Process for producing aromatic polycarbonate and method of storing raw materials thereor

专利摘要:
By storing the aromatic dihydroxy compound and diester carbonate, which are raw materials for producing the aromatic polycarbonate, in consideration of the influence of the atmosphere during storage, the temperature, the temperature difference with the storage tank and the residence time, the aromatic polycarbonate having a good color tone can be obtained. You can get it.
公开号:KR20020040806A
申请号:KR1020027003504
申请日:2001-07-13
公开日:2002-05-30
发明作者:다께모또히데미；사와끼도루；가네꼬게이이찌；사사끼가쯔시
申请人:야스이 쇼사꾸；데이진 가부시키가이샤；
IPC主号:

专利说明:

Production method of aromatic polycarbonate and preservation method of the raw material {PROCESS FOR PRODUCING AROMATIC POLYCARBONATE AND METHOD OF STORING RAW MATERIALS THEREOR}
[2] BACKGROUND ART Polycarbonate resins obtained from interfacial polycondensation of bisphenol A and phosgene are widely used in various applications such as electric and electronic parts, optical parts and automobile parts due to their excellent mechanical and thermal properties. However, the use of toxic phosgene causes a problem of safety, and the use of methylene chloride as a solvent causes many environmental problems. In addition, chlorine derived from methylene chloride or sodium chloride, which is a by-product, remains in the polycarbonate, which causes a problem of corroding metal during various parts molding. Therefore, polycarbonate by the transesterification method which does not use methylene chloride or phosgene is attracting attention in recent years. However, the polycarbonate obtained by the transesterification method receives a long history of heat at a high temperature, so it is difficult to obtain excellent quality such as deterioration of color tone. In particular, recently, in polycarbonates used in optical applications requiring high density and high precision such as DVD, MO, CDR, etc., gelation due to coloration and thermal denaturation due to lack of thermal stability is directly performed. In order to affect the optical properties and mechanical properties such as tensile, bending, and toughness, better color tone improvement and thermal stability improvement of the transesterification polycarbonate is required.
[3] In order to solve this problem, for example, German Patent Publication No. 2439552 sends purified bisphenol A and diphenyl carbonate so that the molar ratio is 30/70 to 70/30, preferably 45/55 to 55/45. After preservation in a molten state, the method of putting in a transesterification kiln and polymerizing is proposed. In Japanese Patent Laid-Open No. 6-32885, in order to reduce the amount of residual metal in polycarbonate, the metal material of the transesterification reaction is made of a metal material containing a metal selected from Fe, Cr, Mo, Ni, Cu, and Cr. The reactor was used, and the water content in the reactor was kept at 500 ppm or less to produce polycarbonate.
[4] Japanese Unexamined Patent Publication No. 6-32886 discloses an aromatic dihydroxy compound which is melted after purification, fed to a reactor in the absence of substantially solid oxygen without solidifying the mixture, and then mixed with a diester carbonate to carry out a polycondensation reaction. Disclosed are methods for producing polycarbonates.
[5] Japanese Laid-Open Patent Publication No. 6-32887 discloses a method for producing an aromatic polycarbonate in which a powdery aromatic dihydroxy compound and a molten diester are mixed in the substantial absence of oxygen and the resulting solution is polycondensed. It is.
[6] Japanese Laid-Open Patent Publication No. 7-26010 discloses a method of transesterifying a dihydroxy compound and a diester carbonate in an atmosphere having an oxygen concentration of 2 ppm or less.
[7] However, no aromatic polycarbonate having a sufficiently good color tone could be obtained by any of the above methods.
[1] The present invention relates to a method for preserving a raw material used for producing an aromatic polycarbonate, and a method for producing an aromatic polycarbonate having excellent color tone by using a raw material stored by the method.
[8] An object of the present invention is to provide a method for preserving a raw material, which is effective for producing an aromatic polycarbonate having excellent color tone.
[9] Another object of the present invention is to provide a method for preserving raw materials in consideration of various parameters of raw material preservation conditions and the correlation between these various parameters, which affect the color tone of the aromatic polycarbonate to be produced.
[10] Still another object of the present invention is to provide a method for producing an aromatic polycarbonate having excellent color tone by using a raw material preserved by the storage method of the present invention.
[11] Still other objects and advantages of the present invention will become apparent from the following description.
[12] According to the present invention, the above objects and advantages of the present invention, first,
[13] The aromatic dihydride characterized in that the mixture consisting essentially of the aromatic dihydroxy compound and the diester carbonate is kept in a molten state under the condition that the melt storage parameter (A ₀ ) defined by the following formula (1) becomes 0 or less. It is achieved by the preservation method of the mixture of the hydroxy compound and the diester carbonate (hereinafter referred to as the melt preservation method of the raw material mixture)
[14] _{A 0 = -7.88 + 0.179 × logC} 0 +3.354 × logT 0 +0.0078 × U 0 + 0.0017τ 0 ... (One)
[15] Where C ₀ is the oxygen concentration (ppm) of the atmosphere in the reservoir, T ₀ is the temperature of the melt mixture in the reservoir (° C.), and U ₀ is the temperature difference (° C.) between the temperature of the heating medium of the reservoir and the temperature of the melt mixture And τ ₀ is the average residence time (hr) of the molten mixture in the reservoir).
[16] According to the present invention, the above object and advantages of the present invention, second,
[17] A carbonic acid diester, the formula (2) method of preserving melt keeping parameter carbonic acid diester, which is characterized in that (A ₁₎ maintaining in a molten state under the conditions is not more than 0, defined as (or less, the melt of the carbonic acid diester Storage method).
[18] A ₁ = -8.08 + 0.145 x log C ₁ +3.35 x log T ₁ +0.007 x U ₁ +0.0007 τ ₁ . (2)
[19] Where C ₁ is the oxygen concentration (ppm) of the atmosphere in the reservoir, T ₁ is the temperature of the diester carbonate (° C.), and U ₁ is the temperature difference between the temperature of the heating medium of the reservoir and the diester carbonate ( Τ) and τ ₁ is the average residence time (hr) of diester carbonate in the reservoir).
[20] According to the present invention, the above objects and advantages of the present invention,
[21] Preservation of the carbonic acid diester, characterized in that for holding in powder form the carbonic acid diester, under the following formula (3) conditions that are less than or equal to zero melt keeping parameter (B ₂₎ defined by a (hereinafter, a powder of the carbonic acid diester Is called a preservation method):
[22] B ₂ = -0.425 + 0.131 x log C ₃ +0.047 x log M ₂ -0.0012 T ₃ +0.0017 x τ ₂₃ . (3)
[23] Where C ₃ is the oxygen concentration (ppm) of the atmosphere in the reservoir, M ₂ is the moisture content (ppm) of the diester carbonate in the reservoir, T ₃ is the temperature of the diester carbonate in the reservoir (° C) and τ ₃ is Average residence time (hr) of diester carbonate in the reservoir).
[24] According to the present invention, the above objects and advantages of the present invention are fourth,
[25] The aromatic dihydroxy compound is maintained in a powder state under the condition that the powder storage parameter (B ₁ ) defined by the following formula (4) becomes 0 or less, the method for preserving the aromatic dihydroxy compound (hereinafter, aromatic It is called the powder preservation method of a dihydroxy compound).
[26] B ₁ = -0.425 + 0.131 × log C ₂ +0.047 × log M ₁ -0.0012 × T ₂ +0.0017 τ ₂ . (4)
[27] Where C ₂ is the oxygen concentration (ppm) of the atmosphere in the reservoir, M ₁ is the moisture content (ppm) of the aromatic dihydroxy compound in the reservoir, and T ₂ is the temperature (° C.) of the aromatic dihydroxy compound in the reservoir. And τ ₂ is the average residence time (hr) of the aromatic dihydroxy compound in the reservoir).
[28] Finally, according to the present invention, the above objects and advantages of the present invention,
[29] At least one compound selected from the group consisting of alkali metal compounds and alkaline earth metal compounds and nitrogen-containing basics are stored by storing an aromatic dihydroxy compound and a diester carbonate using at least one of the above-mentioned preservation methods of the present invention. It is achieved by the process for producing an aromatic polycarbonate, which is subjected to transesterification in the presence of a catalyst consisting of a compound.
[30] Preferred Embodiments of the Invention
[31] Hereinafter, the method of the present invention will be described sequentially. First, the melt preservation method of the raw material mixture of the present invention will be described.
[32] The aromatic dihydroxy compound used is a compound having two hydroxy groups directly connected to the aromatic ring.
[33] Specific examples of such aromatic dihydroxy compounds include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), and 1,1-bis (4-hydroxyphenyl). ) Ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5-dichloro Phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 4,4'-dihydroxyphenyl-1,1 bis (4-hydroxyaryl) alkanes such as' -m-diisopropylbenzene and 4,4'-dihydroxyphenyl-9,9-fluorene; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl Cyclohexane, 1-methyl-1- (4-hydroxyphenyl) -4- (dimethyl-4-hydroxyphenyl) methyl-cyclohexane, 4- [1- [3- (4-hydroxyphenyl) -4 -Methylcyclohexyl] -1-methylethyl] -phenol, 4,4 '-[1-methyl-4- (1-methylethyl) -1, 3-cyclohexanediyl] bisphenol, 9,9-bis (4 -Hydroxy-3-methylphenyl) fluorene, 2,2,2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobis- [1H-indene] Bis (hydroxyaryl) cycloalkanes such as -6,6'-diol; Dihydroxyaryl ethers such as bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether Ryu; Dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; Dihydroxydiarylisatins such as 4,4'-dihydroxydiphenyl-3,3'-isatin; Dihydroxy diaryl xanthenes such as 3,6-dihydroxy-9,9-dimethylxanthene; Resorcin, 3-methylresorcin, 3-ethylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, hydroquinone, 2-methylhydroquinone, 2 Dihydroxybenzenes such as ethylhydroquinone, 2-butylhydroquinone, 2-t-butylhydroquinone, 2-phenylhydroquinone and 2-cumylhydroquinone; And dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl and 3,3'-dichloro-4,4'-dihydroxydiphenyl.
[34] Especially, it is mentioned that 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable in the stability which is a monomer and the quantity of the impurity contained therein is small, but it is easy to obtain.
[35] As diester carbonate, specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-credyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, Dibutyl carbonate, dicyclohexyl carbonate and the like are used. Of these, diphenyl carbonate is particularly preferable.
[36] According to the melt preservation method of the mixture of the present invention, the molten mixture of the aromatic dihydroxy compound and the diester carbonate as described above, preferably contained in a ratio of 1.0 to 1.2 mol of diester carbonate per mol of the aromatic dihydroxy compound. The molten mixture is kept in a molten state under the condition that the melt storage parameter (A ₀ ) defined by the following formula (1) becomes zero or less:
[37] _{A 0 = -7.88 + 0.179 × logC} 0 +3.354 × logT 0 +0.0078 × U 0 + 0.0017τ 0 ... (One)
[38] Where C ₀ is the oxygen concentration (ppm) of the atmosphere in the reservoir, T ₀ is the temperature of the melt mixture in the reservoir (° C.), and U ₀ is the temperature difference (° C.) between the temperature of the heating medium of the reservoir and the temperature of the melt mixture And τ ₀ is the average residence time (hr) of the molten mixture in the reservoir).
[39] By employing a melt keeping parameter (A ₀₎ that is less than the melt retention conditions in which a value of zero or minus zero may produce a superior color tone of polycarbonate. If the melt storage parameter (A ₀ ) exceeds zero, the color tone of the polycarbonate obtained is significantly deteriorated, which is not preferable. More preferably, the melting preservation parameter (A ₀ ) is stored under the condition indicating the range of -0.6 or more and -0.001 or less.
[40] The good and bad of the obtained polycarbonate color tone are measured by the Lab value of the pellet (short diameter x long diameter x length (mm) = 2.5 x 3.3 x 3.0) of a polycarbonate, and is determined by the b value used as a measure of yellowness. Polycarbonates prepared by the conventional transesterification process are easily yellowed when subjected to a long heat history at a high temperature, such as during polymerization or molding, so that the b value of the pellet becomes a value exceeding zero. It was difficult.
[41] However, it has been clarified by the present inventors that pellets having a b-value of zero or less can be produced by producing an aromatic polycarbonate using as a raw material the molten mixture stored by the above-described storage method.
[42] In the formula (1), C ₀ represents the oxygen concentration of the atmosphere in the storage tank, and the smaller the concentration maintains the melt storage parameter (A ₀ ) below zero in order to reduce the influence of coloring by the oxidation reaction in the storage tank. It is preferable at the point. For this reason, the storage tank is sufficiently substituted with an inert gas such as nitrogen and helium having a low oxygen concentration, and if necessary, the inert gas is bubbled or melted in the molten mixture to remove trace oxygen contained in the raw material itself. It is preferable to employ | adopt the method etc. which make it pass a deoxidation agent.
[43] T ₀ , U ₀ and τ ₀ respectively represent the melt mixture temperature, the temperature difference between the melt mixture and the heating medium and the average residence time of this mixture in the reservoir. In order to suppress the thermal history and oxidation reaction under melting, the smaller one is preferable. In order to eliminate local temperature variation and residence time variation, it is preferable to always stir-mix the storage tank.
[44] The temperature of the molten mixture in the storage tank is not particularly limited as long as it can stably store the molten mixture and can be easily transported to the liquid phase. Preferably, it is crystallization temperature +1 degreeC or more and 220 degrees C or less, More preferably, it is crystallization temperature +1 degreeC or more and 200 degrees C or less. For example, an equimolar mixture of bisphenol A and diphenyl carbonate is about 125 ° C.
[45] This inventor analyzed the degree of contribution of each factor to the b value of the polycarbonate manufactured on such conditions as a factor, and came to obtain said Formula (1). Since these conditions affect the color tone of the polycarbonate to be produced, it is preferable to continue the measurement as far as possible before the start of polymerization and to keep the melt storage parameter (A ₀ ) at or below zero.
[46] The molten mixture to be stored is preferably a mixture which is substantially free of a transesterification catalyst of an aromatic dihydroxy compound and a diester carbonate during storage. The inclusion of a transesterification catalyst is undesirable because the accuracy of the formula of the melt storage parameter is deteriorated since the aromatic monohydroxy compound is by-produced.
[47] The method for preserving the molten mixture of the present invention has a particularly significant effect when the melt holding time exceeds 2 hours.
[48] Moreover, it is preferable that a molten storage tank is comprised with the material which has corrosion resistance with respect to a molten mixture. For example, stainless steel, such as SUS304, SUS304L, SUS316, SUS316L, SUS630, SCS13, SCS14, SCS16, SCS19; Carbon steel subjected to plating of HCr (hard chromium), nickel or the like, stellite coating, or HIP (hot hydrostatic press) method or the like is preferable. In particular, stainless steel is preferable. Further, preferably, the pipes and pipe joints of the melt storage tank are also made of the same material. Although the material may be different in the reservoir, the pipe and the pipe joint, it is preferable to reduce the effect of thermal expansion by using the same material in terms of the strength and dead space of the pipe. In particular, it is preferable to consider the effect of stress at high temperature as the material used for the pipe has already undergone heat treatment.
[49] In addition, there is no restriction | limiting in particular in the apparatus type used for a molten storage tank, The well-known vertical type stirrer, the horizontal type stirring tank, etc. which are equipped with the stirring apparatus by heating by a heating medium can be used. Especially, it is preferable to use the stirring tank of a vertical type | mold batch, for example.
[50] According to the inventor's research, in addition to the method of melt-preserving the mixture of the aromatic dihydroxy compound and the diester carbonate as described above, the color tone is also good by the method of preserving the aromatic dihydroxy compound or the diester carbonate under appropriate conditions separately. It became clear that aromatic polycarbonates can be prepared. Next, these methods will be described, and these methods include a melt preservation method and a powder preservation method of diester carbonate and a powder preservation method of an aromatic dihydroxy compound.
[51] According to the melt storage method of the diester carbonate, the diester carbonate is kept in a molten state under the condition that the melt storage parameter (A ₁ ) defined by the following formula (2) becomes 0 or less:
[52] A ₁ = -8.08 + 0.145 x log C ₁ +3.35 x log T ₁ +0.007 x U ₁ +0.0007 τ ₁ . (2)
[53] Where C ₁ is the oxygen concentration (ppm) of the atmosphere in the reservoir, T ₁ is the temperature of the diester carbonate (° C.), and U ₁ is the temperature difference between the temperature of the heating medium of the reservoir and the diester carbonate ( Τ) and τ ₁ is the average residence time (hr) of diester carbonate in the reservoir).
[54] More preferable melt storage parameter (A ₁ ) is -1.6 to -0.001.
[55] In the above formula (1), C ₁ represents the oxygen concentration of the atmosphere in the storage tank, and the smaller the concentration keeps the melting preservation parameter (A ₁ ) below zero in order to reduce the influence of coloring by the oxidation reaction in the storage tank. Preferred at For this reason, inert gas is bubbled or melted in the molten diester, for example, in order to sufficiently substitute the inert gas such as nitrogen and helium having a low oxygen concentration and to remove the trace oxygen contained in the raw material itself as necessary. It is preferable to employ | adopt the method etc. which let diester carbonate pass through a deoxidizer.
[56] T ₁ , U ₁ and τ ₁ represent the temperature of the molten diester, the temperature difference between the molten diester and the heating medium, and the average residence time of the molten diester in the reservoir, respectively. For the sake of sake, it is preferable that the time is as short as possible, and that the inside of the storage tank is always stirred and mixed in order to eliminate local temperature unevenness and residence time unevenness.
[57] The temperature of the molten diester carbonate in the storage tank is preferably at least 250 ° C of the melting point of the diester carbonate, more preferably at least 200 ° C of the melting point of the diester carbonate.
[58] Examples of the diester carbonate to be melt-preserved include the same ones described above for the melt-preservation method of the raw material mixture. Among them, diphenyl carbonate is preferable.
[59] In addition, according to the powder preservation method of diester carbonate, the diester carbonate is maintained in the powder state under the condition that the powder storage parameter (B ₂ ) defined by the following formula (3) becomes zero or less:
[60] _{B 2 = -0.425 + 0.131 × logC} 3 +0.047 × logM 2 -0.0012T 3 +0.0017 × τ 3 ... (3)
[61] Where C ₃ is the oxygen concentration (ppm) of the atmosphere in the reservoir, M ₂ is the moisture content (ppm) of the diester carbonate in the reservoir, T ₃ is the temperature of the diester carbonate in the reservoir (° C) and τ ₃ is Average residence time (hr) of diester carbonate in the reservoir).
[62] More preferable powder storage parameter (B ₂ ) is -0.7 to -O.0001.
[63] In the above formula (3), C ₃ represents the oxygen concentration of the atmosphere in the storage tank, and in order to reduce the influence of coloring by the oxidation reaction in the storage tank, the smaller the concentration is preferable in that the powder preservation parameter (B ₂ ) is smaller. . For this reason, it is preferable to fully substitute inert gas, such as nitrogen and helium, with little oxygen concentration in a storage tank.
[64] M ₂ represents the water content of the diester carbonate in the storage tank. Since the presence of water promotes the hydrolysis of raw materials, oligomers, and polymers in the polymerization kiln, and increases the production of coloring factor components by hydrolysis, a smaller moisture content is preferable.
[65] T ₃ represents the powder temperature of the diester carbonate in the storage tank. The higher the temperature of the powder preservation is preferable because the powder preservation parameter (B ₂ ) can be kept small.
[66] tau ₃ represents the average residence time of the diester carbonate in the reservoir. In order to avoid the incorporation of substances which adversely affect other color tones during storage in the reservoir, the shorter time is preferable because the powder storage parameter (B ₂ ) can be kept small.
[67] In addition, it is desirable to always stir and mix the storage tank in order to eliminate local temperature variation and residence time variation, and it is stored in this tank until just before the polymerization kiln, and the moisture content, oxygen concentration, and powder temperature are frequently measured and recorded. practice to preserve, making sure that the powder keeping parameter (B ₂₎ is less than zero are preferred.
[68] The temperature of diester carbonate powder in a storage tank becomes like this. Preferably it is -50 degreeC or more and less than melting | fusing point of diester carbonate, More preferably, it is -30 degreeC or more and 50 degrees C or less.
[69] Examples of the diester carbonate to be preserved in the powder include the same ones described above for the melt storage method of the raw material mixture. Among these, diphenyl carbonate is preferable.
[70] In addition, aromatic powder according to the preservation method of the dihydroxy compound, the aromatic dihydroxy compounds, to the powder keeping parameter (B _l), which is defined by the formula (4) is held in a powder state under the condition that not more than 0:
[71] B ₁ = -0.425 + 0.131 × log C ₂ +0.047 × log M ₁ -0.0012 × T ₂ +0.0017 τ ₂ . (4)
[72] Where C ₂ is the oxygen concentration (ppm) of the atmosphere in the reservoir, M ₁ is the moisture content (ppm) of the aromatic dihydroxy compound in the reservoir, and T ₂ is the temperature (° C.) of the aromatic dihydroxy compound in the reservoir. And τ ₂ is the average residence time (hr) of the aromatic dihydroxy compound in the reservoir).
[73] More preferable powder storage parameter (B ₁ ) is -0.7 to -0.0001.
[74] In the above formula (4), C ₂ represents the oxygen concentration of the atmosphere in the storage tank, and in order to reduce the influence of coloring by the oxidation reaction in the storage tank, the smaller the concentration is preferable in that the powder preservation parameter (B ₁ ) is smaller. . For this reason, it is preferable to fully substitute inert gas, such as nitrogen and helium, with little oxygen concentration in a storage tank.
[75] M ₁ represents the moisture content of the aromatic dihydroxy compound in the storage tank. Since the presence of water promotes the hydrolysis of raw materials, oligomers and polymers in the polymerization kiln, and increases the generation of coloring factor components by hydrolysis, it is preferable that the moisture content is small.
[76] T ₂ represents the powder temperature of the aromatic dihydroxy compound in the storage tank. The higher powder storage temperature is preferable because the powder storage parameter (B ₁ ) can be kept small.
[77] τ ₂ represents the average residence time of the aromatic dihydroxy compound in the reservoir. In order to avoid the incorporation of substances which adversely affect other color tones during storage in the storage tank, the shorter time is preferable because the powder storage parameter (B ₁ ) can be kept small.
[78] Also, in order to eliminate local temperature irregularities and residence time unevenness, it is preferable that the storage tank is always stirred and mixed, and stored in the storage tank until just before the polymerization kiln, and the moisture content, oxygen concentration, and powder temperature are measured and recorded from time to time. the keeping parameter (B ₁₎ is preferably placed to conservation, making sure that it is less than zero.
[79] The temperature of the aromatic dihydroxy compound powder in the storage tank is preferably less than -50 ° C or less than the melting point of the aromatic dihydroxy compound, more preferably -30 ° C or more and 50 ° C or less.
[80] Examples of the aromatic dihydroxy compound to be preserved in the powder include those similar to those described above regarding the melt storage method of the raw material mixture. Among these, 2, 2-bis (4-hydroxyphenyl) propane is preferable.
[81] In addition, in the above-mentioned melt preservation method of the diester carbonate, the powder preservation method of the diester carbonate, and the powder preservation method of the aromatic dihydroxy compound, the matters not described are the same as those described regarding the melt preservation method of the raw material mixture. Or by adding facts apparent to those skilled in the art.
[82] As a preferred embodiment of the melt preservation method of the above-described raw material mixture of the present invention,
[83] (a) Method of using aromatic dihydroxy compound preserved by powder preservation method of aromatic dihydroxy compound
[84] (b) using diester carbonate preserved by powder preservation of diester carbonate or
[85] (c) The method of using the diester carbonate preserve | saved by the melting | preservation method of diester carbonate is mentioned. By producing an aromatic polycarbonate using as a raw material the molten raw material mixture preserved by the above preferred embodiment, it is possible to produce a polycarbonate having a negative b value, which is more excellent in color tone.
[86] Next, the manufacturing method of the aromatic polycarbonate by this invention is demonstrated.
[87] In the manufacturing method of the aromatic polycarbonate of this invention, the thing in which the raw material of at least any one of an aromatic dihydroxy compound and diester carbonate was preserve | saved by the at least one storage method of the said storage method of this invention is used.
[88] Specific examples include (i) a method of using a mixture of an aromatic dihydroxy compound and a diester carbonate, which is preserved by a melt preservation method of a raw material mixture, and (ii) a method of preserving by a powder preservation method of an aromatic dihydroxy compound. A method of using an aromatic dihydroxy compound, (iii) a method of using a diester carbonate preserved by a powder preservation method of diester carbonate, and (iv) a diester carbonate preserved by a melt preservation method of a diester carbonate. The method to use is mentioned. The combination of the above (ii) method and (iii) method or the above (ii) method and (iv) method is a preferred embodiment of the above (ii) method.
[89] The manufacturing method of the aromatic polycarbonate of this invention is characteristic from the point which uses the raw material which applied at least one of the storage methods of this invention as mentioned above. The raw material mixture is subjected to transesterification of one or more compounds selected from the group consisting of alkali metal compounds and alkaline earth metal compounds in the presence of a catalyst consisting of a nitrogen-containing basic compound.
[90] Examples of the alkali metal compound include alkali metal hydroxides, carbonates, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearates, borohydrides, benzoates, phosphates, bisphenols, and phenols. Salts; and the like.
[91] Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium nitrate, potassium nitrate, and nitric acid Lithium, sodium nitrite, potassium nitrite, lithium nitrite, sodium sulfite, potassium sulfite, lithium sulfite, sodium cyanate, potassium cyanate, lithium cyanate, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, sodium stearate, Potassium stearate, lithium stearate, sodium borohydride, potassium borohydride, lithium borohydride, sodium phenyl borate, potassium phenyl borate, lithium phenyl borate, sodium benzoate, potassium benzoate, lithium benzoate, sodium hydrogen phosphate, dihydrogen phosphate Potassium, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, sodium salt of phenol, potassium salt, lithium salt, etc. are mentioned among them. In the disodium salt of bisphenol A and the sodium salt of phenol are preferably used.
[92] Examples of alkaline earth metal compounds include hydroxides, carbonates, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearates, benzoates, bisphenols, and phenol salts of alkaline earth metals. Can be mentioned.
[93] Specifically, calcium hydroxide, barium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, strontium carbonate, calcium acetate, barium acetate, strontium acetate, calcium nitrate, barium nitrate, nitrate Strontium, calcium nitrite, barium nitrite, strontium nitrite, calcium sulfite, barium sulfite, strontium sulfite, calcium cyanate, barium cyanate, strontium cyanate, calcium thiocyanate, barium thiocyanate, strontium thiocyanate, calcium stearate, Barium stearate, strontium stearate, calcium borohydride, barium borohydride, barium borohydride, calcium benzoate, barium benzoate, strontium benzoate, calcium salt of bisphenol A, barium salt, strontium salt, calcium salt of phenol, barium salt, strontium salt, etc. Can be mentioned.
[94] In the present invention, if desired, as the alkali metal compound of the catalyst, (a) an alkali metal salt of an art complex of a group 14 element of the periodic table or (b) an alkali metal salt of oxo acid of an element of a group 14 of the periodic table can be used. The element of group 14 of a periodic table says silicon, germanium, and tin.
[95] By using these alkali metal compounds as a polycondensation reaction catalyst, it has the advantage that a polycondensation reaction can advance rapidly and fully. In addition, undesirable side reactions such as branching reactions generated during the polycondensation reaction can be suppressed to a low level.
[96] (a) As an alkali metal salt of the art complex of the 14th element of a periodic table, the thing of Unexamined-Japanese-Patent No. 7-268091 is used preferably. Specifically, the compound of germanium (Ge); NaGe (OMe) ₅ , NaGe (OEt) ₅ , NaGe (OPr) ₅ , NaGe (OBu) ₅ , NaGe (OPh) ₅ , LiGe (OMe) ₅ , LiGe (OBu) ₅ , LiGe (OPh) ₅ have.
[97] Examples of the compound of tin (Sn) include NaSn (OMe) ₃ , NaSn (OMe) ₂ (OEt), NaSn (OEt) ₃ , NaSn (OPr) ₃ , NaSn (OnC ₆ H ₁₃ ) ₃ , NaSn (OMe) ₅ , NaSn (OEt) ₅ , NaSn (OBu) ₅ , NaSn (OnC ₁₂ H ₂₅ ) ₅ , NaSn (OPh) ₅ , NaSnBu ₂ (OMe) ₃ .
[98] (B) Alkali metal salts of oxo acids of the Periodic Table 14 element include, for example, alkali metal salts of silicic acid, alkali metal salts of stanic acid, alkali metal salts of germanium (II) acid, Alkali metal salts of germanium (IV) acid are mentioned as a preferable thing.
[99] The alkali metal salts of silicic acid are, for example, acidic or neutral alkali metal salts of monosilicic acid or its condensates, and examples thereof include monosodium orthosilicate, disodium orthosilicate, trisodium orthosilicate and tetrasodium silicate. have.
[100] Alkali metal salts of tartaric acid are, for example, acidic or neutral alkali metal salts of monostanic acid or condensates thereof, and examples thereof include disodium monotartrate salt (Na ₂ SnO ₃ .xH ₂ O, x = 0 to 5), Monotartrate tetrasodium salt (Na ₄ SnO ₄ ).
[101] The alkali metal salt of germanium (II) acid is, for example, an acidic or neutral alkali metal salt of monogermanic acid or a condensate thereof, and examples thereof include monosodium germanium salt (NaHGeO ₂ ).
[102] Alkali metal salts of germanium (IV) acid are, for example, acidic or neutral alkali metal salts of monogernium (IV) acid or its condensates, for example orthogermanic acid monolithium salts (LiH ₃ GeO ₄ ), ortho there may be mentioned the di sodium salt germanium, germanium ortho acid tetrasodium salt, di-germanium di sodium salt (Na ₂ Ge2O _5), germanium tetra-di sodium salt _{(Na 2 Ge 5 O 11)} .
[103] The alkali metal compound or alkaline earth metal compound as the catalyst as described above is used when the alkali metal element or alkaline earth metal element in the catalyst is 1 × 10 ^-8 to 5 × 10 ^-5 equivalents per mole of aromatic dihydroxy compound. It is preferably used. A more preferable ratio is the ratio used as 5 * 10 <^-7> -1 * 10 <^-5> equivalent with respect to the same reference | standard. Outside the range of use, it is not preferable because there is a problem that adversely affects the various physical properties of the obtained polycarbonate, or the transesterification reaction does not proceed sufficiently to obtain a high molecular weight polycarbonate.
[104] Here, the equivalent of the alkali metal compound and the alkaline earth metal compound referred to herein means the product of the sum of the number of alkali metal elements or alkaline earth metal elements contained in one molecule of the catalyst and the number of moles of the catalyst, indicating that the catalyst is one molecule. When one alkali metal element (monovalent) is contained in one mole of the catalyst, one mole of the catalyst is equivalent to one equivalent of the catalyst, and when one alkaline earth metal element (divalent) is contained, one mole of the catalyst is equivalent to two equivalents of the catalyst. do. In addition, when two alkali metal elements (monovalent) are contained in 1 molecule of catalysts, 1 mol of catalysts will be equal to 2 equivalents of catalysts.
[105] As the nitrogen-containing basic compound used as a catalyst, for example, tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), Ammonium hydroxides having alkyl, aryl, alkylaryl groups, such as benzyltrimethylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH) and hexadecyltrimethylammonium hydroxide; Tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine and hexadecyldimethylamine; Or tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammoniumtetraphenylborate (Me ₄ NBPh ₄ ), tetrabutylammoniumtetraphenylborate (Bu _And basic salts such as ₄ NBPh ₄ ).
[106] It is preferable to use the said nitrogen-containing basic compound in the ratio whose ammonium nitrogen atom in a nitrogen-containing basic compound becomes 1 * 10 <^{-5> -5} * 10 <^-3> equivalent per mole of aromatic dihydroxy compound. A more preferable ratio is the ratio used as 2x10 <^{-5> -5} * 10 <^-4> equivalent with respect to the same reference | standard. A particularly preferable ratio is the ratio which becomes 5x10 <^{-5> -5} * 10 <^-4> equivalent with respect to the same reference | standard.
[107] Here, the equivalent of the nitrogen-containing basic compound catalyst as used herein means the product of the total number of basic nitrogen compounds contained in one molecule of the catalyst and the number of moles of the catalyst, and one basic nitrogen element (monovalent) is contained in one molecule of the catalyst. In this case, one mole of the catalyst is equal to one equivalent of the catalyst. For example, one mole of tetramethylammonium hydroxide (Me ₄ NOH) is equivalent to one equivalent of catalyst.
[108] In the polycondensation reaction as described above, one type of cocatalyst selected from the group consisting of an oxo acid and an oxide of a copper element of the Periodic Table 14 element can coexist with the catalyst as necessary.
[109] By using these cocatalysts in a specific ratio, branching reactions which are likely to be produced during the polycondensation reaction, generation of foreign matters in the apparatus during molding processing, and burning without impairing the terminal blocking reaction and the polycondensation reaction rate It is possible to more effectively suppress undesirable side reactions such as burning.
[110] Examples of the oxo acid of the 14th element of the periodic table include silicic acid, tartaric acid and germanium acid.
[111] Examples of the oxide of element 14 of the periodic table include silicon monoxide, silicon dioxide, tin monoxide, tin dioxide, germanium monoxide, germanium dioxide and these condensates.
[112] The cocatalyst is preferably present at a rate such that the metal elements of Group 14 of the periodic table in the cocatalyst are 50 mol (atoms) or less per 1 mol (atoms) of the alkali metal elements in the polycondensation reaction catalyst. When the cocatalyst is used at a ratio of more than 50 mol (atoms) of copper metal elements, the polycondensation reaction rate is delayed, which is undesirable.
[113] The cocatalyst is more preferably present at a rate such that the metal element of Group 14 of the periodic table of the cocatalyst is 0.1 to 30 mol (atoms) per 1 mol (atoms) of the alkali metal element of the polycondensation reaction catalyst.
[114] These catalyst systems have the advantage of being able to proceed the polycondensation reaction and the terminal blockade reaction quickly and sufficiently by using in the polycondensation reaction. In addition, undesirable side reactions such as branching reactions generated in the polycondensation reaction system can be suppressed to a low level.
[115] In preparing an aromatic polycarbonate by a transesterification reaction by reacting an aromatic dihydroxy compound and a diester carbonate under heating and melting, heating the aromatic dihydroxy compound and a diester carbonate under normal pressure or reduced pressure and under an inert gas atmosphere. The above-mentioned catalyst is added to the molten mixture obtained by stirring, and the transesterification reaction is started. In this case, the diester carbonate and the aromatic dihydroxy compound have a diester carbonate per mol of the aromatic dihydroxy compound, preferably 1.00 to 1.20 mol, more preferably 1.005 to 1.10 mol, still more preferably 1.01 to 1.05 mol. It is used in proportion. In addition, aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,10-decanediol and the like may be used as dicarboxylic acids, for example, succinic acid, isophthalic acid and 2,6- Naphthalenedicarboxylic acid, adipic acid, cyclohexanecarboxylic acid, terephthalic acid and the like can be used as oxyacids such as lactic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and the like.
[116] Reaction temperature is 140-300 degreeC normally, and it is preferable to raise reaction temperature with progress of superposition | polymerization. In addition, the pressure of the reaction system is preferably carried out by reducing the pressure of the system or facilitating the remaining or releasing of phenol produced by circulating a large amount of inert gas.
[117] There is no restriction | limiting in particular in the apparatus type of the polycondensation reactor used for implementing this invention, Usually, a vertical stirring tank, a horizontal stirring tank, a ruther, etc. can be used.
[118] More specifically, in the case of carrying out the reaction batchwise, an aromatic dihydroxy compound and a diester carbonate were added to the first stirring tank in which the rectification column was installed at the molar ratio, and replaced with an inert gas. Thereafter, after heating and melting, a predetermined amount of the polymerization catalyst is added thereto, the system is heated while degassing in vacuo to perform initial polymerization, and then the reaction solution is transferred to a second stirring tank without a rectifying column to further increase the system into a high vacuum. Moreover, it is preferable to continue superposition | polymerization until the temperature is also raised and it becomes predetermined polymerization degree. At this time, in order to maintain the concentration in the reaction system of the nitrogen-containing basic compound in the range of the present invention, for example, an appropriate amount of nitrogen-containing basic compound may be added and reacted during the reaction in the first stirring tank or during the transfer to the second stirring tank. Can be.
[119] When the reaction is carried out continuously, a plurality of stirring tanks are used, and among these, the first polymerization tank having a low viscosity of the reactants is used a vertical stirring tank having a rectifying column, and the viscosity of the reactants is high, resulting in the addition of aromatics. In the late polymerization tank, where it is difficult to remove the monohydroxy compound, these are installed in series using a horizontal stirring tank or a biaxial luder, and the molten raw material and the catalyst are sent to the first polymerization tank, and the predetermined polymerization degree is continuously obtained from the final polymerization tank. Extracting the polycarbonate of is performed preferably. At this time, in order to maintain the concentration in the reaction system of the nitrogen-containing basic compound in the range of the present invention, an appropriate amount of nitrogen-containing basic compound can be added and reacted with each polymerization tank including, for example, the first stirring tank.
[120] In addition, in this invention, it can be set as the form which uses the above-mentioned melt storage tank and the vertical type stirring tank which performs an initial polymerization reaction, or uses both as a separate stirring tank.
[121] In this way, the catalyst activator may be added to the polycarbonate obtained by the method of the present invention after transfer from the final polymerization tank or from the final polymerization tank. This catalyst deactivator significantly lowers the activity of the catalyst. As the deactivator of the polymerization catalyst by transesterification used in the present invention, known deactivators such as those described in JP-A-8-59975 are effectively used. Used. Especially, the ammonium salt of sulfonic acid, the phosphonium salt of sulfonic acid, and the ester of sulfonic acid are preferable.
[122] Especially, the ammonium salt and phosphonium salt of sulfonic acid are preferable, The said salt of paratoluene sulfonic acid, such as the said salt of dodecylbenzene sulfonic acid, such as a dodecylbenzene sulfonic acid tetrabutyl phosphonium salt, and a parabutyl ammonium salt of paratoluene sulfonic acid, is more preferable. . As esters of sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, benzene sulfonate, benzene sulfonate octyl, benzene sulfonate phenyl, paratoluene sulfonate methyl, paratoluene sulfonate butyl, paratoluene sulfonate octyl, paratoluene sulfonate phenyl, etc. This is preferably used. In the present invention, dodecylbenzene sulfonic acid tetrabutyl phosphonium salt and paratoluene sulfonic acid tetrabutylammonium salt are most preferably used among these catalyst deactivators.
[123] Such catalyst deactivator used in the present invention may be added to the polycarbonate alone, or may be added to the polycarbonate simultaneously as a mixture of water and the catalyst deactivator.
[124] The addition amount of the catalyst deactivator to the polycarbonate obtained by melt polymerization in the present invention is a ratio of 0.5 to 50 equivalents per 1 equivalent of the main polycondensation catalyst selected from alkali metal compounds and alkaline earth metal compounds, preferably 0.5 to 10 equivalents. It is used in the ratio of equivalents, More preferably, the ratio of 0.8-5 equivalents. Here, the equivalent of the catalyst deactivator represents the number of sites capable of reacting with each monovalent value of the catalyst metal present in one molecule of the deactivator, and the relationship between moles and equivalents of the catalyst deactivator indicates that the reaction site is contained in one molecule of deactivator. When one is present, 1 mole is equal to 1 equivalent, and when two reaction sites are present, 1 mole is equal to 2 equivalents. This generally corresponds to using at a ratio of 0.01 to 500 ppm per polycarbonate resin.
[125] These catalyst deactivators are dissolved or dispersed directly or in a suitable solvent, and then added to and mixed with the polycarbonate in a molten state. The equipment used to perform such an operation is not particularly limited. For example, a biaxial luther is preferable, and a biaxial luther with a vent is particularly preferably used when the catalyst deactivator is dissolved or dispersed in a solvent. .
[126] Moreover, in this invention, various other additives can be added to a polycarbonate in the range which does not inhibit the objective of this invention. This additive is preferably added to the polycarbonate in the molten state together with the catalyst deactivator. Such additives include, for example, heat stabilizers, epoxy compounds, ultraviolet absorbers, mold release agents, colorants, slip agents, antiblocking agents, lubricants, organic fillers, inorganic fillers, and the like.
[127] Among these, heat stabilizers, ultraviolet absorbers, mold release agents, colorants and the like are particularly generally used, and these may be used in combination of two or more kinds.
[128] As a heat resistant stabilizer used for this invention, a phosphorus compound, a phenol type stabilizer, an organic thioether type stabilizer, a hindered amine type stabilizer, etc. are mentioned, for example.
[129] As a ultraviolet absorber, a general ultraviolet absorber is used, For example, a salicylic acid type ultraviolet absorber, a benzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, etc. are mentioned.
[130] As a mold release agent, generally known mold release agents can be used. For example, hydrocarbon type release agents such as paraffins, fatty acid type release agents such as stearic acid, fatty acid amide release agents such as stearic acid amide, alcohol type release agents such as stearyl alcohol and pentaerythrite, Fatty acid ester type | system | group release agents, such as glycerin monostearate, and silicone oil type release agents, such as silicone oil, etc. are mentioned.
[131] As the colorant, organic or inorganic pigments and dyes can be used.
[132] Although there is no restriction | limiting in particular in the addition method of these additives, For example, you may add directly to a polycarbonate, and you may prepare and add a master pellet.
[133] Moreover, in order to improve rigidity etc. in the range which does not impair the objective of this invention, the polycarbonate obtained by the method of this invention can mix | blend a solid filler and / or thermoplastic resins other than the polycarbonate of this invention. It is also possible to provide a carbonate composition.
[134] Hereinafter, although an Example and a comparative example of this invention are described in detail, this example is for illustrating this invention, and this invention is not limited at all by these. In addition, "ppm" and "part" in an Example and a comparative example are "weight ppm" or "weight part" unless there is particular notice. In addition, the physical properties of the raw material and the obtained polycarbonate in the following Examples and Comparative Examples were measured by the following method.
[135] 1) oxygen concentration
[136] The oxygen concentration in nitrogen discharged from the storage tank in which the raw materials were melted and stored was measured by an OA-1 type oxygen analyzer manufactured by Aichi Sankyo Co., Ltd.
[137] 2) temperature
[138] The temperature of the melt mixture and the heating medium was measured by a commercially available thermocouple, and the difference between them was calculated. The temperature of the heating medium is the temperature just before being introduced into the crude jacket that is melt mixed, and is the maximum temperature required to maintain the temperature of the molten mixture. The oxygen concentration and temperature were measured from the start of melting to just before the start of polymerization. In addition, the temperature of powder was measured with the thermocouple marketed normally. The oxygen concentration and temperature were measured from the start of storage to just before the start of polymerization.
[139] 3) moisture content
[140] The moisture content of 10 g of the quantified sample was measured using a fine trace moisture meter CZA-3000 manufactured by Chinosha Co., Ltd. to obtain a moisture content.
[141] 4) Viscosity Average Molecular Weight
[142] Intrinsic viscosity was measured for the 0.7 g / dl methylene chloride solution using the Uberode-type viscometer, and the viscosity average molecular weight was calculated | required by following formula (II).
[143] [η] = 1.23 x 10 ^-4 x Mw ^0.83 (II)
[144] [In the said Formula (II), [(eta)] shows intrinsic viscosity and Mw shows a viscosity average molecular weight. "
[145] 5) Hue (b value)
[146] Lab values of polycarbonate pellets (short diameter × long diameter × length (mm) = 2.5 × 3.3 × 3.0) were measured by a reflection method using ND-100lDP manufactured by Nippon Denshoku Kogyo Co., Ltd., and b value was used as a measure of yellowness. .
[147] Example 1
[148] Into a vertical batch SUS316 autoclave equipped with a rectifying tower, a stirrer and a jacket, and connected to an oxygen analyzer, 1000 parts of bisphenol A and 960 parts of diphenyl carbonate were added, and nitrogen was adjusted to 10 ppm. The heating medium of 135 degreeC was distribute | circulated to the jacket of an autoclave so that liquid temperature might be 130 degreeC, spraying at L / min, and hold for 10 hours. At this point, the oxygen analyzer read 12 ppm and the A ₀ value in the equation of the present invention was -0.541. Subsequently, 5 x 10 ^-7 equivalents of sodium phenoxide and 1 x 10 ^-4 equivalents of tetramethylammonium hydroxide are added to the metal with respect to 1 mol of bisphenol A, and the pressure is reduced for 1 hour while heating to 220 캜. It was 4.0 kPa (30 mmHg) over, and this state was continued for 1 hour, and most phenol was distilled off. Subsequently, the pressure reduction degree was 133 Pa (lmmHg) over 1 hour, heating up to 270 degreeC, and reaction was performed for 1 hour after that, and the polycarbonate of viscosity average molecular weight 15200 was obtained. The polycarbonate in the molten state was extruded from the die and pelletized by a pelletizer. The results are shown in Table 1.
[149] Example 2
[150] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected, and the heat medium at 185 ° C was passed through the mixture so as to have a liquid temperature of 180 ° C, and maintained for 10 hours. At this point, the oxygen analyzer read 11 ppm and the A ₀ value in the equation of the present invention was -0.073. The results are shown in Table 1.
[151] Example 3
[152] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected, and it carried out by the same method as Example 1 except having flowed 140 degreeC heat medium so that liquid temperature might be 130 degreeC, and maintaining for 40 hours. At this point, the oxygen analyzer read 10 ppm and the A ₀ value in the equation of the present invention was -0.465. The results are shown in Table 1.
[153] Example 4
[154] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected, and the same method as in Example 1 was carried out except that the heat medium at 170 ° C. was passed through the mixture so as to have a liquid temperature of 160 ° C. and maintained for 40 hours. At this point, the oxygen analyzer read 10 ppm and the A ₀ value in the equation of the present invention was -0.162. The results are shown in Table 1.
[155] Example 5
[156] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected, and the same method as in Example 1 was carried out except that the heat medium at 160 ° C. was circulated so as to have a liquid temperature of 130 ° C. and maintained for 10 hours. At this point, the oxygen analyzer read 10 ppm and the A ₀ value in the equation of the present invention was -0.360. The results are shown in Table 1.
[157] Example 6
[158] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected, and it carried out by the method similar to Example 1 except having passed the heat medium of 135 degreeC, and hold | maintained for 10 hours so that liquid temperature might be 130 degreeC. At this point, the oxygen analyzer read 48 ppm and the A ₀ value in the equation of the present invention was -0.433. The results are shown in Table 1.
[159] Example 7
[160] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected, and it carried out by the method similar to Example 1 except having flowed 140 degreeC heat medium so that liquid temperature might be 130 degreeC, and hold | maintained for 10 hours. At this point, the oxygen analyzer read 53 ppm and the A ₀ value in the equation of the present invention was -0.386. The results are shown in Table 1.
[161] Example 8
[162] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected, and the same procedure as in Example 1 was carried out except that the heat medium at 160 ° C. was passed through the mixture so as to have a liquid temperature of 130 ° C. and maintained for 10 hours. At this point, the oxygen analyzer read 50 ppm and the A ₀ value in the equation of the present invention was -0.235. The results are shown in Table 1.
[163] Example 9
[164] Nitrogen in which the oxygen concentration was adjusted to 100 ppm was injected, and the heating was carried out in the same manner as in Example 1 except that the heat medium at 135 ° C was passed through the mixture so as to have a liquid temperature of 130 ° C, and maintained for 10 hours. At this point, the oxygen analyzer read 108 ppm and the A ₀ value in the equation of the present invention was -0.370. The results are shown in Table 1.
[165] Example 10
[166] Nitrogen in which the oxygen concentration was adjusted to 100 ppm was injected, and the same method as in Example 1 was carried out except that the heat medium at 140 ° C was passed through the mixture so as to have a liquid temperature of 130 ° C, and maintained for 40 hours. At this point, the oxygen analyzer read 102 ppm and the A ₀ value in the equation of the present invention was -0.284. The results are shown in Table 1.
[167] Example 11
[168] Nitrogen in which the oxygen concentration was adjusted to 100 ppm was injected, and the same method as in Example 1 was carried out except that the heat medium at 160 ° C. was passed through the mixture so as to have a liquid temperature of 130 ° C. and maintained for 10 hours. At this point, the oxygen analyzer read 109 ppm and the A ₀ value in the equation of the present invention was -0.174. The results are shown in Table 1.
[169] Comparative Example 1
[170] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected, and the heating was carried out in the same manner as in Example 1 except that the heat medium at 190 ° C was passed through the mixture so as to have a liquid temperature of 180 ° C, and maintained for 40 hours. At this point, the oxygen analyzer read 11 ppm and the A ₀ value in the equation of the present invention was 0.017. The results are shown in Table 1.
[171] Comparative Example 2
[172] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected, and the heating was carried out in the same manner as in Example 1 except that the heat medium at 210 ° C. was passed through the mixture so as to have a liquid temperature of 180 ° C. and maintained for 10 hours. At this point, the oxygen analyzer read 12 ppm and the A ₀ value in the equation of the present invention was 0.128. The results are shown in Table 1.
[173] Comparative Example 3
[174] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected, and the same method as in Example 1 was carried out except that the heat medium at 185 ° C was passed through the mixture so as to have a liquid temperature of 180 ° C, and maintained for 10 hours. At this point, the oxygen analyzer read 48 ppm and the A ₀ value in the equation of the present invention was 0.041. The results are shown in Table 1.
[175] Comparative Example 4
[176] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected, and the heating was carried out in the same manner as in Example 1 except that the thermal medium at 190 ° C was passed through and maintained for 10 hours so that the liquid temperature was 180 ° C. At this point, the oxygen analyzer read 52 ppm and the A ₀ value in the equation of the present invention was 0.086. The results are shown in Table 1.
[177] Comparative Example 5
[178] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected, and the heating was carried out in the same manner as in Example 1 except that the thermal medium at 190 ° C was passed through the mixture so as to have a liquid temperature of 160 ° C, and maintained for 10 hours. At this point, the oxygen analyzer read 57 ppm and the A ₀ value in the equation of the present invention was 0.078. The results are shown in Table 1.
[179] Comparative Example 6
[180] Nitrogen in which the oxygen concentration was adjusted to 100 ppm was injected, and the same method as in Example 1 was carried out except that the heat medium at 185 ° C was passed through the mixture so as to have a liquid temperature of 180 ° C, and maintained for 10 hours. At this point, the oxygen analyzer read 112 ppm and the A ₀ value in the equation of the present invention was 0.107. The results are shown in Table 1.
[181] Comparative Example 7
[182] Nitrogen in which the oxygen concentration was adjusted to 100 ppm was injected, and the heating was carried out in the same manner as in Example 1 except that the heat medium at 170 ° C. was circulated so as to have a liquid temperature of 160 ° C. and maintained for 40 hours. At this point, the oxygen analyzer read 101 ppm and the A ₀ value in the equation of the present invention was 0.017. The results are shown in Table 1.
[183] Comparative Example 8
[184] Nitrogen in which the oxygen concentration was adjusted to 100 ppm was injected, and it carried out by the method similar to Example 1 except having flowed 180 degreeC heat medium so that liquid temperature might be 150 degreeC, and hold | maintained for 10 hours. At this point, the oxygen analyzer read 109 ppm and the A ₀ value in the equation of the present invention was 0.034. The results are shown in Table 1.
[185] Example 12
[186] 1000 parts of bisphenol A was put into the 3 L storage container made of SUS316 connected with the oxygen analyzer, and the nitrogen adjusted to the oxygen concentration of 0.1 ppm in 20 degreeC was sprayed at 2 L / min for 20 hours, stirring. This bisphenol A was referred to as reference bisphenol A. The water content of this standard bisphenol A was ND (less than 1 ppm) and the oxygen concentration was 0.1 ppm. Nitrogen which adjusted oxygen concentration to 10 ppm at 20 degreeC was stirred for 0.5 hours at 2 L / min, stirring this reference bisphenol A, and it hold | maintained again at -10 degreeC for 12 hours, stirring and adding 0.05 part of water. This bisphenol A had a water content of 48 ppm and an oxygen content of 10 ppm. The B ₁ value in the equation of the present invention at this time was -0.183. 1 000 parts of bisphenol A and 960 parts of diphenyl carbonate melted and held at 90 ° C. were placed in a vertical batch reactor equipped with a rectifying tower and a stirrer, and 5 × 10 ⁻⁷ equivalents of sodium was added as an alkali metal compound to 1 mol of bisphenol A. 1 x 10 ^-4 equivalent of tetramethylammonium hydroxide was added to the phenoxide and the nitrogen-containing basic compound, and the pressure was reduced to 4 kPa (30 mmHg) over 1 hour while heating to 220 ° C. Time continued most of the phenol was distilled off. Subsequently, the pressure reduction degree was 133 Pa (1 mmHg) over 1 hour, heating up to 270 degreeC, and reaction was performed for 1 hour after that, and the polycarbonate of viscosity average molecular weight 15200 was obtained. The polycarbonate in the molten state was diced and pelletized by a pelletizer. b value was -0.4. The results are shown in Table 2.
[187] Example 13
[188] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.05 part of water was added to maintain the solution at 10 DEG C for 12 hours. This bisphenol A had a water content of 47 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.207. The results are shown in Table 2.
[189] Example 14
[190] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.05 part of water was added thereto, followed by the same method as in Example 12 except that the mixture was maintained at 10 ° C for 120 hours. This bisphenol A had a water content of 45 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.024. The results are shown in Table 2.
[191] Example 15
[192] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.05 part of water was added to maintain the mixture at 30 ° C. for 12 hours. This bisphenol A had a water content of 45 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.232. The results are shown in Table 2.
[193] Example 16
[194] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.05 part of water was added thereto, followed by the same method as in Example 12 except that the mixture was kept at 30 ° C for 120 hours. This bisphenol A had a water content of 48 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.047. The results are shown in Table 2.
[195] Example 17
[196] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added to maintain the mixture at -10 ° C for 12 hours, in the same manner as in Example 12. This bisphenol A had a water content of 94 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.169. The results are shown in Table 2.
[197] Example 18
[198] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added and held at 10 ° C for 12 hours to carry out in the same manner as in Example 12. This bisphenol A had a water content of 97 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.192. The results are shown in Table 2.
[199] Example 19
[200] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added to maintain the solution at 10 ° C. for 120 hours to carry out in the same manner as in Example 12. This bisphenol A had a water content of 98 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.008. The results are shown in Table 2.
[201] Example 20
[202] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added and held at 30 ° C. for 12 hours to carry out in the same manner as in Example 12. This bisphenol A had a water content of 94 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.217. The results are shown in Table 2.
[203] Example 21
[204] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added to maintain the mixture at 30 ° C. for 120 hours. This bisphenol A had a water content of 93 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.033. The results are shown in Table 2.
[205] Example 22
[206] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added to maintain the resultant at -10 ° C for 12 hours. This bisphenol A had a water content of 476 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.136. The results are shown in Table 2.
[207] Example 23
[208] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added thereto, followed by the same method as in Example 12 except that the mixture was kept at 10 ° C for 12 hours. This bisphenol A had a water content of 483 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.159. The results are shown in Table 2.
[209] Example 24
[210] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added thereto, followed by the same method as in Example 12 except that the mixture was kept at 30 ° C for 12 hours. This bisphenol A had a water content of 491 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.183. The results are shown in Table 2.
[211] Example 25
[212] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.01 part of water was added thereto, followed by the same method as in Example 12, except that the mixture was kept at -10 ° C for 12 hours. This bisphenol A had a water content of 8 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.128. The results are shown in Table 2.
[213] Example 26
[214] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.01 part of water was added to maintain the mixture at 30 ° C. for 12 hours. This bisphenol A had a water content of 8 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.176. The results are shown in Table 2.
[215] Example 27
[216] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.05 part of water was added to carry out in the same manner as in Example 12 except that the mixture was kept at -10 ° C for 12 hours. This bisphenol A had a water content of 44 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.093. The results are shown in Table 2.
[217] Example 28
[218] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.05 part of water was added thereto, followed by the same method as in Example 12 except that the mixture was kept at 30 ° C for 12 hours. This bisphenol A had a water content of 48 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.139. The results are shown in Table 2.
[219] Example 29
[220] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added thereto, followed by the same method as in Example 12, except that the mixture was kept at -10 ° C for 12 hours. This bisphenol A had a water content of 95 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.077. The results are shown in Table 2.
[221] Example 30
[222] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added and held at 30 ° C. for 12 hours to carry out in the same manner as in Example 12. This bisphenol A had a water content of 92 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.126 The results are shown in Table 2.
[223] Example 31
[224] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added thereto, followed by the same method as in Example 12 except that the mixture was kept at -10 ° C for 12 hours. This bisphenol A had a water content of 471 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.044. The results are shown in Table 2.
[225] Example 32
[226] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added to maintain the mixture at 30 ° C. for 12 hours. This bisphenol A had a water content of 474 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.092. The results are shown in Table 2.
[227] Example 33
[228] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.01 part of water was added thereto, followed by the same method as in Example 12, except that the mixture was kept at -10 ° C for 12 hours. This bisphenol A had a water content of 8 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.049. The results are shown in Table 2.
[229] Example 34
[230] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.01 part of water was added to maintain the mixture at 30 ° C. for 12 hours. This bisphenol A had a water content of 7 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.099. The results are shown in Table 2.
[231] Example 35
[232] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.05 part of water was added thereto, followed by the same method as in Example 12, except that the mixture was kept at -10 ° C for 12 hours. This bisphenol A had a water content of 42 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.015. The results are shown in Table 2.
[233] Example 36
[234] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.05 part of water was added to maintain the mixture at 30 ° C. for 12 hours. This bisphenol A had a water content of 46 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.061. The results are shown in Table 2.
[235] Example 37
[236] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added and held at 10 ° C for 12 hours to carry out in the same manner as in Example 12. This bisphenol A had a water content of 93 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.023. The results are shown in Table 2.
[237] Example 38
[238] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added thereto, followed by the same method as in Example 12, except that the mixture was kept at 30 ° C for 12 hours. This bisphenol A had a water content of 97 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.046. The results are shown in Table 2.
[239] Example 39
[240] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added thereto, followed by the same method as in Example 12 except that the mixture was kept at 30 ° C for 12 hours. This bisphenol A had a water content of 465 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to -0.014. The results are shown in Table 2.
[241] Example 40
[242] Nitrogen adjusted to an oxygen concentration of 0.1 l ppm at 20 ° C. was sprayed at 2 L / min for 20 hours while stirring and putting 1000 parts of bisphenol A into a 3L storage container made of SUS316 connected to an oxygen analyzer. . This bispetol A was referred to as reference bispetol A. The moisture of this reference bispetol A was ND (less than 1 ppm) and the oxygen concentration was 0.1 ppm. The nitrogen which adjusted the oxygen concentration to 10 ppm was sprayed at 2 L / min for 0.5 hour at 20 degreeC, stirring this reference bispetol A, and it hold | maintained again at 10 degreeC for 12 hours, adding and stirring 0.05 part of water. . This bispetol A had a water content of 47 ppm and an oxygen content of 10 ppm. The value of B ₁ in the equation of the present invention at this point was equivalent to -0.207. 1000 parts of diphenyl carbonate was put into the same storage container, and the nitrogen adjusted to the oxygen concentration of 0.1 ppm in 20 degreeC was sprayed at 2 L / min for 20 hours. This diphenyl carbonate was used as reference diphenyl carbonate. The moisture of this reference diphenyl carbonate was ND (less than 1 ppm), and the oxygen concentration was 0.1 ppm. While stirring this reference diphenyl carbonate, the nitrogen which adjusted the oxygen concentration to 10 ppm was sprayed at 2 L / min for 0.5 hours at 20 degreeC, and it hold | maintained again at -10 degreeC for 12 hours, stirring and adding 0.05 part of water. . This diphenyl carbonate had a water content of 44 ppm and an oxygen content of 10 ppm. The value of B ₂ in the equation of the present invention at this point was equivalent to -0.184.
[243] 1 000 parts of bisphenol A and 960 parts of diphenyl carbonate were placed in a vertical batch reactor equipped with a rectifying tower and a stirrer, and 5 × 10 ^-7 equivalents of sodium phenoxide and 1 × 10 ^- of basic nitrogen as the metal per mole of bisphenol A. ⁴ equivalents of tetramethylammonium hydroxide were added, the pressure reduction degree was made into 4 kPa (30 mmHg) over 1 hour, heating to 220 degreeC, and this state was continued for 1 hour, and most phenols were distilled off. Subsequently, while raising the temperature to 270 ° C, the pressure was reduced to 133 Pa (lmmHg) over 1 hour, and then, the reaction was carried out for 1 hour to obtain a polycarbonate having a viscosity average molecular weight of 15200. The polycarbonate in the molten state was diced and pelletized by a pelletizer. Table 2 shows the storage conditions and results of bisphenol A.
[244] Comparative Example 9
[245] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added to maintain the mixture at −10 ° C. for 120 hours. This bisphenol A had a water content of 49 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.001. The results are shown in Table 2.
[246] Comparative Example 10
[247] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added to maintain the mixture at −10 ° C. for 120 hours. This bisphenol A had a water content of 95 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.015. The results are shown in Table 2.
[248] Comparative Example 11
[249] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added to maintain the resultant at −10 ° C. for 96 hours, in the same manner as in Example 12. This bisphenol A had a water content of 470 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.007. The results are shown in Table 2.
[250] Comparative Example 12
[251] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added to maintain the solution at 10 ° C. for 108 hours. This bisphenol A had a water content of 489 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.004. The results are shown in Table 2.
[252] Comparative Example 13
[253] Nitrogen in which the oxygen concentration was adjusted to 10 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added thereto, followed by the same method as in Example 12 except that the mixture was maintained at 30 ° C for 132 hours. This bisphenol A had a water content of 499 ppm and an oxygen content of 10 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.021. The results are shown in Table 2.
[254] Comparative Example 14
[255] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.01 parts of water were added to maintain the resultant at −10 ° C. for 96 hours, in the same manner as in Example 12. This bisphenol A had a water content of 7 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.012. The results are shown in Table 2.
[256] Comparative Example 15
[257] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.01 parts of water were added to maintain the mixture at 30 ° C. for 120 hours. This bisphenol A had a water content of 9 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.010. The results are shown in Table 2.
[258] Comparative Example 16
[259] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.05 part of water was added to maintain the result at -10 ° C for 72 hours, in the same manner as in Example 12. This bisphenol A had a water content of 48 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.011. The results are shown in Table 2.
[260] Comparative Example 17
[261] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and was carried out in the same manner as in Example 12 except that 0.05 parts of water was added and maintained at 30 ° C for 96 hours. This bisphenol A had a water content of 46 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.003. The results are shown in Table 2.
[262] Comparative Example 18
[263] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added thereto, followed by the same method as in Example 12, except that the mixture was maintained at -10 ° C for 60 hours. This bisphenol A had a water content of 95 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.005. The results are shown in Table 2.
[264] Comparative Example 19
[265] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added thereto and maintained at 30 ° C. for 96 hours. This bisphenol A had a water content of 91 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.017. The results are shown in Table 2.
[266] Comparative Example 20
[267] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added thereto, followed by the same method as in Example 12 except that the mixture was maintained at -10 ° C for 48 hours. This bisphenol A had a water content of 490 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.018. The results are shown in Table 2.
[268] Comparative Example 21
[269] Nitrogen in which the oxygen concentration was adjusted to 50 ppm was injected into the standard bisphenol A, and 0.50 parts of water was added to maintain the mixture at 30 ° C. for 72 hours. This bisphenol A had a water content of 499 ppm and an oxygen content of 50 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.011. The results are shown in Table 2.
[270] Comparative Example 22
[271] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.01 parts of water were added to maintain the result at -10 ° C for 48 hours, in the same manner as in Example 12. This bisphenol A had a water content of 7 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.010. The results are shown in Table 2.
[272] Comparative Example 23
[273] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.01 parts of water were added to maintain the mixture at 30 ° C. for 72 hours. This bisphenol A had a water content of 9 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.008. The results are shown in Table 2.
[274] Comparative Example 24
[275] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.05 part of water was added to maintain the solution at -10 ° C for 24 hours, in the same manner as in Example 12. This bisphenol A had a water content of 48 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.008. The results are shown in Table 2.
[276] Comparative Example 25
[277] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.05 part of water was added to maintain the mixture at 30 ° C. for 48 hours. This bisphenol A had a water content of 49 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.001. The results are shown in Table 2.
[278] Comparative Example 26
[279] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added to maintain the solution at 10 ° C. for 36 hours. This bisphenol A had a water content of 95 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.019. The results are shown in Table 2.
[280] Comparative Example 27
[281] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 0.10 parts of water was added thereto and maintained in the same manner as in Example 12 except that the mixture was maintained at 30 ° C for 48 hours. This bisphenol A had a water content of 91 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.014. The results are shown in Table 2.
[282] Comparative Example 28
[283] Nitrogen in which the oxygen concentration was adjusted to 200 ppm was injected into the standard bisphenol A, and 50 parts of water were added to maintain the solution at 30 ° C. for 24 hours. This bisphenol A had a water content of 480 ppm and an oxygen content of 200 ppm. B ₁ value in the equation of the present invention at this point was equivalent to 0.007. The results are shown in Table 2.
[284] Example 41
[285] 960 parts of diphenyl carbonate was put into the vertical type SUS316 autoclave equipped with the rectifier tower, the stirrer, and the jacket, and connected to the oxygen analyzer, and the nitrogen whose oxygen concentration was adjusted to 10 ppm was injected at 2 L / min. The heat medium of 130 degreeC was distribute | circulated to the jacket of an autoclave so that the liquid temperature of diphenyl carbonate might be 120 degreeC, and it hold | maintained for 100 hours. At this point, the oxygen analyzer read 12 ppm and the A ₁ value in the equation of the present invention was -0.818. Subsequently, 1000 parts of bisphenol A, 5 × 10 ^-7 equivalents of sodium phenoxide as a metal per mol of bisphenol A and 1 × 10 ^-4 equivalents of tetramethylammonium hydroxide were added with basic nitrogen, and heated to 220 ° C. Was 4.0 kPa (30 mmHg) over 1 hour, and this state was continued for 1 hour, and most phenol was distilled off. Subsequently, while raising the temperature to 270 ° C, the pressure was reduced to 133 Pa (lmmHg) over 1 hour, and then, the reaction was carried out for 1 hour to obtain a polycarbonate having a viscosity average molecular weight of 15200. The polycarbonate in the molten state was diced and pelletized by a pelletizer. The results are shown in Table 3.
[286] Comparative Example 29
[287] A heat medium of 230 ° C. was added to a liquid batch of diphenyl carbonate so that the liquid temperature of diphenyl carbonate was 220 ° C. while 960 parts of diphenyl carbonate was injected into a vertical batch of SUS316 autoclave and nitrogen was adjusted to an oxygen concentration of 10 ppm. It was distributed to the jacket of the autoclave and maintained for 100 hours. At this point, the oxygen analyzer read 12 ppm and the A ₁ value in the equation of the present invention was 0.064. A polycarbonate was obtained by polymerization in the same manner as in Example 41 except this. The results are shown in Table 3.
[288] Example 42
[289] 1000 parts of bisphenol A was put into the storage container made from SUS316 connected with the oxygen analyzer, and the nitrogen which adjusted to 0.1 ppm of oxygen at 20 degreeC was purged at 2 L / min for 20 hours. This bisphenol A was referred to as reference bisphenol A. The water content of this standard bisphenol A was ND (less than 1 ppm), and the oxygen concentration was 0.1 ppm. Nitrogen adjusted to an oxygen concentration of 10 ppm at 20 ° C was purged at 2 L / min for 0.5 hour while stirring the standard bisphenol A, and 0.05 part of water was added thereto, followed by stirring at 30 ° C for 12 hours. This bisphenol A had a water content of 45 ppm and an oxygen content of 10 ppm. The value of B ₁ in the equation of the present invention at this point was equivalent to -0.232. 960 parts of this bisphenol A and diphenyl carbonate were placed in a vertical batch reactor equipped with a rectifying column and a stirrer, and nitrogen was adjusted to adjust the oxygen concentration to 10 ppm, and the heat medium at 135 ° C. was heated so that the liquid temperature of the mixture was 130 ° C. Circulation was maintained for 10 hours. At this point, the oxygen analyzer read 12 ppm and the A ₀ value in the equation of the present invention was -0.541. A polycarbonate was obtained by polymerization in the same manner as in Example 41 except this. The results are shown in Table 3.
[290] Example 43
[291] 1000 parts of bisphenol A was put into the storage container made from SUS316 connected with the oxygen analyzer, and it stirred, and the nitrogen adjusted to 0.1 ppm of oxygen at 20 degreeC was purged at 2 L / min for 20 hours. This bisphenol A was referred to as reference bisphenol A. The water content of this standard bisphenol A was ND (less than 1 ppm), and the oxygen concentration was 0.1 ppm. The nitrogen which adjusted the oxygen concentration to 10 ppm was purged at 2 L / min for 0.5 hours at 20 degreeC, stirring this reference bisphenol A, and it hold | maintained at 30 degreeC for 12 hours, stirring and adding 0.05 part of water. This bisphenol A had a water content of 45 ppm and an oxygen content of 10 ppm. The value of B ₁ in the equation of the present invention at this point was equivalent to -0.232. 960 parts of bisphenol A and diphenyl carbonate were placed in a vertical batch reactor equipped with a rectifying tower and a stirrer, and nitrogen was adjusted at an oxygen concentration of 100 ppm, and a 160 ° C. heat medium was circulated so that the liquid temperature was 130 ° C. Hold for 10 hours. At this point, the oxygen analyzer read 109 ppm and the A ₀ value in the equation of the present invention was -0.174. A polycarbonate was obtained by polymerization in the same manner as in Example 41 except this. The results are shown in Table 3.
[292] Example 44
[293] 960 parts of diphenyl carbonate was put into the vertical batch type SUS316 autoclave equipped with a rectification tower, a stirrer, and a jacket, and injected with 2 L / min of nitrogen which adjusted the oxygen concentration to 10 ppm. The heat medium of 130 degreeC was distribute | circulated to the jacket of an autoclave so that the liquid temperature of diphenyl carbonate might be 120 degreeC, and it hold | maintained for 100 hours. At this point, the oxygen analyzer read 12 ppm and the A ₁ value in the equation of the present invention was -0.818. Subsequently, 1000 parts of bisphenol A were added, nitrogen which adjusted the oxygen concentration to 10 ppm was injected, and the heat medium of 135 degreeC was circulated and hold | maintained for 10 hours so that liquid temperature might be 130 degreeC. At this point, the oxygen analyzer read 12 ppm and the A ₁ value in the equation of the present invention was -0.541. A polycarbonate was obtained by polymerization in the same manner as in Example 41 except this. The results are shown in Table 3.
[294] Example 45
[295] 960 parts of diphenyl carbonate was put into a vertical batch SUS316 autoclave equipped with a rectifying tower, a stirrer and a jacket, and connected to an oxygen analyzer. The heat medium of 130 degreeC was distribute | circulated to the jacket of an autoclave so that the liquid temperature of phenyl carbonate might be 120 degreeC, and it hold | maintained for 100 hours. At this point, the oxygen analyzer read 12 ppm and the A ₁ value in the equation of the present invention was -0.818. Subsequently, 1000 parts of bisphenol A were added, nitrogen which adjusted the oxygen concentration to 100 ppm was injected, and 160 degreeC heat medium was distribute | circulated and hold | maintained for 10 hours so that liquid temperature might be 130 degreeC. At this point, the oxygen analyzer read 109 ppm and the A ₀ value in the equation of the present invention was -0.174. A polycarbonate was obtained by polymerization in the same manner as in Example 41 except this. The results are shown in Table 3.
[296] Example 46
[297] 960 parts of diphenyl carbonate was put into the storage container made from SUS316 connected with the oxygen analyzer, and the nitrogen which was adjusted to 0.1 ppm of oxygen at 20 degreeC was purged at 2 L / min for 20 hours. This diphenyl carbonate was used as reference diphenyl carbonate. The moisture of this reference diphenyl carbonate was ND (less than 1 ppm), and the oxygen concentration was 0.1 ppm. The nitrogen which adjusted the oxygen concentration to 10 ppm was purged at 2 L / min for 0.5 hour at 20 degreeC, stirring this reference diphenyl carbonate, and it hold | maintained at -10 degreeC for 12 hours, adding 0.05 part of water and stirring. This diphenyl carbonate had a water content of 44 ppm and an oxygen content of 10 ppm. The value of B ₂ in the equation of the present invention at this point was equivalent to -0.184. 1000 parts of diphenyl carbonate and bisphenol A were placed in a vertical batch reactor equipped with a rectifying tower and a stirrer, and nitrogen was adjusted at an oxygen concentration of 10 ppm, and the thermal medium at 135 ° C. was passed through so that the liquid temperature was 130 ° C. Hold for 10 hours. At this point, the oxygen analyzer read 12 ppm and the A ₀ value in the equation of the present invention was -0.541. A polycarbonate was obtained by polymerization in the same manner as in Example 41 except this. The results are shown in Table 3.
[298] Example 47
[299] 960 parts of diphenyl carbonate was put into the storage container made from SUS316 connected with the oxygen analyzer, and the nitrogen which was adjusted to 0.1 ppm of oxygen at 20 degreeC was purged at 2 L / min for 20 hours. This diphenyl carbonate was used as reference diphenyl carbonate. The moisture of this reference diphenyl carbonate was ND (less than 1 ppm), and the oxygen concentration was 0.1 ppm. Nitrogen adjusted to an oxygen concentration of 10 ppm at 20 ° C was purged at 2 L / min for 0.5 hours while stirring the standard diphenyl carbonate, and 0.05 parts of water was added and kept at -10 ° C for 12 hours while stirring. This diphenyl carbonate had a water content of 44 ppm and an oxygen content of 10 ppm. The value of B ₂ in the equation of the present invention at this point was equivalent to -0.184. 1,000 parts of diphenyl carbonate and bisphenol A were placed in a vertical batch reactor equipped with a rectifying tower and a stirrer, and nitrogen was adjusted at an oxygen concentration of 100 ppm, and a 160 ° C. heat medium was passed through so that the liquid temperature was 130 ° C. Hold for 10 hours. At this point, the oxygen analyzer read 109 ppm and the A ₀ value in the equation of the present invention was -0.174. A polycarbonate was obtained by polymerization in the same manner as in Example 41 except this. The results are shown in Table 3.
[300] Example 48
[301] 960 parts of diphenyl carbonate was put into the vertical batch type SUS316 autoclave equipped with a rectification tower, a stirrer, and a jacket, and injected with 2 L / min of nitrogen which adjusted the oxygen concentration to 10 ppm. The heat medium of 130 degreeC was distribute | circulated to the jacket of an autoclave so that the liquid temperature of diphenyl carbonate might be 120 degreeC, and it hold | maintained for 100 hours. At this point, the oxygen analyzer read 12 ppm and the A ₁ value in the equation of the present invention was -0.818.
[302] Furthermore, 1000 parts of bisphenol A was put into the SUS316 storage container connected with the oxygen analyzer, and the nitrogen which was adjusted to 0.1 ppm of oxygen at 20 degreeC was purged at 2 L / min for 20 hours. This bisphenol A was referred to as reference bisphenol A. The water content of this standard bisphenol A was ND (less than 1 ppm), and the oxygen concentration was 0.1 ppm. The nitrogen which adjusted the oxygen concentration to 10 ppm was purged at 2 L / min for 0.5 hours at 20 degreeC, stirring this reference bisphenol A, and it hold | maintained at 30 degreeC for 12 hours, stirring and adding 0.05 part of water. This bisphenol A had a water content of 45 ppm and an oxygen content of 10 ppm. The value of B ₁ in the equation of the present invention at this point was equivalent to -0.232. The polycarbonate was obtained by superposing | polymerizing in the same method as Example 41 using the diphenyl carbonate and bisphenol A adjusted above. The results are shown in Table 3.
[303] Example 49
[304] 960 parts of diphenyl carbonate was put into a vertical batch SUS316 autoclave equipped with a rectifying tower, a stirrer and a jacket and connected to an oxygen analyzer, and injected with 2 L / min of nitrogen having an oxygen concentration adjusted to l0 ppm. The heat medium of 130 degreeC was distribute | circulated to the jacket of an autoclave so that the liquid temperature of diphenyl carbonate might be 120 degreeC, and it hold | maintained for 100 hours. At this point, the oxygen analyzer read 12 ppm and the A ₁ value in the equation of the present invention was -0.818.
[305] Furthermore, 1000 parts of bisphenol As were put into the SUS316 storage container connected with the oxygen analyzer and stirred, and the nitrogen adjusted to 0.1 ppm of oxygen at 20 degreeC was purged at 2 L / min for 20 hours. This bisphenol A was referred to as reference bisphenol A. The water content of this standard bisphenol A was ND (less than 1 ppm), and the oxygen concentration was 0.1 ppm. The nitrogen which adjusted the oxygen concentration to 200 ppm was purged at 2 L / min for 0.5 hours at 20 degreeC, stirring this reference bisphenol A, and it hold | maintained at 30 degreeC for 12 hours, adding 0.5 part of water and stirring. This bisphenol A had a water content of 465 ppm and an oxygen content of 200 ppm. The value of B ₁ in the equation of the present invention at this point was equivalent to -0.014. The polycarbonate was obtained by superposing | polymerizing in the same method as Example 41 using the diphenyl carbonate and bisphenol A adjusted above. The results are shown in Table 3.
[306]
[307]
[308]
[309]
[310]

权利要求:
Claims (24)
[1" claim-type="Currently amended] Aromatic dihydride, characterized in that the mixture consisting essentially of the aromatic dihydroxy compound and diester carbonate is kept in a molten state under the condition that the melt storage parameter (A ₀ ) defined by the following formula (1) becomes 0 or less. Preservation method of a mixture of oxy compound and diester carbonate:
_{A 0 = -7.88 + 0.179 × logC} 0 +3.354 × logT 0 +0.0078 × U 0 + 0.0017τ 0 ... (One)
Where C ₀ is the oxygen concentration (ppm) of the atmosphere in the reservoir, T ₀ is the temperature of the melt mixture in the reservoir (° C.), and U ₀ is the temperature difference (° C.) between the temperature of the heating medium of the reservoir and the temperature of the melt mixture And τ ₀ is the average residence time (hr) of the molten mixture in the reservoir).
[2" claim-type="Currently amended] The method according to claim 1, wherein the mixture substantially free of the transesterification catalyst of the aromatic dihydroxy compound and the diester carbonate is the mixture.
[3" claim-type="Currently amended] The method of claim 1 wherein the aromatic dihydroxy compound is 2,2-bis (4-hydroxyphenyl) propane.
[4" claim-type="Currently amended] The method of claim 1 wherein the diester carbonate is diphenyl carbonate.
[5" claim-type="Currently amended] The method according to claim 1, wherein the mixture containing the aromatic dihydroxy compound and the diester carbonate in a ratio of 1.0 to 1.2 moles of diester carbonate per mole of the aromatic dihydroxy compound is the mixture.
[6" claim-type="Currently amended] The method according to claim 1, wherein the mixture is kept in a molten state at a temperature higher than the temperature at which the crystals are precipitated at a lower temperature and lower than 300 ° C.
[7" claim-type="Currently amended] The method of claim 1 wherein the melt retention parameter (Ao) is between -0.6 and -0.001.
[8" claim-type="Currently amended] The method of claim 1 wherein the retention time is greater than two hours.
[9" claim-type="Currently amended] Preservation of the carbonic acid diester, characterized in that for holding the carbonic acid diester, under the following formula (2) conditions that are less than or equal to zero melt keeping parameter (A ₁₎ defined by the molten state:
A ₁ = -8.08 + 0.145 x log C ₁ +3.35 x log T ₁ +0.007 x U ₁ +0.0007 τ ₁ . (2)
Where C ₁ is the oxygen concentration (ppm) of the atmosphere in the reservoir, T ₁ is the temperature of the diester carbonate (° C.), and U ₁ is the temperature difference between the temperature of the heating medium of the reservoir and the diester carbonate ( Τ) and τ ₁ is the average residence time (hr) of diester carbonate in the reservoir).
[10" claim-type="Currently amended] 10. The process of claim 9 wherein the diester carbonate is diphenyl carbonate.
[11" claim-type="Currently amended] 10. The method of claim 9, wherein the melt keeping parameter (A _l) is -1.6 ~ -0.001.
[12" claim-type="Currently amended] A method for preserving an aromatic dihydroxy compound, wherein the aromatic dihydroxy compound is kept in a powder state under the condition that the powder storage parameter (B ₁ ) defined by the following formula (4) becomes 0 or less:
B ₁ = -0.425 + 0.131 × log C ₂ +0.047 × log M ₁ -0.0012 × T ₂ +0.0017 τ ₂ . (4)
Where C ₂ is the oxygen concentration (ppm) of the atmosphere in the reservoir, M ₁ is the moisture content (ppm) of the aromatic dihydroxy compound in the reservoir, and T ₂ is the temperature (° C.) of the aromatic dihydroxy compound in the reservoir. And τ ₂ is the average residence time (hr) of the aromatic dihydroxy compound in the reservoir).
[13" claim-type="Currently amended] 13. The method of claim 12, wherein the aromatic dihydroxy compound is 2,2-bis (4-hydroxyphenyl) propane.
[14" claim-type="Currently amended] The method according to claim 12, wherein the powder storage parameter (B _l ) is -0.7 to -0.0001.
[15" claim-type="Currently amended] Preservation of the carbonic acid diester, characterized in that for holding in powder form the carbonic acid diester, under the following formula (3) conditions that are less than or equal to zero the powder keeping parameter (B ₂₎ which is defined as:
_{B 2 = -0.425 + 0.131 × logC} 3 +0.047 × logM 2 -0.0012T 3 +0.0017 × τ 3 ... (3)
Where C ₃ is the oxygen concentration (ppm) of the atmosphere in the reservoir, M ₂ is the moisture content (ppm) of the diester carbonate in the reservoir, T ₃ is the temperature of the diester carbonate in the reservoir (° C) and τ ₃ is Average residence time (hr) of diester carbonate in the reservoir).
[16" claim-type="Currently amended] A process according to claim 15 wherein the diester carbonate is diphenyl carbonate.
[17" claim-type="Currently amended] The method according to claim 15, wherein the powder storage parameter (B ₂ ) is -0.7 to -0.0001.
[18" claim-type="Currently amended] The method according to claim 1, wherein, as the aromatic dihydroxy compound, an aromatic dihydroxy compound preserved by the storage method according to claim 12 is used.
[19" claim-type="Currently amended] The method according to claim 1, wherein as diester carbonate, diester carbonate stored by the storage method according to claim 9 is used.
[20" claim-type="Currently amended] The method according to claim 1, wherein as diester carbonate, diester carbonate stored by the storage method according to claim 15 is used.
[21" claim-type="Currently amended] A catalyst comprising a nitrogen-containing basic compound and at least one compound selected from the group consisting of an alkali metal compound and an alkaline earth metal compound, wherein the molten mixture of the aromatic dihydroxy compound and diester carbonate stored by the storage method of claim 1 is selected from the group consisting of alkali metal compounds and alkaline earth metal compounds. Process for producing an aromatic polycarbonate, characterized in that the transesterification in the presence.
[22" claim-type="Currently amended] The aromatic dihydroxy compound and diester carbonate which were preserve | saved by the preservation method of Claim 12 are ester in presence of the catalyst which consists of a nitrogen-containing basic compound and 1 or more types of compounds chosen from the group which consists of an alkali metal compound and an alkaline earth metal compound. A method for producing an aromatic polycarbonate, characterized in that the exchange reaction.
[23" claim-type="Currently amended] 23. The method according to claim 22, wherein as the diester carbonate, a diester carbonate stored by the storage method according to claim 9 is used.
[24" claim-type="Currently amended] The method according to claim 22, wherein as the diester carbonate, a diester carbonate stored by the storage method according to claim 15 is used.

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同族专利:

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公开号 | 公开日

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EP1243607A1|2002-09-25|

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KR20070042210A|2007-04-20|

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WO2002006374A1|2002-01-24|

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KR100760489B1|2007-10-04|

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JP5066320B2|2012-11-07|

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TW527375B|2003-04-11|

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EP1243607A4|2003-05-02|

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KR100740069B1|2007-07-16|

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US20020183477A1|2002-12-05|

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CN1392884A|2003-01-22|

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US6605686B2|2003-08-12|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-07-18|Priority to JP2000217436

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2000-07-18|Priority to JPJP-P-2000-00217436

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2000-07-24|Priority to JPJP-P-2000-00221983

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2000-07-24|Priority to JP2000221983

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2001-07-13|Application filed by 야스이 쇼사꾸, 데이진 가부시키가이샤

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2002-05-30|Publication of KR20020040806A

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2007-10-04|Application granted

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2007-10-04|Publication of KR100760489B1

优先权:

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申请号 | 申请日 | 专利标题

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JP2000217436|2000-07-18|

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JPJP-P-2000-00217436|2000-07-18|

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JPJP-P-2000-00221983|2000-07-24|

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JP2000221983|2000-07-24|