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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/092—Polycarboxylic acids
• • 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 a polyimide precursor composition and a polyimide.
• Polyimide is a resin that has excellent properties such as not only heat resistance but also chemical resistance, radiation resistance, electrical insulation, and mechanical properties. In order to make polyimide a material suitable for various uses, studies are actively being conducted to improve the functionality of polyimide.
• Patent Document 1 In recent years, studies have been made to reduce the coloring of polyimide, which has excellent heat resistance, in order to use it as a substitute for glass (for example, Patent Document 1).
• Patent Document 1 describes the production of fluorinated polyimide using a fluorine-containing compound as a raw material by suppressing the content of Pb and Na as one method for reducing coloring of polyimide.
• fluorine-containing compounds are difficult to manufacture and very expensive, fluorinated polyimides are also disadvantageous in terms of cost.
• Patent Document 1 describes another method of producing polyimide using an alicyclic acid dianhydride as a raw material, but this method is also not economical because the raw material is very expensive.
• Patent Document 2 describes a method of adding tetracarboxylic acid to a polyimide precursor as a method for making polyimide highly functional.
• Ring-opened pyromellitic acid (1,2,5,6-benzenetetracarboxylic acid) is added to a polyimide precursor to prepare a polyimide precursor with low viscosity and increased solid content concentration, and then ring-opened polyimide precursor is prepared.
• a method for obtaining polyimide by chemical reaction is described, there is no description of coloring the polyimide.
• an object of the present invention is to provide a polyimide precursor composition that can obtain a polyimide film with low coloration, and a polyimide obtained from the above composition.
• the present inventors have made extensive studies to achieve the above object. As a result, by adding a specific amount of a compound represented by the formula (A) described below to a polyamic acid obtained by polycondensing a diamine and a carboxylic dianhydride, a cyclization reaction is caused.
• the present invention was completed based on the discovery that the polyimide film has little coloration. That is, the present inventors have found that the above problem can be solved by the following configuration.
• (1) Contains a polyamic acid obtained by polycondensing a diamine and a carboxylic dianhydride, and a compound represented by the formula (A) described below, A polyimide precursor composition, wherein the content of the compound is 0.5 to 5.0 mol% relative to the content of the carboxylic dianhydride.
• (2) The polyimide precursor composition according to (1) above, wherein the diamine is an aromatic diamine.
• (3) The polyimide precursor composition according to (1) or (2) above, wherein the carboxylic dianhydride is an aromatic carboxylic dianhydride.
• a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as a lower limit value and an upper limit value.
• each component may be used alone or in combination of two or more.
• the content of the component refers to the total content unless otherwise specified.
• the fact that the obtained polyimide film has little coloration and excellent mechanical properties and thermal properties is also referred to as "the effects of the present invention are excellent.”
• composition of the present invention is Contains a polyamic acid obtained by polycondensing a diamine and a carboxylic dianhydride, and a compound represented by the formula (A) described below (hereinafter also referred to as a "specific compound”), A polyimide precursor composition in which the content of the specific compound is 0.5 to 5.0 mol% with respect to the content of the carboxylic dianhydride (unit derived from the carboxylic dianhydride). be.
• the composition of the present invention has such a configuration, it is considered that the above-mentioned problems can be solved.
• the reason for this is not clear, but it is thought to be approximately as follows. It is believed that when a film of the composition of the present invention is subjected to heat treatment or the like, the polyamic acid in the composition is cyclized and the specific compound acts as a crosslinking agent and reacts with the polyamic acid. Therefore, it is thought that the polyimide obtained is one into which a specific compound has been introduced.
• the specific compound has a fluorene structure, it is thought that it acts as a component that reduces coloration, and as a result, a polyimide film with low coloration is obtained.
• the above polyamic acid is a polyamic acid obtained by polycondensing a diamine and a carboxylic dianhydride.
• the diamine used when polycondensing polyamic acid is not particularly limited.
• the diamine include at least one diamine selected from the group consisting of aromatic diamine, alicyclic diamine, linear aliphatic diamine, and branched aliphatic diamine.
• aromatic diamines include 3,5-diaminobenztrifluoride, 2,5-diaminobenztrifluoride, 3,3'-bistrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-bistrifluoro Methyl-5,5'-diaminodiphenyl, bis(trifluoromethyl)-4,4'-diaminodiphenyl, bis(fluorinated alkyl)-4,4'-diaminodiphenyl, dichloro-4,4'-diaminodiphenyl, Dibromo-4,4'-diaminodiphenyl, bis(fluorinated alkoxy)-4,4'-diaminodiphenyl, diphenyl-4,4'-diaminodiphenyl, 4,4'-bis(4-aminotetrafluorophenoxy)tetra Fluorobenzene, 4,4'-bis(4-aminotetrafluoroph
• aromatic diamines include 4,4'-diaminodiphenyl ether (ODA), p-phenylenediamine, m-tolidine, 2,2'-bis(trifluoromethyl)benzidine, etc. because of the superior effects of the present invention. is preferred.
• ODA 4,4'-diaminodiphenyl ether
• p-phenylenediamine p-phenylenediamine
• m-tolidine 2,2'-bis(trifluoromethyl)benzidine, etc. because of the superior effects of the present invention. is preferred.
• alicyclic diamines examples include 4,4'-methylenebis(cyclohexylamine), trans-1,4-cyclohexanediamine, isophoronediamine, trans-1,4-diaminocyclohexane, 1,3-diaminoadamantane, 2, 2-bis(4-aminocyclohexyl)propane, 2,2-bis(4-aminocyclohexyl)hexafluoropropane, 1,4-cyclohexanebis(methylamine), 2,5-bis(aminomethyl)bicyclo[2.
• alicyclic diamine examples include 4,4'-methylenebis(cyclohexylamine) and trans-1,4-cyclohexanediamine.
• linear aliphatic diamines examples include 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, Examples include 1,8-octamethylene diamine and 1,9-nonamethylene diamine. Two or more of these may be used in combination.
• Examples of branched aliphatic diamines include 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 5-methyl-1, Examples include 9-nonanediamine. Two or more of these may be used in combination.
• the carboxylic dianhydride is not particularly limited as long as it does not significantly impair the polymerization reactivity of the polyimide precursor and the required properties of the polyimide obtained from the polyimide precursor.
• Examples of the carboxylic dianhydride include at least one carboxylic dianhydride selected from the group consisting of aromatic carboxylic dianhydrides, alicyclic carboxylic dianhydrides, and chain aliphatic carboxylic dianhydrides. Preferably, it is anhydrous. Among these, aromatic carboxylic dianhydrides are more preferred.
• aromatic carboxylic dianhydride examples include pyromellitic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.
• Acid dianhydride 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride
• Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride examples include 4,4'-oxydiphthalic dianhydride and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Two or more of these may be used in combination.
• aromatic carboxylic dianhydride pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, etc. are preferable.
• alicyclic tetracarboxylic dianhydride include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bicyclo[2. 2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and the like. Two or more of these may be used in combination.
• chain aliphatic tetracarboxylic dianhydrides examples include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, and the like. can be mentioned. Two or more of these may be used in combination.
• the ratio of polycondensation of diamine and carboxylic dianhydride is preferably 0.90 to 1.00 mol, and 0.95 to 1.00 mol of carboxylic dianhydride per 1 mol of diamine, since the effects of the present invention are better. 0.98 mol is more preferable.
• the polyamic acid is preferably one obtained by polycondensing a diamine and a carboxylic dianhydride in a solvent.
• solvent The above-mentioned solvent may be used as long as it can dissolve the monomers diamine and carboxylic dianhydride, and its type is not particularly limited, but it is preferably a polar solvent.
• amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
• cyclic ester solvents such as ⁇ -caprolactone and ⁇ -methyl- ⁇ -butyrolactone; carbonate solvents such as ethylene carbonate and propylene carbonate; glycol solvents such as triethylene glycol; m-cresol, p-cresol, 3-chlorophenol
• Preferred examples include phenolic solvents such as 4-chlorophenol; acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like.
• amide solvents are preferred, and N,N-dimethylacetamide is more preferred, since the effects of the present invention are better.
• L represents a single bond or a divalent linking group.
• the above L is preferably a single bond because the effects of the present invention are more excellent.
• divalent linking group is not particularly limited, and specific examples thereof include linear, branched, or cyclic divalent aliphatic hydrocarbon groups (e.g., methylene group, ethylene group, propylene group, etc.). alkylene group), divalent aromatic hydrocarbon group (e.g.
• R L represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
• BPAF-TA 9,9-bis(3,4-dicarboxyphenyl)fluorene
• BPF-TA 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene
• BPF-TA 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene
• the content of the specific compound is 0.0% relative to the content of carboxylic dianhydride (unit derived from carboxylic dianhydride) used in the polycondensation of the polyamic acid mentioned above. It is 5 to 5.0 mol%.
• the content of the above-mentioned specific compound is preferably 1.0 to 4.0 mol%, since the effects of the present invention are more excellent and it is easily soluble in a solvent.
• the content of the specific compound relative to the content of carboxylic dianhydride (unit derived from carboxylic dianhydride) used in polycondensation of polyamic acid is also simply referred to as "content of specific compound.”
• composition of the present invention preferably further contains a solvent because the effects of the present invention are more excellent.
• a solvent for polycondensation of polyamic acid.
• the concentration of the above-mentioned polyamic acid is not particularly limited, but it is preferably 5 to 35% by mass, and 7 to 30% by mass because the effects of the present invention are better. More preferred.
• composition of the present invention may contain components other than those mentioned above.
• Specific examples of such components include oxidation stabilizers, fillers, silane coupling agents, photosensitizers, photopolymerization initiators, and sensitizers.
• diamine is dissolved in a polymerization solvent, and carboxylic dianhydride powder is gradually added thereto, followed by stirring using a mechanical stirrer.
• the temperature during stirring is preferably 0 to 100°C, more preferably 5 to 60°C.
• the stirring time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours.
• the lower limit concentration of the monomers (diamine and carboxylic dianhydride) in the polymerization solvent is preferably 5% by mass, and 7% by mass because the degree of polymerization of the polyamic acid solution increases and the toughness of the polyimide can be improved. More preferred.
• the upper limit concentration of the monomers (diamine and carboxylic dianhydride) in the polymerization solvent is preferably 35% by mass, more preferably 30% by mass.
• Powder of a specific compound is added to this polyamic acid solution and stirred using a mechanical stirrer.
• the temperature during stirring is preferably 0 to 100°C, more preferably 5 to 60°C.
• the stirring time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.
• composition of the present invention is diluted, if necessary, and used in the next step of producing polyimide.
• the polyimide of the present invention is a polyimide obtained by subjecting the composition of the present invention described above to a cyclization reaction.
• the method of the cyclization reaction is not particularly limited, and a known method of cyclizing a polyimide precursor can be adopted.
• the composition of the present invention (polyimide precursor solution) is applied onto a substrate made of glass, steel, aluminum, silicon, etc., and dried in an oven.
• the drying temperature is preferably 40 to 180°C, more preferably 50 to 150°C.
• a film (polyimide precursor film) of the composition of the present invention is obtained.
• the obtained polyimide precursor film is heated on the substrate. This causes a cyclization reaction to produce a polyimide film on the substrate.
• the heating temperature is preferably 200°C or higher, more preferably 250°C or higher.
• the heating temperature is preferably 430°C or lower, more preferably 400°C or lower.
• the cyclization reaction is preferably carried out in vacuum or in an inert gas such as nitrogen, but may be carried out in air as long as the heating temperature is not too high.
• the cyclization reaction can also be carried out by a method other than heating the polyimide precursor film.
• the polyimide precursor film can be immersed in a solution containing a dehydrating agent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine.
• a polyimide-containing solution can be easily produced by heating the polyimide precursor solution as it is or after appropriately diluting it with the same solvent to 150 to 200°C.
• a solution containing polyimide will also be referred to as a polyimide solution.
• toluene, xylene, etc. may be added in order to azeotropically distill off water and the like which are by-products of the cyclization reaction.
• a base such as ⁇ -picoline may be added as a catalyst.
• the polyimide can also be isolated as a powder by dropping the obtained polyimide solution into a large amount of a poor solvent such as water or methanol, and then filtering it.
• a polyimide solution can also be obtained by redissolving the polyimide powder in the above-mentioned polymerization solvent.
• a polyimide film can also be formed by applying a polyimide solution onto a substrate and drying it. The drying temperature is preferably 40 to 400°C, more preferably 100 to 250°C.
• a polyimide molded body can be manufactured by heating and compressing polyimide powder. The temperature during hot compression is preferably 200 to 450°C, more preferably 250 to 430°C. Additives such as oxidation stabilizers, fillers, silane coupling agents, photosensitizers, photopolymerization initiators, and sensitizers can be added to the polyimide as necessary.
• BPAF-TA 9,9-bis(3,4-dicarboxyphenyl)fluorene
• the obtained polyimide precursor solution was applied to a glass substrate and heated and dried at 100°C (30 minutes), then 150°C (30 minutes), and then 200°C (30 minutes) to form a polyimide precursor composition.
• a film (polyimide precursor film) was obtained.
• the obtained polyimide precursor film showed flexibility and no breakage was observed in the 180° bending test. This indicates that the obtained polyimide precursor (polyamic acid) has a sufficiently high molecular weight.
• the obtained polyimide precursor film was heat-treated on the substrate at 200° C. (10 minutes), then 250° C. (30 minutes), and then 350° C. (30 minutes) to perform cyclization. In this way, a flexible polyimide film with a thickness of about 50 ⁇ m was obtained. The obtained polyimide film did not break in the 180° bending test and showed flexibility.
• Example 2 Changed 9,9-bis(3,4-dicarboxyphenyl)fluorene (BPAF-TA) to 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene (BPF-TA) Except for this, a polyimide precursor composition was produced in the same manner as in Example 1, and a polyimide film was produced.
• BPAF-TA 9,9-bis(3,4-dicarboxyphenyl)fluorene
• the obtained polyimide precursor solution was applied to a glass substrate and heated and dried at 100°C (30 minutes), then 150°C (30 minutes), and then 200°C (30 minutes) to form a polyimide precursor composition.
• a film (polyimide precursor film) was obtained.
• the obtained polyimide precursor film showed flexibility and no breakage was observed in the 180° bending test. This indicates that the obtained polyimide precursor (polyamic acid) has a sufficiently high molecular weight.
• the obtained polyimide precursor film was heat-treated on the substrate at 200° C. (10 minutes), then 250° C. (30 minutes), and then 350° C. (30 minutes) to perform cyclization. In this way, a flexible polyimide film with a thickness of about 50 ⁇ m was obtained. The obtained polyimide film did not break in the 180° bending test and showed flexibility.
• Example 4 Changed 9,9-bis(3,4-dicarboxyphenyl)fluorene (BPAF-TA) to 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene (BPF-TA) Except for this, a polyimide precursor composition was produced in the same manner as in Example 3, and a polyimide film was produced.
• a polyimide precursor composition was produced in the same manner as in Example 1, except that 9,9-bis(3,4-dicarboxyphenyl)fluorene (BPAF-TA) was not added, and a polyimide film was produced. .
• BPAF-TA 9,9-bis(3,4-dicarboxyphenyl)fluorene
• Example 2 The polyimide precursor composition was prepared in the same manner as in Example 1, except that 9,9-bis(3,4-dicarboxyphenyl)fluorene (BPAF-TA) was changed to ring-opened pyromellitic acid (PMTA). manufactured products and manufactured polyimide membranes.
• BPAF-TA 9,9-bis(3,4-dicarboxyphenyl)fluorene
• PMTA ring-opened pyromellitic acid
• a polyimide precursor composition was produced in the same manner as in Example 3, except that 9,9-bis(3,4-dicarboxyphenyl)fluorene (BPAF-TA) was not added, and a polyimide film was produced. .
• BPAF-TA 9,9-bis(3,4-dicarboxyphenyl)fluorene
• Total light transmittance The total light transmittance (%) of the polyimide film was measured using a turbidity meter (HAZE METER NDH 5000, manufactured by Nippon Denshoku Kogyo). The results are shown in Table 1. It can be said that the higher the total light transmittance, the lower the coloring.
• Glass transition temperature Tg
• Dynamic viscoelasticity measurement was performed using a dynamic viscoelasticity measurement device (DMAQ800, manufactured by TA Instruments), and the loss peak at a frequency of 0.1Hz and a heating rate of 5°C/min was used to determine the temperature of the polyimide film.
• the glass transition temperature [°C] was determined. The results are shown in Table 1. It can be said that the higher the glass transition temperature, the better the thermal properties.
• thermogravimetric analyzer manufactured by Shimadzu Corporation, DTG-60
• the temperature at which the initial mass of the polyimide film decreases by 5% during the heating process at a heating rate of 10°C/min in nitrogen [°C] was measured. The higher the temperature, the higher the thermal properties (thermal stability).
• thermomechanical analysis was performed using a thermomechanical analyzer (TMA60, manufactured by Shimadzu Corporation), and the elongation of the test piece at a load of 1.6 g/film thickness of 1 ⁇ m and a heating rate of 10 °C/min was found to be 50 to 150 °C.
• the linear thermal expansion coefficient [ppm/K] of the polyimide film was determined as an average value in the range of . It can be said that the smaller the linear thermal expansion coefficient, the better the thermal properties.
• content relative to carboxylic dianhydride represents the content [mol%] of the added carboxylic acid (dianhydride) relative to the content of carboxylic dianhydride, which is the carboxylic acid component of polyamic acid. , corresponds to the content of the specific compound described above for Examples 1 to 4.
• the polyimide film obtained from the polyimide precursor composition of the present invention is suitable as an optical resin for display materials, etc., and can be expected to be used in various industrial fields.

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