Calcomine Black | 1937-37-7

• 物质功能分类: 染料及颜料 - 染料 - 直接染料
• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: Calcomine Black
• 英文别名: sodium;4-amino-3-[[4-[4-[(2,4-diaminophenyl)diazenyl]phenyl]phenyl]diazenyl]-5-hydroxy-6-phenyldiazenylnaphthalene-2,7-disulfonic acid
• CAS: 1937-37-7
• 化学式: C34H27N9NaO7S2+
• 分子量: 760.8
• InChiKey: SZKZLHLJJLRYKJ-UHFFFAOYSA-N

物化性质

• 熔点：
  109-110°C
• 溶解度：
  DMSO（轻微）、甲醇（轻微、加热）、水（轻微）
• 物理描述：
  C.i. direct black 38 appears as gray-black microcrystals or black powder. (NTP, 1992)
• 颜色/状态：
  Grey-black powder
• 沸点：
  Decomposes (NTP, 1992)
• 稳定性/保质期：

  如果按照规格使用和储存，则不会分解，未有已知危险反应，应避免与氧化物接触。

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  53
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  298
• 氢给体数：
  6
• 氢受体数：
  16

ADMET

代谢

单次剂量（每公斤100毫克）的纯化直接黑38染料给仓鼠服用后，通过尿液检测，在排泄的前8小时内揭示了尿液中存在高水平的联苯胺、单乙酰联苯胺、二乙酰联苯胺、4-氨基联苯以及联苯胺和4-氨基联苯的碱性可水解结合物。

SINGLE DOSE (100 MG/KG) OF PURIFIED DIRECT BLACK 38 ADMIN TO HAMSTERS REVEALED BY URINE ASSAY HIGH LEVELS OF BENZIDINE, MONOACETYLBENZIDINE, DIACETYLBENZIDINE, 4-AMINOBIPHENYL, & ALKALINE HYDROLYZABLE CONJUGATES OF BENZIDINE & 4-AMINOBIPHENYL DURING 1ST 8 HR OF EXCRETION

来源:Hazardous Substances Data Bank (HSDB)

代谢

直接黑38在动物中被代谢成人类致癌物联苯胺。

DIRECT BLACK 38 WAS SHOWN TO BE METABOLIZED IN ANIMALS TO HUMAN CARCINOGEN BENZIDINE.

来源:Hazardous Substances Data Bank (HSDB)

代谢

警告也由美国国立职业安全与健康研究所（NIOSH）的初步现场研究结果指出，这些结果显示，与这些相同染料（直接黑38、直接棕95和直接蓝6）一起工作的人类也会在尿液中排出高于预期的联苯胺水平。实验室和现场研究都表明，这些由联苯胺衍生的染料可以被代谢为联苯胺，这种物质存在于动物和人类的尿液中。根据短期研究的数据，美国国家癌症研究所的科学家们认为，接触由联苯胺衍生的染料存在致癌的可能性，最有可能是通过动物体内染料代谢转化为联苯胺的机制。

Caution is also indicated by preliminary results from the NIOSH field studies showing that humans working with these same dyes /Direct Black 38, Direct Brown 95, and Direct Blue 6/ also excrete higher than expected levels of benzidine in their urine. Both laboratory and field studies indicate that these benzidine derived dyes can be metabolized to benzidine, which is present in the urine of animals and humans. Based on the data from the short-term study, National Cancer Institute scientists believe that a cancer causing potential exists on exposure to the benzidine derived dyes, most likely through the mechanism of metabolic conversion of the dyes to benzidine in the animal system.

来源:Hazardous Substances Data Bank (HSDB)

代谢

在为期13周的亚慢性毒性研究中，在大鼠和小鼠的尿液中发现了联苯胺和单乙酰联苯胺，这些动物接触了直接黑38染料。分析4周和12周（大鼠）以及3周和11周（小鼠）后的24小时尿液样本显示，食物中染料浓度与排出的联苯胺量之间存在明确的关系。小鼠将更多的染料生物转化为联苯胺，而大鼠则转化较少。

Benzidine and monoacetylbenzidine were found in the urine of rats and mice on the course of 13-week subchronic toxicity studies with Direct Black 38. Analysis of 24-hour urine samples 4 and 12 weeks (rats) and 3 and 11 weeks (mice) later showed a clear-cut relationship between the concentration of dyestuff in the food consumed and the amount of benzidine excreted. Mice biotransformed considerably more dye to benzidine than did rats.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

致癌性分类：1）人类证据：不足；2）动物证据无数据。对人类致癌风险的总体评估为2A组：该物质很可能对人类致癌。/来自表格；联苯胺基染料/

Classification of carcinogenicity: 1) evidence in humans: inadequate; 2) No data for evidence in animals. Overall summary evaluation of carcinogenic risk to humans is Group 2A: The agent is probably carcinogenic to humans. /From table; Benzidine-based dyes/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

染料代谢成联苯胺：已知对人来说是致癌物质。/染料代谢成联苯胺（联苯胺染料类）/

Dyes Metabolized to Benzidine: known to be human carcinogens. /Dyes Metabolized to Benzidine (Benzidine Dye Class)/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 医疗监测

尿液细胞学监测在评估染料厂工人肿瘤方面已被证明是有用的。该系统包括两阶段测试：定期尿液细胞学检查，然后在可疑情况下进行泌尿科检查。/联苯胺/

Urine cytology surveillance has proved useful in evaluating tumors in dyestuff plant workers. The system consists of two-stage tests: periodic urine cytology, followed by, in suspicious cases, urological examinations. /Benzidine/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 医疗监测

对于"致癌物"的预防措施：每当需要进行医疗监测时，尤其是在暴露于致癌物的情况下，应就.../细胞遗传学和其他/可能变得有用或必须进行的测试做出特别决定。/化学致癌物/

PRECAUTIONS FOR "CARCINOGENS": Whenever medical surveillance is indicated, in particular when exposure to a carcinogen has occurred, ad hoc decisions should be taken concerning ... /cytogenetic and/or other/ tests that might become useful or mandatory. /Chemical Carcinogens/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

在研究了200名日本膀胱癌患者的病例对照死亡研究之后，人们发现与联苯胺基染料的人类暴露与随后膀胱肿瘤的发展之间存在强烈关联。这些患者主要是和服画家和染工。和服画家有一个习惯，就是通过在嘴唇之间划动画笔来形成笔尖，这导致他们摄入染料。其他几项病例对照死亡研究也表明，纺织和皮革工业中发展膀胱癌的风险增加，这两个行业都是直接染料的大用户。然而，关于联苯胺衍生物染料的参考文献只有少数几篇。在俄罗斯，一项关于纺织染工使用联苯胺衍生物染料早期发现膀胱肿瘤的医疗研究发现，膀胱损伤的发生率异常，其中一些被认为具有癌前性质。在那些潜在暴露于这些染料风险最高的工人中发现了最多的此类损伤。/联苯胺基染料/

A strong association relating human exposure to benzidine based dyes with the subsequent development of bladder tumors was presented after a case-control mortality study of 200 bladder cancer patients in Japan. The patients were found to have been predominantly kimono painters and dyers. The kimono painters had a habit of forming a point on their brushes by drawing the brush between their lips, which allowed for ingestion of the dyes. Several other case-control mortality studies indicate an increased risk of developing bladder cancer in the textile and leather industries, both large users of direct dyes. However, only a few references have been made concerning benzidine-derived dyestuffs. In Russia, a medical study concerning the early detection of bladder tumors among textile dyers using benzidine-derived dyes revealed an unusual incidence of bladder lesions, some of which were suggested as being of a precancerous nature. The greatest number of such lesions were found in those workers with the highest potential exposure to these dyes. /Benzidine-based dyes/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在小规模生产直接黑38的单元中，对18名工人的尿液样本进行了高压液相色谱检测，以确定是否存在联苯胺和单乙酰、二乙酰联苯胺。所有尿液样本中均发现了乙酰化代谢物，除两例外，所有样本中均发现了联苯胺。两名工人在尿液中排出了非常高水平的联苯胺及其代谢物。这项研究突显了在尚未对联苯胺基染料制造进行监管的发展中国家此类单元中膀胱癌的潜在风险。

Urine samples of 18 workers in a small scale unit manufacturing Direct Black 38 were /determined/ by high-pressure liquid chromatography for the presence of benzidine and mono and diacetyl benzidine. Acetylated metabolites were found in all the urine samples, and benzidine was found in all except two. Two workers excreted very high levels of benzidine and its metabolites in their urine. This study highlights the potential risk of bladder cancer in such units of developing countries where manufacture of benzidine based dyes is yet to be regulated.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

对两种偶氮染料在大鼠和家兔体内的皮肤吸收时间过程进行了研究。研究使用了以联苯胺为基的染料CI直接黑38和一种相关的染料CI直接黑19，后者用对苯二胺基团代替了联苯胺。在雄性新西兰白兔和雄性Fischer 344大鼠的左背部分剃毛后，将放射性标记的染料涂抹在2厘米乘2厘米的区域内。CI直接黑38处理的放射性在大鼠的尿液和粪便中出现的量微不足道。在144小时内，尿液中放射性物质的累积排泄量为皮肤总剂量的0.05%，粪便中为0.16%。CI直接黑38处理的兔在144小时内的放射性物质累积排泄量更高：尿液为皮肤总剂量的3.12%，粪便为5.12%。在144小时时，两种动物CI直接黑38处理的放射性物质排泄量仍在增加。CI直接黑38在实验条件下对兔皮肤的稳定性不如CI直接黑19，尽管皮肤渗透性和微生物群落的差异可能部分负责。

The time course of dermal absorption of two azo dyes was investigated in rats and rabbits. A benzidine derived dye, CI Direct Black 38 and a related dye CI Direct Black 19 which contained a p-phenylenediamine moiety instead of benzidine, were employed. Specific pathogen free male New Zealand white rabbits and male Fischer 344 rats were shaved on the left dorsum and radiolabeled dye was applied to a 2 centimeter by 2 centimeter area. ... Radioactivity from CI Direct Black 38 treated rats appeared in urine and feces in negligible quantities. Cumulative excretion of radioactivity at 144 hours was 0.05% of the total dermal dose in the urine and 0.16% in the feces. Cumulative excretion of radioactivity from CI Direct Black 38 dosed rabbits was higher at 144 hours: 3.12% of total dermal dose in urine and 5.12 in feces. At 144 hours excretion of radioactivity from CI Direct Black 38 dosed animals of both species was still increasing. ... CI Direct Black 38 is less stable on rabbit skin under experimental conditions than CI Direct Black 19, although differences in skin permeability and microflora may be partially responsible

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• TSCA：
  Yes
• 危险品标志：
  T
• 安全说明：
  S45,S53
• 危险类别码：
  R63,R45
• WGK Germany：
  3
• 海关编码：
  29299090
• RTECS号：
  QJ6160000

制备方法与用途

化学性质
棕黑色的粉状物，溶于水中呈现绿光黑色，稍溶于乙醇，呈绿光蓝黑色，并且能够溶解在溶纤素中而不溶于其他有机溶剂。当与浓硫酸接触时会显深红光蓝色，稀释后则呈现紫酱色至红光黑色的沉淀；在浓硝酸中的表现是黄棕色溶液，在浓盐酸中则是暗红光黑色溶液。其水溶液加入浓盐酸时会产生紫酱色沉淀，而加浓氢氧化钠液，则生成灰色沉淀。对纤维素纤维染色时，染料吸尽性良好，温度为80℃时亲合力最大，可以进行拔染。

用途
主要用于棉、麻、粘胶等纤维素纤维织物的染色及印花，也可用于蚕丝、锦纶及其混纺织物的染色。此外，还能应用于皮革、生物和木材的染色以及塑料着色，并可作为赤色墨水的原料。直接黑BN是一种常用的黑色染料，常单独使用于黑色染色中，同时也经常与棕色混合以产生各种咖啡色。

用途
主要用于棉、麻、粘等纤维素纤维织物的染色与印花。

用途
除了上述应用外，还可用于细胞学、组织学染色。

生产方法
直接黑BN的基本原料包括联苯胺、H酸、苯胺和间苯二胺。首先，将联苯胺进行重氮化处理，然后与H酸偶合（第一次偶合）。接下来，苯胺经过重氮化后与第一次的偶合物进行第二次偶合；随后，再与间苯二胺进行第三次偶合。通过盐析、过滤和干燥等步骤最终制得产品。具体的原料用量为：每吨联苯胺（100%）需要180公斤苯胺、300公斤H酸（100%）、70公斤间苯二胺（100%）、190公斤纯碱（工业级）、195公斤亚硝酸钠（工业级）、25公斤碳酸钙、550公斤盐酸（31%）和150升氨水（20%），此外还需要40公斤元明粉。

类别
有毒物品

毒性分级
低毒

急性毒性
口服-大鼠 LD50: 7600 毫克/公斤；吸入-大鼠 LCL0: 180,000 毫克/立方米/1小时

刺激数据
眼睛-兔子 100毫克 中度

可燃性危险特性
可燃，燃烧会产生有毒的氮氧化物、硫氧化物和氧化钠烟雾

储运特性
库房需通风、低温干燥

灭火剂
干粉、泡沫、沙土、二氧化碳、雾状水