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To meet product safety, environmental protection, and health requirements, materials and products using pigments must comply with regulatory requirements in countries and regions around the world. The most important and concerning of these are requirements for chemical substance control, particularly the chemical requirements for colorants, which are important additives in product materials. These requirements cover a wide range of consumer products, including toys, textile materials and accessories (such as zippers and buttons), cosmetics (such as nail polish and lipstick), electronic and electrical products, food containers and food contact materials or products, and automotive materials.
Kimyasalların Akut Toksisitesi
The most commonly used metric for measuring acute toxicity is the LD50 (lethal dose). LD50 stands for the median lethal dose. A simple definition is the dose required to cause death in 50% of a group of test animals, such as rats. The LD50 is expressed in mg/kg body weight. Lower LD50 values indicate a more potent poison; higher LD50 values indicate a less toxic poison. The European Union defines three acute toxicity categories (rat oral) for substances.
LD50 ≤ 25 mg/kg; extremely toxic
LD50 = 25-200 mg/kg; toxic
LD50 = 200-2000 mg/kg; harmful
Regarding the acute toxicity of colorants, a monograph reviewed 194 pigments and found that the majority had oral LD50 values greater than 5000 mg/kg, with no reported values below 2000 mg/kg. Considering that the oral LD50 value of table salt (NaCl) is 3000 mg/kg, this would be equivalent to an average-weight person ingesting 350g of pigment, which is unlikely. Therefore, the conclusion is that colorants generally have low acute toxicity. Pigments are typically excreted through the gastrointestinal tract, not through the urine.
Organik Pigmentlerdeki Safsızlıklar
Organic pigments are widely used as colorants in plastic consumer products, cosmetics, toys, and food packaging. Therefore, in addition to the toxicological and ecological properties of the pure pigments, the potential for trace impurities generated during production must be considered, potentially impacting their use in these consumer products. Possible impurities are listed below.
(1) Certain heavy metal compounds Some organic pigments (C.I. Pigment Red 48:1) use heavy metal salts (barium) as pigments and are therefore not recommended for use in food packaging materials and toys.
(2) Aromatic amines Aromatic amines are only allowed to appear in very low amounts as components of pigment synthesis in organic pigments. For use in food contact packaging materials, the upper limit has been clearly defined: Aromatic primary amines: <500ppm (mg/kg, total amount); 4-aminobiphenyl, benzidine, 2-naphthylamine, 2-methyl-4-chloroaniline: <10ppm (mg/kg, total amount).
(3) Polychlorinated biphenyls Polychlorinated biphenyls (PCBs) are mainly harmful because their persistent residues in the environment are more harmful than to humans. In the EU, chemicals containing 50ppm or more of polychlorinated biphenyls (PCBs) or PCTs are classified as polychlorinated biphenyls.
(4) Dioxins Pigment Violet 23 is prepared by condensing tetrachlorobenzoquinone with N-ethylcarbazole. During the synthesis process, a small amount of dioxins is inevitably formed.
Bischlorobiphenyl Pigmentlerin Güvenliği
Yellow-orange organic pigments synthesized from 3,3-bischlorobenzidine (DCB) are important azo pigments. DCB pigments are a key component of plastic coloring due to their vibrant color, high tinting strength, and affordability. Examples include Pigment Yellow 13, 14, 17, 81, and 83, and Pigment Orange 13 and 34.
Concerns persist about whether DCB series pigments used in chemical fiber non-woven textile materials, clothing zippers and button accessories, and food packaging materials meet the safety requirements of domestic and international ecological and environmental regulations.
Bischlorobenzidine is a probable carcinogen. The International Agency for Research on Cancer (IARC) classifies compounds into three categories based on their carcinogenicity: 1 – Carcinogenic to humans; 2A – Probably carcinogenic to humans; and 2B – Possibly carcinogenic to humans.
Bischlorobenzidine is a Category 2B carcinogen, and its carcinogenicity primarily occurs through the formation of adducts with nucleotides (DNA), leading to DNA mutagenesis. Polychlorinated biphenyls (PCBs) are highly bioaccumulative and difficult to biodegrade, significantly damaging the human endocrine system. Consequently, strict international regulations exist. The European Union prohibits the use of products containing PCBs exceeding 10 mg/kg; the United States prohibits the production, processing, sale, and use of products containing PCBs exceeding 25 mg/kg. The International Association for Research and Testing of Textile Ecology (Oske-Tex Standard 100 Special Technical Conditions for General Machines) stipulates that the content of 24 aromatic amines shall not exceed 20 mg/kg, and DCB is listed among them, see Table 1.
Tablo 1. Oeko-Tex Standard 100 24 aromatik amini listeler
Seri numarası
isim
CAS Numarası
Seri numarası
isim
CAS Numarası
1
4-Aminoanilin
92-67-1
13
3,3-Dimetil-4,4-diaminodifenilmetan
838-88-0
2
Benzidin
92-87-5
14
2-Metoksi-5-metilanilin
120-71-8
3
2-Metil-4-benzidin
95-69-2
15
4,4-Metilenbis(o-kloroanilin)
101-14-4
4
2-Naftilamin
91-59-8
16
4,4-Diaminodifenil eter
101-80-4
5
o-Aminoazotoluen
97-56-3
17
4,4-Diaminodifenil sülfür
139-65-1
6
2-Amino-4-nitrotoluidin
99-55-8
18
o-Benzilamin
95-53-4
7
p-Kloroanilin
106-47-8
19
2,4-Diaminotoluen
95-80-7
8
2,4-Diaminoanisol
615-05-4
20
2,4,5-Trimethylaniline
137-17-7
9
4,4-Diaminodifenilmetan
101-77-9
21
o-Anisidin
90-04-0
10
3,3-Dikloroanilin
91-94-1
22
2,4-Dimetilanilin
95-68-1
11
3,3-Dimetoksibenzidin
119-90-4
23
2,6-Dimetilanilin
87-62-7
12
3,3-Dimetilbenzidin
119-93-7
24
p-Aminoazobenzen
1960-9-3
Not: Kategori 1: İnsanlar için kanserojen olan aromatik aminler (4 tip, 1 ila 4);
Kategori 2: Hayvanlar için kanserojen olan ve insanlar için kanserojen olabilecek aromatik aminler (20 tür, 5 ila 24).
İnorganik Pigmentlerdeki Ağır Metaller
Titanyum dioksit, karbon siyahı ve ultramarin hariç, tüm inorganik pigmentler ağır metaller içerir. Diğer maddeler gibi ağır metaller de belirli konsantrasyonların üzerinde bulunduklarında insanlar ve çevre için tehlikeli kabul edilirler. Diğer ağır metallerin varlığı ağır metalin türüne ve formuna bağlıdır.
4.1 Krom Ağır Metal
Krom oksitler ya üç değerlikli ya da altı değerlikli krom içerir ve etkileri önemli ölçüde değişir. Altı değerlikli krom bileşikleri (kromatlar) oksijen açığa çıkararak üç değerlikli krom bileşiklerine dönüşme eğilimine sahiptir ve bu da organizmalar üzerinde güçlü oksitleyici ve toksik etkilere neden olur. İnsanlar, hayvanlar ve bitkiler için üç değerlikli krom bileşiklerinden 1.000 kata kadar daha toksiktirler.
Kurşun kromat pigmentler: Kurşun kromat pigmentleri, her ikisi de kronik tehlikelere sahip olan kurşun ve altı değerlikli krom içerir. Kurşun kromat düşük çözünürlüklü bir kurşun bileşiğidir. Çözünmüş kurşun, hidroklorik asit ve mide asidinde vücutta kurşun birikimine yol açan konsantrasyonlarda bulunur. Yüksek düzeyde kurşunun yutulması hemoglobin sentezini bozabilir. İhtiyati bir önlem olarak, Avrupa Birliği kurşun kromatı Kategori 3 kanserojen (kanserojen potansiyel şüphesi) olarak sınıflandırmıştır.
Krom Oksit Pigment Yeşili Krom oksit pigment yeşili sadece üç değerlikli krom içerir. Doğal koşullar altında, krom oksit pigment yeşilinden serbest krom partikülleri açığa çıkmaz. Güçlü asit koşulları altında bile (pH = 1-2), sadece küçük bir miktar (mg/kg) krom (III) açığa çıkar. Krom (III) oksit sadece ısıtıldığında, özellikle alkali koşullar altında krom (VI)'ya oksitlenebilir.
4.2 Kadmiyum Ağır Metal
Cadmium pigments are compounds with low solubility, but are soluble in dilute acid (at concentrations equivalent to gastric acid). Long-term oral ingestion of cadmium pigments can cause accumulation in the body. The European Commission has classified cadmium sulfide as a Class III carcinogen, but cadmium pigments are not included.
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