WO2021033655A1 - 樹脂原料用組成物 - Google Patents

樹脂原料用組成物 Download PDF

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Publication number
WO2021033655A1
WO2021033655A1 PCT/JP2020/030935 JP2020030935W WO2021033655A1 WO 2021033655 A1 WO2021033655 A1 WO 2021033655A1 JP 2020030935 W JP2020030935 W JP 2020030935W WO 2021033655 A1 WO2021033655 A1 WO 2021033655A1
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Prior art keywords
component
area
polyesterimide
composition
range
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PCT/JP2020/030935
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English (en)
French (fr)
Japanese (ja)
Inventor
匡彦 西原
利恵 藤岡
勝徳 高橋
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本州化学工業株式会社
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Application filed by 本州化学工業株式会社 filed Critical 本州化学工業株式会社
Priority to JP2021540933A priority Critical patent/JPWO2021033655A1/ja
Priority to KR1020227003662A priority patent/KR20220051330A/ko
Priority to CN202080054438.1A priority patent/CN114222778B/zh
Publication of WO2021033655A1 publication Critical patent/WO2021033655A1/ja
Priority to JP2024214096A priority patent/JP2025032249A/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
    • C08G73/16—Polyester-imides

Definitions

  • the present invention relates to a composition for a resin raw material used for producing a resin having excellent mechanical properties.
  • Polyimide has not only excellent heat resistance but also characteristics such as chemical resistance, radiation resistance, electrical insulation, and excellent mechanical properties. Therefore, it is a flexible printed circuit (FPC) substrate, TAB (Tape Automated Bonding). It is widely used in various electronic devices such as base materials for substrates, protective films for semiconductor elements, and interlayer insulating films for integrated circuits. In addition to these properties, polyimide has become increasingly important in recent years due to its simplicity of manufacturing method, extremely high film purity, and ease of property improvement using various available monomers.
  • the compound represented by the following formula (a), 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol-bis (trimeritate unhydride) (hereinafter, "compound” (Sometimes referred to as “a”) has a high glass transition temperature, a low coefficient of linear thermal expansion equivalent to that of a metal foil, an extremely low water absorption rate, a high elastic modulus, sufficient toughness, and sufficient adhesion to a metal foil. It is a compound useful as a raw material for a polyesterimide resin (for example, Patent Documents 1 and 2).
  • an object of the present invention is to provide a composition for a resin raw material capable of producing a polyesterimide resin having extremely excellent mechanical properties as compared with the prior art.
  • composition ratio Component A is 99.0 area% or more and 99.99 area% or less with respect to the total amount of all components detected by gel permeation chromatography using a differential refractometer as a detector.
  • B is 0.005 area% or more and 0.4 area% or less.
  • R represents a hydrogen atom or R 1- CO- (where R 1 is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms). 2.
  • a method for producing a polyesterimide which comprises a step of obtaining a body (i) and then a step of imidizing the body (ii).
  • Component A is 99.0 area% or more and 99.99 area% or less with respect to the total amount of all components detected by gel permeation chromatography using a differential refractometer as a detector.
  • B is 0.005 area% or more and 0.4 area% or less.
  • R represents a hydrogen atom or R 1- CO- (where R 1 is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms).
  • the present invention it is possible to provide a composition for a resin raw material capable of producing a polyesterimide resin having extremely excellent mechanical properties as compared with the conventional one. Furthermore, since it was found that specific impurities affect the mechanical properties, it is possible to produce a polyesterimide resin having tougher mechanical properties from the composition for resin raw materials in which the specific impurities are reduced. Become.
  • the composition for a resin raw material of the present invention contains the compound a "2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-represented by the following formula (a) as the component A. It contains "diol-bis (trimeritate unhydride)" as a main component.
  • the content of component A in the composition for resin raw materials of the present invention is 99.0 area% or more with respect to the total amount of all components detected by gel permeation chromatography using a differential refractometer as a detector. It is 99.99 area% or less.
  • the lower limit is preferably 99.1 area% or more, and more preferably 99.3 area% or more.
  • it is contained in the range of 0.005 area% or more and 0.4 area% or less.
  • the upper limit is preferably 0.35 area% or less, more preferably 0.3 area% or less, further preferably 0.2 area% or less, and particularly preferably 0.15 area% or less.
  • the lower limit may be preferably 0.01 area% or more from the viewpoint of suppressing a decrease in the yield of the target component A in the case of repeated purification.
  • the polyesterimide resin obtained by using the composition for a resin raw material containing a compound represented by the following formula (b) in an amount of more than 0.4 area% by the above measurement has significantly deteriorated mechanical properties. .. (In the formula, R represents a hydrogen atom or R 1- CO- (where R 1 is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms).
  • component B in the composition for a resin raw material of the present invention include the following compound b1 in which "R" in the above formula (b) is a hydrogen atom.
  • the compound b1 is a compound produced as a reaction intermediate when the compound a is synthesized by the "acid halide method" which is one of the methods for producing a composition for a resin raw material of the present invention, which will be described later.
  • the reaction formula for producing compound b1 by the "acid halide method” is shown below.
  • R in the above formula (b) is R 1- CO-, and "R 1 " is an alkyl having 1 carbon atom.
  • the following compound b2 which is a group can be mentioned.
  • the compound b2 is a compound produced as a reaction intermediate when the compound a is synthesized by the "transesterification method” which is one of the methods for producing a composition for a resin raw material of the present invention, which will be described later.
  • the reaction formula for producing compound b2 by the "transesterification method” is shown below.
  • the compound b2 is also a compound produced by reacting the produced compound b1 with acetic anhydride when acetic anhydride is used in the reaction post-treatment step in the above-mentioned "acid halide method".
  • the reaction formula is shown below.
  • ⁇ Manufacturing method 1 "Acid halide method”>
  • the “acid halide method” which is one of the methods for producing the composition for a resin raw material of the present invention, will be described below.
  • This "acid halide method” reacts 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol with trimellitic anhydride halide as shown in the reaction formula below.
  • This is a method for producing the composition for a resin raw material of the present invention containing the compound a as a main component.
  • trimellitic anhydride halide used in the above “acid halide method” includes trimellitic anhydride chloride (corresponding to the compound in the above reaction formula), trimellitic anhydride bromide, trimellitic anhydride iodide, and trimellitic anhydride fluoride.
  • trimellitic anhydride chloride is preferably used because it is inexpensive and easily available.
  • the amount of these trimellitic anhydride halides used is usually 2 to 3 mol with respect to 1 mol of 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol. Preferably 2.1 to 2.5 mol is used.
  • hydrogen halide is generated by the reaction of 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol and trimellitic anhydride halide.
  • bases are not particularly limited, but organic tertiary amines such as pyridine, triethylamine, N, N-dimethylaniline, epoxies such as propylene oxide, and inorganic bases such as potassium carbonate and sodium hydroxide are used. It is possible to do.
  • pyridine is preferably used from the viewpoint of separation operation after the reaction, cost, toxicity and the like.
  • the above-mentioned "acid halide method” is a solution of 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol of the same solvent in anhydrous trimellitic acid halide dissolved in a solvent.
  • the reaction is started by mixing.
  • a base such as pyridine is contained in a solution of 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol, which is a mixed solution.
  • a solution of trimellitic anhydride halide is mixed with a solution of 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol. Then, by-products are more likely to be produced than the former mixing method. Therefore, the former mixing method, that is, 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4 dissolved in the same type of solvent in a solution of trimellitic acid halide dissolved in the solvent. A method of mixing a solution of'-diol is preferable.
  • the molar ratio of the starting material to the base used in the reaction is 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol / trimellitic anhydride halide / base. It is preferably in the range of 0 / 2.1 to 2.5 / 3.0 to 5.0.
  • the above solutions are mixed at a low temperature.
  • the temperature in the reaction system is preferably in the range of ⁇ 10 to 10 ° C., more preferably in the range of ⁇ 5 to 7 ° C., and particularly preferably in the range of 0 to 5 ° C. There is no limitation on the mixing time, but 2 to 4 hours is preferable.
  • post-stirring 1 a temperature in the reaction system is preferably in the range of -10 to 10 ° C, more preferably in the range of -5 to 7 ° C, and in the range of 0 to 5 ° C. It is particularly preferable to carry out with.
  • "Post-stirring 1" is preferably performed within about 5 hours in such a temperature range, and more preferably 2 to 3 hours.
  • post-stirring 2 is preferably carried out in a reaction system in a temperature range of 50 to 75 ° C., more preferably in a range of 55 to 70 ° C., and particularly preferably in a range of 60 to 65 ° C. .. "Post-stirring 2" is preferably performed within about 5 hours in such a temperature range, and more preferably 2 to 3 hours.
  • the solvent that can be used in the above "acid halide method” is not particularly limited as long as it does not inhibit the reaction, but tetrahydrofuran, 1,4-dioxane, picolin, pyridine, acetone, chloroform, toluene, xylene, and dichloromethane.
  • tetrahydrofuran, ⁇ -butyrolactone, ⁇ -valerolactone, acetonitrile and the like are preferably used from the viewpoint of rapidly carrying out the reaction and suppressing the residual of the reaction intermediate compound b1.
  • the “transesterification method” which is one of the methods for producing a composition for a resin raw material of the present invention, will be described below.
  • This "transesterification method” is a dicarboxylic acid ester of 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol and trimellitic anhydride as shown in the following reaction formula.
  • This is a method for producing the composition for a resin raw material of the present invention containing compound a as a main component by reacting with an acid.
  • R 1 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms).
  • dicarboxylic acid ester of 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol used in the above "ester exchange method” include 2, 2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol-bis (acetate), 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4, 4'-diol-bis (propionate), 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol-bis (butyrate), 2,2', 3,3' , 5,5'-Hexamethyl-biphenyl-4,4'-diol-bis (benzoate), 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol-bis (benzoate) Naftate) and the like.
  • 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol dicarboxylic acid esters can be produced by conventionally known methods, and for example, 2,2.
  • Examples thereof include a method of reacting', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol with a carboxylic acid anhydride or a carboxylic acid halide.
  • the amount of trimellitic anhydride used in the above "transesterification method" is based on 1 mol of the dicarboxylic acid ester of 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol.
  • reaction temperature of the above-mentioned "transesterification reaction” is usually in the range of 100 to 300 ° C., preferably in the range of 150 to 250 ° C., and particularly preferably in the range of 200 to 230 ° C.
  • a base as a catalyst in the reaction.
  • these bases include organic alkali metal compounds such as alkali metal hydroxides, carbonates and hydrogen carbonate compounds, alkali metal alcohols, phenols and salts with organic carboxylic acids.
  • Alkali metal compounds and the like can be used, and specific examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium acetate, sodium acetate, potassium acetate and the like.
  • the amount of these bases used is in the range of 0.001 to 10 mol% with respect to 1 mol of the dicarboxylic acid ester of 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol. , Preferably in the range of 0.005 to 5 mol%.
  • reaction solvent in the reaction for the reason of improving operability and reaction speed during industrial production.
  • the solvent that can be used is not particularly limited as long as it is not distilled from the reaction vessel at the above reaction temperature and is inert to the transesterification reaction.
  • alkylaryl ethers such as phenitol and butylphenyl ether
  • aromatic hydrocarbon ether solvents such as diphenyl ethers such as diphenyl ether and dip-tolyl ether
  • fragrances such as biphenyl and terphenyl.
  • alkyl-substituted naphthalenes such as diisopropylnaphthalene, aliphatic hydrocarbons such as decalin and kerosine, polyalkylene glycol ethers such as tetraethylene glycol dimethyl ether and diethylene glycol dibutyl ether, Therm S series (manufactured by Nippon Steel Chemical Co., Ltd.) ), KSK-OIL series (manufactured by Soken Kagaku Co., Ltd.), or Neo SK-OIL series (manufactured by Soken Kagaku Co., Ltd.) and other organic solvents.
  • alkyl-substituted naphthalenes such as diisopropylnaphthalene
  • aliphatic hydrocarbons such as decalin and kerosine
  • polyalkylene glycol ethers such as tetraethylene glycol dimethyl ether and diethylene glycol dibutyl ether
  • the amount used is usually 1 to 10 with respect to 1 part by weight of the dicarboxylic acid ester of 2,2', 3,3', 5,5'-hexamethyl-biphenyl-4,4'-diol. It is in the range of parts by weight, preferably 2 to 3 parts by weight.
  • the reaction product obtained by the above reaction is usually used as the component B in order to keep the content of the compound represented by the formula (b) in a specific range. It can be purified and obtained.
  • a known method can be used, but it is preferably carried out by a method of crystallization and reslurry (suspension of a solid in a solvent).
  • reslurry suspension of a solid in a solvent.
  • the solvent that can be used for crystallization and reslurry is not particularly limited as long as it is an inert solvent with component A, but specifically, anhydrous acetic acid, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and tetrahydrofuran. , Methyl isobutyl ether, methyl isopropyl ether, toluene, xylene, ethylbenzene, ⁇ -butyrolactone, ⁇ -valerolactone, acetonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
  • the amount of the solvent used includes component A, component B and other impurities to be purified. It is in the range of 5 to 50 parts by weight, more preferably in the range of 10 to 30 parts by weight, and particularly preferably in the range of 1 to 20 parts by weight with respect to 1 part by weight of the total amount of the composition.
  • the temperature at the time of melting is in the range of 100 to 200 ° C., more preferably in the range of 110 to 180 ° C., further preferably in the range of 110 to 160 ° C., and particularly preferably in the range of 120 to 140 ° C.
  • the cooling temperature is in the range of 0 ° C. to 50 ° C., more preferably in the range of 10 to 40 ° C., and even more preferably in the range of 15 to 30 ° C.
  • the conditions of the reslurry method differ depending on the solvent used and cannot be unequivocally determined. For example, when ⁇ -butyrolactone is used, the amount of the solvent used includes component A, component B and other impurities to be purified.
  • the treatment temperature is preferably in the range of 100 to 200 ° C, more preferably in the range of 110 to 180 ° C, still more preferably in the range of 110 to 160 ° C, and particularly preferably in the range of 120 to 140 ° C. ..
  • the reslurry treatment may be carried out for about 0.5 to 3 hours.
  • various conditions should be changed as appropriate in consideration of the boiling point of the solvent, the solubility of component A, component B, other impurities to be purified, and the composition containing them.
  • the solution in which the composition containing component A, component B and other impurities is dissolved is filtered to separate the inorganic salt by filtration.
  • a high-purity product with further reduced metal components such as inorganic salts can be obtained.
  • an acid anhydride such as acetic anhydride or heat treatment. It can be returned to carboxylic acid anhydride by such means.
  • the purified product obtained by these purification steps may contain the solvent used, it is preferable to remove the solvent and dry it.
  • the method for removing the solvent is not particularly limited, and examples thereof include a method in which heating is performed under normal pressure or reduced pressure to distill off the solvent.
  • a polyesterimide can be produced by the step (i) of reacting the composition for a resin raw material of the present invention with a diamine to obtain a polyesterimide precursor (polyamic acid), and then the step (ii) of imidizing the polyesterimide precursor.
  • Step of obtaining polyesterimide precursor (polyamic acid)>
  • the reaction of the composition for a resin raw material of the present invention with a diamine is carried out.
  • diamine is first dissolved in a polymerization solvent, and the composition for a resin raw material of the present invention, which is an acid dianhydride having substantially the same molar amount as diamine, is added to this solution. Gradually add and react.
  • the temperature at this time is in the range of 0 to 100 ° C, preferably in the range of 5 ° C to 80 ° C, more preferably in the range of 10 to 60 ° C, further preferably in the range of 15 to 40 ° C, and 20 to 30 ° C.
  • the range is particularly preferred.
  • the raw material monomer concentration is usually in the range of 5 to 50% by weight.
  • the diamine that can be used is not particularly limited, but aromatic diamines and aliphatic diamines can be used.
  • aromatic diamine include p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4-aminophenyl-4'-aminobenzoate, benzidine, 3,3'-dihydroxybenzidine, 2,2'.
  • TFMB -Bis (trifluoromethyl) benzidine
  • 1,4-bis (4-aminophenoxy) benzene 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene
  • 2,2-bis (4- (4-aminophenoxy) phenyl) propane 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane
  • 2,2-bis (4-aminophenyl) fluorene and the like can be mentioned, and 2,2'-bis (trifluoromethyl) benzidine (TFMB) is particularly preferable.
  • aliphatic diamine examples include 4,4'-methylenebis (cyclohexylamine), 1,4-cyclohexanebis (methylamine), 2,2-bis (4-aminocyclohexyl) propane, and 2,2.
  • examples thereof include -bis (4-aminocyclohexyl) hexafluoropropane, trans-1,4-diaminocyclohexane, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, and 1,6-hexamethylenediamine.
  • the polymerization solvent that can be used, any solvent can be used as long as the raw material monomer, the produced polyesterimide precursor, and the imidized polyesterimide are not dissolved and interfere with the reaction.
  • N Amido solvents such as N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone
  • Cyclic ester solvents such as, ethylene carbonate, carbonate solvents such as propylene carbonate, glycol solvents such as triethylene glycol, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, acetophenone, etc.
  • 1,3-Dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide and the like can be used.
  • amide solvents, cyclic ester solvents, and carbonate solvents, which are aprotic solvents are preferable, and specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Etc. are preferable.
  • an aromatic or aliphatic tetracarboxylic dianhydride other than the composition for a resin raw material of the present invention which is a tetracarboxylic dianhydride
  • a polyesterimide precursor having a larger intrinsic viscosity can be obtained as compared with the case where a conventional raw material is used.
  • a step of imidizing the polyesterimide precursor in order to obtain polyesterimide will be described.
  • a method for imidizing the polyesterimide precursor a known method such as a thermal imidization method for thermally dehydrating and ring-closing and a chemical imidization method using a dehydrating agent can be used. Of these, a chemical imidization method that does not require high-temperature heat treatment and can be imidized under mild conditions is preferable.
  • an azeotropic agent with water such as toluene and xylene is mixed with the reaction solution in the step of obtaining the polyesterimide precursor described above, and water produced as a by-product is removed from the system by heating.
  • Imidization can be performed by reacting while allowing the mixture to react.
  • the reaction temperature at that time is preferably heating to a temperature equal to or higher than the temperature at which water is distilled out from the system, for example, a co-boiling point or higher or 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 130 ° C. or higher. Heating at 150 ° C.
  • a polyesterimide precursor solution obtained by polymerization is cast on a substrate such as glass and dried to form a precursor film. After that, imidization can be performed by heating the entire substrate in the normal pressure or vacuum in the range of 200 to 400 ° C.
  • the above-mentioned polyesterimide precursor solution is adjusted to an appropriate solution viscosity that is easy to stir with the same solvent used at the time of polymerization, and the organic acid anhydride is mixed with the stirrer.
  • a dehydration ring-closing agent (chemical imidizing agent) composed of a basic catalyst is mixed and imidized.
  • the temperature at this time is in the range of 0 to 100 ° C, preferably in the range of 5 to 80 ° C, more preferably in the range of 10 to 60 ° C, further preferably in the range of 15 to 40 ° C, and in the range of 20 to 30 ° C. Is particularly preferable.
  • the organic acid anhydride that can be used at that time is not particularly limited, and examples thereof include acetic anhydride and propionic anhydride. Acetic anhydride is preferably used because of the ease of handling and purification of the reagent.
  • the basic catalyst is not particularly limited, but pyridine, triethylamine, quinoline and the like can be used, but pyridine is preferably used because of the ease of handling and separation of the reagent.
  • the amount of organic acid anhydride in the chemical imidizing agent is in the range of 1 to 10 times the molar amount of theoretical dehydration of the polyesterimide precursor.
  • the amount of the basic catalyst is in the range of 0.1 to 2 times the molar amount of the organic acid anhydride. Since by-products such as chemical imidizing agents and carboxylic acids are mixed in the reaction solution after the chemical imidization, it is necessary to remove them to purify the polyesterimide.
  • a known method can be used for purification. For example, the simplest method is to drop the imidized reaction solution into a large amount of poor solvent (for example, an alcohol solvent such as methanol or ethanol, an aliphatic hydrocarbon solvent such as hexane, etc.) while stirring the polyester.
  • the polyesterimide powder After precipitating the imide, the polyesterimide powder is recovered. If the solid content concentration of the polyimide contained in the reaction solution dropped in the poor solvent is too high, the precipitated polyimide becomes a granular mass, and impurities remain in the coarse particles, or the obtained polyimide powder is used as a solvent. It may take a long time to redissolve. On the other hand, if the concentration is too low, a large amount of poor solvent is required, which may increase the environmental load and the manufacturing cost due to the waste solvent treatment. Therefore, a solvent such as the polymerization solvent may be added to the liquid after the polyesterimide is precipitated.
  • a polyesterimide powder is repeatedly washed until the by-products are removed, and then the powder to which the solvent is attached is dried under reduced pressure to obtain a polyesterimide powder.
  • a polyesterimide having a larger intrinsic viscosity can be obtained as compared with the case where a conventional raw material is used. Further, it is possible to obtain a polyesterimide in which the breaking strength, the average breaking elongation rate, and the maximum elongation rate are all remarkably improved in the tensile strength test result when the film is formed.
  • the obtained polyesterimide can be dissolved in an organic solvent to form a solution.
  • the organic solvent can be appropriately selected according to the intended use of the solution and the processing conditions. In the case of continuous coating for a long period of time, the organic solvent in the polyesterimide solution may absorb moisture in the atmosphere and precipitate polyesterimide. Therefore, for example, triethylene glycol dimethyl ether, ⁇ -butyrolactone or cyclopentanone It is preferable to use a low hygroscopic solvent such as.
  • the solid content concentration can be appropriately selected depending on the intended use of the solution, and is not particularly limited. For example, in the case of a film, the solid content concentration is preferably 5% by weight or more, although it depends on the molecular weight of the polyesterimide, the production method and the thickness of the film to be produced.
  • the obtained polyesterimide solution can be used to mold the polyesterimide into a film.
  • a manufacturing method thereof a known method can be used.
  • a polyesterimide film is obtained by applying a polyesterimide solution on a support such as a glass substrate using a doctor blade or the like and then drying the film. Can be manufactured. Further, in order to remove the residual strain, heat treatment in the range of 150 to 300 ° C. can be performed in an inert gas atmosphere or in a vacuum.
  • the filtered white precipitate was vacuum dried at 60 ° C. to obtain 62.5 g of a product. Then, the obtained product and acetic anhydride were charged in a four-necked flask, reacted at 100 ° C. for 2 hours, and then stirred for 24 hours while cooling to room temperature to form a white precipitate. The precipitate was filtered off and washed with ⁇ -butyrolactone. Then, under reduced pressure, it was dried at 120 ° C. for 1 hour and at 150 ° C. for 1 hour. Further, the obtained precipitate was washed with ⁇ -butyrolactone by holding at 100 ° C.
  • the obtained composition for a resin raw material contains 87.7 area% of compound a as component A of the present invention and 10.4 area% of the total of compound b1 and compound b2 as component B of the present invention. It was a composition to be used.
  • Example 1 The composition for a resin raw material of the present invention was produced.
  • the detailed operation method is as follows. 411.8 g (1.96 mol) of trimellitic anhydride and 1213.0 g of tetrahydrofuran were placed in a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and the container was replaced with nitrogen while stirring and dissolving, and the temperature was 5 ° C or lower. Cooled to.
  • the composition for a resin raw material of the present invention contains 99.4 area% of compound a as component A and 0.1 area% of the total of compound b1 and compound b2 as component B of the present invention. Became clear.
  • the obtained polyamic acid was diluted with dehydrated dimethylacetamide to a solid content concentration of 6.5% by weight.
  • a mixed solution of 24.69 mmol of acetic anhydride and 12.35 mmol of pyridine was slowly added dropwise at room temperature, and the mixture was further stirred for 24 hours after the completion of the addition.
  • the obtained polyimide solution was slowly added dropwise to a large amount of methanol.
  • dimethylacetamide was added to precipitate the fibrous polyimide, which was then filtered off.
  • the obtained white precipitate was washed with methanol and dried under vacuum at 60 ° C.
  • Example 2 In order to evaluate the influence of the content of component B, the composition for resin raw materials of the present invention obtained in Example 1 and the composition for resin raw materials obtained in Synthesis Example 1 above have a component B content of 0.
  • the composition was prepared by mixing based on the weight so as to have an area% of 3 (at this time, the compound a was 99.3 area%).
  • the polyimide precursor was polymerized in the same manner as in Example 1, the intrinsic viscosity at 52 hours was 4.39 dL / g and the intrinsic viscosity at 72 hours was 4.46 dL / g.
  • the chemical imidization reaction and the polyimide film were prepared in the same manner as in Example 1, and the mechanical properties were measured. The results are shown in Table 1 below.
  • Example 1 In the same manner as in Example 2, the composition was prepared by mixing based on the weight so that the content of the component B was 1.0 area% (at this time, the compound a was 98.4 area%).
  • the polyimide precursor was polymerized in the same manner as in Example 1, the intrinsic viscosity at 52 hours was 3.29 dL / g and the intrinsic viscosity at 72 hours was 3.30 dL / g.
  • the chemical imidization reaction and the polyimide film were prepared in the same manner as in Example 1, and the mechanical properties were measured. The results are shown in Table 1 below.
  • Example 2 In the same manner as in Example 2, the composition was prepared by mixing so that the content of component B was 0.5 area% (at this time, compound A was 98.9 area%).
  • the polyimide precursor was polymerized in the same manner as in Example 1, the intrinsic viscosity at 52 hours was 4.24 dL / g and the intrinsic viscosity at 72 hours was 4.26 dL / g.
  • the chemical imidization reaction and the polyimide film were prepared in the same manner as in Example 1, and the mechanical properties were measured. The results are shown in Table 1 below.

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JPH0255733A (ja) * 1988-08-18 1990-02-26 E I Du Pont De Nemours & Co 溶媒抽出によるポリイミド分子量の向上
JP2002322298A (ja) * 2001-04-25 2002-11-08 Kanegafuchi Chem Ind Co Ltd ポリイミドフィルムおよびそのポリイミドフィルムを用いたフレキシブルプリント基板
JP2003238684A (ja) * 2002-02-15 2003-08-27 New Japan Chem Co Ltd ポリアミド酸溶液の製造方法
JP2008101187A (ja) * 2006-09-19 2008-05-01 Asahi Kasei Corp ポリエステルイミドおよびその製造方法
WO2008091011A1 (ja) * 2007-01-26 2008-07-31 Honshu Chemical Industry Co., Ltd. 新規なエステル基含有テトラカルボン酸二無水物類、それから誘導される新規なポリエステルイミド前駆体及びポリエステルイミド
WO2014046180A1 (ja) * 2012-09-19 2014-03-27 本州化学工業株式会社 ポリイミド及びその成形体

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JPS58219238A (ja) * 1982-06-15 1983-12-20 Mitsui Toatsu Chem Inc 芳香族ポリアミド−ポリイミド共重合体の製造法
JPH0255733A (ja) * 1988-08-18 1990-02-26 E I Du Pont De Nemours & Co 溶媒抽出によるポリイミド分子量の向上
JP2002322298A (ja) * 2001-04-25 2002-11-08 Kanegafuchi Chem Ind Co Ltd ポリイミドフィルムおよびそのポリイミドフィルムを用いたフレキシブルプリント基板
JP2003238684A (ja) * 2002-02-15 2003-08-27 New Japan Chem Co Ltd ポリアミド酸溶液の製造方法
JP2008101187A (ja) * 2006-09-19 2008-05-01 Asahi Kasei Corp ポリエステルイミドおよびその製造方法
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Publication number Priority date Publication date Assignee Title
WO2024122557A1 (ja) * 2022-12-06 2024-06-13 本州化学工業株式会社 エステル化合物、樹脂原料用エステル化合物組成物

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