WO2023149435A1 - Composition de résine, objet moulé et film - Google Patents

Composition de résine, objet moulé et film Download PDF

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Publication number
WO2023149435A1
WO2023149435A1 PCT/JP2023/003097 JP2023003097W WO2023149435A1 WO 2023149435 A1 WO2023149435 A1 WO 2023149435A1 JP 2023003097 W JP2023003097 W JP 2023003097W WO 2023149435 A1 WO2023149435 A1 WO 2023149435A1
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Prior art keywords
polyimide
bis
dianhydride
film
resin
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PCT/JP2023/003097
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English (en)
Japanese (ja)
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文康 石黒
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株式会社カネカ
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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
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • 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

Definitions

  • the present invention relates to resin compositions and molded articles such as films.
  • transparent polyimide Because transparent polyimide has transparency and high heat resistance, it is used for display substrates and cover films.
  • a normal polyimide film is obtained by coating a polyamic acid solution, which is a polyimide precursor, on a support in the form of a film, and subjecting it to a high temperature treatment to remove the solvent and perform thermal imidization at the same time.
  • the heating temperature for thermal imidization is high (for example, 300 ° C. or higher), and coloring (increase in yellowness) due to heating is likely to occur, making it difficult to apply to applications requiring high transparency such as cover films for displays. Have difficulty.
  • Patent Document 1 discloses that polyimides containing bis-trimellitic anhydride esters as tetracarboxylic dianhydride components are soluble in low-boiling solvents such as methylene chloride and have excellent transparency and mechanical strength. is described.
  • an object of the present invention is to provide a transparent film having high heat resistance and excellent transparency and light resistance, and a resin composition used for producing the same.
  • the present inventors have found that polyimides having a specific chemical structure and acetylcellulose-based resins show compatibility, and by using a resin composition in which these are mixed, a highly transparent film can be produced without impairing the excellent heat resistance of polyimides. We have found that it is possible, and have solved the above problems.
  • One aspect of the present invention relates to a film and a resin composition containing a polyimide resin and an acetylcellulose resin.
  • the resin composition may contain a polyimide resin and an acetylcellulose resin in a weight ratio ranging from 98:2 to 2:98.
  • the polyimide contains an alicyclic tetracarboxylic dianhydride as the tetracarboxylic dianhydride component, an alicyclic tetracarboxylic dianhydride as the tetracarboxylic dianhydride component, and a fluoroalkyl-substituted benzidine as the diamine component. including.
  • the amount of the alicyclic tetracarboxylic dianhydride relative to the total amount of the tetracarboxylic dianhydride component of the polyimide is preferably 10 to 100 mol%.
  • the alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4 ,5-cyclohexanetetracarboxylic dianhydride and 1,1′-bicyclohexane-3,3′,4,4′tetracarboxylic acid-3,4:3′,4′-dianhydride are preferred.
  • the amount of the fluoroalkyl-substituted benzidine with respect to the total amount of the diamine component of the polyimide is preferably 50 mol% or more.
  • perfluoroalkyl-substituted benzidine such as 2,2'-bis(trifluoromethyl)benzidine is preferred.
  • the degree of acetyl substitution of the acetylcellulose-based resin may be 2.4 or more.
  • the film of one embodiment of the present invention has a thickness of 5 ⁇ m or more and 300 ⁇ m or less, a total light transmittance of 85% or more, a haze of 10% or less, a yellowness of 5.0 or less, and a 1% weight loss temperature of 275 ° C. That's it.
  • the polyimide resin and acetylcellulose resin contained in the resin composition show compatibility, a transparent film with a small haze can be obtained.
  • the polyimide resin and the acetylcellulose resin show compatibility, coloring can be reduced while maintaining the excellent heat resistance of the polyimide, and a transparent film suitable for the cover film of a display can be produced.
  • One embodiment of the present invention is a compatible resin composition containing a polyimide resin and an acetylcellulose resin.
  • Polyimide is obtained by dehydrating and cyclodehydrating polyamic acid obtained by addition polymerization of tetracarboxylic dianhydride (hereinafter sometimes referred to as "acid dianhydride”) and diamine. That is, polyimide is a polycondensation product of tetracarboxylic dianhydride and diamine, and has an acid dianhydride-derived structure (acid dianhydride component) and a diamine-derived structure (diamine component).
  • the polyimide used in the present embodiment is soluble in an organic solvent, and it is particularly preferred that the polyimide is soluble in an organic solvent (methylene chloride, etc.) capable of dissolving the acetylcellulose resin.
  • organic solvent methylene chloride, etc.
  • the polyimide used in this embodiment contains an alicyclic tetracarboxylic dianhydride as an acid dianhydride component.
  • the alicyclic structure of the acid dianhydride component tends to improve the compatibility between the polyimide resin and the acetylcellulose resin.
  • the alicyclic tetracarboxylic dianhydride should just have at least one alicyclic structure, and may have both an alicyclic ring and an aromatic ring in one molecule.
  • the alicyclic ring may be polycyclic and may have a spiro structure.
  • the alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,3-dimethyl cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, 1,1′- Bicyclohexane-3,3',4,4'tetracarboxylic acid-3,4:3',4'-dianhydride, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2′′-
  • 1,2,3,4-cyclobutanetetracarboxylic dianhydride CBDA
  • 1,2,3,4- Cyclopentanetetracarboxylic dianhydride CPDA
  • 1,2,4,5-cyclohexanetetracarboxylic dianhydride H-PMDA
  • 1,1'-bicyclohexane-3,3',4,4' Tetracarboxylic acid-3,4:3′,4′-dianhydride H-PMDA or CBDA is preferred, with H-PMDA or CBDA being particularly preferred.
  • the content of the alicyclic tetracarboxylic dianhydride relative to the total amount of 100 mol% of the acid dianhydride component is preferably 10 mol% or more, and 20 mol%.
  • the above is more preferable, and 30 mol% or more is more preferable, and it may be 35 mol% or more, 40 mol% or more, 45 mol% or more, 50 mol% or more, 55 mol% or more, or 60 mol% or more.
  • Polyimides with a large proportion of alicyclic tetracarboxylic dianhydride in the acid dianhydride component tend to absorb less light in the short wavelength to ultraviolet region of visible light, have excellent transparency, and have excellent light resistance.
  • the polyimide resin exhibits high solubility in organic solvents even when the proportion of the alicyclic tetracarboxylic dianhydride is large. , tend to be excellent in compatibility with acetyl cellulose resins.
  • the polyimide may contain an acid dianhydride other than the alicyclic tetracarboxylic dianhydride as the acid dianhydride component.
  • an acid dianhydride other than the alicyclic tetracarboxylic dianhydride as the acid dianhydride component.
  • fluorine-containing aromatic tetracarboxylic acids are used as acid dianhydride components. It may contain one or more selected from the group consisting of acid dianhydrides, bis(trimellitic anhydride) esters and diphthalic anhydrides having an ether bond.
  • Fluorine-containing aromatic tetracarboxylic dianhydrides include 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2 -Bis ⁇ 4-[4-(1,2-dicarboxy)phenoxy]phenyl ⁇ -1,1,1,3,3,3-hexafluoropropane dianhydride and the like.
  • a bis(trimellitic anhydride) ester is represented by the following general formula (1).
  • X in general formula (1) is an arbitrary divalent organic group, and a carboxy group and a carbon atom of X are bonded at both ends of X.
  • the carbon atoms attached to the carboxy group may form a ring structure.
  • Specific examples of the divalent organic group X include the following (A) to (K).
  • R 1 in formula (A) is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms, and m is an integer of 0 to 4.
  • the group represented by formula (A) is a group obtained by removing two hydroxyl groups from a hydroquinone derivative which may have a substituent on the benzene ring.
  • Hydroquinones having a substituent on the benzene ring include tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone and the like.
  • the bis(trimellitic anhydride) ester is p-phenylene bis( trimellitate anhydride) (abbreviation: TAHQ).
  • R 2 in formula (B) is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms, and n is an integer of 0-4.
  • the group represented by formula (B) is a group obtained by removing two hydroxyl groups from biphenol which may have a substituent on the benzene ring.
  • Biphenol derivatives having a substituent on the benzene ring include 2,2′-dimethylbiphenyl-4,4′-diol, 3,3′-dimethylbiphenyl-4,4′-diol, 3,3′,5, 5'-tetramethylbiphenyl-4,4'-diol, 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol and the like.
  • the group represented by formula (C) is a group obtained by removing two hydroxyl groups from 4,4'-isopropylidenediphenol (bisphenol A).
  • the group represented by formula (D) is a group obtained by removing two hydroxyl groups from resorcinol.
  • p in formula (E) is an integer from 1 to 10.
  • the group represented by formula (E) is a straight-chain diol having 1 to 10 carbon atoms from which two hydroxyl groups have been removed. Examples of linear diols having 1 to 10 carbon atoms include ethylene glycol and 1,4-butanediol.
  • the group represented by formula (F) is a group obtained by removing two hydroxyl groups from 1,4-cyclohexanedimethanol.
  • R 3 in formula (G) is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms, and q is an integer of 0-4.
  • the group represented by formula (G) is a group obtained by removing two hydroxyl groups from bisphenolfluorene which may have a substituent on the benzene ring having a phenolic hydroxyl group. Examples of the bisphenol fluorene derivative having a substituent on the benzene ring having a phenolic hydroxyl group include biscresol fluorene.
  • the bis(trimellitic anhydride) ester is preferably an aromatic ester.
  • X is preferably (A), (B), (C), (D), (G), (H), or (I).
  • (A) to (D) are preferred, and (B) a group having a biphenyl skeleton is particularly preferred.
  • X is a group represented by the general formula (B)
  • X is 2,2',3,3' represented by the following formula (B1) , 5,5′-hexamethylbiphenyl-4,4′-diyl.
  • the acid dianhydride in which X in the general formula (1) is a group represented by the formula (B1) is bis(1,3-dioxo-1,3-dihydroisobenzofuran represented by the following formula (3) -5-carboxylic acid)-2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diyl (abbreviation: TAHMBP).
  • Diphthalic anhydrides having an ether bond include 3,4'-oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride. things, etc. 4'-(4,4'-Isopropylidenediphenoxy)diphthalic anhydride (BPADA) is particularly preferable from the viewpoint of solubility of the polyimide resin and compatibility with the acetylcellulose resin.
  • BPADA 4,4'-(4,4'-Isopropylidenediphenoxy)diphthalic anhydride
  • the total content of tetracarboxylic dianhydride, bis(trimellitic anhydride) ester and diphthalic anhydride having an ether bond is preferably 50 mol% or more, more preferably 60 mol% or more, and 65 mol% or more. is more preferable, and may be 70 mol% or more, 75 mol% or more, 80 mol% or more, 85 mol% or more, 90 mol% or more, or 95 mol% or more.
  • Polyimide contains acid dianhydride components other than alicyclic tetracarboxylic dianhydride, fluorine-containing aromatic tetracarboxylic dianhydride, bis(trimellitic anhydride) ester and diphthalic anhydride having an ether bond. It may contain an acid dianhydride.
  • acid dianhydrides other than the above include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, and 2,2′.
  • the polyimide used in this embodiment contains a fluoroalkyl-substituted benzidine as a diamine-derived structure. Having a fluoroalkyl-substituted benzidine in the diamine-derived structure tends to achieve both the solubility and transparency of the polyimide resin.
  • fluoroalkyl-substituted benzidines examples include 2-(trifluoromethyl)benzidine, 3-(trifluoromethyl)benzidine, 2,3-bis(trifluoromethyl)benzidine, 2,5-bis(trifluoromethyl)benzidine , 2,6-bis(trifluoromethyl)benzidine, 2,3,5-tris(trifluoromethyl)benzidine, 2,3,6-tris(trifluoromethyl)benzidine, 2,3,5,6-tetrakis (trifluoromethyl)benzidine, 2,2′-bis(trifluoromethyl)benzidine, 3,3′-bis(trifluoromethyl)benzidine, 2,3′-bis(trifluoromethyl)benzidine, 2,2′ , 3-bis (trifluoromethyl) benzidine, 2,3,3'-tris (trifluoromethyl) benzidine, 2,2',5-tris (trifluoromethyl) benzidine, 2,2',6-tris ( trifluoromethyl)benzidine, 2,
  • fluoroalkyl-substituted benzidine having a fluoroalkyl group at the 2-position of biphenyl is preferred, and 2,2'-bis(trifluoromethyl)benzidine (hereinafter referred to as "TFMB”) is particularly preferred.
  • TFMB 2,2'-bis(trifluoromethyl)benzidine
  • the content of the fluoroalkyl-substituted benzidine relative to 100 mol% of the total amount of the diamine component is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, 80 mol% or more, 85 mol% or more, or 90 mol% or more. It may be mol% or more.
  • a high content of fluoroalkyl-substituted benzidine tends to suppress coloration of the film and increase heat resistance.
  • the polyimide may contain a diamine other than fluoroalkyl-substituted benzidine as a diamine component.
  • diamines other than fluoroalkyl-substituted benzidine include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether.
  • diaminodiphenylsulfone as the diamine in addition to the fluoroalkyl-substituted benzidine
  • solubility and transparency of the polyimide resin in solvents may be improved.
  • diaminodiphenylsulfones 3,3'-diaminodiphenylsulfone (3,3'-DDS) and 4,4'-diaminodiphenylsulfone (4,4'-DDS) are preferred. 3,3'-DDS and 4,4'-DDS may be used in combination.
  • the content of diaminodiphenylsulfone relative to 100 mol% of the total amount of diamine may be 1 to 40 mol%, 3 to 30 mol%, or 5 to 25 mol%.
  • a polyamic acid is obtained as a polyimide precursor by reacting an acid dianhydride and a diamine, and a polyimide is obtained by cyclodehydration (imidization) of the polyamic acid.
  • a polyimide is obtained by cyclodehydration (imidization) of the polyamic acid.
  • the composition of the polyimide that is, the types and ratios of the acid dianhydride and the diamine
  • the polyimide has transparency and solubility in organic solvents, as well as compatibility with the acetyl cellulose resin. indicates
  • the method for preparing polyamic acid is not particularly limited, and any known method can be applied.
  • acid dianhydride and diamine are dissolved in approximately equimolar amounts (molar ratio of 95:100 to 105:100) in an organic solvent and stirred to obtain a polyamic acid solution.
  • concentration of the polyamic acid solution is usually 5-35% by weight, preferably 10-30% by weight. When the concentration is within this range, the polyamic acid obtained by polymerization has an appropriate molecular weight and the polyamic acid solution has an appropriate viscosity.
  • a method of adding an acid dianhydride to a diamine is preferable in order to suppress the ring opening of the acid dianhydride.
  • they may be added at once or may be added in multiple batches.
  • Various physical properties of the polyimide can also be controlled by adjusting the addition order of the monomers.
  • the organic solvent used for polyamic acid polymerization is not particularly limited as long as it does not react with diamines and acid dianhydrides and can dissolve polyamic acid.
  • organic solvents include urea-based solvents such as methylurea and N,N-dimethylethylurea; sulfoxide or sulfone-based solvents such as dimethylsulfoxide, diphenylsulfone, and tetramethylsulfone; N,N-dimethylacetamide (DMAc); N-dimethylformamide (DMF), N,N'-diethylacetamide, N-methyl-2-pyrrolidone (NMP), ⁇ -butyrolactone, amide solvents such as hexamethylphosphoric triamide, halogenation such as chloroform and methylene chloride Examples include alkyl solvents, aromatic hydrocarbon solvents such as benzene and toluene, and ether solvents such as tetrahydrofuran, 1,
  • Polyimide is obtained by dehydration cyclization of polyamic acid.
  • a method for preparing a polyimide from a polyamic acid solution there is a method in which a dehydrating agent, an imidization catalyst, etc. are added to the polyamic acid solution and imidization proceeds in the solution.
  • the polyamic acid solution may be heated to accelerate imidization.
  • the polyimide resin is precipitated as a solid matter.
  • a solvent suitable for film formation such as a low boiling point solvent, can be applied when preparing a solution for producing a film.
  • the molecular weight of the polyimide (polyethylene oxide equivalent weight average molecular weight measured by gel filtration chromatography (GPC)) is preferably 10,000 to 300,000, more preferably 20,000 to 250,000, and 40,000 to 200,000 is more preferred. If the molecular weight is too small, the strength of the film may be insufficient. If the molecular weight is too large, the compatibility with the cellulose acetate resin may be poor.
  • the polyimide is preferably soluble in low boiling point solvents such as ketone solvents and halogenated alkyl solvents. That polyimide exhibits solubility in a solvent means that it dissolves at a concentration of 5% by weight or more. In one embodiment, the polyimide exhibits solubility in methylene chloride. Since methylene chloride has a low boiling point and the residual solvent can be easily removed during film production, the use of a polyimide resin soluble in methylene chloride is expected to improve film productivity.
  • polyimide preferably has low reactivity.
  • the acid value of polyimide is preferably 0.4 mmol/g or less, more preferably 0.3 mmol/g or less, and even more preferably 0.2 mmol/g or less.
  • the acid value of the polyimide may be 0.1 mmol/g or less, 0.05 mmol/g or less, or 0.03 mmol/g or less.
  • the polyimide preferably has a high imidization rate. A low acid value tends to increase the stability of the polyimide and improve the compatibility with the acetylcellulose resin.
  • acetylcellulose-based resin diacetylcellulose or triacetylcellulose having an acetyl group substitution degree of 2.0 to 3.0 is preferable.
  • the degree of acetyl substitution of acetylcellulose is preferably 2.4 or more, and may be 2.5 or more, 2.6 or more, 2.7 or more, or 2.8 or more. good.
  • the acetylcellulose-based resin may have a substituent other than the acetyl group as long as the degree of substitution of the acetyl group is within the above range.
  • substituents other than the acetyl group include acyl groups such as propionyl group and butyryl group, and alkoxy groups such as methoxy group and ethoxy group.
  • the glass transition temperature of the acetylcellulose resin is preferably 150°C or higher, and may be 160°C or higher or 170°C or higher.
  • a resin composition is prepared by mixing the polyimide resin and the acetylcellulose resin. Since the polyimide resin and the acetylcellulose-based resin can exhibit compatibility at any ratio, the ratio of the polyimide resin and the acetylcellulose-based resin in the resin composition is not particularly limited.
  • the mixing ratio (weight ratio) of the polyimide resin and the acetylcellulose resin may be 98:2-2:98, 95:5-10:90, or 90:10-15:85. There is a tendency that the higher the proportion of the polyimide resin, the better the heat resistance.
  • the ratio of the acetylcellulose resin to the total of the polyimide and the acetylcellulose resin is preferably 10% by weight or more, more preferably 15% by weight. % or more, 20 wt % or more, 25 wt % or more, 30 wt % or more, 35 wt % or more, 40 wt % or more, 45 wt % or more, or 50 wt % or more.
  • the resin composition may be a mixed solution containing a polyimide resin and an acetylcellulose resin.
  • the method of mixing the resins is not particularly limited, and the resins may be mixed in a solid state or mixed in a liquid to form a mixed solution.
  • a polyimide resin solution and an acetylcellulose-based resin solution may be separately prepared and mixed to prepare a mixed solution of a polyimide resin and an acetylcellulose-based resin.
  • the solvent for the solution containing the polyimide resin and the acetylcellulose resin is not particularly limited as long as it exhibits solubility in both the polyimide resin and the acetylcellulose resin.
  • solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; ether solvents such as 1,4-dioxane and dioxolane; methylene chloride and chloroform. and halogenated alkyl solvents such as 1,1,2,2-tetrachloroethane.
  • halogenated alkyl solvents are preferable because they have excellent solubility in both polyimide resins and acetylcellulose resins, have a low boiling point, and are easy to remove residual solvents during film production.
  • the resin composition may be blended with organic or inorganic low-molecular-weight compounds, high-molecular-weight compounds (eg, epoxy resin), and the like.
  • the resin composition may contain flame retardants, ultraviolet absorbers, cross-linking agents, dyes, pigments, surfactants, leveling agents, plasticizers, fine particles, sensitizers and the like.
  • the fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and the like, and may have a porous or hollow structure.
  • Fiber reinforcements include carbon fibers, glass fibers, aramid fibers, and the like.
  • Molding methods include melt methods such as injection molding, transfer molding, press molding, blow molding, inflation molding, calender molding, and melt extrusion molding.
  • a resin composition containing polyimide and an acetylcellulose resin tends to have a lower melt viscosity than polyimide alone, and is excellent in moldability in injection molding, transfer molding, press molding, melt extrusion molding, and the like.
  • the molded body is a film.
  • the film forming method may be either a melt method or a solution method, but the solution method is preferred from the viewpoint of producing a film excellent in transparency and uniformity.
  • a film is obtained by coating a support with a solution containing the polyimide resin and the acetylcellulose resin and removing the solvent by drying.
  • a method for applying the resin solution onto the support a known method using a bar coater, a comma coater, or the like can be applied.
  • a glass substrate, a metal substrate such as SUS, a metal drum, a metal belt, a plastic film, or the like can be used. From the viewpoint of improving productivity, it is preferable to use an endless support such as a metal drum, a metal belt, or a long plastic film as the support and to produce the film by roll-to-roll.
  • a plastic film is used as the support, a material that does not dissolve in the solvent of the film-forming dope may be appropriately selected.
  • the heating temperature is not particularly limited as long as the solvent can be removed and the coloration of the resulting film can be suppressed.
  • the heating temperature may be increased stepwise.
  • the resin film may be peeled off from the support and dried after drying has progressed to some extent. Heating under reduced pressure may be used to facilitate solvent removal.
  • Acetylcellulose-based films may have low toughness, but the use of a compatible system of polyimide and acetylcellulose-based resin may improve the strength of the film.
  • the film may be stretched in one direction or in multiple directions for the purpose of improving the mechanical strength of the film. When the film is stretched, the polymer chains are oriented in the stretching direction, so that the strength of the film in the in-plane direction is improved, and the occurrence of cracks and splits in the film tends to be suppressed.
  • the thickness of the film is not particularly limited, and may be set appropriately according to the application.
  • the thickness of the film is, for example, 5-300 ⁇ m. From the viewpoint of achieving both self-supporting property and flexibility and making a highly transparent film, the thickness of the film is preferably 10 ⁇ m to 100 ⁇ m, and may be 30 ⁇ m to 90 ⁇ m, 40 ⁇ m to 85 ⁇ m, or 50 ⁇ m to 80 ⁇ m. .
  • the thickness of the film used as a cover film for displays is preferably 10 ⁇ m or more. When the film is stretched, the thickness after stretching is preferably within the above range.
  • the haze of the film is preferably 10% or less, more preferably 5% or less, even more preferably 4% or less, and may be 3.5% or less, 3% or less, 2% or less, or 1% or less.
  • the resin composition obtained by mixing polyimide and acetylcellulose resin preferably has a haze of 10% or less when a film having a thickness of 10 ⁇ m is produced.
  • the total light transmittance (TT) of the film is preferably 85% or higher, more preferably 87% or higher, even more preferably 89% or higher, particularly preferably 90% or higher, and may be 91% or higher.
  • the resin composition obtained by mixing polyimide and acetylcellulose resin preferably has a TT of 85% or more when a film having a thickness of 10 ⁇ m is produced.
  • the transmittance of the film at 400 nm is preferably 50% or higher, more preferably 70% or higher, even more preferably 80% or higher, particularly preferably 85% or higher, and may be 90% or higher.
  • the yellowness index (YI) of the film is preferably 5.0 or less, and may be 2.0 or less or 1.0 or less.
  • YI yellowness index
  • the resin composition obtained by mixing polyimide and acetylcellulose resin preferably has a YI of 5.0 or less when a film having a thickness of 10 ⁇ m is produced.
  • the film has a small increase in yellowness ⁇ YI in a light resistance test.
  • the increase in yellowness ⁇ YI of the film after a light resistance test in which the film is irradiated with ultraviolet light at an irradiance of 530 W/m 2 and a black panel temperature of 63° C. with a cumulative irradiation amount of 40.0 MJ/m 2 is preferably 6.0 or less. It is more preferably 5.0 or less, and may be 4.0 or less, 3.0 or less, 2.0 or less, 1.5 or less, or 1.0 or less.
  • the yellowness index YI of the film after the light resistance test is preferably 8.0 or less, more preferably 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.0 or less. It may be 0 or less or 1.0 or less.
  • the YI of the film tends to be smaller than in the case of polyimide resin alone, and ⁇ YI also tends to be smaller. Also, the larger the ratio of the alicyclic acid dianhydride in the acid dianhydride component of the polyimide, the smaller the YI of the film and the smaller the ⁇ YI.
  • the 1% weight loss temperature (Td1) of the film is preferably 275°C or higher, more preferably 280°C or higher, even more preferably 290°C or higher, and may be 300°C or higher.
  • the 5% weight loss temperature (Td5) of the film is preferably 320°C or higher, more preferably 330°C or higher, even more preferably 340°C or higher, and may be 345°C or higher.
  • a film formed from a resin composition containing polyimide and an acetylcellulose resin is less colored and highly transparent, so it is suitable for use as a display material.
  • films with high mechanical strength can be applied to surface members such as display cover windows.
  • the film of the present invention may be provided with an antistatic layer, an easy-adhesion layer, a hard coat layer, an antireflection layer, and the like on the surface.
  • IPA 2-propyl alcohol
  • ⁇ Light resistance> Using a fade meter M6T manufactured by Suga Test Instruments Co., Ltd., a light resistance test was performed by irradiating until the cumulative irradiation dose reached 40.0 MJ/m 2 under the conditions of an irradiance of 530 W/m 2 and a black panel temperature of 63°C. The YI of the film before and after the light resistance test was measured, and the YI increment ⁇ YI after the weather resistance test was transferred to three types.
  • a 1% weight loss temperature (Td1) and a 5% weight loss temperature (Td5) were measured using a simultaneous differential thermal thermogravimetry device (“STA7200” manufactured by Hitachi High-Tech Science). The measurement was performed by weighing 10 mg of the film and increasing the temperature from 30° C. to 400° C. at 10° C./min. Taking the weight at 200° C. as 100%, the temperature at which the weight first fell below 99% was Td1, and the temperature at which the weight first fell below 95% was Td5.
  • Table 1 shows the compositions of the resins of Examples 1 to 3, Comparative Example 1 and Reference Example 4 (the composition of the polyimide and the mixing ratio with the triacetyl cellulose resin) and the evaluation results of the films.
  • the polyimide film of Reference Example 1 which was produced using only the same polyimide resin as that used in Example 1, had a total light transmittance (TT) of 91.7%, whereas the polyimide resin and triacetyl
  • the film of Example 1 which was produced using the composition containing the cellulose resin at a weight ratio of 50:50, had a TT of 92.0% and was excellent in transparency.
  • the polyimide film of Reference Example 1 had a yellowness increase ⁇ YI of 1.4 after the weather resistance test, while the film of Example 1 had a ⁇ YI of 0.4. It can be seen that the film of No. 1 is excellent in light resistance in addition to transparency.
  • the TT of the polyimide film of Reference Example 2 was 91.5%, while the TT of the film of Example 2 was 91.7%.
  • the TT of the polyimide film of Reference Example 3 was 90.7%, while the TT of the film of Example 3 was 91.2%.
  • the ⁇ YI of the polyimide film of Reference Example 2 was 3.6%, while the ⁇ YI of the film of Example 2 was 1.7.
  • the ⁇ YI of the polyimide film of Reference Example 3 was 12.3%, while the ⁇ YI of the film of Example 3 was 5.6. From these results, it can be seen that in Examples 2 and 3 as well, the compatible resin composition of polyimide and acetylcellulose-based resin has superior light resistance to polyimide alone.
  • the films of Examples 1 to 3 had higher Td1 and Td5 than the triacetyl cellulose film of Reference Example 4, and had excellent heat resistance.
  • Comparative Example 1 in which a polyimide containing no alicyclic tetracarboxylic dianhydride was used as the tetracarboxylic dianhydride component, the compatibility between the polyimide and triacetyl cellulose was low, resulting in a significant increase in haze.
  • a polyimide containing an alicyclic tetracarboxylic dianhydride as a tetracarboxylic dianhydride component exhibits compatibility with an acetylcellulose resin, and by using a resin composition in which these are mixed, It can be seen that a film having high transparency and excellent light resistance and heat resistance can be obtained.

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Abstract

La présente invention concerne une composition de résine comprenant un polyimide et une résine acrylique, le polyimide comprenant un dianhydride tétracarboxylique alicyclique en tant qu'au moins une partie d'un composant dianhydride tétracarboxylique et d'une benzidine substituée par un fluoroalkyle en tant que composant diamine. La quantité de dianhydride tétracarboxylique alicyclique peut être de 10 à 100 % en moles par rapport à l'ensemble du composant dianhydride tétracarboxylique du polyimide. Le degré de substitution acétyle d'une résine à base d'acétylcellulose peut être supérieur ou égal à 2,4. La composition de résine peut comprendre le polyimide et la résine à base d'acétylcellulose dans un rapport pondéral dans la plage de 98:2 à 2:98.
PCT/JP2023/003097 2022-02-03 2023-01-31 Composition de résine, objet moulé et film WO2023149435A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015629A (ja) * 2003-06-26 2005-01-20 Mitsubishi Gas Chem Co Inc 溶媒可溶性ポリイミドの製造方法
JP2008045054A (ja) * 2006-08-18 2008-02-28 New Japan Chem Co Ltd 脂環系ポリイミド共重合体及びその製造方法
WO2012133143A1 (fr) * 2011-03-31 2012-10-04 三井化学株式会社 Film composite de microparticules de résine de type polyimide et utilisation de ce dernier
JP2018028694A (ja) * 2012-12-12 2018-02-22 日産化学工業株式会社 組成物及び樹脂皮膜
WO2018225825A1 (fr) * 2017-06-08 2018-12-13 日産化学株式会社 Procédé de fabrication de substrat pour dispositif flexible
JP2019023249A (ja) * 2015-12-11 2019-02-14 コニカミノルタ株式会社 ポリイミドフィルム、フレキシブルプリント基板、ｌｅｄ照明装置及びフレキシブルディスプレイ用前面部材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015629A (ja) * 2003-06-26 2005-01-20 Mitsubishi Gas Chem Co Inc 溶媒可溶性ポリイミドの製造方法
JP2008045054A (ja) * 2006-08-18 2008-02-28 New Japan Chem Co Ltd 脂環系ポリイミド共重合体及びその製造方法
WO2012133143A1 (fr) * 2011-03-31 2012-10-04 三井化学株式会社 Film composite de microparticules de résine de type polyimide et utilisation de ce dernier
JP2018028694A (ja) * 2012-12-12 2018-02-22 日産化学工業株式会社 組成物及び樹脂皮膜
JP2019023249A (ja) * 2015-12-11 2019-02-14 コニカミノルタ株式会社 ポリイミドフィルム、フレキシブルプリント基板、ｌｅｄ照明装置及びフレキシブルディスプレイ用前面部材
WO2018225825A1 (fr) * 2017-06-08 2018-12-13 日産化学株式会社 Procédé de fabrication de substrat pour dispositif flexible

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