WO2012096374A1 - ポリイミド粉体及びポリイミド溶液並びにポリイミド粉体の製造方法 - Google Patents
ポリイミド粉体及びポリイミド溶液並びにポリイミド粉体の製造方法 Download PDFInfo
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- WO2012096374A1 WO2012096374A1 PCT/JP2012/050586 JP2012050586W WO2012096374A1 WO 2012096374 A1 WO2012096374 A1 WO 2012096374A1 JP 2012050586 W JP2012050586 W JP 2012050586W WO 2012096374 A1 WO2012096374 A1 WO 2012096374A1
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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
- C08G73/1003—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/56—Non-aqueous solutions or dispersions
Definitions
- the present invention relates to a polyimide powder and a polyimide solution that can be used for heat-resistant electric material parts, automobile parts, mold forming of screw portions of glass bottles, adhesives, and the like, and a method for producing polyimide powder.
- the polyimide film is pulverized by a machine to obtain a powder.
- a powder made of fine particles of a low molecular weight compound is obtained by subjecting a polyimide film to alkali hydrolysis (see, for example, Patent Document 1).
- Such a powder is used as a molding material either alone or by mixing with another resin or the like.
- the present invention has been made in view of the above points, and provides a polyimide powder having an average particle size of 25 ⁇ m or less and a method for producing the same without containing metal impurities due to mechanical wear such as mechanical grinding. It is the purpose.
- Another object of the present invention is to provide a polyimide solution containing the polyimide powder.
- the polyimide powder of the present invention is an aggregate of fine particles obtained by precipitating polyimide dissolved in a treatment liquid containing a basic substance, and the residual amount of alkali metal in the basic substance contained in the treatment liquid is powder. It is characterized by being 1% or less with respect to the total body mass.
- the polyamic acid in the fine particles is polymerized into polyimide by heating.
- the polyimide solution of the present invention is characterized in that the polyimide powder is dispersed or dissolved in a solvent.
- polyimide solution of the present invention it is preferable that a polyamic acid derived from the fine particles of the polyimide powder is contained, and the polyamic acid can be polymerized to polyimide by heating.
- the polyimide powder production method of the present invention is obtained by dissolving polyimide in a treatment liquid containing a basic substance, and then mixing the treatment liquid and an acidic substance to precipitate the polyimide fine particles to obtain a powder.
- the alkali metal of the basic substance By removing the alkali metal of the basic substance from the powder, the residual amount of the alkali metal is 1% or less with respect to the total amount of the powder.
- the basic substance is preferably potassium hydroxide.
- the polyimide is dissolved in the treatment liquid and then precipitated, it is possible to obtain a powder having an average particle diameter of 25 ⁇ m or less by making the polyimide finer than in the case of mechanical grinding. Further, since mechanical pulverization is not performed, mixing of metal impurities due to wear of the machine can be prevented. Furthermore, since the residual amount of alkali metal is 1% or less with respect to the total amount of powder, the adverse effects of the remaining alkali metal can be reduced, and the decomposition of the polyimide in the fine particles by the remaining alkali metal is difficult to proceed. The compound in the fine particles is less likely to be reduced in molecular weight, and the polymerization of the polyamic acid contained in the fine particles is less likely to be impaired, so that a powder having a high polyimide content can be obtained. is there.
- (A) is a chemical formula showing an example of a compound contained in a raw material polyimide in the present invention
- (b) is a chemical formula showing an example of a compound contained in a polyimide powder before heating
- (c) is after heating. It is a chemical formula which shows an example of the compound contained in the polyimide powder.
- (A) is a chart which shows the DTA curve and Tg curve of the polyimide powder before a heating in this invention
- (b) is a chart which shows the DSC curve of the polyimide powder before a heating same as the above.
- (A) is a chart which shows the DTA curve and Tg curve of the polyimide powder after the heating in this invention
- (b) is a chart which shows the DSC curve of the polyimide powder after the heating same as the above.
- 10 is a chart showing the results of infrared absorption analysis of Comparative Example 3.
- 6 is a chart showing the results of infrared absorption analysis of Comparative Example 1.
- 6 is a chart showing the results of infrared absorption analysis of Comparative Example 2.
- 2 is a chart showing the results of infrared absorption analysis of Example 1.
- FIG. It is a chart which shows the result of the infrared absorption analysis of the heating time of Example 2 for 0 minute.
- Example 2 It is a chart which shows the result of the infrared absorption analysis of the heating time of Example 2 for 30 minutes. It is a chart which shows the result of the infrared absorption analysis of the heating time of Example 2 for 60 minutes. 2 is a chart showing the particle size distribution of Example 1.
- FIG. 10 is a chart showing the particle size distribution of Comparative Example 3. (A) and (b) are scanning electron micrographs of Example 2.
- the polyimide powder of the present invention is an aggregate of fine particles in which a polyimide dissolved (hydrolyzed) in a treatment liquid is deposited.
- the fine particles of the polyimide powder contain polyamic acid.
- the polyimide powder has a particle size distribution of 1 to 500 ⁇ m, for example, and the average particle diameter (median diameter: D 50 ) can be 25 ⁇ m or less.
- D 50 median diameter
- it can be selected by using a sieve or the like.
- mechanical pulverization it is not possible to obtain a polyimide powder having an average particle size of 25 ⁇ m or less because a large force cannot be applied to the raw material polyimide film or molded body. Sometimes mixed.
- the average particle size can be 25 ⁇ m or less.
- the polyimide powder of the present invention cannot be mixed with metal impurities due to wear.
- the average particle size and particle size distribution can be measured by a laser diffraction / scattering method using a particle size analyzer (for example, Microtrack MT3300 manufactured by Nikkiso Co., Ltd.).
- the polyimide powder of the present invention is such that the residual amount of alkali metal derived from the basic substance used in the treatment liquid for dissolving the raw material polyimide is 1% or less by weight with respect to the total amount of the powder. . If the alkali metal remains more than 1% with respect to the total amount of the powder, hydrolysis of the polyimide in the fine particles proceeds and the polyimide has a low molecular weight. For example, pyromellitic dianhydride or 4,4 It is thought that decomposition proceeds to polyimide raw materials such as' -diaminodiphenyl ether.
- the residual amount of the alkali metal derived from the basic substance used in the treatment liquid is 1% or less by weight with respect to the total amount of the powder, the adverse effects due to the remaining alkali metal can be reduced.
- the hydrolysis of fine particles by metal is difficult to proceed, and the number of fine particles whose molecular weight is further reduced after precipitation can be reduced. Therefore, by using the polyimide powder of the present invention alone or mixed with other resins as a molding material, a polyimide reinforcing effect can be obtained, and molding with high heat resistance, high strength and high wear resistance can be obtained. A body can be obtained.
- the minimum of the residual amount of an alkali metal is 0%.
- the production of the polyimide powder of the present invention is performed as follows. First, the raw material polyimide is dissolved (hydrolyzed) with a treatment liquid containing a basic substance.
- a treatment liquid containing a basic substance a basic substance.
- the basic substance at least one of an alkali metal or a salt thereof can be used.
- a strongly basic substance such as potassium hydroxide or sodium hydroxide can be used.
- potassium hydroxide capable of obtaining a polyimide powder with little discoloration from the raw material polyimide is preferable.
- a solvent for the treatment liquid a solution obtained by mixing water and an organic solvent such as glycerin can be used in addition to water.
- the treatment liquid can be prepared by dissolving a basic substance in a solvent.
- 10 to 50 parts by weight, preferably 10 to 40 parts by weight, of the basic substance can be dissolved with respect to 100 parts by weight of the solvent, and the pH of the treatment liquid can be 10 to 14.
- melt dissolution of the raw material polyimide can be performed favorably.
- the raw material polyimide dissolved in the treatment liquid is not particularly limited as long as it contains an imide bond as a repeating unit in the main chain of the polymer, and examples thereof include an aromatic polyimide in which aromatic compounds are directly connected by an imide bond. it can.
- the raw material polyimide may be anything as long as it contains polyimide such as industrial waste such as cutting waste and defective products generated in the process of manufacturing a polyimide film, polyimide product waste, etc. It is preferable to use film cutting waste or defective products.
- the raw material polyimide is dissolved by being immersed in the treatment liquid.
- the polyimide can be blended in a proportion of 40 to 120 parts by weight, preferably 40 to 80 parts by weight with respect to 100 parts by weight of the solvent of the treatment liquid, and the temperature of the treatment liquid is preferably 70 to 100 ° C. Can be set to 70 to 90 ° C., and the processing time can be set to 50 to 100 minutes. Moreover, you may stir as needed. Thereby, melt
- the processing solution is neutralized by adding an acidic substance to precipitate the dissolved polyimide fine particles.
- an acidic substance a strong acid such as hydrochloric acid or a weak acid such as phosphoric acid can be used.
- the addition amount of the acidic substance can be 10 to 50 parts by weight, preferably 10 to 40 parts by weight, with respect to 100 parts by weight of the solvent of the above-mentioned treatment solution. This ensures the precipitation of polyimide fine particles. be able to.
- the pH of the treatment solution in which the polyimide is dissolved can be adjusted to 4 to 6 by adding an acidic substance.
- the neutralized treatment liquid on which the polyimide fine particles are deposited is filtered to separate the powder composed of solid polyimide fine particles.
- Filtration can use a filter press or the like. By this filtration, the solid content of the polyimide fine particles can be separated from the liquid portion containing the alkali metal derived from the basic substance.
- the separated polyimide fine particle powder is washed with water. By this washing with water, the alkali metal derived from the basic substance remaining on the polyimide powder by adhering to the fine particles of the polyimide can be removed (reduced).
- Washing with water can be performed by repeating the step of putting the filtered solid content in water and stirring it until the residual amount of alkali metal is 1% or less (for example, 5 to 10 times). More specifically, for example, a step of mixing water at a temperature of 60 ° C. at a rate of 100 liters with 50 parts by weight of the separated polyimide fine particle powder and stirring for 30 minutes is one step, and this is performed six times. Washing can be performed as is done.
- the polyimide powder obtained as described above can be used as a molding material either alone or by mixing with another resin or the like.
- 10-30% by weight of the polyimide powder is mixed with 10-100 ⁇ m particle size of tetrafluoroethylene resin powder, and the mixture is heated and pressed under conditions of 300-360 ° C. and 10-50 MPa. By doing so, a sheet, a molded product (for example, a sliding part of a rotary bearing) and the like can be manufactured.
- the above polyimide powder 50% by weight of the above polyimide powder, 40% by weight of thermosetting phenol resin, and 10% by weight of carbon black are mixed to form a compound, which is heated at 190 to 250 ° C., 10 to 20 MPa, for 30 to 45 minutes.
- a molded product that can be used for forming a heat-resistant electric material part, an automobile part, a molding of a screw portion of a glass bottle, and the like.
- the molded product which has heat resistance and impact resistance can be manufactured by mixing the said polyimide powder, carbon fiber (carbon fiber), and tetrafluoroethylene powder, and heat-press-molding.
- a polyimide solution can be prepared by dissolving or dispersing the above polyimide powder in a solvent.
- This polyimide solution can be used as an adhesive, a coating agent, and the like, and in particular, can be used as an adhesive having high heat resistance by firmly bonding a metal member.
- a solvent for the polyimide solution an aprotic polar solvent such as N-methyl-2-pyrrolidone (NMP) or dimethylformamide can be used.
- NMP N-methyl-2-pyrrolidone
- the polyimide solution of the present invention can be prepared by blending a solvent in a proportion of 1 to 400 parts by weight, preferably 40 to 300 parts by weight with respect to 100 parts by weight of the polyimide powder.
- the fine particles constituting the polyimide powder of the present invention contain, in addition to polyimide, polyamic acid, which is a precursor of polyimide, and other decomposition products. That is, the raw material polyimide before hydrolysis with the treatment liquid is, for example, a polyimide having a repeating unit represented by the formula (A) as shown in FIG. 1B, it contains a polyimide having a repeating unit represented by the formula (A) in FIG. 1B, a polyamic acid having a repeating unit represented by the formula (B), and a decomposition product represented by the chemical formula of the formula (C). Can be obtained.
- a polyimide having a repeating unit represented by the formula (A) as shown in FIG. 1B it contains a polyimide having a repeating unit represented by the formula (A) in FIG. 1B, a polyamic acid having a repeating unit represented by the formula (B), and a decomposition product represented by the chemical formula of the formula (C).
- the fine particles constituting the polyimide powder of the present invention can improve the polyimide content by heating. This is presumably because the polyamic acid contained in the fine particles is polymerized into polyimide and the polyamic acid is converted to polyimide. Accordingly, the fine particles of the polyimide powder after heating have an improved content of polyimide having a repeating unit represented by the formula (A) as shown in FIG. Polymerization of polyamic acid is started at around 160 ° C., and even when the temperature is 230 ° C. or higher, the polymerization is rarely promoted or the degree of polymerization is high, so the polyimide powder particles are heated at 160 to 230 ° C. It is preferable to improve the polyimide content. Further, the time for the heating is not particularly limited, but the above temperature is preferably maintained for 30 to 60 minutes. This makes it difficult for polyamic acid to be insufficiently polymerized, and an excessive (excessive) N) heating can be avoided.
- Such heating of the fine particles can be performed by heating the polyimide powder.
- a polyimide powder containing a large amount of fine particles having an increased polyimide content can be obtained, and this polyimide powder can be blended into a resin material or a cement material as an aggregate.
- the molded product is heated to polymerize the polyamic acid in the molded product derived from the fine particles of the polyimide powder. Can do. In this case, it is possible to obtain a molded article having an increased content of polyimide and improved heat resistance.
- the polyimide solution is heated to polymerize the polyamic acid in the polyimide solution derived from the fine particles of the polyimide powder. Can do.
- the solvent in the polyimide solution evaporates and a film or a lump is generated with the compound in the polyimide solution.
- the film or lump has an increased polyimide content and improved heat resistance. Is.
- Example 1 As a raw material polyimide, polyimide film Kapton (registered trademark) manufactured by Toray DuPont Co., Ltd. was used.
- potassium hydroxide As a basic substance, potassium hydroxide (KOH) was used, and 40 parts by weight of potassium hydroxide was dissolved in 100 parts by weight of water to prepare a treatment liquid containing the basic substance. The pH of this treatment liquid was 14.
- an acidic substance was added to the treatment liquid in which the polyimide was dissolved, thereby neutralizing the treatment liquid and precipitating dissolved polyimide fine particles in the treatment liquid.
- hydrochloric acid HCl
- 40 parts by weight of 38% strength hydrochloric acid was added to 100 parts by weight of the water in the treatment liquid.
- this neutralization process was stirred until neutralization of the process liquid was completed.
- the treatment liquid on which the polyimide fine particles were deposited was filtered to separate the solid content.
- the separated solid was washed with water. Washing with water was repeated 6 times, with the filtered solid content in water and stirring at room temperature for 20 minutes as one step.
- the solid content washed with water was dehydrated under reduced pressure, and dried at a temperature of 70 to 80 ° C. for 12 hours to obtain a polyimide powder having a water content of 0.5% or less.
- Example 2 As a raw material polyimide, polyimide film Kapton (registered trademark) manufactured by Toray DuPont Co., Ltd. was used.
- potassium hydroxide As a basic substance, potassium hydroxide (KOH) was used, and 20 parts by weight of potassium hydroxide was dissolved in 50 parts by weight of water to prepare a treatment liquid containing the basic substance. The pH of this treatment liquid was 14.
- an acidic substance was added to the treatment liquid in which the polyimide was dissolved, thereby neutralizing the treatment liquid and precipitating dissolved polyimide fine particles in the treatment liquid.
- hydrochloric acid HCl
- the hydrochloric acid and water were added to the treatment liquid over 20 minutes. Moreover, this neutralization process was stirred until neutralization of the process liquid was completed.
- the treatment liquid in which polyimide fine particles were deposited was squeezed for 30 minutes with a filter press and filtered to separate the solid content.
- the separated solid was washed with water. Washing with water was repeated 6 times, with a step of adding 100 liters of water to 50 kg of filtered solid content and stirring for 30 minutes at a pot temperature of 60 ° C.
- the solid content washed with water was dried under reduced pressure (substantially vacuum) for 48 hours to obtain a polyimide powder having a water content of 0.5% or less.
- Example 3 A polyimide solution was prepared by dissolving the polyimide powder of Example 1 in a solvent. NMP was used as the solvent. Moreover, the solvent was blended at a ratio of 300 parts by weight with respect to 100 parts by weight of the polyimide powder to obtain a polyimide solution having a solid concentration of 25%.
- Example 4 In Example 3, a polyimide solution was prepared using the polyimide powder of Example 2 instead of the polyimide powder of Example 1. Others were the same as in Example 3.
- Example 1 In Example 1, the water washing process was performed three times. Except this, polyimide powder was obtained in the same manner as in the example.
- Example 2 In Example 1, no water washing was performed. Except this, polyimide powder was obtained in the same manner as in the example.
- Example 3 The polyimide film used in Example 1 was pulverized by mechanical pulverization.
- a vibration mill manufactured by Chuo Koki was used as the pulverizer.
- Example 4 (Comparative Example 4) In Example 3, a polyimide solution was prepared using the polyimide powder of Comparative Example 1 instead of the polyimide powder of Example 1. Others were the same as in Example 3.
- Example 5 (Comparative Example 5) In Example 3, a polyimide solution was prepared using the polyimide powder of Comparative Example 2 instead of the polyimide powder of Example 1. Others were the same as in Example 3.
- DTA differential thermal analysis
- DSC differential scanning calorimetry
- Tg thermogravimetry
- Example 1 Infrared absorption analysis (IR) measurement of Example 1 and Comparative Examples 1 to 3 was performed.
- FT / IR-670Plus manufactured by JASCO Corporation was used as a measuring device. Charts of each IR spectrum are shown in FIGS.
- peaks 3 and 5 derived from polyimide are shown, and similar peaks 4 and 5 are also observed in Comparative Example 3 which was mechanically pulverized. Therefore, in Example 1, it can be said that the powder is composed of fine particles containing polyimide.
- Example 1 the residual amount of potassium was measured for Example 1 and Comparative Examples 1 and 2 by infrared absorption analysis.
- the residual amount of potassium in Example 1 was 1% with respect to the total weight of the powder.
- the residual amount of potassium in Comparative Example 1 was 3% with respect to the total weight of the powder.
- the residual amount of potassium in Comparative Example 2 was 10% with respect to the total weight of the powder.
- FIG. 8 shows the results (chart) for the heating time of 0 minutes
- FIG. 9 shows the results for the heating time of 30 minutes
- FIG. 10 shows the results for the heating time of 60 minutes.
- the chart of the heating time of 30 minutes or between 60 minutes and 1375 cm -1 and around 1500cm absorbance around -1 is reduced. Therefore, it is considered that imidization of the polyimide powder progressed by heating.
- Example 1 As a result of measuring the particle size distribution and the average particle size of Example 1 and Comparative Example 3 by a laser diffraction / scattering method using Microtrack MT3300 manufactured by Nikkiso Co., Ltd., the particle size distribution is as shown in FIG.
- the average particle size (D 50 ) was 1.06 to 7.78 ⁇ m and the average particle size (D 50 ) was 2.67 ⁇ m.
- the average particle size (D 50 ) was 3.00 to 249.0 ⁇ m as shown in FIG. 50 ) was 32.16 ⁇ m.
- Example 1 it is possible to obtain a polyimide powder having an average particle size smaller than that of Comparative Example 3 and a narrow particle size distribution.
- 13A and 13B show photographs of the polyimide powder of Example 2 taken with a scanning electron microscope. It can be seen from this photograph that the particles of the polyimide powder are smaller than 10 ⁇ m.
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Abstract
Description
原料のポリイミドとしては、東レ・デュポン株式会社製のポリイミドフィルムカプトン(登録商標)を用いた。
原料のポリイミドとしては、東レ・デュポン株式会社製のポリイミドフィルムカプトン(登録商標)を用いた。
実施例1のポリイミド粉体を溶媒に溶解させてポリイミド溶液を調製した。溶媒としてはNMPを用いた。また、ポリイミド粉体100重量部に対して溶媒を300重量部の割合で配合し、固形分濃度25%のポリイミド溶液を得た。
実施例3において、実施例1のポリイミド粉体の代わりに実施例2のポリイミド粉体を用いてポリイミド溶液を調製した。その他は実施例3と同様にした。
実施例1において、水洗の工程を3回とした。これ以外は実施例と同様にしてポリイミド粉体を得た。
実施例1において、水洗を行わなかった。これ以外は実施例と同様にしてポリイミド粉体を得た。
実施例1で用いたポリイミドフィルムを機械粉砕により粉砕した。粉砕機としては、中央加工機製の振動ミルを用いた。
実施例3において、実施例1のポリイミド粉体の代わりに比較例1のポリイミド粉体を用いてポリイミド溶液を調製した。その他は実施例3と同様にした。
実施例3において、実施例1のポリイミド粉体の代わりに比較例2のポリイミド粉体を用いてポリイミド溶液を調製した。その他は実施例3と同様にした。
実施例1、2及び比較例1,2で得られたポリイミド粉体10重量部を加熱した。加熱温度は160℃、200℃、とし、加熱時間はそれぞれの加熱温度で0分間、30分間、60分間とした。そして、各温度と各時間で加熱した後のポリイミド粉体のイミド化率を測定した。イミド化率の測定は、日本分光株式会社製のFT/IR-670Plusを用いて赤外吸収分析(IR)測定を行い、そのチャートを分析した。そして、(IRイミド基(1375cm-1)の吸光度)/(IRベンゼン環(1500cm-1)の吸光度)?100の式でイミド化率を算出した。結果を表1に示す。
実施例2のポリイミド粉体について、加熱前と加熱後(200℃で60分間)のDTA、Tg、DSCを測定した。測定機器は、株式会社リガク製の「DSC8230」を用いた。また、測定は、窒素雰囲気下(流量20ml/分)で行い、昇温速度は10.0℃/分で行なった。加熱前のポリイミド粉体のDTA曲線及びTg曲線を図2(a)に、加熱前のポリイミド粉体のDSC曲線を図2(b)にそれぞれ示す。また、加熱後のポリイミド粉体のDTA曲線及びTg曲線を図3(a)に、加熱後のポリイミド粉体のDSC曲線を図3(b)にそれぞれ示す。
実施例1及び比較例1~3の赤外吸収分析(IR)測定を行った。測定装置としては、日本分光株式会社製のFT/IR-670Plusを用いた。各IRスペクトルのチャートを図4~7に示す。この結果、実施例1ではポリイミドに由来するピーク3、5を示しており、機械粉砕した比較例3にも同様のピーク4、5が見られる。従って、実施例1ではポリイミドを含む微粒子からなる粉体であると言える。一方、比較例1、2ではポリイミドに由来するピークが不鮮明であるため、ポリイミド以外の成分を多く含む微粒子(例えば、ポリイミドが加水分解した低分子量の化合物の微粒子)が析出したと考えられる。
日機装株式会社製のマイクロトラックMT3300を用いたレーザー回折・散乱法により、実施例1と比較例3との粒度分布と平均粒径を測定した結果、実施例では図11に示すように粒度分布が1.06~7.78μmで平均粒径(D50)が2.67μmであったが、比較例3では図12に示すように粒度分布が3.00~249.0μmで平均粒径(D50)が32.16μmであった。このように実施例1では比較例3に比べて平均粒径が小さくて粒度分布に狭いポリイミド粉体を得ることができる。
実施例3、4及び比較例4,5で調製したポリイミド溶液を接着剤として用いた。試験方法は、JIS K6849(接着剤の引張り接着強さ試験方法)等を用いた。この結果、実施例3、4では加熱によりイミド化が進むために強固に接着できたが、比較例4,5ではイミド化が進みにくいために、実施例3,4よりも接着強度が低くなった。
Claims (5)
- 塩基性物質を含む処理液に溶解したポリイミドを析出させて得られる微粒子の集合体であって、前記処理液に含まれる塩基性物質のアルカリ金属の残留量が粉体全量に対して1%以下であることを特徴とするポリイミド粉体。
- 加熱により前記微粒子中のポリアミック酸がポリイミドに重合されて成ることを特徴とする請求項1に記載のポリイミド粉体。
- 請求項1又は2に記載のポリイミド粉体が溶媒に分散乃至溶解されて成ることを特徴とするポリイミド溶液。
- 塩基性物質を含む処理液でポリイミドを溶解した後、この処理液と酸性物質とを混合することにより前記ポリイミドの微粒子を析出させて粉体を得、この粉体から前記塩基性物質のアルカリ金属を除去することによって、粉体全量に対して前記アルカリ金属の残留量を1%以下とすることを特徴とするポリイミド粉体の製造方法。
- 前記塩基性物質が水酸化カリウムであることを特徴とする請求項4に記載のポリイミド粉体の製造方法。
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US8993645B2 (en) | 2012-06-12 | 2015-03-31 | Nakata Coating Co., Ltd. | Compound containing imido group, solution of compound containing imido group and method for producing of compound containing imido group |
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