Aromatic polyamides

Abstract: Aromatic polyamide having good high-temperature resistance and processing ability is obtained when the ratio of storage modulus at the glass transition temperature (Tg) °C to the storage modulus of a temperature of (Tg+100)°C is less than 3. The aromatic polyamide has a recurring unit [ -HN -Ar1 - NHCO - Ar2 - CO- ] wherein Ar1 is a divalent phenylene group represented by and Ar2 is a divalent phenylene group represented by where R is hydrogen or a methyl radical.

Description: This invention relates to a cast or moulded aromatic polyamide having excellent thermal resistance, and more particularly but not exclusively relates to a moulded fibre or film of aromatic polyamide which retains elastic modulus even at high temperatures above the glass transition temperature of the same. Aromatic polyamides are widely used in various fields such as for industrial materials, for protective clothing and for interiors due to excellent mechanical properties, thermal resistance, flame resistance, electrical properties and chemical stability. Aromatic polyamides which have been industrially manufactured and marketed to date are divided into two main classes. One is represented by so-called para-base aromatic polyamide such as poly(para-phenyleneterephthalamide) (hereinafter abbreviated as PPTA). It has characteristics of high crystallinity, high melting point, high mechanical strength, low elongation and high elastic modulus but has poor processing ability as a result of stiffness and low elongation. Since para-base aromatic polyamide is also slightly soluble in common polar organic solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, difficulty is encountered in film forming, spinning and other miscellaneous shaping processing operations. Therefore para-base aromatic polyamide is restricted in its application and is only used as reinforcing filaments for tire cords, structural materials and composites. The other aromatic polyamide class is represented by so-called meta-base aromatic polyamide such as poly(meta-phenyleneisophthalamide) (hereinafter abbreviated as PMIA). The meta-base polyamide has to some extent lower mechanical properties than para-base polyamide but it has an excellent processing ability and is also soluble in the above polar organic solvents. Therefore meta-base polyamide can be used for spinning and film casting, and is widely used for various fields such as flame retardant protective clothing and flameproof clothes, various industrial belts, heat resistant felt, and heat resistant insulation papers and adhesives. PMIA, however, has lower crystallinity than PPTA and causes abrupt reduction in physical properties above the glass transition temperature Tg (above 220°C). Accordingly, PMIA exhibits excellent properties at temperatures below Tg but suffers particular problems at high temperatures above Tg. Even instantaneous use or application over a short period of time leads to shrinkage or a steep reduction in properties, so its field of use has been restricted. As a countermeasure for the prevention of shrinkage, for example, a heat treatment method at high temperatures for PMIA fibers has been disclosed in Japanese Patent Publication No. 17692/1978. The method is, however, unfavourable because deterioration of the surface of the fibers and reduction in properties result from the treatment. Moreover, to prevent heat shrinkage and enhance chemical resistance of films, film forming methods from a polymer solution containing a crosslinking agent have been disclosed in Japanese Patent Publication No. 110128/1980 and 13742/1980. However, selection of the crosslinking agent and optimization of film forming conditions are difficult in these methods. An object of this invention is to provide a moulded or cast aromatic polyamide which can be used up to higher temperatures by maintaining various advantages of PMIA as they are and by inhibiting the above mentioned disadvantages, particularly lowering of properties at temperatures higher than Tg. The present inventors have intensively investigated a variety of monomer combinations in the preparation of polymers for overcoming the aforesaid problems. As a result, they have found that aromatic polyamide consisting of a specific recurring unit and having a methyl side chain can form a film having almost no lowering of storage modulus at a temperature ranging from Tg °C to Tg + 100°C in the investigation of viscoelasticity. The results of the investigation have led to the completion of this invention. This invention relates to a moulded or cast aromatic polyamide fibre or film having a glass transition temperature (Tg) of ranging from not less than 250°C to not more than 400°C and having a ratio of the storage modulus measured at the temperature of Tg (E'(Tg)) to the storage modulus measured under the same conditions at the temperature of Tg plus 100°C (E'(Tg+100°C)) of less than 3 (E'(Tg)/E'(Tg+100°C)<3) , said moulded or cast aromatic polyamide product being obtained by contacting the moulded or cast polyamide with an aqueous N-methylpyrrolidone solution, stretching it and then orienting it with heat-treating at a temperature ranging from Tg of said moulded or cast aromatic polyamide to the temperature of Tg plus 150°C for 1-100 minutes, the moulded or cast aromatic polyamide being made from an aromatic polyamide consisting of a recurring unit of the formula (II): [ -HN - Ar1 - NHCO - Ar2 - CO- ] (II) whereby Ar1 is a divalent arylene group represented by and Ar2 is a divalent phenylene group represented by wherein R is hydrogen or a methyl group, and when said Ar1 is two carbon atoms directly bonded to the nitrogen atoms of the amide linkage bonded to the phenylene group are situated in 2,4- or 2,6-positions to the methyl group, the ratio of said 2,4-positions to 2,6-positions is in a range of from 100:0 to 80:20 or from 0:100 to 20:80, and the two carbon atoms in the Ar2 phenylene group directly bonded to the carbonyl carbon atoms of the amide linkage are bonded in 1,3- or 1,4-positions in a ratio ranging from 0:100 to 20:80, or wherein Ar1 is the two carbon atoms in the Ar2 phenylene group directly bonded to carbonyl carbon atoms of the amide linkage are bonded in 1,3- or 1,4-positions in a ratio ranging from 100:0 to 80:20. The disclosures of GB-A-871 579; EP-A-194,058 and EP-A-7,632 are hereby acknowledged. GB-A-871 579 discloses heat-resistant aromatic polyamides and shaped structures such as films and filaments; some of the polyamides disclosed correspond to the polyamides the subject of the present invention, but there is no teaching of heat treating them so as to overcome the disadvantages noted hereinbefore, i.e. the lowering of properties at temperatures higher than Tg. EP-A-194,058 also discloses polyamides similar to those the subject of the present invention, but again is silent as to the heat treatment of a moulded or cast polyamide film. EP-A-7,632 discloses a specific aromatic polyamide composition suitable for films and fibres, and teaches that in the production of the latter the composition is exposed to heat during part of the inline spinning process. Preferred embodiments of the invention will now be explained in more detail, by way of example, in the following non-limitative description. In this invention, the ratio of storage modulus at the temperature of Tg to that of Tg+100°C is not more than 3, and more preferably not more than 2. It has been found that this ratio maintains thermal resistance of aromatic polyamide particularly by inhibiting the lowering of physical properties at high temperatures above Tg, thereby obtaining aromatic polyamide which can be used up to higher temperatures. The ratio of storage modulus at the temperature of Tg to that of Tg+100°C has been examined as a measure of judging various factors causing property reduction at high temperatures above Tg which is an disadvantage of PMIA. The ratio has been larger than 3 in any case. In this invention, attention has been focused on the ratio and aromatic polyamides have been investigated in order to satisfy the requirement that the ratio is not more than 3. During the course of this investigation, methyl substituted aromatic polyamide having a Tg ranging from 250°C to 400°C and a specific structure of the formula (II) has been examined. As a result, it has been found that the above requirement can be satisfied by subjecting the film prepared from said aromatic polyamide to heat treatment in the temperature range of Tg to Tg+150°C and by measuring the viscoelasticity of resulting film. As to the heat treatment method, the film is fixed between a certain distance and treated at a constant temperature not less than Tg and preferably within the range of Tg - Tg+150°C, for 1 - 100 minutes and preferably for 5 - 60 minutes. It is preferred to treat in the range of Tg - Tg+150°C with a rate of temperature rise of 2 - 10°C/min. Heat treatment is insufficient at temperatures below Tg and polymer deterioration occurs above Tg+150°C. Therefore, good films can not be obtained in these cases. Aromatic polyamide having a polymer Tg not more than 250°C is insufficient in stiffness of molecule and cannot provide a film having favorable high-temperature elastic modulus. On the other hand, aromatic polyamide having a polymer Tg not less than 400°C is also disadvantageous in that the stiffness of molecule is too high or poor solubility in solvents makes processing difficult. As a result, it has been found that the above stated condition can be satisfied with polyamide consisting of the specific structure represented by the formula (II). [-HN-Ar1-NHCO-Ar2-CO-] (II) wherein Ar1 is a divalent arylene group represented by and Ar2 is a divalent phenylene group represented by where R is hydrogen or a methyl group, and when said Ar1 is two carbon atoms directly bonded to nitrogen atoms of amide linkage in the phenylene group are situated in 2,4- or 2,6-positions to methyl group, the ratio of said 2,4-positions to 2,6-positions is in a range of from 100:0 to 80:20 or from 0:100 to 20:80, and two carbon atoms in the Ar2 phenylene group directly bonded to carbonyl carbon atoms of the amide linkage are bonded in 1,3-or 1,4-positions in a ratio ranging from 0:100 to 20:80 or wherein Ar1 is and the two carbon atoms in the Ar 2 phenylene group directly bonded to carbonyl carbon atoms of the amide linkage are bonded in 1,3- or 1,4-positions in a ratio ranging from 100:0 to 80:20. The particularly preferred recurring unit of the formula (II) has one of the following structures: (1) Not less than 95 mole % of the recurring unit is 4-methyl-1,3-phenyleneterephthalamide, (2) Not less than 95 mole % of the recurring unit is 2-methyl-1,4-phenyleneisophthalamide, (3) Not less than 95 mole % of the recurring unit is 2,5-dimethyl-1,4-phenyleneisophthalamide, or (4) Not less than 95 mole % of the recurring unit is 3,3'-dimethyl-4,4'-biphenyleneisophthalamide. Any method can be employed for the preparation of films from aromatic polyamide of this invention. As a general method, for example, polyamide is dissolved in a polar organic solvent such as N-methylpyrrolidone and dimethylacetamide, cast on a glass plate, and allowed to stand for 3 hours at 50-80°C in a hot air drying oven to obtain a self-supporting film containing 20-30 wt.% of the solvent. The film is successively fixed on a pin tenter frame and dried by heating from the room temperature to 240°C under reduced pressure. Besides in the preparation of stretched film, the above self-supporting film is cut into a size of 5 mm x 8 mm, fixed on a drawing machine and stretched 3-8 times at 70-90°C in a 10 wt.% aqueous N-methylpyrrolidone solution. The resulting film is successively dipped in a 5-10 wt.% aqueous N-methylpyrrolidone solution at 90-100°C for 5-60 minutes, washed thoroughly in a hot water stream at 60-90°C and further dried at 150°C for 3 hours under reduced pressure of 2.7-4 hPa (2-3 mmHg) to obtain a stretched film. Storage modulus of the cast film or stretched film at Tg and Tg+100°C can be obtained by measuring viscoelasticity from the room temperature to 450°C. Property of the stretched film is estimated by the formula (I): Aromatic polyamide having the specific structure which satisfies this invention can be easily prepared by known methods. That is, aromatic diamine is reacted with aromatic dicarboxylic acid halide by low temperature solution polymerization, low temperature interfacial polymerization or fusion polymerization. Aromatic polyamide can also be prepared from aromatic diisocyanate and aromatic dicarboxylic acid by solution polymerization at high temperatures. The particularly preferred method is the high-temperature solution polymerization of aromatic diisocyanate and aromatic dicarboxylic acid in accordance with Japanese Laid-Open Patent No. 190517/1986 which was applied by the present inventors. Aromatic diamines which can be used as the raw material for preparing aromatic polyamide of this invention include, for example, tolylene-2,4-diamine, tolylene-2,6-diamine, 2-methyl-1,4-phenylenediamine and 2,5-dimethyl-1,4-phenylenediamine. Examples of aromatic dicarboxylic acid halides which can be reacted with the above diamines include isophthalic acid dihalide and terephthalic acid dihalide. Examples of aromatic diisocyanates which can be suitably used in this invention include tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, 2-methyl-1,4-phenylenediisocyanate and 2,5-dimethyl-1,4-phenylenediisocyanate. Aromatic dicarboxylic acid which can be reacted with above diisocyanates include, for example, isophthalic acid and terephthalic acid. Polyamide of this invention can be used for various applications. Particularly preferred embodiments are such procedures as dissolving polyamide in the polar organic solvent, casting a film and further stretching the resulting film. Effects of the Invention: A moulded or cast aromatic polyamide of this invention which satisfies the formula (I) has very small lowering of storage modulus even at the high temperature region of Tg+150°C. The moulded or cast aromatic polyamide is useful as fibers or films which are excellent in heat resistance and can be applied for various fields such as heat-resistant protective clothing, heat-resistant stretched film substrates, heat-resistant insulation films and thermal insulation films. Example Embodiments of this invention will hereinafter be illustrated in detail by way of examples. Example 1 Preparation example of poly(4-methyl-1,3-phenyleneterephthalamide) A 3 ℓ separable flask equipped with a stirrer, thermometer, condenser, dropping funnel and nitrogen inlet tube was charged with 166.0 g (0.991 mole) of terephthalic acid, 2.038 g of mono potassium terephthalate and 1600 ml of anhydrous N,N′-dimethylethyleneurea in a nitrogen atmosphere. The mixture was heated to 200°C with stirring and added dropwise was a solution of 174.0 g (0.9991 mole) of tolylene-2,4-diisocyanate in 160 ml of anhydrous N,N′-dimethylethyleneurea over 4 hours while maintaining the temperature. The reaction was continued further for an hour. The reaction mixture was cooled to the room temperature and poured into a poor solvent with vigorous stirring to precipitate a white polymer. The polymer was washed with a large amount of water and dried at 150°C for about 3 hours under reduced pressure. The inherent viscosity of the polymer thus obtained was 2.2 (95% H₂SO₄, 0.1%, 30°C). Preparation of a stretched film from poly(4-methyl-1,3-phenyleneterephthalamide) The aromatic polyamide obtained above was dissolved in N-methylpyrrolidone to prepare a dope having a polymer concentration of 15 wt.%. The dope was cast on a glass plate to a thickness of 0.8 mm and pre-dried at 80°C for 3 hours in a hot air oven to form a self-supporting film. Then the film was cut into 5 mm in width by 50 mm in length, set on a drawing machine, dipped in a 10 wt.% aqueous N-methylpyrrolidone solution at 70°C and stretched 5 times at a rate of 30 mm/min. The stretched film was successively fixed in a prescribed length on a metal frame, dipped in a 10 wt.% aqueous N-methylpyrrolidone solution at 98°C for 5 minutes, washed thoroughly in a warm water stream at 65°C and dried at 150°C under reduced pressure of 2.7-4 hPa (2-3 mmHg). Glass transition temperature (Tg), melting point (Tm) and storage modulus (E′) were determined by the following methods with the stretched film thus obtained. Methods of determination 1. Glass transition temperature and melting point in accordance with Differential Scanning Calorimeter (DSC) method Glass transition temperature Tg (°C) Model DSC-2C of Perkin Elmer Co. is used. About 10 mg of film specimen is put in an aluminum sample disk and heated from the room temperature at a rate of 10°C/min in a nitrogen stream having a flow rate of 30 m/min to measure DSC curve. The temperature at which transfer of base line to endothermic side occurs is designated as Tg. Melting point Tm (°C) In the same method as above, the peak temperature of absorption peak at the high-temperature region above Tg is designated as Tm. 2. Storage modulus by viscoelasticity measurement E'(Tg): Storage modulus (Gpa) at the glass transition temperature RHEOVIBRON (Registered Trade Mark) Model DDV-II-Ea of Orientec Co. is used. A stretched film of 60mm in length by 0.025mm in thickness by 3.0mm in width is held by chucks in a chuck distance of 16mm. Viscoelasticity is measured under following conditions. Measuring Condition: Frequency 110 Hz Heating Rate 2.0°C/min. Wave Width 1.6 x 10⁻³ cm (0.05% Dynamic strain to 3.2 cm specimen length) Temperature Range from Ambient Temperature to 450°C Storage modulus at the glass transition temperature Tg is designated as E'(Tg). E'(Tg+100°C): Storage modulus (Gpa) at the temperature of Tg+100°C. Viscoelasticity is measured by the same procedures as for E'(Tg). Storage modulus at the temperature of Tg+100°C is designated as E'(Tg+100°C). The following results were obtained on the above stretched film in accordance with the aforesaid methods of determination. Tg was 320°C, and Tm was 425°C. The stretched film obtained above was fixed between a prescribed distance and heat treated at 350°C for 30 minutes. Storage modulus was measured at Tg and Tg+100°C, that is, 320°C and 420°C respectively. No change was found at all on storage modulus even at temperatures close to melting point. E'(Tg) = E'(320°C) = 2.1 (Gpa) E'(Tg+100°C) = 2.3 (Gpa) The stretched film had a tensile strength of 1280 kgf/cm² (125 MPa) at 25°C and 1015 kgf/cm² (99.5 MPa) at 300°C respectively. Almost no change was found on the appearance of film after storage at 430°C for 5 minutes. Example 2 Preparation example of poly(3,3'-dimethyl-4,4'-biphenyleneisophthalterephthalamide) Polymerization was carried out by using the reaction vessel as Example 1. The vessel was charged with 132.9 g (0.8000 mole) of isophthalic acid, 33.22 g (0.2000 mole) of terephthalic acid, 2.010 g of mono potassium isophthalate and 2000 ml of anhydrous N,N'-dimethylethyleneurea in a nitrogen atmosphere. The mixture was maintained at 200°C and added dropwise over 2 hours was a solution of 264.3 g (1.000 mole) of 3,3'-dimethyl-4,4'-biphenyldiisocyanate in 300 ml of anhydrous N,N'-dimethylethyleneurea. The reaction was further continued for 30 minutes. The reaction mixture was cooled to the room temperature and poured into a large amount of water with vigorous stirring to precipitate the polymer. The polymer was thoroughly washed with a large amount of hot water and dried at 150°C for 10 hours under reduced pressure of 2.7-4 hPa (2-3 mmHg). The polymer had an inherent viscosity of 1.9. Preparation of a stretched film from poly(3,3-dimethyl-4,4'-biphenyleneisophthal-terephthalamide) A stretched film was prepared by the same procedures as Example 1, and Tg and Tm were measured respectively. Tg was 280°C and Tm was 355°C. The stretched film obtained was fixed between a prescribed distance and heat treated at 300°C for 60 minutes. The following storage moduli were obtained at Tg and Tg + 100°C that is, 280°C and 380°C respectively. E'(Tg) = E'(T280°C) = 2.2 (Gpa) E'(Tg+100°C) = E'(T380°C) = 1.9 (Gpa) The stretched film had a tensile strength of 1190 kgf/cm² (117 MPa) at 25°C and 950 kgf/cm² (93 MPa) at 300°C respectively. Almost no change was found on the appearance of the film after storage at 430°C for 5 minutes. Control 1 Viscoelasticity of the stretched film obtained in Example 1 was measured without pre-heat treatment. Storage modulus was measured at Tg (280°C) and Tg+100°C (380°C). E'(Tg) = E'(280°C) = 2.2 (Gpa), E'(Tg+100°C) = E'(380°C) = 0.55 (Gpa), Steep reduction of storage modulus was found at temperatures above Tg. The stretched film suffered severe shrinkage after standing at 430°C for 5 minutes. Control 2 Preparation example of poly(metaphenyleneisophthalamide) A 2 ℓ jacketed separable flask equipped with a stirrer, thermometer and jacketed dropping funnel was charged with 250.2 g (1.232 moles) of isophthalic acid chloride and 600 ml of anhydrous tetrahydrofuran. The solution obtained was cooled to 20°C by introducing refrigerant into the jacket and added dropwise over 20 minutes under vigorous stirring was a solution of 133.7 g (1.237 moles) of metaphenylenediamine in 400 ml of anhydrous tetrahydrofuran. The white emulsion thus obtained was quickly poured with vigorous stirring into ice cooled water containing 2.64 moles of anhydrous sodium carbonate. The temperature of the slurry was raised close to the room temperature. After successively adjusting the pH to 11 with addition of sodium hydroxide, the slurry was filtered. The resulting cake was thoroughly washed with a large amount of water and dried overnight at 150°C under reduced pressure. The inherent viscosity of polymer obtained was 1.4. Preparation of a stretched film from poly(metaphenyleneisophthalamide) A stretched film was prepared by the same procedures as Example 1. The film had a Tg of 280°C and a Tm of 425°C. The following storage moduli were obtained at Tg and Tg+100°C, that is, 280°C and 380°C respectively. E'(Tg) = E'(T280°C) = 2.8 (Gpa) E'(Tg+100°C) = E'(T380°C) = 0.65 (Gpa) The stretched film had a tensile strength of 1310 kgf/cm² (128 MPa) at 25°C and 780 kgf/cm² at (76 MPa) at 300°C. The film suffered severe shrinkage after standing at 430°C for 5 minutes and could not be used. Control 3 Preparation example of poly(4-methyl-1,3-phenyleneisophthalamide) Polymerization was carried out by using the same equipment as Example 1. The separable flask was charged with 166.1 g (1.000 mole) of isophthalic acid, 0.9405 g of mono sodium isophthalate and 1000 ml of anhydrous N,N'-dimethylethyleneurea. The mixture was heated to 200°C in an oil bath and combined dropwise with a solution of 174.1 g (1.000 mole) of tolylene-2,4-diisocyanate in 200 ml of anhydrous N,N'-diethylethyleneurea over 4 hours while maintaining the temperature. The reaction was further continued for an hour. The reaction mixture was cooled to the room temperature and treated with the same procedures as Example 1. The polymer thus obtained had an inherent viscosity of 2.0. Preparation of a stretched film from poly(4-methyl-1,3-phenyleneisophthalamide) A stretched film was prepared by the same procedures as Example 1. The film had a Tg of 260°C and a Tm of 395°C. The following storage moduli were obtained at Tg and Tg+100°C, that is, 260°C and 360°C respectively. Storage modulus fell steeply at the temperatures above Tg. E'(Tg) = E'(T260°C) = 2.0 (Gpa) E'(Tg+100°C) = E'(T360°C) = 0.5 (Gpa) The stretched film had a tensile strength of 1100 kgf/cm² (108 MPa) at 25°C and 770 kgf/cm² (75.5 MPa ) at 300°C respectively. The film suffered severe shrinkage after standing at 430°C for 5 minutes and could not be used.

Claims: A moulded or cast aromatic polyamide fibre or film having a glass transition temperature (Tg) of ranging from not less than 250°C to not more than 400°C and having a ratio of the storage modulus measured at the temperature of Tg(E'(Tg)) to the storage modulus measured under the same conditions at the temperature of Tg plus 100°C (E'(Tg + 100°C)) of less than 3 (E'(Tg)/E'(Tg + 100°C)<3) , said moulded or cast aromatic polyamide product being obtainable by contacting the moulded or cast polyamide with a 10 wt.% aqueous N-methylpyrrolidone solution, stretching it and then orienting it with heat-treating at a temperature ranging from Tg of said moulded or cast aromatic polyamide to the temperature of Tg plus 150°C for 1-100 minutes, the moulded or cast aromatic polyamide being made from an aromatic polyamide consisting of a recurring unit of the formula (II): [ -HN - Ar1 - NHCO - Ar2 - CO- ] (II) whereby Ar1 is a divalent arylene group represented by and Ar2 is a divalent phenylene group represented by wherein R is hydrogen or a methyl group, and when said Ar1 is two carbon atoms directly bonded to the nitrogen atoms of the amide linkage bonded to the phenylene group are situated in 2,4- or 2,6-positions to the methyl group, the ratio of said 2,4-positions to 2,6-positions is in a range of from 100:0 to 80:20 or from 0:100 to 20:80, and the two carbon atoms in the Ar2 phenylene group directly bonded to the carbonyl carbon atoms of the amide linkage are bonded in 1,3- or 1,4-positions in a ratio ranging from 0:100 to 20:80, or wherein Ar1 is the two carbon atoms in the Ar2 phenylene group directly bonded to carbonyl carbon atoms of the amide linkage are bonded in 1,3- or 1,4-positions in a ratio ranging from 100:0 to 80:20. The moulded or cast aromatic polyamide according to claim 1 wherein not less than 95 mole % of the recurring unit is 4-methyl-1,3-phenyleneterephthalamide. The moulded or cast aromatic polyamide according to claim 1 wherein not less than 95 mole % of the recurring unit is 2-methyl-1,4-phenyleneisophthalamide. The moulded or cast aromatic polyamide according to claim 1 wherein not less than 95 mole % of the recurring unit is 2,5-dimethyl-1,4-phenyleneisophthalamide. The moulded or cast aromatic polyamide according to claim 1 wherein not less than 95 mole % of the recurring unit is 3,3'-dimethyl-4,4'-biphenyleneisophthalamide.

Inventors: KATSUOKA HIROTOSHI, KOUNO MASAHIRO, MATSUYAMA AKIO, MIZUTANI KAZUMI, OSAWA MASANORI, SHIZUKA KOHEI, KATSUOKA, HIROTOSHI, KOUNO, MASAHIRO, MATSUYAMA, AKIO, MIZUTANI, KAZUMI, OSAWA, MASANORI, SHIZUKA, KOHEI
Applicants: MITSUI TOATSU CHEMICALS, MITSUI TOATSU CHEMICALS, INC.
Application year: 1988
Main classification: C08G69
IPC codes: C08G69, A47K13, E03D9