azulene ring, fluorene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, Anthraanthrene rings and the like can be mentioned.
  • a benzene ring, a biphenyl ring, a naphthalene ring and a pyrene ring are preferable, and a benzene ring, a biphenyl ring and a naphthalene ring are more preferable. By introducing these rings, the mechanical strength is improved.
  • Examples of the aromatic heterocycle represented by A and R include a silole ring, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and an oxadiazole ring.
  • Triazole ring imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzthiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, thienothiophene ring, carbazole ring, azacarbazole ring (carbazole ring) Any one or more of the carbon atoms constituting the dibenzosilole ring, dibenzofuran ring, dibenzothiophene ring, benzothiophene ring or dibenzofuran ring.
  • a pyridine ring, a pyrimidine ring, a triazine ring, a benzimidazole ring and a quinazoline ring are preferable, and a pyridine ring, a pyrimidine ring and a triazine ring are more preferable.
  • a pyridine ring, a pyrimidine ring and a triazine ring are more preferable.
  • the aliphatic hydrocarbon group having 4 to 39 carbon atoms represented by A and R include groups such as butane, octane and decane.
  • Examples of the alicyclic hydrocarbon group having 4 to 39 carbon atoms represented by A and R include, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.2] oct-7-ene, bicyclo [2 2.2] groups such as octane, dicyclohexylmethane, 3,6-dimethylcyclohexylmethane, 1,4-diphenylcyclohexane and the like.
  • Examples of the divalent aliphatic hydrocarbon group having 2 to 39 carbon atoms represented by A and R include, in addition to a linear or branched aliphatic hydrocarbon group having 2 to 39 carbon atoms, the following structural formula: And the group represented.
  • n represents the number of repeating units, preferably 1 to 5, and more preferably 1 to 3.
  • X is an alkanediyl group having 1 to 3 carbon atoms, that is, a methylene group, an ethylene group, a trimethylene group, or a propane-1,2-diyl group, and a methylene group is preferable.
  • A preferably has the following structure.
  • A-1, A-2, A-5, A-6, A-7, A-8, A-12, A-9, A-19, A-22, A-24, A-26, AC-3, AC-7, AC-10, and AC-11 are preferable because the mechanical strength is improved by improving the rigidity of the main chain.
  • R preferably has the following structure.
  • the above structure is bonded to the carbonyl group in the imide group at the * part.
  • B-1, B-4, B-5, B-6, B-9, B-10, and B-17 are more preferable from the viewpoint of improving transparency due to the effects of electronic effects and steric hindrance. .
  • B-1, B-4, B-5, B-6, B-9, B-14, B-15, B-16, and B-17 have high main chain rigidity and improved mechanical strength. Therefore, it is preferable.
  • B-6 and B-15 from the viewpoint of improving the light resistance to ultraviolet rays.
  • the substituent that can be substituted for A and R is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group (methyl group, ethyl group, n-propyl).
  • the substituent substituted with A is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an amide group, an aryl group, or a perfluoroalkyl group. Transparency improves by containing these groups.
  • Any one of R 1 to R 4 or any one of R 5 to R 8 in the general formula (1) and the general formula (2) has a NICS value in the range of ⁇ 15.0 to ⁇ 8.0.
  • a compound having an aromatic ring having a NICS value of less than ⁇ 15.0 is substantially difficult to synthesize, or has a very low productivity because it introduces a complicated synthesis route by introducing a substituent.
  • Any one of R 1 to R 4 in the general formula (1) and any one of R 5 to R 8 in the general formula (2) is within a range of NICS values from ⁇ 15.0 to ⁇ 8.0. More preferably, it is a terminal group having one or more aromatic rings.
  • R 1 and R 3 in the general formula (1) and R 5 and R 7 in the general formula (2) both have one or more aromatic rings having a NICS value in the range of -15.0 to -8.0.
  • R 1 to R 8 in the general formula (1) and the general formula (2) one or more aromatic rings having a NICS value in the range of ⁇ 15.0 to ⁇ 8.0 are included.
  • a group that is not a terminal group and that is not a terminal group having two or more aromatic rings having a NICS value in the range of -15.0 to -7.0 is not particularly limited. This is the same group as the substituent that can be substituted for A and R in the general formula (2).
  • R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , and R 7 and R 8 may be condensed to form a ring.
  • the NICS value of the terminal group having two or more is preferably ⁇ 8.0 or less, more preferably ⁇ 9.0 or less, and particularly preferably ⁇ 10.0 or less.
  • the mechanical strength is improved by strengthening the interaction between the terminal and the main chain or the terminals.
  • the end group of the polyimide represented by R 1 to R 8 in the general formula (1) and the general formula (2) preferably has the following structure.
  • the * part is bonded to the main chain part of the polyimide.
  • NICS nucleus-independent chemical shift
  • This NICS value is an index used for quantification of aromaticity by magnetic properties. If the ring is aromatic, the ring current effect strongly shields the center of the ring, and conversely if it is antiaromatic. Anti-shielding (J. Am. Chem. Soc. 1996, 118, 6317). Depending on the magnitude of the NICS value, it is possible to determine the strength of the ring current, that is, the degree of contribution of ⁇ electrons to the aromaticity of the ring. Specifically, it represents the chemical shift (calculated value) of a virtual lithium ion arranged directly in the center of the ring, and the larger the value, the stronger the ⁇ property.
  • the NICS value was calculated using Gaussian 09 (Revision C.01, US Gaussian Software). Specifically, first, the structure was optimized using B3LYP (density functional method) as a calculation method and 6-31G * (a function obtained by adding a polarization function to a split valence basis set) as a basis function. Subsequently, using the optimized structure, a dummy atom is placed at the center of the ring for calculating the NICS value, and one point calculation is performed by the NMR shielding constant calculation method (GIAO) with the basis function 6-311 + G ** to which the dispersion function is added. A value obtained by multiplying the NMR shielding constant of the obtained dummy atom by -1 was defined as a NICS value.
  • B3LYP density functional method
  • 6-31G * a function obtained by adding a polarization function to a split valence basis set
  • Table 1 shows the NICS values in typical ring structures described in the literature.
  • a 5-membered aromatic heterocyclic ring such as a pyrrole ring, a thiophene ring, or a furan ring has a larger NICS value than an aromatic hydrocarbon such as a benzene ring or a naphthalene ring.
  • an aromatic five-membered ring is expected to enhance the CH / ⁇ interaction.
  • the intermolecular force contributed by ⁇ electrons includes ⁇ / ⁇ interaction in addition to CH / ⁇ interaction.
  • the ⁇ / ⁇ interaction is an intermolecular force that acts between two aromatic rings. Since an aromatic ring has a high polarizability, it is an intermolecular force that greatly contributes to dispersion force (London dispersion force). For this reason, an aromatic ring having a wide ⁇ -conjugated system has a higher polarizability and is likely to interact with ⁇ / ⁇ .
  • Benzene which is a 6 ⁇ -electron system, has the most stable structure when one benzene ring is placed perpendicular to one benzene ring and a benzene ring and a hydrogen atom interact with each other.
  • Naphthalene (10 ⁇ electrons) and anthracene (14 ⁇ electrons) with a wide system are most stable when the aromatic rings are stacked by ⁇ / ⁇ interaction. Is strong.
  • the NICS value can be controlled by a substituent substituted on the ring, and when the electron donating group is substituted, the NICS value becomes negative and when the electron withdrawing group is substituted, the NICS value tends to become positive.
  • Aromatic, aliphatic or alicyclic tetracarboxylic acids or their derivatives may be used alone or in combination of two or more. Further, other tetracarboxylic acids or derivatives thereof (particularly dianhydrides) may be used in combination as long as they do not impair the solvent solubility of polyimide, the flexibility of the transparent polyimide resin film, the thermocompression bonding property, and the transparency.
  • Examples of such other tetracarboxylic acids or derivatives thereof include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2, 2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1 , 3,3,3-hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, bis (3,4-dicarboxy) Phenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, bis (2,3-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,2
  • 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or biphenyltetracarboxylic dianhydride is excellent in transparency and heat due to heat shrinkage. This is preferable from the viewpoint of easy correction.
  • the repeating unit represented by the formula (1.1) is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, still more preferably 80 to 100 mol%, particularly preferably all the repeating units. Is 90 to 100 mol%.
  • the number of repeating units of formula (1.1) in one molecule of polyimide (A) is 10 to 2000, preferably 20 to 200, and further within this range, the glass transition temperature is 230 to 350 ° C. The temperature is preferably 250 to 330 ° C.
  • the polyamic acid can be obtained by polymerizing at least one of the tetracarboxylic acids and at least one of the diamines in a suitable solvent.
  • the polyamic acid ester is diesterified by ring-opening the tetracarboxylic dianhydride with an alcohol such as methanol, ethanol, isopropanol, or n-propanol, and the obtained diester is converted into the above-mentioned diester in an appropriate solvent. It can be obtained by reacting with a diamine compound. Furthermore, the polyamic acid ester can also be obtained by esterification by reacting the carboxylic acid group of the polyamic acid obtained as described above with an alcohol as described above.
  • the reaction between the tetracarboxylic dianhydride and the diamine compound can be carried out under conventionally known conditions. There are no particular limitations on the order of addition or addition method of the tetracarboxylic dianhydride and the diamine compound.
  • a polycarboxylic acid can be obtained by sequentially adding a tetracarboxylic dianhydride and a diamine compound to a solvent and stirring at an appropriate temperature.
  • the amount of the diamine compound is usually 0.8 mol or more, preferably 1 mol or more with respect to 1 mol of tetracarboxylic dianhydride. On the other hand, it is 1.2 mol or less normally, Preferably it is 1.1 mol or less.
  • the yield of the polyamic acid obtained can be improved by making the quantity of a diamine compound into such a range.
  • the concentration of tetracarboxylic dianhydride and diamine compound in the solvent is appropriately set according to the reaction conditions and the viscosity of the polyamic acid solution.
  • the total mass of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more with respect to the total amount of the solution, while usually 70%. It is not more than mass%, preferably not more than 30 mass%.
  • the reaction temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 20 ° C. or higher, and is usually 100 ° C. or lower, preferably 80 ° C. or lower.
  • the reaction time is not particularly limited but is usually 1 hour or longer, preferably 2 hours or longer, and is usually 100 hours or shorter, preferably 24 hours or shorter.
  • Examples of the polymerization solvent used in this reaction include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene and mesitylene; carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and dichlorobenzene.
  • hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene and mesitylene
  • carbon tetrachloride dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and dichlorobenzene.
  • halogenated hydrocarbon solvents such as fluorobenzene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene; ketone solvents such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N, N— Amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone; aprotic polar solvents such as dimethyl sulfoxide and ⁇ -butyrolactone; pyridine, picoline, lutidine, quinoline and isoquinoline Ring-based solvents; phenols and phenolic solvents such as cresol, but and the like, but is not particularly limited.
  • a polymerization solvent only 1 type can also be used and 2 or more types of solvents can also be mixed and used.
  • an acid anhydride group or an amino group can be arbitrarily selected by using either one of a tetracarboxylic dianhydride and a diamine compound in excess during the polymerization reaction.
  • the terminal group is an acid anhydride terminal
  • the terminal may be sealed with a monofunctional amine compound or isocyanate compound.
  • the amine compound or isocyanate compound used here is not particularly limited as long as it is a monofunctional primary amine compound or isocyanate compound.
  • aniline methylaniline, dimethylaniline, trimethylaniline, ethylaniline, diethylaniline, triethylaniline, aminophenol, methoxyaniline, aminobenzoic acid, biphenylamine, naphthylamine, cyclohexylamine, phenyl isocyanate, xylylene isocyanate, cyclohexyl isocyanate , Methylphenyl isocyanate, trifluoromethylphenyl isocyanate, and the like.
  • terminal group is an amine terminal
  • 4-ethynylphthalic anhydride methylphthalic anhydride, dimethylphthalic anhydride, trimellitic anhydride, naphthalenedicarboxylic anhydride, etc.
  • amides may be formed by reaction with monocarboxylic acid anhydrides or acid chlorides, such as p-methoxybenzoic anhydride, naphthalenecarboxylic acid chloride, 4-acetoxybenzoic acid chloride, thiophene-2-carbonyl chloride, etc. Can be raised.
  • the polyimide is a method in which the polyamic acid solution is heated to imidize the polyamic acid (thermal imidization method), or a polycyclic acid (imidation catalyst) is added to the polyamic acid solution to imidize the polyamic acid. It can be obtained by a method (chemical imidization method).
  • thermo imidization method a method of imidizing polyamic acid by heating the polyamic acid solution
  • a reaction vessel for polymerizing polyamic acid from an acid anhydride and a diamine may be continued as it is and imidized in the reaction vessel.
  • the polyamic acid in the polymerization solvent is heated for, for example, 80 to 300 ° C. for 0.1 to 200 hours to advance imidization.
  • the temperature range is preferably 150 to 200 ° C., and by setting the temperature range to 150 ° C. or higher, imidization can be reliably progressed and completed. It is possible to prevent an increase in the resin concentration due to oxidation of unreacted raw materials and volatilization of the solvent.
  • an azeotropic solvent can be added to the polymerization solvent in order to efficiently remove water generated by the imidization reaction.
  • the azeotropic solvent for example, aromatic hydrocarbons such as toluene, xylene and solvent naphtha, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and dimethylcyclohexane can be used.
  • the amount added is about 1 to 30% by mass, preferably 5 to 20% by mass, based on the total amount of organic solvent.
  • a known ring closure catalyst is added to the polyamic acid in the polymerization solvent to advance imidization.
  • the ring-closing catalyst include aliphatic tertiary amines such as trimethylamine and triethylenediamine, and heterocyclic tertiary amines such as isoquinoline, pyridine and picoline. Examples thereof include substituted nitrogen-containing heterocyclic compounds, N-oxide compounds of nitrogen-containing heterocyclic compounds, substituted or unsubstituted amino acid compounds, aromatic hydrocarbon compounds having an hydroxy group, or aromatic heterocyclic compounds.
  • alkyl imidazole such as dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, N-benzyl-2-methyl Imidazole derivatives such as imidazole, isoquinoline, 3
  • a substituted pyridine such as 5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n-propylpyridine, p-toluenesulfonic acid, etc. can be preferably used. it can.
  • the addition amount of the ring closure catalyst is preferably about 0.01 to 2 times equivalent, particularly about 0.02 to 1 time equivalent to the amic acid unit of the polyamic acid.
  • a dehydrating agent may be added to the polyamic acid solution.
  • a dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, phthalates, and the like. Examples thereof include aromatic acid anhydrides such as acid anhydrides, and these can be used alone or in combination.
  • it is preferable to use a dehydrating agent because the reaction can proceed at a low temperature.
  • it is possible to imidize polyamic acid only by adding a dehydrating agent to the polyamic acid solution it is preferable to imidize by heating or addition of a ring-closing catalyst as described above because the reaction rate is slow. .
  • the polyimide solution imidized in the reaction kettle is advantageous because it is less likely to cause a decrease in molecular weight due to hydrolysis over time than the polyimide solution. Further, since the imidization reaction has progressed in advance, for example, in the case of a polyimide having an imidization rate of 100%, imidization on the cast film is unnecessary, and the drying temperature can be lowered.
  • the ring-closed polyimide may be reprecipitated using a poor solvent or the like, purified to a solid, dissolved in a solvent, and cast and dried to form a film.
  • polyamic acid in order to increase the molecular weight of polyamic acid, it is polymerized and cyclized with dimethylacetamide, solidified with methanol, dried, then made into a solution containing an additive with dichloromethane, then cast and dried.
  • dimethylacetamide solidified with methanol
  • dichloromethane a solution containing an additive with dichloromethane
  • dichloromethane when used as a solvent, it can be used in combination with other solvents.
  • a co-solvent such as tetrahydrofuran (THF), dioxolane, cyclohexanone, cyclopentanone, ⁇ -butyrolactone, ethanol, methanol, butanol, ilopropanol can be used as appropriate.
  • the polyamideimide resin can be synthesized by a usual method. For example, an isocyanate method, an amine method (acid chloride method, low temperature solution polymerization method, room temperature solution polymerization method, etc.), etc., but the polyamideimide resin used in the present invention is preferably soluble in an organic solvent, as described above. For reasons such as ensuring the reliability of peel strength (adhesive strength), production by the isocyanate method is preferred. Also, industrially, it is preferable because the solution at the time of polymerization can be applied as it is.
  • the polyimide resin of the present invention is a transparent polyimide resin.
  • the transparent polyimide resin means a polyimide resin having a total light transmittance of 80% or more when a polyimide film having a thickness of 40 ⁇ m is produced from the polyimide resin.
  • the total light transmittance is more preferably 85% or more, and still more preferably 90% or more. A higher total light transmittance is preferable because transparency increases.
  • the description of the numerical value that the total light transmittance is 80% or more shows the preferable range.
  • the total light transmittance of the transparent polyimide resin film can be measured according to JIS K 7375-2008 for one transparent polyimide resin film sample conditioned for 24 hours in an air conditioning room at 23 ° C. and 55% RH.
  • the measurement can measure the transmittance in the visible light region (range of 400 to 700 nm) using a spectrophotometer U-3300 manufactured by Hitachi High-Technologies Corporation.
  • the total light transmittance 80% or more it can be adjusted by selecting the type of polyimide.
  • the transparent polyimide resin of the present invention is preferably a colorless transparent polyimide resin.
  • a yellow index value (YI value) when a transparent polyimide resin film having a thickness of 40 ⁇ m is made of the transparent polyimide resin is 5.0 or less. More preferably, it is in the range of 0.3 to 2.0, and particularly preferably in the range of 0.3 to 1.6. A smaller yellow index value (YI value) is preferable because coloring is less.
  • the description of the numerical value that the yellow index value (YI value) is 5.0 or less indicates the preferable range.
  • the YI value can be adjusted by selecting the type of polyimide.
  • the yellow index value can be obtained according to the YI (yellow index: yellowness index) of the film defined in JIS K 7103.
  • the yellow index value is measured by preparing a film sample and using a spectrophotometer U-3300 manufactured by Hitachi High-Technologies Corporation and the attached saturation calculation program, etc., as a light source specified in JIS Z 8701.
  • the tristimulus values X, Y and Z of the color are obtained, and the yellow index value is obtained according to the definition of the following formula.
  • the transparent polyimide resin of the present invention preferably has a limit amount (solubility) that dissolves in 100 g of dichloromethane at 25 ° C. from the viewpoint of producing a film with high productivity by the solution casting method. If the solubility is 1 g or more, it can be easily produced by the solution casting method. When the solubility is 50 g or more, it is difficult to form a film at the time of casting the solution, and film formation becomes difficult.
  • the solubility of the polyimide according to the present invention can be adjusted by selecting the type of polyimide used in the present invention.
  • polyimides In order to make polyimides soluble, it is effective to reduce the ratio of the structure of imide groups and aromatic hydrocarbons that work in the direction of increasing the planarity of the molecular skeleton of polyimide. It is also effective to introduce structural isomers, bending groups, aliphatic groups or alicyclic groups instead of aromatic groups, and bulky skeletons such as fluorine atoms and fluorenes.
  • Examples of compounds include alicyclic, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4, 5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, (bicyclo [4.2.0] octane -3,4,7,8-tetracarboxylic dianhydride) bicyclo [2.2.1] heptanedimethanamine, the structure having a bending group is 2,3 ', 3,4'-biphenyltetracarboxylic Acid dianhydride, 3,4'-oxydiphthalic anhydride, 4,4 'oxydiphthalic anhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3
  • Examples of the compound containing a fluorine atom include 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 2,2'-bis (trifluoromethyl) benzidine, 2,2-bis (3-amino-4 -Hydroxyphenyl) hexafluoropropane, compounds containing a fluorene group include 9,9-bis (4-amino-3-fluorophenyl) fluorene, 9,9-bis [4- (3,4-dicarboxyphenoxy) ) -Phenyl] fluorene anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -phenyl] fluorene anhydride, 9,9-Bis (3,4-dicboxyphenyl) fluorene Pilot fluorene Dianhydride It is done.
  • Transparent polyimide resin composition Various resins, additives and solvents can be mixed into the transparent polyimide resin of the present invention to obtain a transparent polyimide resin composition.
  • a transparent polyimide resin composition of the present invention it can be used as a material for a resin molded product or the like, in addition to a manufacturing material such as a transparent polyimide resin film described below.
  • a transparent polyimide resin film can be obtained using the above-described transparent polyimide resin and transparent polyimide resin composition of the present invention.
  • additives It is preferable that the following additives are mixed in the transparent polyimide resin film of the present invention.
  • the transparent polyimide resin film of the present invention can contain a mechanical strength modifier. Since the transparent polyimide resin in the present invention contains an aromatic ring in the main chain and has an aromatic ring having a specific NICS value at the polymer terminal, a compound having an aromatic ring is preferable from the viewpoint of improving mechanical strength. It is more preferable to add a compound containing two or more compounds or a compound containing a heteroaromatic ring, and a compound containing two or more aromatic rings or a nitrogen-containing aromatic heterocyclic compound is particularly preferable.
  • Examples of the preferable compound include compounds represented by general formula (1) and general formula (2) described in International Publication No. 2014/109350, compounds containing a 1,3,5-triazine skeleton, Examples thereof include compounds containing a 3-pyrimidine skeleton and polyesters containing an aromatic ring described in paragraph [0040] of JP2013-232005.
  • the transparent polyimide resin film of the present invention has, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, silicic acid. It is preferable to include a matting agent such as inorganic fine particles such as aluminum, magnesium silicate and calcium phosphate, and a crosslinked polymer. Of these, silicon dioxide is preferable because it can reduce the haze of the film.
  • the primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm.
  • These fine particles preferably form secondary particles having a particle size of 0.1 to 5 ⁇ m and are contained in the polyimide.
  • a preferable average particle size is 0.1 to 2 ⁇ m, and more preferably 0.2 to 0.00. 6 ⁇ m.
  • irregularities having a height of about 0.1 to 1.0 ⁇ m are formed on the film surface, thereby providing appropriate slipperiness to the film surface.
  • the primary average particle diameter of the fine particles used in the present invention is measured by observing the particles with a transmission electron microscope (magnification of 500,000 to 2,000,000 times), observing 100 particles, measuring the particle diameter, and measuring the average. Let the value be the primary average particle size.
  • the transparent polyimide resin film of the present invention preferably contains an ultraviolet absorber from the viewpoint of improving light resistance.
  • the ultraviolet absorber is intended to improve light resistance by absorbing ultraviolet rays of 400 nm or less, and the transmittance at a wavelength of 370 nm is preferably in the range of 0.1 to 30%, more preferably. Is in the range of 1-20%, more preferably in the range of 2-10%.
  • the UV absorbers preferably used in the present invention are benzotriazole UV absorbers, benzophenone UV absorbers, and triazine UV absorbers, and particularly preferably benzotriazole UV absorbers and benzophenone UV absorbers.
  • a discotic compound such as a compound having a 1,3,5-triazine ring is also preferably used as the ultraviolet absorber.
  • the transparent polyimide resin film of the present invention preferably contains two or more kinds of ultraviolet absorbers.
  • a polymeric ultraviolet absorber can be preferably used, and in particular, a polymer type ultraviolet absorber described in JP-A-6-148430 is preferably used. Moreover, it is preferable that the ultraviolet absorber does not have a halogen group.
  • the method of adding the UV absorber is to add the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol, butanol, an organic solvent such as dichloromethane, methyl acetate, acetone, dioxolane, or a mixed solvent thereof, or You may add directly in dope composition.
  • an alcohol such as methanol, ethanol, butanol
  • an organic solvent such as dichloromethane, methyl acetate, acetone, dioxolane, or a mixed solvent thereof, or You may add directly in dope composition.
  • the amount of UV absorber used is not uniform depending on the type of UV absorber, usage conditions, etc., but when the dry film thickness of the transparent polyimide resin film is 15 to 50 ⁇ m, it is 0.5% relative to the transparent polyimide resin film.
  • the range of ⁇ 10% by mass is preferred, and the range of 0.6 ⁇ 4% by mass is more preferred.
  • Antioxidant are also referred to as deterioration inhibitors. When an electronic device or the like is placed in a high humidity and high temperature state, the transparent polyimide resin film may be deteriorated.
  • the antioxidant has a role of delaying or preventing the transparent polyimide resin film from being decomposed by, for example, the residual solvent amount of halogen in the transparent polyimide resin film or phosphoric acid of the phosphoric acid plasticizer. It is preferable to make it contain in the transparent polyimide resin film of invention.
  • a hindered phenol compound is preferably used.
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oct Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred.
  • hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
  • the amount of these compounds added is preferably in the range of 1 ppm to 1.0% by mass relative to the transparent polyimide resin film, and more preferably in the range of 10 to 1000 ppm.
  • Phase difference control agent In order to improve the display quality of image display devices such as liquid crystal display devices, a retardation control agent is added to the transparent polyimide resin film, or an alignment film is formed to provide a liquid crystal layer, derived from a polarizing plate protective film and a liquid crystal layer By compounding the above phase difference, optical compensation ability can be imparted to the transparent polyimide resin film.
  • Examples of the retardation control agent include aromatic compounds having two or more aromatic rings as described in European Patent No. 91656A2, and rod-like compounds described in JP-A-2006-2025. Two or more aromatic compounds may be used in combination.
  • the aromatic ring of the aromatic compound is preferably an aromatic heterocyclic ring including an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring.
  • the aromatic heterocycle is generally an unsaturated heterocycle. Of these, the 1,3,5-triazine ring described in JP-A-2006-2026 is preferable.
  • the compound having the structure represented by the general formula (A1) also functions as a phase difference controlling agent.
  • the compound which has a structure represented by general formula (A1) can provide both the function of both phase difference control and optical value fluctuation
  • the amount of these retardation control agents added is preferably in the range of 0.5 to 20% by mass, preferably in the range of 1 to 10% by mass with respect to 100% by mass of the transparent polyimide resin film resin. It is more preferable.
  • preferable release agents include phosphate ester type surfactants, carboxylic acid or carboxylate type surfactants. Agents, sulfonic acid or sulfonate surfactants, and sulfate ester surfactants are effective. A fluorine-based surfactant in which part of the hydrogen atoms bonded to the hydrocarbon chain of the surfactant is substituted with fluorine atoms is also effective. Examples of the release agent are given below.
  • RZ-1 C 8 H 17 O—P ( ⁇ O) — (OH) 2 RZ-2 C 12 H 25 O—P ( ⁇ O) — (OK) 2 RZ-3 C 12 H 25 OCH 2 CH 2 O—P ( ⁇ O) — (OK) 2 RZ-4 C 15 H 31 (OCH 2 CH 2 ) 5 O—P ( ⁇ O) — (OK) 2 RZ-5 ⁇ C 12 H 25 O (CH 2 CH 2 O) 5 ⁇ 2 -P ( O) -OH RZ-6 ⁇ C 18 H 35 (OCH 2 CH 2 ) 8 O ⁇ 2 —P ( ⁇ O) —ONH 4 RZ-7 (tC 4 H 9 ) 3 —C 6 H 2 —OCH 2 CH 2 O—P ( ⁇ O) — (OK) 2 RZ-8 (iso-C 9 H 19 —C 6 H 4 — O— (CH 2 CH 2 O) 5 —P ( ⁇ O) — (OK) (OH) RZ-9 C 12 H 25 SO 3 Na RZ-10 C 12 H
  • the additive contained in the transparent polyimide resin film of the present invention is not limited to the fine particles.
  • the transparent polyimide resin composition and transparent polyimide resin film of the present invention can contain a dye having absorption in the visible to infrared.
  • a dye having absorption in the visible range for example, it can be used for a specific wavelength cut film or the like that can control the wavelength of the display light source and expand the color range.
  • dye which has absorption in an infrared region can be used for the infrared cut film for sensors, for example. By adding these dyes, it becomes possible to adjust to a desired transmittance.
  • the dye having absorption in the visible to infrared and an organic dye or an inorganic dye can be used.
  • organic dyes examples include phthalocyanine dyes, azo dyes, oxocarbon dyes, cyanine dyes, Ni complex dyes, and the like. From the viewpoint of heat resistance and sharpness of absorption, the organic dye is preferably a phthalocyanine dye, an oxocarbon dye, a cyanine dye, or a Ni complex dye, and more preferably an oxocarbon dye.
  • the inorganic dye include metal oxide fine particles and copper complex compounds. Preferred inorganic dyes include tungsten oxide fine particles, indium oxide fine particles, and copper complex fine particles having phosphonic acid as a ligand, and copper complex fine particles having phosphonic acid as a ligand are more preferable.
  • the copper complex fine particles used in the present invention are preferably copper complex fine particles containing phosphonic acid and copper ions described in JP-A-2002-006101, and alkylphosphonic acids having 2 to 6 carbon atoms and copper ions. Particularly preferred are copper complex-based fine particles containing.
  • the dye having visible to infrared absorption used in the transparent polyimide resin composition and transparent polyimide resin film of the present invention may be dissolved in the resin or dispersed as fine particles.
  • the addition amount of the dye having absorption in the visible to infrared region used in the transparent polyimide resin composition and the transparent polyimide resin film of the present invention is not particularly limited, but is preferably in the range of 0.01 to 80% by mass.
  • a range of 05 to 50% by mass is further preferable, and a range of 0.1 to 30% by mass is particularly preferable. It can adjust to a desired transmittance
  • the addition of 0.01% by mass or more makes it possible to control the transmittance. By setting the content within 35% by mass, bleeding out, dye aggregation, and fine particle aggregation are suppressed, and transparency is improved.
  • the transparent polyimide resin film of the present invention preferably has the above-described total light transmittance and YI value, but other preferable physical property values include the following physical property values.
  • the tensile modulus can be measured by the following method according to JIS K7127. 1) A film is cut out to a size of 100 mm (MD direction) ⁇ 10 mm (TD axis) to obtain a test piece. Using a Tensilon RTC-1225A manufactured by Orientec Co., the distance between chucks is 50 mm, the test piece is pulled in the longitudinal direction (MD direction) of the test piece, and the tensile elastic modulus in the MD direction is measured. The measurement can be performed at 23 ° C. and 55% RH. 2) Similarly, the film is cut into a size of 100 mm (TD direction) ⁇ 10 mm (MD direction) to obtain a test piece.
  • test piece is pulled in the length direction (TD direction) in the same manner as described above, and the tensile elastic modulus in the TD direction is measured. 3) The average value of the tensile elastic modulus in the MD direction and the TD direction obtained in 1) and 2) is calculated.
  • the tensile elastic modulus of the transparent polyimide resin film is preferably 4 GPa or more, and more preferably 5 GPa or more.
  • the haze can be measured according to JIS K 7136 using a haze meter NDH-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). Measured under the conditions of 23 ° C. and 55% RH, the light source of the haze meter is a halogen bulb of 5V9W, and the light receiving part is a silicon photocell (with a relative visibility filter).
  • the method for producing a transparent polyimide resin film of the present invention includes a step of preparing a dope obtained by dissolving the transparent polyimide resin of the present invention in an organic solvent, and a step of casting the dope on a support to form a film. including.
  • the method for producing the transparent polyimide resin film of the present invention includes a step of preparing a dope obtained by dissolving the transparent polyimide resin of the present invention in an organic solvent (dope preparation step), and casting the dope on a support.
  • FIG. 1 is a diagram schematically showing an example of a dope preparation step, a casting step, a drying step, and a winding step of a solution casting film forming method preferable for the present invention.
  • the fine particle dispersion in which the solvent and the matting agent are dispersed by the disperser passes from the charging tank 141 through the filter 144 and is stocked in the stock tank 142.
  • the cycloolefin resin as the main dope is dissolved in the dissolving pot 101 together with the solvent, and a matting agent stored in the stock pot 142 is appropriately added and mixed to form the main dope.
  • the obtained main dope is filtered from the filter 103 and the stock kettle 104 by the filter 106, the additive is added by the merge pipe 120, mixed by the mixer 121, and fed to the pressure die 130.
  • additives for example, UV absorbers, antioxidants, etc.
  • a solvent passed from the additive charging pot 110 through the filter 112 and stocked in the stock pot 113.
  • the main dope is mixed by the merging pipe 120 and the mixer 121 through the filter 115 and the conduit 116.
  • the main dope fed to the pressure die 130 is cast on a metal belt-like support 131 to form a web 132, and peeled at a peeling position 133 after predetermined drying to obtain a film.
  • the peeled web 132 is dried until it reaches a predetermined residual solvent amount while passing through a large number of conveying rollers in the first drying device 134 and then stretched in the longitudinal direction or the width direction by the stretching device 135. After stretching, the film is dried while being passed through the transport roller 137 until it reaches a predetermined residual solvent amount by the second drying device 136, and is wound into a roll by the winding device 138.
  • Dope preparation process In the method for producing the transparent polyimide resin film of the present invention, it is preferable that a dope is prepared by dissolving a transparent polyimide resin in a solvent, and the dope is used to form a film by a solution casting film forming method.
  • a low-boiling solvent having a boiling point of 80 ° C. or lower as the main solvent because the film production process temperature (particularly the drying temperature) can be reduced and the thermal shrinkage can be reduced.
  • “used as a main solvent” means that if it is a mixed solvent, 55% by mass or more is used with respect to the total amount of the solvent, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably. Is 90% by mass or more. Of course, if it is used alone, it becomes 100% by mass.
  • the low boiling point solvent only needs to dissolve polyimide and other additives at the same time.
  • dichloromethane as the non-chlorinated solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, Methyl ethyl ketone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3- Difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2, 2,3,3,3-pentafluoro-1-propanol, nitroethane, methanol, ethanol, n-propanol,
  • the low boiling point solvent having a boiling point of 80 ° C. or less among the above solvents, dichloromethane (40 ° C.), ethyl acetate (77 ° C.), methyl ethyl ketone (79 ° C.), tetrahydrofuran (66 ° C.), acetone (56.5 ° C.) And at least one selected from 1,3-dioxolane (75 ° C.) as a main solvent (the parentheses each represent a boiling point).
  • a poor solvent such as hexane, heptane, benzene, toluene, xylene, chlorobenzene, or o-dichlorobenzene is used to such an extent that the polyimide and the organic compound having a carbonyl group according to the present invention do not precipitate. May be.
  • Alcohol solvents can also be used.
  • the alcohol solvent is preferably selected from methanol, ethanol, and butanol from the viewpoint of improving peelability and enabling high-speed casting. Of these, methanol or ethanol is preferably used. When the ratio of the alcohol in the dope increases, the web gels and peeling from the metal support becomes easy.
  • a method carried out at normal pressure a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544, JP-A-9-
  • Various dissolution methods can be used, such as a method using the cooling dissolution method described in JP-A-95557 or JP-A-9-95538, and a method using high pressure described in JP-A-11-21379.
  • the prepared dope is guided to a filter by a liquid feed pump or the like and filtered.
  • the main solvent of the dope is dichloromethane
  • the gel-like foreign matter in the dope can be removed by filtering the dope at a temperature of boiling point at 1 atm of the dichloromethane + 5 ° C. or more.
  • a preferred temperature range is 45 to 120 ° C, more preferably 45 to 70 ° C, and even more preferably within a range of 45 to 55 ° C.
  • a raw material for the resin used for preparing the dope a material obtained by pelletizing polyimide and other compounds in advance can be preferably used.
  • the prepared dope is fed to a die through a feed pump (for example, a pressurized metering gear pump), and cast on an endless support that moves indefinitely, such as a stainless steel belt or a metal support such as a rotating metal drum. Cast the dope from the die into position.
  • a feed pump for example, a pressurized metering gear pump
  • an endless support that moves indefinitely, such as a stainless steel belt or a metal support such as a rotating metal drum. Cast the dope from the die into position.
  • the metal support in casting (cast) is preferably a mirror-finished surface, and the support is a stainless steel belt or a drum whose surface is plated with a casting, or a metal support such as a stainless steel belt or a stainless steel belt. Is preferably used.
  • the cast width can be in the range of 1 to 4 m, preferably in the range of 1.5 to 3 m, more preferably in the range of 2 to 2.8 m.
  • the support may not be made of metal, for example, polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polybutylene terephthalate (PBT) film, nylon 6 film, nylon 6,6 film, polypropylene film.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • nylon 6 film nylon 6,6 film
  • polypropylene film polypropylene film.
  • a belt made of polytetrafluoroethylene or the like can be
  • the traveling speed of the metal support is not particularly limited, but is usually 5 m / min or more, preferably 10 to 180 m / min, particularly preferably 80 to 150 m / min. As the traveling speed of the metal support increases, entrained gas is more likely to be generated, and the occurrence of film thickness unevenness due to disturbance is more pronounced.
  • the traveling speed of the metal support is the moving speed of the outer surface of the metal support.
  • the die has a shape that becomes gradually narrower toward the discharge port in the vertical cross section with respect to the width direction.
  • the die usually has tapered surfaces on the downstream side and the upstream side in the lower traveling direction, and a discharge port is formed in a slit shape between the tapered surfaces.
  • a die made of metal is preferably used, and specific examples include stainless steel, titanium, and the like. In the present invention, when manufacturing films having different thicknesses, it is not necessary to change to dies having different slit gaps.
  • ⁇ It is preferable to use a pressure die that can adjust the slit shape of the die base and easily make the film thickness uniform.
  • the pressure die include a coat hanger die and a T die, and any of them is preferably used. Even when films with different thicknesses are continuously manufactured, the discharge rate of the dies is maintained at a substantially constant value. Therefore, when a pressure die is used, conditions such as extrusion pressure and shear rate are also substantially reduced. Maintained at a constant value.
  • two or more pressure dies may be provided on the metal support, and the dope amount may be divided and laminated.
  • the solvent evaporation step is a pre-drying step which is performed on a metal support and the cast film is heated on the metal support to evaporate the solvent.
  • a method of appropriately selecting and combining them is also preferable.
  • the surface temperature of the metal support may be the same as a whole or may vary depending on the position.
  • the temperature of the heating air is preferably in the range of 10 to 220 ° C.
  • the temperature of the heating air (drying temperature) is preferably 200 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 120 ° C. or lower.
  • the solvent evaporation step it is preferable to dry the cast film until the residual solvent amount is in the range of 10 to 150% by mass from the viewpoint of the peelability of the cast film and the transportability after peeling.
  • the amount of residual solvent can be expressed by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100
  • M is the mass at a predetermined point of the casting membrane (film)
  • N is the mass when M is dried at 200 ° C. for 3 hours.
  • M when calculating the amount of residual solvent achieved in the solvent evaporation step is the mass of the cast film immediately before the peeling step.
  • the peeling tension when peeling the metal support from the casting film is usually in the range of 60 to 400 N / m. However, if wrinkles are likely to occur during peeling, peeling is performed with a tension of 190 N / m or less. It is preferable.
  • the temperature at the peeling position on the metal support is preferably in the range of ⁇ 50 to 60 ° C., more preferably in the range of 10 to 40 ° C., and in the range of 15 to 40 ° C. Is most preferred.
  • the peeled film may be sent directly to the stretching process, or may be sent to the stretching process after being sent to the first drying process so as to achieve a desired residual solvent amount.
  • the film is sequentially sent to the first drying step and the stretching step after the peeling step.
  • the first drying step is a drying step in which the film is heated and the solvent is further evaporated.
  • the drying means is not particularly limited, and for example, hot air, infrared rays, a heating roller, microwaves and the like can be used. From the viewpoint of simplicity, it is preferable to dry with hot air or the like while transporting the film with rollers arranged in a staggered manner.
  • the drying temperature is preferably in the range of 30 to 200 ° C., taking into account the amount of residual solvent and the stretching ratio during conveyance.
  • the drying temperature is preferably 200 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 120 ° C. or lower.
  • the heat shrinkage rate of the film can be increased.
  • the stretching operation may be performed in multiple stages. Moreover, when performing biaxial stretching, simultaneous biaxial stretching may be performed and you may implement in steps.
  • stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible.
  • the preferred draw ratio for simultaneous biaxial stretching can be in the range of x1.01 to x1.5 in both the width direction and the longitudinal direction.
  • the amount of residual solvent at the start of stretching is preferably in the range of 0.1 to 200% by mass.
  • the amount of the residual solvent is 0.1% by mass or more, the effect of improving the flatness by stretching is obtained, and if it is 200% or less, stretching is easy.
  • the film may be stretched in the longitudinal direction or the width direction, preferably in the width direction, so that the film thickness after stretching is in a desired range.
  • the transparent polyimide resin film is preferably stretched in a temperature range of (Tg ⁇ 200) to (Tg + 100) ° C. with respect to the glass transition temperature (Tg). If it extends in the said temperature range, since a extending
  • the stretching temperature is more preferably in the range of (TgL ⁇ 150) to (TgH + 50) ° C.
  • the self-supporting film peeled from the support can be stretched in the longitudinal direction by regulating the running speed with a stretching roller.
  • the entire width of the film is held with clips or pins in the width direction in the entire drying process or a part of the process as disclosed in JP-A-62-46625.
  • a method of drying while drying (referred to as a tenter method), among which a tenter method using a clip is preferably used.
  • the film stretched in the longitudinal direction or the unstretched film is preferably introduced into the tenter in a state where both ends in the width direction are held by the clip, and stretched in the width direction while running with the tenter clip.
  • stretching in the width direction stretching in the width direction of the film at a stretching speed in the range of 50 to 1000% / min is preferable from the viewpoint of improving the flatness of the film.
  • the stretching speed is 50% / min or more, the planarity is improved and the film can be processed at high speed, which is preferable from the viewpoint of production aptitude, and if it is within 1000% / min, the film is broken. Can be processed without any problem.
  • More preferable stretching speed is in the range of 100 to 500% / min.
  • the stretching speed is defined by the following formula.
  • Stretching speed (% / min) [(d 1 / d 2 ) ⁇ 1] ⁇ 100 (%) / t
  • d 1 is the width dimension in the stretching direction of the resin film after stretching
  • d 2 is the width dimension in the stretching direction of the resin film before stretching
  • t is the time (min) required for stretching. .
  • the stretching step usually, after stretching, holding and relaxation are performed. That is, in this step, it is preferable to perform a stretching step for stretching the film, a holding step for holding the film in a stretched state, and a relaxation step for relaxing the film in the stretched direction in this order.
  • the drawing at the draw ratio achieved in the drawing step is held at the drawing temperature in the drawing step.
  • the relaxation stage the stretching in the stretching stage is held in the holding stage, and then the stretching is relaxed by releasing the tension for stretching.
  • the relaxation step may be performed at a temperature lower than the stretching temperature in the stretching step.
  • the stretched film is heated and dried.
  • a means for preventing the mixing of used hot air by installing a nozzle capable of exhausting used hot air (air containing solvent or wet air) is also preferably used.
  • the hot air temperature is more preferably in the range of 40 to 350 ° C.
  • the drying time is preferably about 5 seconds to 30 minutes, more preferably 10 seconds to 15 minutes.
  • the heating and drying means is not limited to hot air, and for example, infrared rays, heating rollers, microwaves, etc. can be used. From the viewpoint of simplicity, it is preferable to dry with hot air or the like while transporting the film with rollers arranged in a staggered manner.
  • the drying temperature is preferably in the range of 40 to 150 ° C. from the viewpoint of easy heating shrinkage. More preferably, it is 40 to 120 ° C.
  • the second drying step it is preferable to dry the film until the residual solvent amount is 0.5% by mass or less.
  • Winding process is a process of winding up the obtained transparent polyimide resin film, and cooling to room temperature.
  • the winding machine may be a commonly used one, and can be wound by a winding method such as a constant tension method, a constant torque method, a taper tension method, a program tension control method with a constant internal stress, or the like.
  • the thickness of the transparent polyimide resin film is not particularly limited, and is preferably in the range of 1 to 200 ⁇ m, particularly 1 to 100 ⁇ m, for example.
  • both ends of the transparent polyimide resin film sandwiched between tenter clips when stretched and conveyed may be slit.
  • the slit end portion of the transparent polyimide resin film is preferably cut into a width of 1 to 30 mm, then dissolved in a solvent and reused as a recycled material.
  • Each process from the solvent evaporation process to the winding process described above may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas. Moreover, each process, especially a drying process and a extending process, are performed in consideration of the explosion limit concentration of the solvent in the atmosphere.
  • Heating process After the winding step, a heating step of further heat-treating the transparent polyimide resin film dried in the second drying step in order to improve imidization in the polymer chain molecules and between the polymer chain molecules to improve mechanical properties. You can go.
  • the said 2nd drying process may serve as a heating process.
  • the heating means is performed using a known means such as hot air, an electric heater, or a microwave.
  • a known means such as hot air, an electric heater, or a microwave.
  • the electric heater the above-described infrared heater can be used.
  • the heating step if the transparent polyimide resin film is heated rapidly, problems such as an increase in surface defects occur, and therefore it is preferable to select a heating method as appropriate.
  • the heating step is preferably performed in a low oxygen atmosphere.
  • the heating temperature in the second drying step and the heating step exceeds 450 ° C.
  • the energy required for heating becomes very large, resulting in an increase in manufacturing cost and an increase in environmental load.
  • the following is preferable.
  • the transparent polyimide resin film of the present invention is preferably long, specifically, preferably has a length in the range of about 100 to 10,000 m, and is wound into a roll. Further, the width of the transparent polyimide resin film of the present invention is preferably 1 m or more, more preferably 1.4 m or more, and particularly preferably 1.4 to 4 m.
  • the transparent polyimide resin film of the present invention can be used as a coating film in addition to the single film as described above.
  • a transparent polyimide resin composition (infrared absorbing composition) of the present invention containing an infrared absorbing compound is applied as an infrared absorbing layer on a silicon wafer or a color filter for an image sensor and dried to form a film.
  • the film can be used as it is without being peeled off, or can be used without being peeled off by applying a transparent polyimide resin composition as an infrared absorbing layer to an elemental glass or phosphoric acid glass and drying it.
  • the infrared absorbing layer is preferably a near infrared absorbing layer.
  • the film thickness of the infrared absorbing layer is usually 20 to 200 ⁇ m, preferably 50 to 100 ⁇ m.
  • it is usually 0.1 to 100 ⁇ m, preferably 0.5 to 10 ⁇ m.
  • the transparent polyimide resin film of the present invention may be formed on a substrate, and there is no particular limitation on the type of glass, plastic and the like, and it may be transparent or opaque.
  • the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, transparent electrodes such as ITO, and transparent resin films.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel
  • the glass substrate is not particularly limited as long as it is a glass substrate containing silicate as a main component, and examples thereof include a quartz glass substrate having a crystal structure.
  • an absorption glass substrate in which CuO or the like is added to fluorophosphate glass or phosphate glass, a borosilicate glass substrate, a soda glass substrate, a colored glass substrate, an alkali-free glass substrate, a quartz glass substrate, or the like is used.
  • glass substrates such as alkali-free glass substrates and low ⁇ -ray glass substrates are preferred.
  • the other constituent layers constituting the image sensor are not particularly limited.
  • the dielectric multilayer film is configured by alternately laminating a low refractive index dielectric film and a high refractive index dielectric film.
  • the low refractive index and the high refractive index mean having a low refractive index and a high refractive index with respect to the refractive index of the adjacent layer.
  • the high refractive index dielectric film preferably has a refractive index (nd) of 1.6 or more, more preferably in the range of 2.2 to 2.5.
  • the high refractive index dielectric film material include Ta 2 O 5 , TiO 2 , and Nb 2 O 5 . Of these, TiO 2 is preferable from the viewpoints of film formability, reproducibility in refractive index, and stability.
  • the low refractive index dielectric film preferably has a refractive index (nd) of less than 1.6, more preferably 1.45 or more and less than 1.55, and even more preferably 1.45 to 1. Within the range of .47.
  • the low refractive index dielectric material include SiO x N y .
  • SiO 2 is desirable from the viewpoints of film reproducibility, stability, economy, and the like.
  • a vacuum film formation process such as a CVD method, a sputtering method, or a vacuum deposition method, or a wet film formation process such as a spray method or a dip method can be used.
  • the average transmittance of light having a wavelength of 430 to 620 nm is preferably 90% or more, more preferably 92% or more, and further preferably 95% or more in the spectral transmittance curve at an incident angle of 0 °.
  • the average transmittance of light having a wavelength of 710 to 1100 nm is preferably 10% or less, more preferably 8% or less, and further preferably 5% or less.
  • the dielectric multilayer film is preferably 15 or more, more preferably 25 or more, more preferably 30 or more as the total number of laminated layers of the low refractive index dielectric layer and the high refractive index dielectric layer. Is more preferable. However, when the total number of laminated layers increases, the warp of the dielectric multilayer film increases, and the total film thickness increases.
  • the film thickness is preferably thin from the viewpoint of reducing the thickness of the optical filter after satisfying the preferred number of seat layers.
  • the film thickness of such a dielectric multilayer film is preferably in the range of 2 to 10 ⁇ m.
  • the transparent polyimide resin film of the present invention can be preferably used as a transparent FPC, an in-vehicle film, a film member of an image display device, and a sensor film.
  • the device to be applied is not particularly limited.
  • an organic electroluminescence (EL) image display device a liquid crystal image display device (LCD), an organic photoelectric conversion device, a touch panel, a polarizing plate, a retardation film, a transparent FPC film, an image Examples include an infrared cut film for sensors, an infrared cut film for iris authentication, and the like.
  • the polyimide resin film of the present invention can be used as a transparent conductive film for a touch panel by providing the film with a transparent conductive layer.
  • the shape of the pattern of the transparent conductive layer is not particularly limited as long as it is a pattern that works well as a touch panel (for example, a capacitive touch panel).
  • a touch panel for example, a capacitive touch panel.
  • a touch panel can be produced by laminating a transparent conductive film patterned on the x-axis and a transparent conductive film patterned on the y-axis using an adhesive film and providing a cover glass on the outermost surface.
  • a touch panel display device can be manufactured by combining with a display device.
  • the transparent polyimide resin film of the present invention can be used as an LED substrate to provide an LED certification device.
  • a composite substrate with a double-sided substrate or an aluminum plate can be used.
  • heat dissipation is required as the brightness of the LED increases, it is possible to improve the heat dissipation by combining with an aluminum plate.
  • the present invention can also be applied to an organic electroluminescence lighting device using an organic material.
  • the transparent polyimide resin film of the present invention can also be used as a front member for a flexible display.
  • a flexible display on which a front member for flexible display is mounted for example, an organic EL device in which an organic functional layer such as a light emitting layer is laminated on a substrate, a gas barrier film, a film color filter, polarizing plate protection on one side or both sides A polarizing plate including a film, a film-type touch sensor, and the like are laminated in this order.
  • the front member for flexible display is laminated
  • the transparent polyimide resin film of this invention may be used for the board
  • Dicarboxylic acid anhydrides and diamines used for the synthesis of polyimide were samples purified by recrystallization or column chromatography.
  • Example 1 ⁇ Preparation of polyimide resin film 1> To a 4-neck flask equipped with a dry nitrogen gas inlet tube, a condenser, a Dean-Stark agglomerator filled with toluene, and a stirrer, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1, 4,4.4 g (0.10 mol) of 3,3,3-hexafluoropropane dianhydride (manufactured by Daikin Industries, Ltd.) was added to N, N-dimethylacetamide (400 g), and the mixture was stirred at room temperature under a nitrogen stream.
  • 2,2-bis (3,4-dicarboxyphenyl) -1,1,1, 4,4.4 g 2,2-bis (3,4-dicarboxyphenyl) -1,1,1, 4,4.4 g (0.10 mol) of 3,3,3-hexafluoropropane dianhydride (manufactured by Daikin Industries, Ltd.) was added
  • IR absorption analysis (IR) measurement was performed using FT / IR-670Plus manufactured by JASCO Corporation. Absorbance of IR imide group (near 1375CM -1 ) / (absorbance of IR benzene ring (near 1500 cm -1 )) )), It was confirmed that the imidation ratio was 95% or more.
  • Polyimide resin films 2 to 60 were obtained by the same molar ratio and synthesis method as those of polyimide resin film 1 except that the monomers used and the end-capping compounds were changed to compounds capable of obtaining the partial structure shown in Table 2.
  • a plurality of dicarboxylic acid anhydrides when a plurality of dicarboxylic acid anhydrides are used, a plurality of types of dicarboxylic acid anhydrides are dissolved simultaneously, and when a plurality of diamine compounds are used, they are simultaneously dissolved in N, N-dimethylacetamide. It was added dropwise to the reaction solution later.
  • the total amount of the dicarboxylic acid to be used, the total amount of the diamine compound, and the total amount of the end-capping agent were added so as to have the same molar amount as the material constituting the polyimide resin film 1. Moreover, when using together 2 types of dicarboxylic acid or a diamine compound, the mixing ratio of 2 types of compounds was added by equimolar amount of 1: 1.
  • the imidization rate was measured by the same method as for the polyimide resin film 1, and it was confirmed that the imidization rate was 95% or more.
  • 2,2′-bis (trifluoromethyl) benzidine (32.0 g, 0.10 mol) was added thereto, and the mixture was heated and stirred at 40 ° C. for 10 hours.
  • the reaction solution was uniformly cast on a stainless steel belt support at a temperature of 40 ° C. and a width of 150 mm. The temperature of the stainless steel belt was controlled at 40 ° C.
  • the stainless steel belt was put into a 50 ° C. vacuum oven and the pressure was reduced to 0.1 kPa, followed by heat drying for 1 hour. Thereafter, the temperature was set to 220 ° C., and heat drying was performed for 6 hours. The oven was cooled and the film was peeled from the stainless steel belt to obtain a polyimide resin film 61 having a thickness of 40 ⁇ m. It was confirmed that the imidation ratio was 95% or more by the same method as for the polyimide resin film 1.
  • Polyimide resin films 62 to 64 were obtained by the same molar ratio and synthesis method as those of the polyimide resin film 61 except that the monomers used and the end-capping compounds were changed to compounds that give the partial structures shown in Table 2.
  • the imidization rate was measured by the same method as that for the polyimide resin film 1, and it was confirmed that the imidization rate was 95% or more.
  • Polyimide resin films 65 to 73 were obtained by the same molar ratio and synthesis method as those of the polyimide resin film 1 except that the monomers used and the end-capping compounds were changed to compounds capable of obtaining the partial structures shown in Table 2. It was confirmed that the imidation ratio was 95% or more by the same method as for the polyimide resin film 1.
  • a polyimide resin having a terminal sealed with phthalic anhydride was prepared in the same manner as described in paragraphs [0094] to [0096] of JP2012-251080A.
  • the obtained resin was uniformly cast on a stainless steel belt support at a temperature of 40 ° C. and a width of 150 mm so that the thickness after drying was 40 ⁇ m.
  • the temperature of the stainless steel belt was controlled at 40 ° C.
  • the stainless steel belt was put into a reduced pressure oven at 50 ° C., the pressure was reduced to 0.1 kPa, and heating was performed at a reduced pressure for 30 minutes. Thereafter, the temperature was raised to 200 ° C. by 1 ° C. in 1 minute while maintaining the reduced pressure, and then heated under reduced pressure for 4 hours.
  • the oven was cooled and the film was peeled from the stainless steel belt to obtain a polyimide resin film 74 having a thickness of 40 ⁇ m.
  • the terminal group of the synthesized comparative compound was made to have the following partial structure.
  • the * part is bonded to the main chain part of the polyimide.
  • the elastic modulus, bending resistance, and YI value of the polyimide resin films 1 to 74 produced as described above were evaluated as follows.
  • the weight average molecular weights of the polyimide resin films 1 to 74 were all in the range of 100,000 to 250,000.
  • the prepared polyimide resin film was stored for 24 hours in an environment of 23 ° C. and 55% RH. Thereafter, the elastic modulus was measured according to the method described in JIS K7127 under the environment of 23 ° C. and 55% RH. Tensilon RTA-100 manufactured by Orientec Co., Ltd. was used as the tensile tester. The shape of the test piece was No. 1 type test piece, and the test speed was 10 mm / min. Based on the numerical value of the obtained elastic modulus, it was evaluated according to the following criteria.
  • a 5.0 GPa or more B 4.0 GPa or more and less than 5.0 GPa C less than 4.0 GPa (bending resistance)
  • the prepared polyimide resin film was subjected to a bending resistance test (sliding bending test) using a bending fatigue tester. Evaluation was continued under the conditions of a load of 500 G, a refraction angle of 135 °, a refraction cycle of 175 cpm, and a refractive portion locality radius of 0.38 mm until the bent portion became cloudy by visual observation.
  • the polyimide resin film of the present invention was an excellent polyimide resin film with no white turbidity at the bent portion even when the number of folding times was 5000 times or more, and little curling after the bending test.
  • the yellow index value is measured according to JIS Z8701 using the spectrophotometer U-3300 manufactured by Hitachi High-Technologies Corporation and the attached saturation calculation program. The tristimulus values X, Y, and Z of the light source color being obtained were obtained, and the yellow index value was obtained according to the following formula.
  • the YI value was evaluated as a measure of the transparency of the polyimide resin film.
  • Yellow index (YI) 100 (1.28X-1.06Z) / Y A: Less than 2.0 B: 2.0 or more and less than 4.0 C: 4.0 or more and less than 5.0 D: 5.0 or more and less than 6.0
  • YI Yellow index
  • the NICS values in the table were calculated using Gaussian 03 (Revision B.03, US Gaussian software). Specifically, from the structure optimized using B3LYP (density functional method) as the calculation method and 6-31 + G (function in which the diffusion gauss function is added to the split valence basis set) as the basis function, the NMR shielding constant It is calculated by a calculation method (GIAO).
  • GIAO a calculation method
  • the NICS value was calculated by substituting the * part of the partial structure of the exemplified compound and the comparative compound with a saturated hydrocarbon.
  • evaluation 1 is the value of the ring with the largest NICS value among the aromatic rings, and was classified according to the following criteria.
  • D The ring with the largest NICS value among the aromatic rings The value of is greater than ⁇ 8.0
  • the evaluation 2 is the case where there are two or more aromatic rings, and was classified according to the following criteria.
  • Example 2 Of the polyimide resin films prepared in Example 1, polyimide resin film numbers 1, 6, 30, 43 to 57, 66, 69, 70, 72 were redissolved in a mixed solvent of dichloromethane and ethanol, and film number 24 , 33 were redissolved in cyclohexanone, and each polyimide resin film was prepared by the following method.
  • polyimide resin film C1 ⁇ Preparation of polyimide resin film C1>
  • the polyimide resin film 1 produced in Example 1 was dissolved in 30 g, 200 g of dichloromethane, and 5 g of ethanol, formed on a glass substrate at 25 ° C., and then peeled and dried by heating in an oven at 120 ° C. for 20 minutes for 40 ⁇ m polyimide. Resin film C1 was obtained.
  • a polyimide resin film C2 was produced in the same manner as the production of the polyimide resin film C1, except that the polyimide resin film to be re-dissolved was changed to the polyimide resin film 6 of Example 1.
  • Polyimide resin films C3 and C4 were produced in the same manner as the production of the polyimide resin film C1, except that the polyimide resin film 24 and the polyimide resin film 33 were changed and the solvent was changed to 200 g of cyclohexanone.
  • Polyimide resin films C5 to C24 were produced in the same manner as the production of the polyimide resin film C1, except that the polyimide resin film 1 was changed to a film having the resin composition shown in the table.
  • the transparent polyimide resin film of the present invention had good elastic modulus, bending resistance, and YI value.
  • Example 3 The following additives were added to the polyimide resin films C1 to C24 obtained in Example 2 at a ratio of 5% by mass with respect to the polyimide resin to prepare polyimide resin films D1 to D24 in the same manner as in Example 2. Evaluation similar to Example 2 was performed with respect to each obtained polyimide resin film.
  • the transparent polyimide resin film of the present invention had good elastic modulus, bending resistance, and YI value.
  • the dimensional stability due to wet heat is improved when stored in an environment of 60 ° C. and 90% RH for 500 hours.
  • Example 4 ⁇ Preparation of polyimide resin film E1> 30 g of the polyimide resin film 11 prepared in Example 1, 200 g of dichloromethane, 5 g of ethanol, and 30 mg of the following infrared-absorbing organic dye 1 were added and dissolved, formed on a glass substrate at 25 ° C., and 120 ° C. after peeling. Was dried in an oven for 20 minutes to obtain a 40 ⁇ m polyimide resin film E1.
  • polyimide resin film E2> 30 g of the polyimide resin film 44 prepared in Example 1, 200 g of dichloromethane, 5 g of ethanol, and 30 mg of the following organic dye 1 were added and dissolved, and the film was formed on a glass substrate at 25 ° C.
  • Polyimide resin films E6 to E10 were produced in the same manner except that the organic dye of the polyimide resin films E1 to E5 was changed to the organic dye 2.
  • Polyimide resin films E11 to E15 were produced in the same manner except that the organic dye of the polyimide resin films E1 to E5 was changed to the organic dye 3.
  • An IR cut filter was produced by forming a dielectric multilayer film on the polyimide resin films E1 to E15 by the following method.
  • a dielectric composed of two layers of a 30 nm layer made of Al 2 O 3 and a 165 nm layer made of SiO 2 is used.
  • the body layer was formed in this order.
  • the refractive index of the layer made of Al 2 O 3 formed was 1.60, and the refractive index of the layer made of SiO 2 formed was 1.45.
  • An image sensor was prepared using the composition as a mixed color filter with reference to Japanese Patent Application Laid-Open No. 2016-72266.
  • polyimide resin films E4 to E5, E9 to E10, and E14 to E15 did not satisfy sufficient performance.
  • the polyimide resin films E4 to E5, E9 to E10, and E14 to E15 are considered to be due to the progress of decomposition of the organic dye due to the heat and stress applied during the dielectric multilayer film fabrication process and sensor fabrication.
  • Example 5 An IR cut filter was prepared by forming a polyimide thin film to which a dielectric multilayer film and a dye were added on a glass substrate by the following method.
  • Asahi Glass fluorophosphate glass substrate NF-50TX (hereinafter referred to as “glass substrate A”) having a size of 76 mm ⁇ 76 mm ⁇ 0.214 mm is obtained by using Asahi Glass hydrofluoroether solvent Asahiklin (registered trademark) AE3000 (trade name). Washed for 10 minutes with a sonic cleaner. A high refractive index film and a low refractive index film are alternately formed on one main surface of the cleaned glass substrate A obtained above using an IAD vacuum vapor deposition apparatus, and then totaled.
  • dielectric multilayer film R a near-infrared reflective dielectric multilayer film (hereinafter, dielectric multilayer film R) as a first dielectric multilayer film having 40 layers (total layer thickness: 5950 nm). ) was formed. Note that TiO 2 was used as the high refractive index material, and SiO 2 was used as the low refractive index material.
  • the glass substrate A having the dielectric multilayer film R obtained above was washed again with an ultrasonic cleaner for 20 minutes using the Asahi Glass hydrofluoroether solvent Asahiklin (registered trademark) AE3000.
  • a 30 nm layer made of Al 2 O 3 and a 170 nm layer made of SiO 2 were formed using a vacuum deposition apparatus. These two dielectric layers were formed in this order.
  • the refractive index of the layer made of Al 2 O 3 formed was 1.60
  • the refractive index of the layer made of SiO 2 formed was 1.45.
  • An image pickup device was manufactured using the composition as a mixed color filter with reference to Japanese Patent Application Laid-Open No. 2016-72266.
  • a CMOS sensor and a CCD sensor using the laminates 1 to 3, 6 to 8, and 11 to 13 were used. Showed good performance.
  • the laminates 4, 5, 9, 10, 14, and 15 did not satisfy sufficient performance.
  • the laminates 4, 5, 9, 10, 14, and 15 are considered to have been caused by the decomposition of the organic dye due to heat and stress applied during the dielectric multilayer film production process and sensor production.
  • the present invention is used for a transparent polyimide resin film, a transparent polyimide resin composition, a transparent polyimide resin film, an infrared absorbing composition, an infrared cut filter, and a method for producing a transparent polyimide resin film, which have good film transparency and excellent mechanical strength. can do.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La résine polyimide transparente selon la présente invention est caractérisée en ce qu'au moins l'une des extrémités du polyimide présente, soit un groupe terminal présentant un cycle aromatique qui présente une valeur NICS (nucleus-independent chemical shift - déplacement chimique indépendant du noyau)se situant dans la plage allant de -15,0 à -8,0, soit un groupe terminal présentant deux cycles aromatiques ou plus qui présentent une valeur NICS se situant dans la plage de -15,0 à -7,0.
PCT/JP2017/036735 2016-10-12 2017-10-11 Résine polyimide transparente, composition de résine polyimide transparente, film de résine polyimide transparente, composition absorbant les infrarouges, filtre bloquant les infrarouges et procédé de production pour un film de résine polyimide transparent WO2018070398A1 (fr)

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WO2020159183A1 (fr) * 2019-02-01 2020-08-06 주식회사 엘지화학 Film polymère à base de polyimide et substrat pour dispositif d'affichage et dispositif optique, l'utilisant chacun
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KR20210038274A (ko) * 2019-09-30 2021-04-07 주식회사 엘지화학 폴리이미드계 수지 필름 및 이를 이용한 디스플레이 장치용 기판, 및 광학 장치
KR20210038249A (ko) * 2019-09-30 2021-04-07 주식회사 엘지화학 폴리이미드계 수지 필름 및 이를 이용한 디스플레이 장치용 기판, 및 광학 장치
US20220208903A1 (en) * 2020-12-30 2022-06-30 Lg Display Co., Ltd. Organic light emitting display device and manufacturing method thereof
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KR102427759B1 (ko) 2019-09-30 2022-07-29 주식회사 엘지화학 폴리이미드계 수지 필름 및 이를 이용한 디스플레이 장치용 기판, 및 광학 장치
KR102427758B1 (ko) 2019-09-30 2022-07-29 주식회사 엘지화학 폴리이미드계 수지 필름 및 이를 이용한 디스플레이 장치용 기판, 및 광학 장치
KR102427760B1 (ko) 2019-09-30 2022-08-01 주식회사 엘지화학 폴리이미드계 수지 필름 및 이를 이용한 디스플레이 장치용 기판, 및 광학 장치
US20220208903A1 (en) * 2020-12-30 2022-06-30 Lg Display Co., Ltd. Organic light emitting display device and manufacturing method thereof

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