Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
  • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a transparent polyimide copolymer (hereinafter also simply referred to as “polyimide copolymer”), and in particular, highly satisfies solvent solubility, storage stability, heat resistance, mechanical strength, and heat yellowing,
• the present invention relates to a transparent polyimide copolymer excellent in practicality, a polyimide resin composition and a molded body, and a method for producing the copolymer.
• LEDs Light Emitting Diodes
• LEDs Light Emitting Diodes
• a reflective layer is generally constructed on the circuit board surface in order to efficiently extract light emitted from the LED to the front surface.
• the reflective layer material used here is achieved by filling a transparent resin with a high concentration of a white pigment.
• polyimide is known as a polymer material having the highest level of heat resistance, chemical resistance, and electrical insulation among organic materials.
• "Kapton (registered trademark)” from DuPont synthesized from pyromellitic dianhydride (PMDA) and 4,4'-diaminodiphenyl ether (pDADE), biphenyltetracarboxylic dianhydride (BPDA) and paraphenylenediamine “UPILEX (registered trademark)” of Ube Industries, Ltd. synthesized from (pPD) is widely used as a heat-resistant insulating material in the electric and electronic industry.
• these polyimides have the disadvantage of being colored yellowish brown in the steady state due to intramolecular conjugation and the formation of charge transfer complexes.
• an aromatic compound is not used at all as a polyimide constituent unit, and a method using an all-aliphatic polyimide composed entirely of aliphatic and / or alicyclic compounds (for example, patents)
• Semi-aliphatic polyimide that achieves both heat resistance and transparency by making either one of acid dianhydride or diamine an aromatic compound and the other an aliphatic and / or alicyclic compound.
• Patent Document 2 a flexible polyimide that suppresses the formation of intermolecular charge transfer complexes by incorporating a sterically bulky substituent or an acid dianhydride or diamine having a bent structure as a structural unit (For example, see Patent Documents 3 and 4), using a structural strain of a 7-membered cyclic dianhydride to forcibly form a node in a ⁇ -conjugated system and localize ⁇ electrons
• Patent Document 5 a method for imparting transparency (see, for example, Patent Document 5) has been proposed.
• the method using the above-mentioned flexible polyimide is excellent in solubility in organic solvents and transparency, but sufficient heat resistance can be ensured by a decrease in glass transition temperature (Tg) due to the bent structure. There wasn't.
• the method using the aliphatic polyimide or the semi-aliphatic polyimide cannot avoid the decrease in mechanical strength, the decrease in thermal decomposition temperature, and the yellowing due to oxidation during heating. Further, the method using the flexible polyimide causes a decrease in the glass transition temperature due to a decrease in the imide group concentration in the polyimide resin, and the heat resistance at a practical level cannot be ensured.
• the method of making polyimide transparent by using a dianhydride having a 7-membered ring structure and encouraging ⁇ -electron conjugation by using its structural strain is effective in terms of transparency and heat resistance. However, since it has an unstable structure of a seven-membered ring, there is a possibility that a problem occurs in mechanical strength and heat-resistant yellowing.
• the present invention has been made in order to solve the above problems, and is a transparent polyimide copolymer that is highly satisfactory in solvent solubility, storage stability, heat resistance, mechanical strength, and heat yellowing resistance, and has excellent practicality. It aims at providing the manufacturing method of a polyimide resin composition, a molded object, and this copolymer.
• the present inventor has solved the above problems by copolymerizing a predetermined acid dianhydride with a diamine and / or diisocyanate having a predetermined structure. As a result, the present invention has been completed.
• the present invention [1] (A) 4,4′-oxydiphthalic dianhydride and / or 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride; (B) the following general formulas (1) to (3), (Wherein X is an amino group or isocyanate group, R 1 to R 8 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or 1 to 4 carbon atoms) One or more diamines and / or diisocyanates represented by: at least one of R 1 to R 8 is not a hydrogen atom; A transparent polyimide copolymer obtained by copolymerization of
• R 1 to R 4 is not a hydrogen atom
• An oligomer production process for producing a transparent polyimide copolymer oligomer by copolymerizing For the transparent polyimide copolymer oligomer produced in the oligomer production process, (C) a polyimide copolymer production process for producing a transparent polyimide copolymer by copolymerizing a second acid dianhydride and (D) a second diamine and / or diisocyanate;
• the manufacturing method of the transparent polyimide copolymer characterized by having.
• the following method was used in order to achieve both transparency and heat resistance (high Tg) of the polyimide copolymer.
• the present inventor has focused on the imide group concentration in the polyimide main chain skeleton as a factor for controlling the glass transition temperature of polyimide.
• the imide group concentration increases, the glass transition temperature also increases.
• an increase in the imide group concentration causes a decrease in transparency and solvent solubility.
• the present inventor improved the above problems by using a monocyclic or bicyclic (B) component having a bulky substituent at the ortho position of the amino group and / or isocyanate group and having a bent structure. I found out that I can do it. Specifically, intermolecular interactions can be weakened by introducing bulky substituents or bent structures into the main chain skeleton. This reduction in the intermolecular interaction can suppress the formation of the charge transfer complex and improve the solvent solubility.
• the transparency of the polyimide copolymer was realized by using the component (A), and the glass transition temperature and the solvent solubility were improved while maintaining the transparency by using the component (B).
• a transparent polyimide copolymer, a polyimide resin composition and a molded article which are highly satisfactory in solvent solubility, storage stability, heat resistance, mechanical strength and heat yellowing resistance and excellent in practicality, and the copolymer.
• a method for producing a polymer can be provided.
• the transparent polyimide copolymer of the present invention comprises (A) 4,4′-oxydiphthalic dianhydride and / or 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, (B) the following general formulas (1) to (3), (Wherein X is an amino group or isocyanate group, R 1 to R 8 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or 1 to 4 carbon atoms) And at least one of R 1 to R 8 is not a hydrogen atom) and is copolymerized with one or more diamines and / or diisocyanates.
• the polyimide copolymer is excellent in heat resistance, transparency and heat-resistant yellowing as compared with conventional transparent polyimide copolymers, and also has the advantage of excellent storage stability and mechanical strength. Yes.
• transparent means that the total light transmittance is 85% or more when the transparent polyimide copolymer of the present invention is formed into a film having a thickness of 20 ⁇ m.
• the terminal group of the transparent polyimide copolymer in the present invention is preferably not an amine terminal.
• an amine terminal By not having an amine terminal, it is possible to avoid the point that it is easy to form a charge transfer complex by interacting with an imide carbonyl group when the terminal group of the polyimide copolymer is an amino group.
• the amino group is susceptible to oxidation, and it can be avoided that the chromophore is formed by oxidation over time to reduce transparency and heat yellowing.
• the terminal group of the transparent polyimide copolymer can be made not to be an amine terminal by the method shown below.
• an acid anhydride group and an amino group can be arbitrarily selected by using either one of acid dianhydride and diamine and / or diisocyanate at the time of synthesis in excess.
• the acid anhydride terminal may be left without performing the subsequent treatment, or may be hydrolyzed to obtain a dicarboxylic acid. Moreover, it is good also as ester using C4 or less alcohol. Furthermore, you may seal a terminal
• the amine compound and / or isocyanate compound used here is not particularly limited as long as it is a monofunctional primary amine compound and / or isocyanate compound.
• aniline methylaniline, dimethylaniline, trimethylaniline, ethylaniline, diethylaniline, triethylaniline, aminophenol, methoxyaniline, aminobenzoic acid, biphenylamine, naphthylamine, cyclohexylamine, phenyl isocyanate, xylylene isocyanate, cyclohexane
• examples thereof include hexyl isocyanate, methylphenyl isocyanate, trifluoromethylphenyl isocyanate and the like.
• the terminal group is an amine terminal, it is possible to prevent the amino group from remaining at the terminal by sealing the terminal amino group with a monofunctional acid anhydride.
• a monofunctional acid anhydride if it is a monofunctional acid anhydride which becomes dicarboxylic acid or tricarboxylic acid when hydrolyzed, it can be used without particular limitation.
• maleic anhydride methylmaleic anhydride, dimethylmaleic anhydride, succinic anhydride, norbornene dicarboxylic acid anhydride, 4- (phenylethynyl) phthalic anhydride, 4-ethynylphthalic anhydride, phthalate Acid anhydride, methylphthalic anhydride, dimethylphthalic anhydride, trimellitic anhydride, naphthalenedicarboxylic anhydride, 7-oxabicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] Heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, 4-oxatricyclo [5.2 .2.0 2,6] undecane-3,5-dione, octahydro-1,3-dioxo-isobenzofuran-5-car
• diethyltoluenediamine in which two of R 1 to R 4 in the general formula (1) or (2) are an ethyl group and the remaining two are a methyl group and a hydrogen atom. Is preferred. Further, among R 5 to R 8 in the general formula (3), an alkyl group having 1 to 4 carbon atoms is preferable.
• the second acid dianhydride can be used without particular limitation as long as it is an acid dianhydride conventionally used in the production of polyimide.
• an acid dianhydride conventionally used in the production of polyimide.
• aromatic acid dianhydride pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride
• silicon-containing acid dianhydrides examples include 4,4 ′-(dimethylsilylene) bis (phthalic acid) 1, 2: 1 ′, 2′-dianhydride, and 4,4 ′-(methylethylsilylene).
• fluorine-containing acid dianhydrides examples include 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic acid dianhydride and 3,4 ′-(2,2-hexafluoroisopropylidene) diphthalic acid dianhydride. 3,3 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, 4,4 ′-[2,2-hexafluoroisopropylidenebis [(1,4-phenylene) oxy]] diphthalate Examples thereof include acid dianhydrides.
• fluorene cardo type acid dianhydride examples include 5,5 ′-[9H-fluorene-9,9-diylbis (4,1-phenyleneoxy)] bis (isobenzofuran-1,3-dione), 5,5 Examples include '-[9H-fluorene-9,9-diylbis (1,1'-biphenyl-5,2-diyloxy)] bis (isobenzofuran-1,3-dione).
• ester acid dianhydrides include ethylene glycol bis (trimellitic anhydride), 1,4-phenylene bis (trimellitate anhydride), 1,3-phenylene bis (trimellitate anhydride), 1,2-phenylene bis (trimellitate) Anhydride), bis (1,3-dihydro-1,3-dioxoisobenzofuran-5-carboxylic acid) -2-acetoxypropane-1,3-diyl, 5,5 ′-[ethylenebis (oxy)] Bis (isobenzofuran-1,3-dione), bis (1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid) oxybis (methyleneoxymethylene), 4,4 ′-[isopropylidenebis ( 4,1-phenyleneoxycarbonyl)] bisphthalic dianhydride and the like.
• Examples of the aliphatic acid dianhydride include 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,1′-bicyclohexane-2,3,3′4.
• Aliphatic ester acid dianhydrides include bis (1,3-dioxo-1,3,3a, 4,5,6,7,7a-octahydroisobenzofuran-5-carboxylic acid) biphenyl-4,4 '-Diyl, bis (1,3-dioxo-1,3,3a, 4,5,6,7,7a-octahydroisobenzofuran-5-carboxylic acid) 1,4-phenylene, bis (1,3- And dioxo-1,3,3a, 4,5,6,7,7a-octahydroisobenzofuran-5-carboxylic acid) -2-methyl-1,4-phenylene.
• (C) 2nd acid dianhydride may be used by 1 type, you may use it, mixing 2 or more types of acid dianhydrides, (C) 2nd acid dianhydride.
• the amount of is preferably 2 mol or less per 1 mol of component (A).
• (D) 2nd diamine and / or diisocyanate what is normally used for manufacture of a polyimide copolymer can be used if it is a range which does not impair the effect of the said invention.
• the following general formulas (4) to (21) (Wherein X independently represents —NH 2 , —NCO, —CH 2 NH 2 , —CH 2 NCO, R 1 to R 8 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a trifluoromethyl group, or an aryl group, R 9 R 12 is independently an alkyl group or aryl group having 1 to 4 carbon atoms, Y is independently R 21 and R 22 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, Y is independently R 21 and R 22 are each independently a hydrogen atom, an alkyl group having
• the polyimide copolymer of the present invention may be obtained by copolymerizing the component (A) and the component (B).
• the (A) component and the (B) component are copolymerized to obtain a polyimide copolymer unit having a mass average molecular weight of about 700 to 80,000.
• the second acid dianhydride and / or (D) the second diamine and / or diisocyanate may be copolymerized.
• the mass average molecular weight is preferably 20,000 to 200,000, more preferably 35,000 to 150,000.
• the concentration of the polyimide copolymer in the organic solvent is not particularly limited, but can be, for example, about 5 to 35% by mass. Even if the concentration of the polyimide copolymer is less than 5% by mass, it can be used. However, if the concentration is dilute, the work efficiency of polyimide copolymer coating and the like deteriorates. On the other hand, when it exceeds 35% by mass, the fluidity of the polyimide copolymer is poor, application and the like become difficult, and the workability is deteriorated.
• the copolymerization is carried out in an organic solvent, but the organic solvent used in that case is not particularly limited.
• organic solvent used in that case is not particularly limited.
• N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, N, N-dimethylformamide, N, N-diethylacetamide, etc., gamma-butyrolactone, alkylene glycol monoalkyl ether, alkylene glycol dialkyl ether, alkyl Carbitol acetate and benzoate can be preferably used.
• These organic solvents may be used alone or in combination of two or more.
• a known imidization catalyst can be used.
• pyridine may generally be used as an imidization catalyst, but in addition to this, substituted or unsubstituted nitrogen-containing heterocyclic compounds, N-oxide compounds of nitrogen-containing heterocyclic compounds, substituted or unsubstituted amino acids Examples thereof include an aromatic hydrocarbon compound having a hydroxyl group or an aromatic heterocyclic compound.
• lower alkyl imidazoles such as 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, N-benzyl Imidazole derivatives such as -2-methylimidazole, substituted pyridines such as isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n-propylpyridine, etc. , P-toluenesulfonic acid and the like can be preferably used.
• the amount of the imidization catalyst used 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.
• an azeotropic solvent can be added to the organic solvent in order to efficiently remove water generated by the imidization reaction.
• aromatic hydrocarbons such as toluene, xylene, and solvent naphtha
• alicyclic hydrocarbons such as cyclohexane, methylcyclosexane, and dimethylcyclohexane
• the amount added is about 1 to 30% by mass, preferably 5 to 20% by mass, based on the total amount of organic solvent.
• the polymerization temperature and the polymerization time are preferably 1 to 200 hours in a temperature range of 150 ° C. to 200 ° C.
• the polymerization temperature By setting the polymerization temperature to 150 ° C. or higher, it is possible to avoid the possibility that imidization does not proceed or is not completed.
• the temperature By setting the temperature to 200 ° C. or lower, it is possible to prevent an increase in the resin concentration due to oxidation of the solvent and unreacted raw materials and volatilization of the solvent solvent.
• the transparent polyimide copolymer of the present invention is produced by a chemical imidization method, in the copolymer production step of copolymerizing the component (A) and the component (B), for example, in an organic solvent, acetic anhydride, etc.
• the dehydrating agent and a catalyst such as triethylamine, pyridine, picoline, or quinoline are added to the polyamic acid solution, and then the same operation as in the thermal imidization method is performed. Thereby, the transparent polyimide copolymer of this invention can be obtained.
• the polymerization temperature and the polymerization time are preferably 1 to 200 hours in a temperature range from ordinary temperature to about 150 ° C.
• a dehydrating agent is used, but an organic acid anhydride, for example, an aliphatic acid anhydride, an aromatic acid anhydride, an alicyclic acid anhydride, a heterocyclic type, is used.
• An acid anhydride or a mixture of two or more thereof can be used.
• Specific examples of the organic acid anhydride include acetic anhydride and the like.
• an imidization catalyst and an organic solvent are used, but the same one as in the thermal imidization method can be used.
• the polymerization method may be carried out by any known method and is not particularly limited.
• the method may be a method in which the whole amount of the component (A) is put in an organic solvent, and then the component (B) is added to the organic solvent in which the component (A) is dissolved to polymerize.
• the total amount of the components may be put in an organic solvent, and then the polymerization may be performed by adding the component (A) to the organic solvent in which the component (B) is dissolved.
• the component (A) and the component (B) may be copolymerized.
• a (A) component and (B) component may be copolymerized, a polyimide copolymer oligomer may be manufactured, and a transparent polyimide copolymer may be manufactured using the obtained polyimide copolymer oligomer.
• (C) the second acid dianhydride and / or (D) the second diamine and / or diisocyanate may be copolymerized with the polyimide copolymer oligomer.
• the (C) second acid dianhydride, (D) the second diamine and / or diisocyanate those described above can be used.
• the oligomer is preferably acid-terminated.
• an organic solvent used for manufacturing the polyimide copolymer of the present invention based on each of the above imidation methods, A catalyst, an azeotropic solvent and a dehydrating agent can be appropriately selected and used. Moreover, as manufacturing conditions at the time of manufacturing the said polyimide copolymer oligomer, it can carry out on the same conditions as each above-mentioned imidation method.
• the polyimide resin composition of the present invention comprises the transparent polyimide copolymer of the present invention containing at least one or more of the following fillers, colorants, organic solvents, and other additives.
• the content of the transparent polyimide copolymer of the present invention relative to the total solid mass of the polyimide resin composition of the present invention is preferably in the range of 5% by mass to 99.9% by mass.
• the content of optional components other than the transparent polyimide copolymer is not a problem as long as the object of the present invention is not impaired, but is 0.1% by mass to the total solid mass of the polyimide resin composition. It is preferable to make it contain in 95 mass%.
• filler examples include inorganic fillers such as silica, alumina and mica, and organic fillers such as PTFE and polyimide.
• a suitable colorant selected from the group consisting of an organic pigment, an inorganic pigment, and a dye can be selected and used as necessary.
• the organic solvent is not particularly limited as long as the transparent polyimide copolymer of the present invention can be dissolved alone or as a mixed solution.
• N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, N, N-dimethylformamide, N, N-diethylacetamide, etc., gamma-butyrolactone, alkylene glycol monoalkyl ether, alkylene glycol dialkyl ether, alkyl Carbitol acetate and benzoate can be preferably used.
• These organic solvents may be used alone or in combination of two or more.
• additives examples include polymerization inhibitors, thickeners, thixotropic agents, precipitation inhibitors, antioxidants, dispersants, pH adjusters, antifoaming agents, leveling agents, surfactants, various resins, and the like. be able to.
• the polyimide resin composition of the present invention is suitable for applications such as paints, printing inks, adhesives, coating materials for organic EL, color filters, and base polymers of photosensitive polymers.
• the method for producing the polyimide resin composition of the present invention is not particularly limited, and a known method can be used. For example, after dissolving the polyimide copolymer of the present invention in various solvents, a method of mixing and dispersing the filler and various additives, a method of melt kneading using an extruder, a Banbury mixer, etc. can be mentioned. .
• the molded body of the present invention is obtained by molding the polyimide resin composition of the present invention.
• the molded article of the present invention includes an optical fiber, an optical waveguide, an optical filter, a lens, an optical filter, an adhesive sheet, an interphase insulating film, a semiconductor insulating protective film, a TFT (Thin Film Transistor) liquid crystal insulating film, a liquid crystal alignment film, and a solar cell protective film. It is suitable for applications such as films, sheets that can be used for electronic materials such as films, antireflection films, flexible display substrates, and circuit boards.
• the method for producing the molded article of the present invention is not particularly limited, and a known method can be used.
• a method of forming a film, a film or a sheet the polyimide copolymer of the present invention
• Examples of the method include a method of distilling off the solvent to form a molded product after injection into the mold.
• the polyimide copolymer of the present invention is spin coated, dipped, sprayed, casted, etc. according to its viscosity and the like. What is necessary is just to dry, after apply
• any material may be used according to the use of the final product.
• textile products such as cloth, glass, polyethylene terephthalate, polyethylene naphthalate, polyethylene, polycarbonate, triacetyl cellulose, cellophane, polyimide, polyamide, polyphenylene sulfide, polyetherimide, polyethersulfone, aromatic polyamide, polysulfone, etc.
• materials include synthetic resins, metals, ceramics, and papers.
• the substrate may be transparent, or may be colored by blending various pigments and dyes with the material constituting the substrate, and the surface may be processed into a mat shape.
• an ordinary heating and drying furnace may be used for drying the coated transparent polyimide copolymer of the present invention.
• the atmosphere in the drying furnace include air, inert gas (nitrogen, argon), and vacuum.
• the drying temperature can be appropriately selected depending on the boiling point of the solvent in which the polyimide copolymer of the present invention is dissolved, but is usually 80 to 350 ° C., preferably 100 to 320 ° C., particularly preferably 120 to 250 ° C. That's fine.
• the drying time may be appropriately selected depending on the thickness, concentration, and type of solvent, and may be about 1 second to 360 minutes.
• a product having the transparent polyimide copolymer of the present invention as a film can be obtained as it is, or a film can be obtained by separating the film from the substrate.
• a molded body when a molded body is obtained using a mold, a predetermined amount of the polyimide resin composition of the present invention is injected into the mold (particularly a rotating mold is preferable), and then the same temperature as the molding conditions of the film, A molded body can be obtained by drying over time.
• Example 1 In a 500 mL separable four-necked flask equipped with a stainless steel vertical stirrer, nitrogen inlet tube, and Dean-Stark apparatus, 56.11 g (0.18 mol) of 4,4′-oxydiphthalic anhydride (ODPA), DETDA32 0.09 g (0.18 mol), gamma butyrolactone (GBL) 326.87 g, pyridine 2.85 g, and toluene 33 g were charged, and the inside of the reaction system was purged with nitrogen. ODPA was dissolved by stirring for 30 minutes at 80 ° C. in a nitrogen stream, and then heated to 180 ° C. and stirred for 6 hours.
• ODPA 4,4′-oxydiphthalic anhydride
• DETDA32 0.09 g (0.18 mol)
• GBL gamma butyrolactone
• one of R 1 to R 3 is a methyl group and two are ethyl groups.
• Example 2 In the same apparatus as in Example 1, 46.80 g (0.15 mol) of ODPA, 38.16 g (0.15 mol) of 4,4′-diamino-3,3 ′, 5,5′-tetramethyldiphenylmethane, GBL147. 67 g, 2.39 g of pyridine, and 50 g of toluene were charged, and the reaction system was purged with nitrogen. ODPA was dissolved by stirring for 30 minutes at 80 ° C. in a nitrogen stream, and then heated to 180 ° C. and stirred for 7 hours. Water produced by the reaction was distilled out of the reaction system by azeotropy with toluene.
• Example 3 In the same apparatus as in Example 1, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) 44.70 g (0.1 mol), DETDA 17.83 g (0.1 mol) , GBL128.44 g, pyridine 3.16 g, and toluene 50 g were charged, and the reaction system was purged with nitrogen. 6FDA was dissolved by stirring for 30 minutes at 80 ° C. in a nitrogen stream, and then heated to 180 ° C. and stirred for 6 hours. Water generated during the reaction was removed from the reaction system as an azeotrope with toluene and pyridine.
• 6FDA 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride
• one of R 1 to R 3 is a methyl group and two are ethyl groups.
• Example 4 The same apparatus as in Example 1 was charged with 32.57 g (0.105 mol) of ODPA, 12.48 g (0.07 mol) of DETDA, 100 g of GBL, 2.77 g of pyridine, and 50 g of toluene, and the inside of the reaction system was purged with nitrogen. ODPA was dissolved by stirring for 30 minutes at 80 ° C. in a nitrogen stream, and then heated to 180 ° C. and stirred for 2 hours. Water produced by the reaction was distilled out of the reaction system by azeotropy with toluene.
• one of R 1 to R 3 is a methyl group and two are ethyl groups.
• Example 5 In the same apparatus as in Example 1, 32.57 g (0.105 mol) of ODPA, 12.48 g (0.07 mol) of DETDA, 96.91 g of N-methyl-2-pyrrolidone (NMP), 2.77 g of pyridine, and 50 g of toluene. The reaction system was charged with nitrogen. ODPA was dissolved by stirring for 30 minutes at 80 ° C. in a nitrogen stream, and then heated to 180 ° C. and stirred for 2 hours. Water produced by the reaction was distilled out of the reaction system by azeotropy with toluene.
• NMP N-methyl-2-pyrrolidone
• one of R 1 to R 3 is a methyl group and two are ethyl groups.
• Example 6 10 parts of titanium dioxide (Typaque R-830, manufactured by Ishihara Sangyo Co., Ltd.) and 10 parts of GBL were mixed and stirred until uniform to obtain a titanium dioxide dispersion. To this titanium dioxide dispersion, 50 parts of the transparent polyimide varnish obtained in Example 4 was added, and the mixture was stirred until it became uniform while vacuum degassing. The obtained white composition was lined using a 400 mesh polyethylene filter to remove coarse particles, thereby obtaining a white ink containing 80 parts of titanium dioxide with respect to 100 parts of transparent polyimide resin.
• one of R 1 to R 3 is a methyl group and two are ethyl groups.
• ⁇ Comparative Example 3 10 parts of titanium dioxide (Typaque R-830, manufactured by Ishihara Sangyo Co., Ltd.) and 10 parts of NMP were mixed and stirred until uniform to obtain a titanium dioxide dispersion. To this titanium dioxide dispersion, 83 parts of the wholly alicyclic polyimide varnish obtained in Comparative Example 2 and 42 parts of NMP as a diluent solvent were added and stirred until uniform while vacuum degassing. The resulting white composition was lined up using a 400 mesh polyethylene filter to remove coarse particles, thereby obtaining a white ink containing 80 parts of titanium dioxide with respect to 100 parts of the wholly alicyclic polyimide resin.
• the polyimide copolymer obtained in Comparative Example 2 could not maintain the film shape under the film formation conditions for film formation evaluation, a film formed under the following conditions was used for the subsequent evaluation.
• the polyimide copolymer obtained in Comparative Example 2 was applied to a silicon wafer by a spin coat method, and temporarily dried on a hot plate at 120 ° C. for 10 minutes. The temporarily dried film was peeled from the silicon wafer, fixed to a stainless steel frame, and dried at 200 ° C. for 1 hour.
• ⁇ Thickness measurement> The thickness of the film produced by the film formability evaluation was measured. For the measurement, an ABC Digimatic Indicator (manufactured by Mitutoyo Corporation) was used. The obtained results are shown in Tables 1 and 2.
• the glass transition temperature was measured using the film produced by the film formability evaluation.
• the measurement used DSC6200 (made by Seiko Instruments Inc.). In addition, it heated to 500 degreeC with the temperature increase rate of 10 degree-C / min, and applied the midpoint glass transition temperature as the glass transition temperature. The obtained results are shown in Tables 1 and 2.
• Total light transmittance The total light transmittance was measured in accordance with JISK7361 using the film produced in the film formability evaluation. For the measurement, a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used. The obtained results are shown in Tables 1 and 2.
• Example 6 and Comparative Example 3 The varnish obtained in Example 6 and Comparative Example 3 was applied to a polyimide film (Kapton 200EN) by a spin coat method, fixed to a stainless steel frame, and dried in a constant temperature bath at 120 ° C. for 10 minutes, and then 200 Drying was performed at a temperature of 1 ° C. for 1 hour to obtain a film in which 18 ⁇ m of white polyimide was formed on Kapton 200EN.
• the color difference meter CR-5 manufactured by Konica Minolta Co., Ltd.
• the obtained film was measured for whiteness and yellowness according to ASTM E313-73.
• the heat-resistant yellowing in the present invention was evaluated by the numerical change in whiteness and yellowness before and after the heat treatment. Specifically, heat treatment was performed for 10 seconds in a 260 ° C. solder bath or in a thermostatic bath at 200 ° C. for 5 hours, and the whiteness and yellowness before and after that were measured. In terms of whiteness, the larger the number, the higher the whiteness of the coating film. The higher the whiteness after the heat treatment, the more the whiteness can be maintained after the heat treatment. Moreover, it shows that heat-resistant yellowing is so high that the numerical difference before and behind heat processing is small. Regarding yellowness, the larger the value, the stronger the yellowness, and the larger the value after heat treatment, the stronger the yellowness of the coating film. Moreover, it shows that heat yellowing is low, so that the numerical difference before and behind heat processing is large.
• the polyimide copolymer of the present invention exhibits excellent heat resistance with a glass transition temperature of 270 ° C. or higher while maintaining high transparency with a total light transmittance of 85% or higher. .
• due to its excellent heat resistance it has excellent resistance to yellowing caused by long-term exposure to a drying process for distilling off the solvent and high temperatures, and damages the hue of colorants and the like. It has no characteristics.

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