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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.
Acute toxiciteit van chemische stoffen
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.
Onzuiverheden in organische pigmenten
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.
Veiligheid van bischlorobifenylpigmenten
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.
Tabel 1. Oeko-Tex Standaard 100 vermeldt 24 aromatische aminen
Serienummer
naam
CAS-nummer
Serienummer
naam
CAS-nummer
1
4-Aminoaniline
92-67-1
13
3,3-Dimethyl-4,4-diaminodifenylmethaan
838-88-0
2
Benzidine
92-87-5
14
2-Methoxy-5-methylaniline
120-71-8
3
2-Methyl-4-benzidine
95-69-2
15
4,4-Methyleenbis(o-chlooraniline)
101-14-4
4
2-Naftylamine
91-59-8
16
4,4-diaminodifenylether
101-80-4
5
o-Aminoazotolueen
97-56-3
17
4,4-diaminodifenylsulfide
139-65-1
6
2-Amino-4-nitrotoluïdine
99-55-8
18
o-benzylamine
95-53-4
7
p-chlooraniline
106-47-8
19
2,4-diaminotolueen
95-80-7
8
2,4-diaminoanisol
615-05-4
20
2,4,5-trimethylaniline
137-17-7
9
4,4-diaminodifenylmethaan
101-77-9
21
o-Anisidine
90-04-0
10
3,3-Dichlooraniline
91-94-1
22
2,4-dimethylaniline
95-68-1
11
3,3-Dimethoxybenzidine
119-90-4
23
2,6-dimethylaniline
87-62-7
12
3,3-Dimethylbenzidine
119-93-7
24
p-Aminoazobenzeen
1960-9-3
Opmerking: Categorie 1:Â Aromatische aminen die kankerverwekkend zijn voor mensen (4 typen, 1 tot 4);
 Categorie 2: Aromatische aminen die kankerverwekkend zijn voor dieren en kankerverwekkend kunnen zijn voor mensen (20 types, 5 tot 24).
Zware metalen in anorganische pigmenten
Met uitzondering van titaniumdioxide, roet en ultramarijn bevatten alle anorganische pigmenten zware metalen. Net als andere stoffen worden zware metalen als gevaarlijk voor mens en milieu beschouwd als ze boven bepaalde concentraties aanwezig zijn. De aanwezigheid van andere zware metalen hangt af van het type en de vorm van het zware metaal.
4.1 Chroom Zwaar Metaal
Chroomoxiden bevatten driewaardig of zeswaardig chroom en hun effecten variëren aanzienlijk. Zeswaardige chroomverbindingen (chromaten) hebben een sterke neiging om te veranderen in driewaardige chroomverbindingen, waarbij zuurstof vrijkomt, wat leidt tot sterke oxiderende en toxische effecten op organismen. Ze zijn tot 1000 keer giftiger voor mensen, dieren en planten dan driewaardige chroomverbindingen.
Loodchromaatpigmenten: Loodchromaatpigmenten bevatten lood en zeswaardig chroom, die beide chronische gevaren inhouden. Loodchromaat is een loodverbinding met een lage oplosbaarheid. Opgelost lood wordt aangetroffen in zoutzuur en maagzuur in concentraties die leiden tot loodaccumulatie in het lichaam. Inname van hoge concentraties lood kan de hemoglobinesynthese verstoren. Als voorzorgsmaatregel heeft de Europese Unie loodchromaat geclassificeerd als een carcinogeen van categorie 3 (vermoedelijk carcinogeen potentieel).
Chroomoxidepigment groen Chroomoxidepigment groen bevat alleen driewaardig chroom. Onder natuurlijke omstandigheden komen er geen vrije chroomdeeltjes vrij uit het chroomoxidepigment groen. Zelfs onder sterk zure omstandigheden (pH = 1-2) komt slechts een kleine hoeveelheid (mg/kg) chroom(III) vrij. Chroom(III)oxide kan alleen bij verhitting worden geoxideerd tot chroom(VI), vooral onder alkalische omstandigheden.
4.2 Zware metalen cadmium
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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