JP4427493B2 - Block copolymerized polyimide composition soluble in ketone and / or ether solvent and process for producing the same - Google Patents

Description

  The present invention relates to a polyimide composition soluble in a ketone and / or ether solvent and a method for producing the same. Since polyimide has excellent heat resistance, electrical insulation, mechanical properties and chemical resistance, it is applied to electricity, electronic parts, semiconductors, communication equipment, peripheral parts and circuits.

  Since the polyimide resin is hardly soluble in an organic solvent, it is necessary to form a polyamic acid in a polar solvent, and then heat and dehydrate to form a film.

  In recent years, a solvent-soluble polyimide has been found and used for coating as a liquid crystal alignment film and an insulating film of a flexible substrate.

  However, non-aqueous solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethyl sulfoxide are used as the solvent for dissolution.

  Polyimide varnishes and polyimide inks using these non-aqueous solvents have the disadvantage that the surface of the resulting film or molded product is whitened when used in an environment where the relative humidity exceeds 50%.

  Even if these whitened films and molded products are heated and dried, not only the polyimide's original tough film can be obtained, but also the original characteristics such as electrical characteristics cannot be obtained.

The cause of this white Kegen elephant is a solvent used to dissolve the polyimide, N- methylpyrrolidone, N, N- dimethylformamide, there is a high water absorption of the non-aqueous solvent such as dimethyl sulfoxide.

  For this reason, in order to use a polyimide resin dissolved in these solvents for coating or the like, it has been necessary to devise measures such as blowing dry air or nitrogen gas into the coating apparatus or covering the coating apparatus so that moisture does not enter from the surroundings.

  In addition, when used as an electronic material, it is necessary to remove dust and impurities from the polyimide resin with a fine filtration device. In this case as well, the receiver such as a filtration device and a basket is replaced with dry air or nitrogen gas, Or it was necessary to devise such as covering to prevent moisture from entering from the surroundings.

  Furthermore, in the process of making these polyimide resins into ink, in the process of mixing with filler by roll treatment or mill, etc., dry air or nitrogen gas is similarly blown, or the whole apparatus is covered so that moisture does not enter from the surroundings, etc. Ingenuity was necessary.

  Even if such a device is used, there is a defect such that a slight amount of moisture enters while the polyimide resin is stored, the viscosity of the resin changes, and the resin cannot withstand repeated use.

  The object of the present invention is a ketone that causes this whitening phenomenon, which is completely different from non-aqueous solvents such as N-methylpyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide and the like having high water absorption, and has not been dissolved in the past. It is to provide a block copolymerized polyimide composition soluble in water and ether.

As a result of intensive studies, the present inventors have found a block copolymerized polyimide composition soluble in ketones and / or ethers which are less susceptible to moisture from the surroundings and a method for producing the same, and have completed the present invention.
That is, the present invention synthesizes in a polar solvent, precipitates, filters, and drys the obtained block copolymerized polyimide using a poor solvent, and then re-dissolves in the ketone and / or ether solvent. A method for producing a composition comprising a block copolymerized polyimide dissolved in a solvent , wherein the block copolymerized polyimide is a block copolymerized polyimide obtained by polymerization in the presence of a lactone and a base catalyst. Provide a method .

  A soluble block copolymerized polyimide composition is synthesized by sequential reaction of tetracarboxylic dianhydride and diamine in a ketone and / or ether solvent in the presence of an acid catalyst.

  As described above, according to the present invention, when a filler or the like is mixed with polyimide using a mortar, automatic mortar, vormeal, three rolls, or the like, it is difficult to be affected by moisture in the air. In addition, when forming a film by a method such as a die coater, curtain coater, roll coater, gravure coater, screen printing, spinner, etc., it becomes less susceptible to the influence of moisture in the air, making it possible to use polyimide even in a somewhat humid environment.

  Examples of the tetracarboxylic dianhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, bicyclo (2,2,2) -oct-7-ene-2, 3,5,6-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic dianhydride, 2,2-bis (3,4-dicarboxylicoxyphenyl) Hexafluoropropane dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, and the like. These may be used alone or in combination of two or more. It can be used in conjunction look.

  Examples of the diamine include siloxane diamine, bis (3-aminopropyl) ether ethane, N, N-bis (3-aminopropyl) ether, 1,4bis (3-aminopropyl) piperazine, isophorone diamine, 1,3′- Bis (aminomethyl) cyclohexane, 3,3′-dimethyl-4,4′-diaminodicyclohexanemethane, 4,4′-methylenebis (cyclohexylamine), 4,4′-diaminodiphenyl ether, 3,4′diaminodiphenyl ether, 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, bis [4- (4-a Nophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′bis (4-aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 4,4 Examples include '-diaminodiphenyl sulfide, 3,3' diamino-4,4 'dihydroxybiphenyl sulfone, and these can be used alone or in combination of two or more.

  Silicone diamines are commercially available: BY16-853U, BY16-853C (product of Toray Dow Corning Silicone Co., Ltd., trade name), X-22-1660B-3, KF-8010, X-22-161A (Shin-Etsu) Chemical Industry Co., Ltd. products and trade names) can be used.

  Block copolymerized polyimide in ketone, ether or ketone and ether mixed solvent is heated in ketone, ether or ketone and ether mixed solvent in the presence of acid catalyst produced by lactone and base, and tetracarboxylic dianhydride And diamine are dehydrated and imidized, and water generated during the reaction is removed from the reaction system by azeotropy with the reaction solvent. When synthesizing with a polar solvent such as NMP, toluene is added as an azeotropic solvent.

  Usually, the solvent for polyimide is a polar solvent such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like. These solvents can be synthesized by adding polyimide to a ketone and / or ether solvent at 40 wt% or less.

  As the lactone, γ-valerolactone is used, and as the base, pyridine, N-methylmorpholine or the like is used, and an acid generated by an equilibrium reaction can be used as a catalyst.

  Multi-component block copolymers can be improved in photosensitivity, adhesiveness, water repellency, mechanical properties, etc. by incorporating a functional part and a structural part in the molecule. By making a solvent-soluble polyimide oligomer by this reaction, it is possible to increase the solubility of a polyimide that is hardly soluble in ketone, ether, or a mixed solvent of ketone and ether.

  The ketone solvent of the present invention is easy to work in coating and mixing processes, and the solvent after molding needs to be easily removed, and the boiling point is desirably 80 ° C. or higher and 180 ° C. or lower.

  As such ketone solvents, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone , Acetylacetone, diacetone alcohol, and cyclohexene 1-one are used.

  In particular, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetylacetone, and diacetone alcohol are inexpensive and optimal as general-purpose solvents.

  The ether solvent of the present invention is required to be easy to work in coating and mixing processes, and to be easily removed after molding, and preferably has a boiling point of 60 ° C. or higher and 200 ° C. or lower.

  Examples of such ether solvents include dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, ethyl isoamyl ether, ethyl t-butyl ether, ethyl benzyl ether, diethylene glycol dimethyl ether, cresyl methyl ether, anisole, and phenetole. Used.

  In particular, tetrahydrofuran, anisole, phenetole, and diethylene glycol dimethyl ether are inexpensive and optimal as general-purpose solvents.

  Of course, these solvents can be used alone, but they may be used in a mixture, and it goes without saying that the mixing ratio has an optimum range depending on the resin composition.

  In the coating and drying process, a mixed system is preferable because the polyimide resin composition can be used stably.

Therefore, ketones, polystyrene-reduced weight average molecular weight of soluble polyimide block copolymer in an ether or a ketone and ether mixed solvent 10, 000-200, in the range of 000 practical.

  When the molecular weight is high, the solubility in a solvent tends to be poor.

  For this reason, the polystyrene conversion weight average molecular weight of the block copolymerized polyimide soluble in ketone, ether, or ketone and ether mixed solvent is practically in the range of 10.000 to 200.000.

  Examples 1, 2 and 3 specifically exemplify methods for synthesizing block copolymerized polyimides soluble in ketones, ethers or mixed solvents of ketones and ethers.

  Usually, the solvent for polyimide is a polar solvent such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like.

  All of these solvents have a high boiling point and cannot be easily replaced with ketones and ethers used in the present invention.

  Therefore, it is necessary to remove the reaction solvent by precipitating the polyimide synthesized using a polar solvent such as NMP using a poor solvent such as methanol.

  These steps may be performed by a conventional purification method for polymer resins.

  After the resin is precipitated, it is filtered and dried.

  The dried block copolymerized polyimide powder is dissolved in ketone, ether or a mixed solvent of ketone and ether.

  At this time, if it is difficult to dissolve, it is dissolved by heating up to the boiling point of the solvent.

  If necessary, the time required for dissolution can be shortened by stirring.

  A block copolymerized polyimide is synthesized in a polar solvent such as NMP, precipitated, washed and dried with a poor solvent such as methanol, and then the polyimide powder is redissolved in ketone, ether or a mixed solvent of ketone and ether. Examples 4 and 5 specifically illustrate the production method of the soluble block copolymer polyimide.

  Hereinafter, the present invention will be described in detail with reference to some examples. The present invention is not limited to these examples because various solvent-soluble block copolymerized polyimide compositions can be obtained by combining various tetracarboxylic dianhydrides, diamines, and solvents.

[ Reference Example 1] 3.4.3 '. 4'-biphenyltetracarboxylic dianhydride (manufactured by Ube Industries, molecular weight 294.25, hereinafter referred to as BPDA) 4.41 g (15 mmol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane ( 12.32 g (30 mmol) manufactured by Wakayama Seika Co., Ltd., molecular weight 410.5, hereinafter referred to as BAPP), 0.15 g (1.5 mmol) of γ-valerolactone and 2.4 g (3 mmol) of pyridine as a catalyst, solvent Anisole 64.75g was charged. First, the mixture was stirred at room temperature in a nitrogen atmosphere at 100 rpm for 0.5 hr. After a uniform solution was reached, the temperature was raised in an oil bath at 180 ° C. and stirred at 180 rpm for 1 hour. During the reaction, azeotropic water was removed. After the completion of the one-step reaction, the mixture was cooled to room temperature, and charged with 8.83 g (30 mmol) of BPDA, 13.80 g (15 mmol) of silicone oil (product of Toray Dow Corning Silicone Co., Ltd. By 853U), and 150 g of anisole as a solvent. After stirring for about 1 hour at 100 rpm at room temperature, the temperature was raised in an oil bath at 180 ° C., and the reaction was stirred for 2 hours and 45 minutes at 180 rpm. During that time, the water accumulated every hour was drained. The polymer concentration of the polyimide solution thus obtained was 15 wt%. When the molecular weight of this polyimide was measured by gel permeation chromatography (Tosoh product), the polystyrene equivalent molecular weight was the number average molecular weight (Mn 9225, weight average molecular weight (Mw) 21437, Z average molecular weight (Mz) 37515, Mw / Mn = 2.32, Mz / Mn = 4.07.

[ Reference Example 2] 5.88 g (20 mmol) of BPDA, 9.20 g (10 mmol) of silicone oil (manufactured by Toray Dancolling Co., Ltd., product number By16-853U, amine equivalent: 460) as a catalyst, γ-valerolactone 0.3 g (3 mmol) and 0.47 g (6 mmol) of pyridine, 40 g of anisole as a solvent, and 11 g of NMP were charged. First, the mixture was stirred at room temperature in a nitrogen atmosphere at 100 rpm for 0.5 hr. After a uniform solution was reached, the temperature was raised in an oil bath at 180 ° C. and stirred at 180 rpm for 1 hour. During the reaction, azeotropic water was removed. After completion of the one-step reaction, the mixture was cooled to room temperature, and bicyclo [2,2,2] oct-2-ene-2,3,5,6-tetracarboxylic dianhydride (manufactured by Aldrich, molecular weight 248.19, hereinafter BCD 2.48 g (10 mmol), isophoronediamine (product of Tokyo Chemical Industry Co., Ltd., molecular weight 170.25) 3.41 g (20 mmol), and 39.56 g of anisole as a solvent were charged. After stirring at 100 rpm for about 1 hour at room temperature, the temperature was raised in an oil bath at 180 ° C., and the mixture was stirred at 180 rpm for 4 hours for reaction. During that time, the water accumulated every hour was drained. The polymer concentration of the polyimide solution thus obtained was 18 wt%. When the molecular weight of this polyimide was measured by gel permeation chromatography (Tosoh product), the polystyrene equivalent molecular weight was the number average molecular weight (Mn 11481, weight average molecular weight (Mw) 24431, Z average molecular weight (Mz) 39756, Mw / Mn = 2.13, Mz / Mn = 3.38.

[ Reference Example 3] 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 264.23, hereinafter referred to as CP acid) 10.57 g (40 mmol), bis [4- (3-aminophenoxy) phenyl] sulfone (manufactured by Wakayama Seika Co., Ltd., molecular weight 432.5, hereinafter referred to as m-BAPS) 8.65 g (20 mmol), γ -0.4 g (4 mmol) of valerolactone and 0.63 g (8 mmol) of pyridine and 20 g of cyclohexanone as a solvent were charged. First, the mixture was stirred at room temperature in a nitrogen atmosphere at 100 rpm for 0.5 hr. After a uniform solution was reached, the temperature was raised in an oil bath at 180 ° C. and stirred at 180 rpm for 1 hour. During the reaction, azeotropic water was removed. After the completion of the one-step reaction, the mixture was cooled to room temperature, and charged with 8.21 g (20 mmol) of BAPP and 40.64 g of cyclohexanone as a solvent. After stirring at 100 rpm for about 1 hour at room temperature, the mixture was heated in an oil bath at 180 ° C. and stirred at 180 rpm for 2 hours for reaction. During that time, the water accumulated every hour was drained. The polymer concentration of the polyimide solution thus obtained was 30 wt%. When the molecular weight of this polyimide was measured by gel permeation chromatography (Tosoh product), the polystyrene equivalent molecular weight was the number average molecular weight (Mn ) 7042, weight average molecular weight (Mw) 11574, Z average molecular weight (Mz) 17551, Mw / Mn = 1.64, Mz / Mn = 2.49.

[Example 1 ] 35.31 g (120 mmol) of BPDA, 55.54 g (60 mmol) of silicone oil (product of Toray Dandanring, product number By16-853U, amine equivalent: 460) 8 g (18 mmol) and 2.85 g (36 mmol) of pyridine, 150 g of N-methylpyrrolidone (hereinafter referred to as NMP) and 40 g of toluene were charged as a solvent. First, the mixture was stirred at room temperature in a nitrogen atmosphere at 100 rpm for 0.5 hr. After a uniform solution was reached, the temperature was raised in an oil bath at 180 ° C. and stirred at 180 rpm for 1 hour. During the reaction, the azeotrope of toluene and water was removed. After the completion of the one-step reaction, the mixture was cooled to room temperature, BPDA 17.65 g (60 mmol), silicone oil (product of Toray Dow Corning Silicone By-853U) 27.60 g (30 mmol), 3,4 'diaminodiphenyl ether (Wakayama Seiko) Chemical product, molecular weight 200.2, hereinafter referred to as m-DADE) 12.01 g (60 mmol), 1,3-bis (4-aminophenoxy) benzene (manufactured by Wakayama Seika Co., Ltd., molecular weight 292.34, hereinafter m-TPE 8.77 g (30 mmol) NMP200 g and toluene 30 g were charged as a solvent. After stirring at room temperature at 100 rpm for about 1 hour, the bath was heated to 180 ° C. and stirred at 180 rpm for 4 hours 30 minutes to react. During that time, when it collected every hour, the azeotrope of toluene and water was removed. The polymer concentration of the polyimide solution thus obtained was 30 wt%.

  After cooling the polyimide varnish obtained by the above synthesis method to room temperature, it is gradually put into methanol while stirring, and the resulting polyimide precipitate is finely pulverized with a mixer, and the pulverized polyimide powder is then mixed with methanol. Washed 3 times and filtered by suction filtration. The polyimide powder thus obtained was dried using a vacuum dryer at room temperature for 3 hours, at 60 ° C. for 1 hour, and further at 90 ° C. for 1 hour. Anisole was added to the dried polyimide powder so that the solid content was 24%, and the mixture was stirred at room temperature for about 30 minutes. Some of the powder was dissolved, but most of the powder was still in the powder state. The mixture was heated and stirred for about 30 minutes, and the polyimide powder was dissolved into a uniform solution. The fluidity was maintained even after cooling to room temperature. When the molecular weight of this polyimide was measured by gel permeation chromatography (Tosoh product), the polystyrene equivalent molecular weight was as follows: number average molecular weight (Mn) 13890, weight average molecular weight (Mw) 31456, Z average molecular weight (Mz) 47203, Mw. /Mn=2.26 and Mz / Mn = 3.39.

  Even after 2 weeks, this polyimide solution did not increase in viscosity and maintained fluidity. An ink for screen printing was prepared using this liquid in an environment where the temperature was 25 ° C. and the humidity was 60%. While a three-roll is used to mix the filler with the polyimide varnish and the kneading is performed with the roll, the surface area where the polyimide comes into contact with the air is increased, and the influence of moisture contained in the air becomes considerably susceptible. Usually, when NMP is used as a solvent, NMP absorbs moisture within 10 minutes and the surface of the polyimide is whitened. However, when anisole was used as a solvent, it was hardly affected by moisture in the air when kneaded with a roll, and no whitening phenomenon was observed on the surface of the polyimide even after 40 minutes of exposure to the air.

[Example 2 ] 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride (HimiLinzGes.mbH product, molecular weight 322.23, hereinafter referred to as BTDA), which was operated in the same manner as in Reference Example 1. ) 25.78 g (80 mmol), 6.81 g (40 mmol) of isophoronediamine, 1.20 g (12 mmol) of γ-valerolactone as a catalyst and 1.90 (24 mmol) of pyridine, 100 g of N-methylpyrrolidone as a solvent, Charge 30 g of toluene. The mixture was stirred at room temperature in a nitrogen atmosphere at 100 rpm for 0.5 hr. After becoming a uniform solution, the temperature was raised to 180 ° C., and the mixture was stirred at 180 rpm for 1 hour. During the reaction, the azeotrope of toluene and water was removed. 8. Cooled to room temperature, 34.6 g (80 mmol) of m-BAPS, cyclohexane-1,2,4,5-tetracarboxylic dianhydride (New Nippon Rika Co., Ltd., molecular weight 226.25, hereinafter referred to as H-PMDA) 05 g (40 mmol), 115.76 g of N-methylpyrrolidone as a solvent and 30 g of toluene were added and stirred at room temperature for 1 hour, and then stirred at 180 ° C. and 180 rpm for 3 hours. The polymer concentration of the polyimide solution thus obtained was 25 wt%.

  After cooling the polyimide varnish obtained by the above synthesis method to room temperature, it was gradually added to methanol while stirring, the resulting polyimide precipitate was finely pulverized with a mixer, and the pulverized polyimide powder was filtered, Washed 3 times with methanol. The polyimide powder thus obtained was dried in a vacuum dryer at room temperature for 3 hours, at 60 ° C. for 1 hour, and further at 90 ° C. for 1 hour. Cyclohexanone was added to the dried polyimide powder so that the solid content was 20%, and the mixture was stirred at room temperature for 30 minutes to dissolve a part of the powder, but the majority was still in the powder state. The temperature was raised to 100 ° C. and stirred for 30 minutes, so that the polyimide powder was uniformly dissolved. When the molecular weight of this polyimide was measured by gel permeation chromatography (Tosoh product), the polystyrene equivalent molecular weight was as follows: number average molecular weight (Mn) 18664, weight average molecular weight (Mw) 102276, Z average molecular weight (Mz) 325769, Mw. /Mn=5.47 When this polyimide solution was applied onto a SUS substrate using a spinner and allowed to stand for 30 minutes, no whitening phenomenon was observed on the surface of the polyimide coating film. On the other hand, when polyimide using NMP as a solvent was used, the polyimide surface gradually became white from the surroundings within 5 minutes. The whole thing turned white after about 10 minutes.

Claims (3)

The block copolymerized polyimide synthesized in a polar solvent was precipitated using a poor solvent, filtered, dried, then redissolved in the ketone and / or ether solvent, dissolved in the ketone and / or ether solvent. A method for producing a composition comprising a block copolymerized polyimide, wherein the block copolymerized polyimide is a block copolymerized polyimide obtained by polymerization in the presence of a lactone and base catalyst . The process according to claim 1, wherein the polar solvent is N-methylpyrrolidone, N, N-dimethylformamide, N, N dimethylacetamide or dimethyl sulfoxide. The method according to claim 1 or 2, wherein the poor solvent is methanol.