| Front page | | Contents | | Previous | | Next |

Mapping and health assessment of chemical substances in shoe care products

3 Mapping

3.1 Mapping of products on the market
3.2 Kortlęgning af indholdsstoffer
     3.2.1 Solvents
     3.2.2 Wax, grease and oil
     3.2.3 Polymers
     3.2.4 Propellants
     3.2.5 Dyes
     3.2.6 Fragrances
     3.2.7 Surfactants
     3.2.8 Preservatives
     3.2.9 Other substances
3.3 Summary
3.4 Estimation of consumption
3.5 Selection of products for analysis

The purpose of phase 1 is to create an overview of shoe care products on the market and of what those products contain.

Phase 1 includes the following sub-activities:

• Mapping of shoe care products on the market
• Mapping of ingredients in shoe care products
• Estimate of consumption
• Selection of analysis parameters and products for analysis

In phase 1, shoe care products on the retail market have been mapped through visits to supermarkets, shoe stores, sporting good stores and heel bars as well as through contact to suppliers and manufacturers.

Experience shows that it is often hard to obtain complete composition information from the manufacturers and the first step has therefore been to obtain safety data sheets as well as sales numbers for Denmark.

3.1 Mapping of products on the market

The mapping is based on visits to the retail trade including supermarkets, shoe stores, sporting good stores and heel bars.

If a product was found in several colour nuances it was included as one product.

In addition, suppliers and manufacturers have been contacted for further information on the products in the form of safety data sheet and technical data sheets.

Table 1 lists the identified suppliers.

Table 1 Identified suppliers of shoe care products

The following brands were found on the market:

• Woly
• TiT
• Coxy
• Gold Quality
• Collonil
• Punch
• Boston
• KIWI
• Nikwax
• Other

Other products include sale products that are not part of the regular selection and smaller or unknown brands including products based on natural ingredients.

A total of 191 products were identified of which some are found in several colour nuances. Contact to the supplier revealed that 2 of the products had been discontinued. When these 2 products are subtracted there is thus a total of 189 products on the market.

The products can be divided into different product categories as seen in table 2. The division has been carried out from an estimation based on sales material received from the supplier as several of the products have more than one function, e.g. cleaning and impregnation or impregnation and colour refreshing.

The category ”Other specialty products” consists of a mixed group of products including “Shoe stretch”, i.e. products that can be used if the shoe pinches, products for treatment of soles etc..

Table 2 Overview of number of products in each category

Generally, the largest selection of products is found in heel bars and in stoe stores. More than 100 different products were identified (including different colour tones) in a single heel bar. In addition, it is mainly this type of store that carries specialty products such as shoe dyes in less ordinary colours, grain polish, odour removers etc. while supermarkets sell more commonly used products such as shoe polish (neutral, black, blue and brown), leather grease and impregnation products.

9 suppliers have been identified while there are 4 manufacturers. Some products can be found more than once in the mapping as some stores sell products under ”own label”. These products have been included with both product names as the ordinary consumer is unable to see that the products are the same.

Figure 1 Distribution of products in categories in %

The products are marketed primarily as paste (27%), liquid (33%) and aerosol (35%) as shoe polish is most often a paste, plejemidler most often liquids and impregnation products are usually aerosol products. Some products are foam or in the shape of a sponge impregnated with a liquid and only one product is a powder.

Table 3 Distribution in state

Figure 2 Distribution of products in state

3.2 Kortlægning af indholdsstoffer

Indholdsstoffer i skoplejemidler er primært kortlagt ved hjælp af de oplysninger, der fremgår af produkternes sikkerhedsdatablade og ved hjælp af litteraturen.

It has been possible to obtain safety data sheets for 172 of the 189 products corresponding to 91% of the products.

Information on ingredients (CAS-no., amount in the product and classification) is based in information in the safety data sheets for the products.

85 different ingredients have been identified. Substances with the same name and/or CAS-no. but with different classification have been included as 2 different substances. This is the case for e.g. naphtha (raw oil), hydrogen treated heavy CAS-no.: 64742-48-9 and stearylaminoxethylat. The classification of the substances can be seen in table 16 in chapter 5.

The reason why to kulbrintedestillater with the same CAS-no. can have different classification is that they are complex mixtures that can have a varied composition depending on the origin and destillation interval of the raw oil. Therefore, these destillates should be selvvurderes by the supplier or manufacturer and it is therefore not necessarily a mistake when two destillates do not have the same classification. The same is the case for surfactants that also do not have an unambiguously defined composition. The number of substances distributed on their function can be seen in table 4.

Table 4 Number of ingredients distributed on function

Figure 4 Number of ingredients distributed on their function in the product

Table 5 lists the ingredients with substance names and according to function indicating occurrence, i.e. in how many products the substance is found. The statement of occurrence has corrected for the same products having different names so that the ingredients have been included only once.

Table 5 Ingredients listed according to function and occurrence in the product

1) Softenser
2) Sun filter, stabilisor
3) Softener, flame retardant
4) Cross binder

From table 5 it can be seen that the most frequent ingredents in the 189 products are:

• 2-propanol (46 products, 24 %)
• propane (34 products, 18 %)
• butane (34 products, 18 %)
• naphtha (raw oil), hydrogen treated heavy (26 products, 14 %)
• naphtha (raw oil), hydrogen treated light (18 products, 9,5 %)
• heptane/heptane mixture (19 products, 10 %)
• test gasoline (aromat free) (19 products, 10 %)

3.2.1 Solvents

Organic solvents can dissolve grease, wax and oil. The solvents are used to dissolve the oils and waxes that are added to the products to make the footwear water-repellent. After application, the solvents evaporise and leave a water-repellent membrane on the footwear. The organic solvents can also be added to the products to clean grease and oil stains on the footwear.

29 different solvents have been registered. The solvents are distributed on: hydrocarbon destillates (13), aromatic hydrocarbons (2 – xylene and toluen), alcohols and glycols (8), acetates (3) and ketones (3). The most freqent are hydrocarbon destillates and isopropanol. Solvents are contained in all product types except for leather grease.

Test gasoline is a German designation for mineral turpentine CAS-no: 64742-82-1. Typical boiling point interval for mineral turpentine of this type is from 130-200°C. Seidegrensenbenzin is a kulbrinte destillate with a special boiling point interval in this case of 100 to 140°C. You also call this type of hydrocarbons SPB (special boiling point), special gasoline or extraction gasoline.

3.2.2 Wax, grease and oil

Wax, grease and oil is used in the products as softeners and water-repellent agents.

The registred types of wax and oil can be divided into natural (e.g. beeswax and olive oil), mineral (e.g. paraffin wax and vaseline) and synthetic (silicone oil). Silicone oils are used as impregnation as a water-repellent surface is formed on the footwear after application. Silicone is found in a total of 10 products: octamethyltrisiloxan (2 products) polydimethylsiloxan (1 product) as well as unspecified silicone (7 products).

3.2.3 Polymers

Polymers are compounds formed by small building blocks and chained together to form a network of molecules that form a film or surface coating on the materials on which they are applied.

The registration shows that a further 8 products contain polymers of which 2 are a unspecified resin (also called resin or polymer), in 1 case it is a maleinat resin and in 5 of the cases fluorcarbon resin.

Fluorcarbon resins are typically used as impregnation agents along with silicone.

3.2.4 Propellants

The most common propellants are butane and propane that are found in 34 aerosol products. It is no coincidence that the two substances have the same occurrence as a mixture of butane and propane is often used as a propellant. A few products contain isobutane instead of butane.

The combined occurrence of heptane is 19 products. As seen in table 16 in chapter 5, heptane is registered with two different classifications of which one corresponds to CAS-no: 142-82-5 corresponding ot the official classificaiton. As it is not immediately possible to determine what the designation ”heptane mixture” covers, and as no CAS-no. has been stated, it is not possible to determine whether the other classification is correct.

3.2.5 Dyes

A total of 7 dyes have been registered of which 2 have been stated with specific name and CAS-no., see table 6.

Table 6 Registered named dyes

This table can be supplemented with the dyes stated in table 7 which have been found using udtrækket from SPIN (impregnation products). In addition to these dyes there may, however, be a significantly larger amount of dyes in shoe care products, including titan dioxide and carbon black as mentioned in the introduction. However, information about dyes can rarely be found in the safety data sheets for the products.

Table 7 Dyes in impregnation products registered in SPIN

3.2.6 Fragrances

It has been registered that 5 products contain fragrances, but the fragrance has only been specified in one case: D-limonen. Significantly more of the products probably contrain perfume as several of the water-based shoe polishes and plejemidler are scented. Fragrances can be added to obtain a scent or to camouflage a bad scent.

3.2.7 Surfactants

Most of the surfactants are nonionic surfactants, but a sigle anionic surfactant (natriumlaureth-4-carboxylat), a fatty acid amine (stearylaminoxethylat) and an ammonium soap have, however, been found. Of the surfactants, stearylaminoxethylat is the most common as it is found in a total of 12 products. Ifralan is a trade name, but it is probably a nonionic surfactant of the alkylphenolethoxylat type. The surfactants may have been added due to their cleaning (grease dissolving) effect, in order to make it easier for the tending substances to penetrate the footwear or as emulgators in water-based products.

3.2.8 Preservatives

3 preservatives have been registered, two of which are found in 3 products while the last one is only found in one product. This means that 7 products contain a preservative. The actual number of products containing preservatives is probably larger as approximately 10-15% are water-based prodcuts and these must be assumed to be preserved. The water-based products are mainly found among the cleaning and tending products.

3.2.9 Other substances

In addition to the above, 10 substances have been registered in the category ”Other substances” including natural plant juices and flower nectar as well as ingredients that work as softeners, stabilisors and flame retardants.

3.3 Summary

The mapping of ingredients confirms the assumption that there are unwanted substances in shoe care products.

A large part of the registered products contain different types of solvents – most common are 2-propanol (water-miscible products) and hydrocarbon destillates (solvent-based (non water-miscible) products and aquous emulsions). Solvents of the C_9-12 isoalkane type, which are listed on the EPA list of unwanted substances, are not specifically stated as ingredients in any of the products for which information about ingredients is available.

Products have primarily been selected for analysis among products for which there was not already information available about ingredients.

It is expected that the water-based products, including aqous emulsions, may contain preservatives.

Two of the products contain dibutylphthalat in amounts of < 2.5 %. Dibutylphthalat is classified as toxic to reproduction according to the Order on Classification

It is not legal to sell products for private use if the content of dibutylphthalat is 0.5 % or above, i.e. the products may be illegal. However, information has subsequently indicated that both products are no longer on the market.

3.4 Estimation of consumption

It has been attempted to obtain a view of the relative amounts sold of the different producty types by contacting the individual suppliers. The relative amounts are important in the determination of which products are selected for analysis and in connection with the subsequent exposure assessment.

It has, however, only been possible to obtain information from 4 suppliers.

The sale of shoe care prodcuts in 2003 has been stated at 50,000 kg (50 tonnes) based on the information received with a distribution on product categories as shown in figure 5.

As not all suppliers have wished to inform us of sale numbers, the combined sold amount in Denmark is actually higher than the above informed amounts, but the percentage distribution on product types is assumed to be correct.

As can be seen from the figure, the sale of impregnation products in 2003 was approximately 29 tonnes and the impregnation products made up 58% of the sale of shoe care products. The sale of shoe polish (the sum of creams and liquid products) as approximately 20.5 tonnes corresponding ot 41% of the shoe care products sold. Other shoe care products made up approximately 1%, corresponding to approximately 0.5 ton.

Figure 5 Sale in 2003 distributed on product types.

3.5 Selection of products for analysis

Base on previous reports and extractions from the SPIN database it can be predicted that the products may contain the following subtsances, listen on the EPA list of unwanted substances:

• C_9-12 isoalkanes (impregnation products)
• Octamethylcyclotetrasiloxane (silicone-based impregnation products)
• PFOS-compounds (impregnation and shoe polish)
• Certain azo-dyes (coloured shoe polish and plejemidler) as well as other problematic substances such as
• Preservatives including isothiazolinones (water-based products)
• Various solvents (including benzene, trichlorethylen og 1,1,1-trichlorethan)

The mapping of ingredients supports this assumption as the products contain substances such as fluorcarbon resin, silicone, preservatives and dyes. In addition, a large number of the products contain solvents. In order to assess whether the products contain any of the above-menioned problematic substances, an analysis programme has been established which contain the following analyses:

• Organic solvents (found in non water-miscible products and possibly in aquous emulsions)
• Preservatives (used in water-based products and emulsions)
• Chlormethyl- and methylisothiazolones (preservative in water-based products)
• X-ray (screening for heavy metals which can i.e be found as impurities and be contained in dyes)
• Octamethylcyclotetrasiloxan (may be found in products containing silicone)
• PFOS-compounds (may be found in products containing fluorcarbon resin)
• Azo-dyes ^[14] (may be found in products containing red, yellow, orange and brown dyes)
• C₉-C₁₂ isoalkanes (may be found in products containing organic solvents, known to occur in certain impregnation products).

The criteria for selection of products for analysis have been:

• The products must represent different product categories
• The prodcuts must represent different suppliers
• The products must represent different states
• The must be a reasonable assumption that the product contains problematic substances – alternatively the ingredients in the product must be unknown or the amount of an ingredient should be controlled.

Thus, 14 products (approximately 7%) have been selected for analysis. The distribution on product types, supplier and state can be seen in table 8.

Table 8 Products selected for analysis

Red, brown and yellow-brown nuances have been selected for the coloured products.

Fodnoter

[10] Number of different products, each product is found in several colour nuances

[11] 2 of these products do not contain drivgas but rather are bottles with a pump mechanism

[12] The actual number of different subtsances is probably smaller as testbenzin without statement of CAS-no. may be covered by one of the other CAS-numbers.

[13] The actual number of dyes is much larger but the dyes are typically not stated in the safety data sheet.

[14] Among the dyes, the following pigments are potential PBT-substances: C.I. Pigment Yellow 83, C.I. Pigment yellow 13, C.I. Pigment orange 13, C.I. Pigment red 224 and C.I. Pigment yellow 14.

| Front page | | Contents | | Previous | | Next | | Top |

Version 1.0 June 2005, © Danish Environmental Protection Agency