JP4621591B2 - Nigrosine dye and method for producing the same - Google Patents
Nigrosine dye and method for producing the same Download PDFInfo
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- JP4621591B2 JP4621591B2 JP2005513461A JP2005513461A JP4621591B2 JP 4621591 B2 JP4621591 B2 JP 4621591B2 JP 2005513461 A JP2005513461 A JP 2005513461A JP 2005513461 A JP2005513461 A JP 2005513461A JP 4621591 B2 JP4621591 B2 JP 4621591B2
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- nigrosine dye
- nigrosine
- dye according
- aniline
- acid
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- 238000004519 manufacturing process Methods 0.000 title claims description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 151
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 235000011054 acetic acid Nutrition 0.000 claims description 8
- 230000002269 spontaneous effect Effects 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 239000011964 heteropoly acid Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000010998 test method Methods 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 3
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims description 3
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 230000020169 heat generation Effects 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- 239000000975 dye Substances 0.000 description 54
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- -1 aromatic carboxylic acids Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B59/00—Artificial dyes of unknown constitution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring (AREA)
Description
本発明は、非自然発火性のニグロシン染料及びその製造方法に関するものである。 The present invention relates to a non-pyrophoric nigrosine dye and a method for producing the same.
1867年、Coupierはアニリンに塩酸と鉄(Fe)または塩化鉄(FeCl2)の存在下でニトロベンゼンを作用させることによりニグロシンを得た。その後、この方法を基本として様々な改良が施されてきた(特許文献1乃至5)。In 1867, Cupier obtained nigrosine by reacting aniline with nitrobenzene in the presence of hydrochloric acid and iron (Fe) or iron chloride (FeCl 2 ). Since then, various improvements have been made based on this method (Patent Documents 1 to 5).
このような合成方法の改良にも拘わらず、得られたニグロシン染料には、自然発火し易い、すなわち貯蔵中や輸送の途中で自然発火が生じ易いという危険性が存在していた。 Despite such improvements in the synthesis method, the obtained nigrosine dye has a risk of spontaneous ignition, that is, spontaneous ignition occurs during storage or transportation.
この自然発火性を抑制する方法として、自然発火性のあるニグロシン塩基を、アニリン中で、酸素を含むガスと接触させるという技術が特許文献6(特許文献7)開示されている。しかし、特許文献6(特許文献7)に開示された方法によって得られたニグロシン染料も非自然発火性への変換は全く不十分であることが分かった。
本発明は、従来技術に存した上記のような課題に鑑み行われたものであって、その目的とするところは、非自然発火性のニグロシン染料およびその製造方法を提供することにある。 The present invention has been made in view of the above problems existing in the prior art, and an object thereof is to provide a non-pyrophoric nigrosine dye and a method for producing the same.
本発明者等は非自然発火性ニグロシンを得るべく鋭意検討した結果、ガスクロマトグラフ法によって測定されるニグロシン中のアニリン量と自然発火性との間に明確な関連のあることを見出した。 As a result of intensive studies to obtain non-pyrophoric nigrosine, the present inventors have found that there is a clear relationship between the amount of aniline in nigrosine measured by gas chromatography and the spontaneous ignition.
ニグロシンは、通常、アニリンを夾雑物として含有している。本発明者等は、ニグロシン中のアニリン量をガスクロマトグラフ法(以下、「GC法」とも言う。)により定量した場合におけるガスクロマトグラフ装置の試料導入部温度と測定されるアニリン含量との関係に着目した。試料導入部温度が特定温度以下である場合、試料導入部温度とニグロシン中のアニリン含有量定量値に実質的な変化は認められず、夾雑物として存在しているアニリン(以下、「夾雑物アニリン」と言う。)がほぼそのまま定量される。 Nigrosine usually contains aniline as a contaminant. The inventors pay attention to the relationship between the temperature of the sample introduction part of the gas chromatograph and the measured aniline content when the amount of aniline in nigrosine is quantified by gas chromatography (hereinafter also referred to as “GC method”). did. When the sample introduction part temperature is below a specific temperature, there is no substantial change between the sample introduction part temperature and the quantitative value of the aniline content in nigrosine, and aniline existing as a contaminant (hereinafter, “contamination aniline”). ")" Is almost quantified as it is.
ところが試料導入部温度が前記特定温度を超えると、温度が高くなるに伴いニグロシン中のアニリン含有量定量値が徐々に増加する。これは、ニグロシン構造の一部が分解して遊離するアニリン(以下「遊離アニリン」と言う。)が生じるためであると考えられ、この遊離アニリン量の多/少がニグロシンの自然発火性の高/低に関連しているものと認められる。試料導入部温度を、前記特定温度を上回る温度であって、十分な量の遊離アニリンが生じる適切な温度に設定し、測定アニリン量から夾雑物アニリン量を差し引けば、遊離アニリン量の多/少が算出される。 However, when the sample introduction part temperature exceeds the specific temperature, the quantitative value of the aniline content in nigrosine gradually increases as the temperature increases. This is considered to be due to the generation of aniline that is liberated by decomposition of a part of the nigrosine structure (hereinafter referred to as “free aniline”). The amount of this free aniline is high / low in the pyrophoric nature of nigrosine. / Perceived to be related to low. If the sample introduction part temperature is set to an appropriate temperature at which a sufficient amount of free aniline is generated, which is higher than the specific temperature, and the amount of impurities aniline is subtracted from the measured aniline amount, the amount of free aniline / Small is calculated.
ガラス製試料導入部を備えたガスクロマトグラフ装置により、前記試料導入部温度を200℃として測定したアニリン含有量(夾雑物アニリンの含有量に対応)をA重量%、前記試料導入部温度を260℃として測定したアニリン含有量(夾雑物アニリンと遊離アニリンの合計含有量に対応)をB重量%とした場合に、B−Aの値(遊離アニリンの含有量に対応)が小さくなるにつれて自然発火性が低下し、B−A≦0.04重量%であるニグロシン染料は非自然発火性となる。従来のニグロシン染料に、B−A≦0.04重量%のものは見当たらない。 The aniline content (corresponding to the content of impurities aniline) measured by a gas chromatograph apparatus equipped with a glass sample introduction part at a sample introduction part temperature of 200 ° C. was A wt%, and the sample introduction part temperature was 260 ° C. As the B-A value (corresponding to the content of free aniline) becomes smaller when the aniline content (corresponding to the total content of impurities aniline and free aniline) is B wt%, , And a nigrosine dye having B-A ≦ 0.04% by weight becomes non-pyrophoric. There are no conventional nigrosine dyes with B-A ≦ 0.04% by weight.
すなわち本発明のニグロシン染料は、ガラス製試料導入部を備えたガスクロマトグラフ装置により、前記試料導入部温度を200℃として測定したアニリン含有量をA重量%、前記試料導入部温度を260℃として測定したアニリン含有量をB重量%とした場合に、B−A≦0.04重量%であることを特徴とする。 That is, the nigrosine dye of the present invention was measured with a gas chromatograph apparatus equipped with a glass sample introduction part, with the aniline content measured at 200 ° C. and the sample introduction part temperature at 260 ° C. When the aniline content is B wt%, B−A ≦ 0.04 wt%.
ニグロシン染料における自然発火性の判定は、所定の国連勧告に従って行うことができる。上記本発明のニグロシン染料は、国連勧告「危険物の輸送についての勧告−試験及び基準マニュアル−改訂第3版(クラス4,自己発熱性物質のための試験方法」[Recommendations on the TRANSPORT OF DANGEROUSGOODS−Manual of Tests and Criteria−Third revised edition(Class4,Test method for self−heating substances)]に従って、1辺10cmの立方体容器に収容し、140℃の温度を維持する試験において、24時間以内に自然発火及び200℃以上の発熱の何れもが生じないものである。 The determination of pyrophoric properties in nigrosine dyes can be made according to predetermined UN recommendations. The nigrosine dye of the present invention is produced by the United Nations Recommendation “Recommendations on the Transport of Dangerous Goods—Tests and Standards Manual—Revised 3rd Edition (Test Method for Class 4, Self-heating Substances” [Recommendations on the TRANSPORT OF DANGEROUSGOODS- According to Manual of Tests and Criteria-Third revised edition (Class 4, Test method for self-heating substrates)] None of the heat generation at 200 ° C. or higher occurs.
本発明者等は、従来のニグロシン染料における上記のような遊離アニリンの発生原因及び自然発火性について鋭意検討した結果、遊離アニリンの発生は、ニグロシン成分の一部分解によるものであり、ニグロシン成分の一部分解により発生する熱の蓄積が発火の一つの原因であると推定した。本発明のニグロシン染料の製造方法は、ニグロシン成分の一部分解による遊離アニリン量を減少させることができるニグロシン染料を製造しようとしたものである。 As a result of intensive studies on the cause and spontaneous ignition of the free aniline as described above in the conventional nigrosine dye, the present inventors have found that the generation of free aniline is due to partial decomposition of the nigrosine component, and a part of the nigrosine component. The accumulation of heat generated by the solution was presumed to be one cause of ignition. The method for producing a nigrosine dye of the present invention is intended to produce a nigrosine dye capable of reducing the amount of free aniline due to partial decomposition of the nigrosine component.
すなわち、本発明のニグロシン染料の製造方法は、上記本発明のニグロシン染料を製造する方法であって、中和処理されたニグロシンベースを加熱処理することを特徴とする。 That is, the method for producing a nigrosine dye of the present invention is a method for producing the nigrosine dye of the present invention, wherein the neutralized nigrosine base is heated.
本発明のニグロシン染料は非自然発火性であるため、安全性が高く、貯蔵や輸送等における取り扱いが容易である。また本発明のニグロシン染料の製造方法によれば、従来の自然発火性のニグロシン染料から本発明の非自然発火性のニグロシン染料を容易に得ることができる。 Since the nigrosine dye of the present invention is non-pyrophoric, it is highly safe and easy to handle in storage, transportation and the like. Moreover, according to the manufacturing method of the nigrosine dye of this invention, the non-pyrophoric nigrosine dye of this invention can be easily obtained from the conventional pyrophoric nigrosine dye.
本発明のニグロシン染料を特定するためのアニリン量測定についてのより具体的な方法は、特に限定されず、ニグロシン染料に含まれるアニリンをガラス製試料導入部温度が200℃の場合と260℃の場合の何れにおいても再現性良く定量できればよい。後記実施例及び比較例におけるA重量%及びB重量%(ガラス製試料導入部温度をそれぞれ200℃及び260℃としてガスクロマトグラフ装置により測定したアニリン含有量)の測定を行なった方法を、その一例として挙げる。 A more specific method for measuring the amount of aniline for specifying the nigrosine dye of the present invention is not particularly limited, and when the aniline contained in the nigrosine dye has a glass sample introduction part temperature of 200 ° C. and 260 ° C. In any case, it is only necessary to be able to quantify with good reproducibility. As an example, a method of measuring A weight% and B weight% (an aniline content measured by a gas chromatograph apparatus with glass sample introduction part temperatures of 200 ° C. and 260 ° C., respectively) in Examples and Comparative Examples described later is used. I will give you.
精秤した試料0.1gに、エタノール:クロロホルム=1:1の混合溶媒9mlと、内部標準液(精秤したp−ニトロトルエン0.1gを、エタノール:クロロホルム=1:1[体積比]の混合溶媒に溶解させ、総量100mlに調製したもの)1mlを加え、超音波処理を20分間行なったものを、孔径:0.45μmのフィルターで濾過した濾液1μl(マイクロリットル)を、次のようなガスクロマトグラフ装置のガラス製試料導入部に注入して試料のアニリン量を定量する。 To 0.1 g of a precisely weighed sample, 9 ml of a mixed solvent of ethanol: chloroform = 1: 1 and an internal standard solution (0.1 g of precisely weighed p-nitrotoluene, ethanol: chloroform = 1: 1 [volume ratio]) 1 ml of a solution dissolved in a solvent and adjusted to a total volume of 100 ml) and subjected to ultrasonic treatment for 20 minutes, 1 μl (microliter) of a filtrate filtered through a filter having a pore size of 0.45 μm, and the following gas chromatograph The amount of aniline in the sample is quantified by injecting it into the glass sample introduction part of the graph apparatus.
ガスクロマトグラフ装置については、次の通りである。
ガスクロマトグラフィ:HP5890(ヒューレットパッカード社製)
カラム:DB−1701(30m×0.53mmI.D.×1.0μm Film)J&W社製
オーブン:100℃−260℃(10℃/min)
導入部(Injection port):ガラス製,200℃又は260℃,スプリット比(split ratio)10:1
検出器(Detector):水素炎イオン化検出器(FID),280℃
注入体積:1μlThe gas chromatograph apparatus is as follows.
Gas chromatography: HP5890 (manufactured by Hewlett-Packard Company)
Column: DB-1701 (30 m × 0.53 mm ID × 1.0 μm Film) J & W oven: 100 ° C.-260 ° C. (10 ° C./min)
Injection port: glass, 200 ° C. or 260 ° C., split ratio 10: 1
Detector: Hydrogen ionization detector (FID), 280 ° C
Injection volume: 1 μl
なお、カラムは他のもの、例えばDB−5(J&W社製)等を用いてもよい。 Other columns such as DB-5 (manufactured by J & W) may be used.
ニグロシン染料における自然発火性の判定を行なうための上記試験、すなわち国連勧告「Recommendations on the TRANSPORT OF DANGEROUSGOODS−Manual of Tests and Criteria−Third revised edition(Class4,Test method for self−heating substances)」に従って、1辺10cmの立方体容器に収容し、140℃の温度を維持する試験は、具体的には次のように行ない得る。後記実施例及び比較例においても次に示す自然発火性試験により自然発火性を判定した。 The above test for determining the pyrophoric properties of nigrosine dyes, namely according to the UN recommendation “Recommendations on the TRANSPORT OF DANGEROOUSGOODS- Manual of tests-Criteria-Thirdfested Specifically, the test for storing in a cubic container having a side of 10 cm and maintaining a temperature of 140 ° C. can be performed as follows. In the examples and comparative examples described later, the spontaneous ignition was determined by the following spontaneous ignition test.
目開きが0.053mmのステンレス製の網で作られた一辺が10cmの立方体であって上部が開放されている試料容器にサンプルを充填し、サンプルを充填した試料容器を、その試料容器を内部に収容し得る大きさの立方体であって、目開きが0.595mmのステンレス製の網で作られた上部が開放されている試料容器カバーに収納し、それを、恒温槽の中央部に吊り下げた、目開きが0.595mmのステンレス製の網で作られ、その大きさが縦15cm、横15cm、高さ25cmであるかごの内側中央部に設置する。また、サンプルの中心部及び恒温槽内部の温度が測定できるように温度計(熱電対)を設置する。恒温槽内部の温度を140℃に設定し、以後24時間この温度を保持すると共に、サンプルの温度を24時間連続測定して記録する。24時間以内に、発火が認められるか又はサンプルの温度が200℃を超えた場合は、その時点でテストを中止する。テスト開始から、発火が認められるか又はサンプルの温度が200℃に達するまでの時間を発火までの時間とする。 The sample container is filled with a sample container made of a stainless steel net with a mesh opening of 0.053 mm and one side of which is a 10 cm cube, and the upper part is open, and the sample container is filled with the sample container. Is stored in a sample container cover that is made of a stainless steel net with an opening of 0.595 mm and is suspended in the center of the thermostatic chamber. It is made of a stainless steel net with a mesh opening of 0.595 mm and has a size of 15 cm in length, 15 cm in width, and 25 cm in height. In addition, a thermometer (thermocouple) is installed so that the temperature in the center of the sample and the temperature chamber can be measured. The temperature inside the thermostat is set to 140 ° C., and this temperature is maintained for 24 hours, and the temperature of the sample is continuously measured and recorded for 24 hours. If ignition is observed within 24 hours or the temperature of the sample exceeds 200 ° C., the test is stopped at that point. The time from the start of the test until the ignition is recognized or the temperature of the sample reaches 200 ° C. is the time until the ignition.
本発明のニグロシン染料は、例えば、自然発火性ニグロシン染料を、溶媒中、加熱処理することにより製造することができる。より具体的な例としては、次のような製法を挙げることができる。
(1)自然発火性ニグロシン染料の有機酸存在下における加熱処理The nigrosine dye of the present invention can be produced, for example, by subjecting a pyrophoric nigrosine dye to heat treatment in a solvent. More specific examples include the following production methods.
(1) Heat treatment of pyrophoric nigrosine dye in the presence of organic acid
自然発火性のニグロシン染料を、溶媒中、触媒として有機酸を用いて加熱処理することにより、本発明のニグロシン染料を得ることができる。 The nigrosine dye of the present invention can be obtained by heat-treating a pyrophoric nigrosine dye in a solvent using an organic acid as a catalyst.
有機酸としては、pKaが0以上であるものが好ましく、より好ましくはpKaが3乃至5である有機酸である。特に好ましいのは、式(1)で表される脂肪族又は芳香族カルボン酸類である。 The organic acid is preferably an organic acid having a pKa of 0 or more, and more preferably an organic acid having a pKa of 3 to 5. Particularly preferred are aliphatic or aromatic carboxylic acids represented by the formula (1).
このようなカルボン酸類の具体例としては、ギ酸、蓚酸、酢酸、プロピオン酸、酪酸等の脂肪族カルボン酸類;安息香酸、フタル酸類、ベンゼントリカルボン酸類、ベンゼンテトラカルボン酸類等の芳香族カルボン酸類を挙げることができる。
塩酸、硫酸等の無機酸や有機酸の中でも有機スルホン酸等の比較的強い酸(PKa<0)では、一般に、B−A≦0.04%の非自然発火性のニグロシン染料を得ることは難しい。Specific examples of such carboxylic acids include aliphatic carboxylic acids such as formic acid, succinic acid, acetic acid, propionic acid, and butyric acid; aromatic carboxylic acids such as benzoic acid, phthalic acids, benzenetricarboxylic acids, and benzenetetracarboxylic acids. be able to.
With relatively strong acids (PKa <0) such as organic sulfonic acids among inorganic acids and organic acids such as hydrochloric acid and sulfuric acid, it is generally possible to obtain non-pyrophoric nigrosine dyes with BA ≦ 0.04%. difficult.
触媒として有機酸を用いる場合、加熱処理の温度は100℃以上250℃以下が好ましい。より好ましくは160℃以上220℃以下である。 When an organic acid is used as the catalyst, the temperature for the heat treatment is preferably 100 ° C. or higher and 250 ° C. or lower. More preferably, it is 160 degreeC or more and 220 degrees C or less.
加熱処理時間は、原料として用いるニグロシンによって異なるが、一般には5乃至48時間である。処理時間が極端に短いと十分な効果が得られない場合がある。 The heat treatment time varies depending on nigrosine used as a raw material, but is generally 5 to 48 hours. If the processing time is extremely short, sufficient effects may not be obtained.
(2)自然発火性ニグロシン染料の、金属酸化物又はヘテロポリ酸存在下における加熱処理
自然発火性のニグロシン染料を、溶媒中、触媒として金属酸化物又はヘテロポリ酸を用いて加熱処理することにより、本発明のニグロシン染料を得ることができる。(2) Heat treatment of pyrophoric nigrosine dye in the presence of a metal oxide or heteropoly acid By subjecting pyrophoric nigrosine dye to heat treatment using a metal oxide or heteropoly acid as a catalyst in a solvent, The inventive nigrosine dye can be obtained.
前記金属酸化物は、シリカ、アルミナ、シリカアルミナ、チタニア、酸化モリブデン(VI)、酸化タングステン(VI)、及び酸化バナジウム(V)から選ばれた1又は2以上とすることができる。 The metal oxide may be one or more selected from silica, alumina, silica alumina, titania, molybdenum oxide (VI), tungsten oxide (VI), and vanadium oxide (V).
また前記ヘテロポリ酸は、H3PMo6W6O40、H3PW12O40、H3PMo12O40、H3PMo10W2O40、H3PMo10V2O40、H4SiW12O40、及びH4GeMo12O40から選ばれた1又は2以上とすることができる。Also, the heteropolyacid, H 3 PMo 6 W 6 O 40, H 3 PW 12 O 40, H 3 PMo 12 O 40, H 3 PMo 10 W 2 O 40, H 3 PMo 10 V 2 O 40, H 4 SiW 12 O 40, and H 4 can be Gemo 12 1 or 2 or more selected from O 40.
触媒として金属酸化物又はヘテロポリ酸を用いる場合、加熱処理の温度は50℃以上250℃以下が好ましい。より好ましくは、100℃以上220℃以下である。 When using a metal oxide or heteropolyacid as a catalyst, the temperature of the heat treatment is preferably 50 ° C. or higher and 250 ° C. or lower. More preferably, it is 100 degreeC or more and 220 degrees C or less.
加熱処理時間は、原料として用いるニグロシンによって異なるが、一般には5乃至48時間である。処理時間が極端に短いと十分な効果が得られない場合がある。 The heat treatment time varies depending on nigrosine used as a raw material, but is generally 5 to 48 hours. If the processing time is extremely short, sufficient effects may not be obtained.
(3)自然発火性ニグロシン染料の無触媒での加熱処理
自然発火性のニグロシン染料を、溶媒中、無触媒で加熱処理することによっても、本発明のニグロシン染料を得ることができる。(3) Non-catalytic heat treatment of pyrophoric nigrosine dye The nigrosine dye of the present invention can also be obtained by heat-treating a pyrophoric nigrosine dye in a solvent without a catalyst.
無触媒の場合の加熱温度は、200℃以上300℃以下が好ましい。より好ましくは220℃以上250℃以下である。 The heating temperature in the case of no catalyst is preferably 200 ° C. or higher and 300 ° C. or lower. More preferably, it is 220 degreeC or more and 250 degrees C or less.
加熱処理時間は、原料として用いるニグロシンによって異なるが、一般には10乃至60時間である。処理時間が極端に短いと十分な効果が得られない場合がある。 The heat treatment time varies depending on nigrosine used as a raw material, but is generally 10 to 60 hours. If the processing time is extremely short, sufficient effects may not be obtained.
上記製法において出発原料として用いる自然発火性のニグロシン染料(ニグロシン)は、いかなる方法で製造されたものであってもよいが、中和処理されたニグロシンベース(具体例としては、C.I.ソルベントブラック5、C.I.ソルベントブラック7及びこれらの誘導体)であることが望ましい。より好ましくは、C.I.ソルベントブラック7である。自然発火性のニグロシン染料(ニグロシン)というのは、上記国連勧告に従って、1辺10cmの立方体容器に収容し、140℃の温度を維持する試験において、24時間以内に自然発火又は200℃以上の発熱の何れかが生じるものを言う。 The pyrophoric nigrosine dye (nigrosine) used as a starting material in the above production method may be produced by any method, but a neutralized nigrosine base (for example, CI solvent Black 5, CI Solvent Black 7 and derivatives thereof are desirable. More preferably, C.I. I. Solvent Black 7. A pyrophoric nigrosine dye (nigrosine) is contained in a cubic container with a side of 10 cm and maintained at a temperature of 140 ° C in accordance with the above-mentioned UN recommendations. Anything that occurs.
上記何れの製法も、無溶媒下でも可能であるが、後処理工程の利便性等の点から、溶媒を使用することが好ましい。 Any of the above-mentioned production methods can be carried out in the absence of a solvent, but it is preferable to use a solvent from the viewpoint of convenience of the post-treatment process.
溶媒としてはアルコール系溶媒、芳香族系溶媒、非プロトン性極性溶媒、アミン系溶媒等、様々なものが使用できるが、その中でも芳香族アミン類が適する。 As the solvent, various solvents such as alcohol solvents, aromatic solvents, aprotic polar solvents, amine solvents and the like can be used, among which aromatic amines are suitable.
このような芳香族アミン類の例としては、アニリン、メチルアニリン、ジメチルアニリン、エチルアニリン、ジエチルアニリン、o−トルイジン、m−トルイジン、p−トルイジン、ベンジルアミン、ジベンジルアミン、トリベンジルアミン、ジフェニルアミン、トリフェニルアミン、α−ナフチルアミン、β−ナフチルアミン等を挙げることができる。これらの中、各種置換基を有する又は非置換のアニリン類が好適であり、アニリンが最も好ましい。 Examples of such aromatic amines include aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, o-toluidine, m-toluidine, p-toluidine, benzylamine, dibenzylamine, tribenzylamine, diphenylamine. , Triphenylamine, α-naphthylamine, β-naphthylamine and the like. Of these, anilines having various substituents or unsubstituted are preferred, and aniline is most preferred.
また上記製法は、加熱処理を加圧下で行うこともできる。 Moreover, the said manufacturing method can also perform heat processing under pressure.
また、上記何れの製法も、用いる溶媒によっては、オートクレーブを用いて処理温度を上げることができる。 In any of the above production methods, depending on the solvent used, the treatment temperature can be increased using an autoclave.
以下、本発明を実施例により更に具体的に説明するが、本発明の内容はこれらの実施例に限定されるものではない。なお、以下の記述における「%」は「重量%」を意味する。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, the content of this invention is not limited to these Examples. In the following description, “%” means “% by weight”.
実施例1
市販されている中和処理されたニグロシンベースである、自然発火性ニグロシン(B−A=0.11%)1.0kgとアニリン2.0kgの混合液に酢酸(pKa=4.56)10gを加え、撹拌しながら大気下で20時間還流させた(この時の溶液温度は約190℃)。その後、約30℃まで放冷し、次いで2%NaOH水溶液1L(リットル)で2回洗浄し、更に水洗した。 Example 1
10 g of acetic acid (pKa = 4.56) is added to a mixture of 1.0 kg of pyrophoric nigrosine (BA = 0.11%) and 2.0 kg of aniline, which is a commercially available neutralized nigrosine base. In addition, the mixture was refluxed in the atmosphere for 20 hours with stirring (the solution temperature at this time was about 190 ° C.). Thereafter, the mixture was allowed to cool to about 30 ° C., then washed twice with 1 L (liter) of 2% NaOH aqueous solution and further washed with water.
得られたニグロシン染料を減圧乾燥後GC分析したところ、試料導入部温度200℃の場合のアニリン量Aは0.21%、試料導入部温度260℃の場合のアニリン量Bは0.24%、すなわちB−A=0.03%であった。このニグロシン染料は、上記自然発火性試験で24時間後も発火しなかった。 GC analysis of the obtained nigrosine dye after drying under reduced pressure revealed that the aniline amount A was 0.21% when the sample introduction part temperature was 200 ° C., and the aniline amount B was 0.24% when the sample introduction part temperature was 260 ° C. That is, B−A = 0.03%. This nigrosine dye did not ignite after 24 hours in the above pyrophoric test.
実施例2
環流処理時間を30時間としたこと以外は実施例1と同様に処理したところ、得られたニグロシン染料における試料導入部温度200℃の場合のアニリン量Aは0.21%、試料導入部温度260℃の場合のアニリン量Bは0.22%、すなわちB−A=0.01%であった。このニグロシン染料は上記自然発火性試験で24時間後も発火しなかった。 Example 2
When the treatment was conducted in the same manner as in Example 1 except that the reflux treatment time was 30 hours, the aniline content A in the obtained nigrosine dye at a sample introduction part temperature of 200 ° C. was 0.21%, and the sample introduction part temperature 260. The amount B of aniline at 0.2 ° C. was 0.22%, that is, B−A = 0.01%. This nigrosine dye did not ignite after 24 hours in the above pyrophoric test.
実施例3
酢酸に代えてプロピオン酸(pKa=4.67)20gを用いたこと以外は実施例1と同様に処理したところ、得られたニグロシン染料における試料導入部温度200℃の場合のアニリン量Aは0.18%、試料導入部温度260℃の場合のアニリン量Bは0.20%、すなわちB−A=0.02%であった。このニグロシン染料は上記自然発火性試験で24時間後も発火しなかった。 Example 3
The same treatment as in Example 1 was conducted except that 20 g of propionic acid (pKa = 4.67) was used in place of acetic acid. As a result, the amount of aniline A at the sample introduction part temperature of 200 ° C. in the obtained nigrosine dye was 0. When the sample introduction part temperature was 260 ° C., the aniline amount B was 0.20%, that is, B−A = 0.02%. This nigrosine dye did not ignite after 24 hours in the above pyrophoric test.
実施例4
酢酸に代えて安息香酸(pKa=4.00)20gを用いたこと以外は実施例1と同様に処理したところ、得られたニグロシン染料における試料導入部温度200℃の場合のアニリン量Aは0.15%、試料導入部温度260℃の場合のアニリン量Bは0.18%、すなわちB−A=0.03%であった。このニグロシン染料は上記自然発火性試験で24時間後も発火しなかった。 Example 4
When the same treatment as in Example 1 was performed except that 20 g of benzoic acid (pKa = 4.00) was used instead of acetic acid, the amount of aniline A at the sample introduction part temperature of 200 ° C. in the obtained nigrosine dye was 0. When the sample introduction part temperature was 260 ° C., the aniline amount B was 0.18%, that is, B−A = 0.03%. This nigrosine dye did not ignite after 24 hours in the above pyrophoric test.
実施例5
酢酸に代えてカラムクロマトグラフ用シリカゲル(和光純薬社製)40gを用い、還流後、濾過によりシリカゲルを除去したこと以外は実施例1と同様に処理したところ、得られたニグロシン染料における試料導入部温度200℃の場合のアニリン量Aは0.52%、試料導入部温度260℃の場合のアニリン量Bは0.54%、すなわちB−A=0.02%であった。このニグロシン染料は上記自然発火性試験で24時間後も発火しなかった。 Example 5
In place of acetic acid, 40 g of silica gel for column chromatography (manufactured by Wako Pure Chemical Industries, Ltd.) was used, and after refluxing, the same treatment as in Example 1 was carried out except that the silica gel was removed by filtration. The aniline amount A was 0.52% when the part temperature was 200 ° C., and the aniline amount B was 0.54% when the sample introduction part temperature was 260 ° C., that is, B−A = 0.02%. This nigrosine dye did not ignite after 24 hours in the above pyrophoric test.
実施例6
環流処理時間を24時間としたこと以外は実施例5と同様に処理したところ、得られたニグロシン染料における試料導入部温度200℃の場合のアニリン量Aは0.63%、試料導入部温度260℃の場合のアニリン量Bは0.64%、すなわちB−A=0.01%であった。このニグロシン染料は上記自然発火性試験で24時間後も発火しなかった。 Example 6
When the treatment was conducted in the same manner as in Example 5 except that the reflux treatment time was 24 hours, the amount of aniline A in the obtained nigrosine dye when the sample introduction part temperature was 200 ° C. was 0.63%, and the sample introduction part temperature 260 The aniline content B at 0 ° C. was 0.64%, that is, B−A = 0.01%. This nigrosine dye did not ignite after 24 hours in the above pyrophoric test.
実施例7
シリカゲルに代えてモレキュラシーブス4A(アルドリッチ社製:シリカアルミナ)40gを用いたこと以外は実施例5と同様に処理したところ、得られたニグロシン染料における試料導入部温度200℃の場合のアニリン量Aは0.31%、試料導入部温度260℃の場合のアニリン量Bは0.33%、すなわちB−A=0.02%であった。このニグロシン染料は上記自然発火性試験で24時間後も発火しなかった。 Example 7
When the same treatment as in Example 5 was performed except that 40 g of molecular sieves 4A (Aldrich: silica alumina) was used instead of silica gel, the amount of aniline in the obtained nigrosine dye when the sample introduction part temperature was 200 ° C. A When the sample introduction part temperature was 260 ° C., the aniline amount B was 0.33%, that is, B−A = 0.02%. This nigrosine dye did not ignite after 24 hours in the above pyrophoric test.
実施例8
シリカゲルに代えてH3PMo6W6O40を30g用いたこと以外は実施例6と同様に処理したところ、得られたニグロシン染料における試料導入部温度200℃の場合のアニリン量Aは0.11%、試料導入部温度260℃の場合のアニリン量Bは0.12%、すなわちB−A=0.01%であった。このニグロシン染料は上記自然発火性試験で24時間後も発火しなかった。 Example 8
When the same treatment as in Example 6 was performed except that 30 g of H 3 PMo 6 W 6 O 40 was used instead of silica gel, the amount of aniline A at a sample introduction part temperature of 200 ° C. in the obtained nigrosine dye was 0.00. The amount of aniline B was 11% when the sample introduction part temperature was 260 ° C. and was 0.12%, that is, B−A = 0.01%. This nigrosine dye did not ignite after 24 hours in the above pyrophoric test.
実施例9
シリカゲルに代えてH3PMo10V2O40を40g用いたこと以外は実施例5同様に処理したところ、得られたニグロシン染料における試料導入部温度200℃の場合のアニリン量Aは0.11%、試料導入部温度260℃の場合のアニリン量Bは0.13%、すなわちB−A=0.02%であった。このニグロシン染料は上記自然発火性試験で24時間後も発火しなかった。 Example 9
When the same treatment was conducted as in Example 5 except that 40 g of H 3 PMo 10 V 2 O 40 was used instead of silica gel, the amount of aniline A at the sample introduction part temperature of 200 ° C. in the obtained nigrosine dye was 0.11. %, And the sample introduction part temperature 260 ° C., the aniline amount B was 0.13%, that is, B−A = 0.02%. This nigrosine dye did not ignite after 24 hours in the above pyrophoric test.
実施例10
自然発火性ニグロシン(B−A=0.11%)1.0kgとアニリン1.0kgの混合液を、オートクレーブ中で、撹拌下220℃で48時間加熱処理した。 Example 10
A mixture of 1.0 kg of pyrophoric nigrosine (BA = 0.11%) and 1.0 kg of aniline was heat-treated at 220 ° C. for 48 hours with stirring in an autoclave.
得られたニグロシン染料を減圧乾燥後GC分析したところ、GC試料導入部温度200℃の場合のアニリン量Aは0.21%、試料導入部温度260℃の場合のアニリン量Bは0.25%、すなわちB−A=0.04%であった。このニグロシン染料は上記自然発火性試験で24時間後も発火しなかった。 When the obtained nigrosine dye was dried under reduced pressure and analyzed by GC, the amount of aniline A at a GC sample introduction part temperature of 200 ° C. was 0.21%, and the amount of aniline B at a sample introduction part temperature of 260 ° C. was 0.25%. That is, B−A = 0.04%. This nigrosine dye did not ignite after 24 hours in the above pyrophoric test.
比較例1(特許文献6及び7に示された実施例1)
実施例1で用いた自然発火性のニグロシン1.0kgとアニリン2.0kgの混合物を良く撹拌しながら、75℃で16時間空気(500ml/min)を吹き込んだ。次いでこの溶液を、アニリン等の揮発分が1%以下になるまで乾燥させた後、冷却した。 Comparative Example 1 ( Example 1 shown in Patent Documents 6 and 7)
Air (500 ml / min) was blown at 75 ° C. for 16 hours while thoroughly stirring the mixture of 1.0 kg of pyrophoric nigrosine and 2.0 kg of aniline used in Example 1. The solution was then dried until the volatile content of aniline or the like was 1% or less, and then cooled.
得られた生成物をGC分析したところ、GC試料導入部温度200℃の場合のアニリン量Aは0.51%、試料導入部温度260℃の場合のアニリン量Bは0.63%、すなわち、B−A=0.12%であった。特許文献6及び7では、得られたサンプルは非発火性であると記されているが、上記自然発火性試験法によると6.6時間後に発火した。 When the obtained product was analyzed by GC, the amount of aniline A when the GC sample introduction part temperature was 200 ° C. was 0.51%, and the amount of aniline B when the sample introduction part temperature was 260 ° C. was 0.63%, B−A = 0.12%. In Patent Documents 6 and 7, it is described that the obtained sample is non-ignitable, but it ignited after 6.6 hours according to the above pyrophoric test method.
比較例2(特許文献6及び7に示された実施例2)
実施例1で用いた自然発火性のニグロシン1.0kgとアニリン2.0kgの混合物を良く撹拌しながら、50乃至55℃で20時間空気(16l/min[リットル/分])を吹き込んだ。次いでこの溶液を、アニリン等の揮発分が1%以下になるまで乾燥させた後、冷却した。 Comparative Example 2 ( Example 2 shown in Patent Documents 6 and 7)
Air (16 l / min [liter / min]) was blown in at 50 to 55 ° C. for 20 hours while thoroughly stirring the mixture of 1.0 kg of pyrophoric nigrosine and 2.0 kg of aniline used in Example 1. The solution was then dried until the volatile content of aniline or the like was 1% or less, and then cooled.
得られた生成物をGC分析したところ、試料導入部温度200℃の場合のアニリン量Aは0.44%、試料導入部温度260℃の場合のアニリン量は0.53%、B−A=0.09%であった。特許文献6及び7では、得られたサンプルは非発火性であると記されているが、上記自然発火性試験法によると7.0時間後に発火した。 When the obtained product was analyzed by GC, the amount of aniline A at a sample introduction part temperature of 200 ° C. was 0.44%, the amount of aniline at a sample introduction part temperature of 260 ° C. was 0.53%, and B−A = It was 0.09%. In Patent Documents 6 and 7, it is described that the obtained sample is non-ignitable, but it ignited after 7.0 hours according to the above pyrophoric test method.
比較例3
酢酸に代えて塩酸(pKa=−7.0)10gを用いる以外は実施例1と同様に処理したところ、得られた生成物における試料導入部温度200℃の場合のアニリン量Aは0.47%、試料導入部温度260℃の場合のアニリン量Bは0.78%、すなわち、B−A=0.31%であった。このサンプルは3.5時間後に発火した。 Comparative Example 3
When the same treatment as in Example 1 was performed except that 10 g of hydrochloric acid (pKa = −7.0) was used instead of acetic acid, the amount of aniline A at the sample introduction part temperature of 200 ° C. in the obtained product was 0.47. %, And the sample introduction part temperature 260 ° C., the aniline amount B was 0.78%, that is, B−A = 0.31%. This sample ignited after 3.5 hours.
比較例4
酢酸に代えてトルエンスルホン酸(pKa=−6.5)20gを用いる以外は実施例1と同様に処理したところ、得られた生成物における試料導入部温度200℃の場合のアニリン量Aは0.57%、試料導入部温度260℃の場合のアニリン量Bは0.83%、すなわち、B−A=0.26%であった。このサンプルは3.2時間後に発火した。 Comparative Example 4
When the same treatment as in Example 1 was carried out except that 20 g of toluenesulfonic acid (pKa = −6.5) was used instead of acetic acid, the amount of aniline A at the sample introduction part temperature of 200 ° C. in the obtained product was 0. When the sample introduction part temperature was 260 ° C., the aniline amount B was 0.83%, that is, B−A = 0.26%. This sample ignited after 3.2 hours.
比較例5
環流処理時間を極端に短く(3時間)した以外は実施例1と同様に処理したところ、得られた生成物における試料導入部温度200℃の場合のアニリン量Aは0.20%、試料導入部温度260℃の場合のアニリン量Bは0.26%、すなわちB−A=0.06%であった。このサンプルは13.5時間後に発火した。 Comparative Example 5
When the treatment was carried out in the same manner as in Example 1 except that the reflux treatment time was extremely short (3 hours), the amount of aniline A at the sample introduction part temperature of 200 ° C. in the obtained product was 0.20%. The aniline content B at a part temperature of 260 ° C. was 0.26%, that is, B−A = 0.06%. This sample ignited after 13.5 hours.
比較例6
環流処理時間を極端に短く(3時間)した以外は実施例5と同様に処理したところ、得られた生成物における試料導入部温度200℃の場合のアニリン量Aは0.19%、試料導入部温度260℃の場合のアニリン量Bは0.30%、すなわちB−A=0.11%であった。このサンプルは7.0時間後に発火した。 Comparative Example 6
When the treatment was carried out in the same manner as in Example 5 except that the reflux treatment time was extremely short (3 hours), the amount of aniline A at the sample introduction part temperature of 200 ° C. in the obtained product was 0.19%. The aniline content B at a part temperature of 260 ° C. was 0.30%, that is, B−A = 0.11%. This sample ignited after 7.0 hours.
表1に実施例及び比較例の結果をまとめた。
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JPS56141354A (en) * | 1980-04-04 | 1981-11-05 | American Cyanamid Co | Non-ignitable nigrosine base |
JPH0488064A (en) * | 1990-07-31 | 1992-03-19 | Orient Chem Ind Ltd | Production of azine dye having excellent heat-resistance and light-resistance |
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JPS56141354A (en) * | 1980-04-04 | 1981-11-05 | American Cyanamid Co | Non-ignitable nigrosine base |
JPH0488064A (en) * | 1990-07-31 | 1992-03-19 | Orient Chem Ind Ltd | Production of azine dye having excellent heat-resistance and light-resistance |
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