ANALYSIS OF ALTERNATIVES non-confidential report - ECHA

ANALYSIS OF ALTERNATIVES

non-confidential report

Legal name of applicant(s): DEZA, a.s.

Substance: Dibutyl phthalate

Use title: Use in ceramic sheets and printing pastes for production of

capacitors and lambda sensor elements

Use number: Use 3


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CONTENTS

1. SUMMARY ............................................................................................................................................. 1

1.1. Background to this Application for Authorisation ......................................................................................... 1 1.1.1. Applicant and Uses .......................................................................................................................................... 1 1.1.2. The role of plasticizers ..................................................................................................................................... 2

1.2. Summary of Issues Considered When Determining the Approach to the AoA ............................................... 2

2. ANALYSIS OF SUBSTANCE FUNCTION.......................................................................................... 3

2.1. Background of the use of DBP in the manufacture of ceramic sheets and printing pastes ............................ 3

2.2. Descriptions of the use of DBP ...................................................................................................................... 4

2.3. Conditions of DBP use ................................................................................................................................... 9 2.3.1. Technical requirements for DBP and alternative substances ........................................................................ 11

3. IDENTIFICATION OF POSSIBLE ALTERNATIVES ................................................................... 11

3.1. Description of efforts made to identify possible alternatives .......................................................................11 3.1.1. Research and development ........................................................................................................................... 11 3.1.2. Data searches ................................................................................................................................................ 11 3.1.3. Consultations ................................................................................................................................................. 13

3.2. List of potential alternatives ........................................................................................................................13

4. SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES ................................... 16

4.1. ALTERNATIVE 1 ............................................................................................................................................16

4.2. ALTERNATIVE 2 ............................................................................................................................................16

4.3. ALTERNATIVE 3 ............................................................................................................................................16

4.4. ALTERNATIVE 4 ............................................................................................................................................16

4.5. ALTERNATIVE 5 ............................................................................................................................................16

4.6. ALTERNATIVE 6 ............................................................................................................................................17

5. OVERALL CONCLUSIONS ON SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES FOR USE 3 .................................................................................................................... 17

5.1. Conclusion on the technical feasibility of commercially proven alternatives ...............................................18

5.2. Conclusion on the economic feasibility of commercially proven alternatives ..............................................18

5.3. Conclusion on risk reduction potential of commercially proven alternatives ...............................................18

5.4. Overall conclusion........................................................................................................................................18


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FIGURES

Figure 1: Description of production ceramic chip capacitors-part 1 (Johanson Dielectrics) .............. 4 Figure 2 Description of production ceramic chip capacitors-part 2 (Johanson Dielectrics) ................ 4 Figure 3: Description of production ceramic chip capacitors (Lee, 2008) ......................................... 5

Figure 4: The principle of ceramic slurry preparing ........................................................................... 6 Figure 5: Manufacture dielectric paste and sheet formation (TDK, 2008) ......................................... 6 Figure 6: Electrode printing and sheet layering (TDK, 2008) ............................................................ 7 Figure 7: Cutting and sintering ............................................................................................................ 8 Figure 8: Application of terminal electrode, inspection and packaging (TDK, 2008) ........................ 8

Figure 9: The structure of ceramic capacitor (With, 1993; He, 2004) ................................................. 8

TABLE

Table 1. Parameters for DBP use in the manufacture of ceramic types............................................. 10 Table 2. Key information sources used in the identification of potential alternatives ....................... 12 Table 3. Key information sources used in the collection of information on the properties of potential

alternatives ......................................................................................................................................... 12

Table 4. Identities and REACH registration status of alternative substances .................................... 14 Table 5. Comparison of selected potential alternative substances against key technical comparison

criteria ................................................................................................................................................ 15


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1. SUMMARY

1.1. Background to this Application for Authorisation

1.1.1. Applicant and Uses

The applicant, DEZA, a.s. (hereafter referred to as “the applicant” or “DEZA”), is a Czech

manufacturer of dibutyl phthalate (DBP), EC No. 201-557-4, CAS No. 84-74-2. Dibutyl phthalate is

manufactured at site in Otrokovice, approximately 60 km from Valašské Meziříčí. DBP made by

DEZA is consumed in a number of uses; one of the smaller ones is the use of the substance by a

small number of EU-based companies in production of ceramic sheets and printing pastes used for

manufacture of capacitors and lambda sensor elements. The DBP is used as a plasticiser in slurry

for ceramic sheets and printing pastes manufacture and the use for which Authorisation is sought is:

1. Use in ceramic sheets and printing pastes for production of capacitors and lambda sensor

elements

The hazard profile of DBP, together with the potential risks that this substance may pose, has been

the subject of extensive expert assessment including a European risk assessment report (EU RAR

2003, Danish EPA 2011). This assessment reached a number of conclusions which indicated that

concern was warranted with regard to human exposures (including workers, consumers and from

exposure via the environment) and some environmental compartments.

DBP was included in the candidate list for Authorisation following ECHA’s decision ED/67/2008

on 28 October 2008, based upon its classification as Toxic to Reproduction, Category 2 (i.e.

Category 1B, under CLP); this was based largely on information from the EU RAR, supplemented

by limited additional information (ECHA 2009). DBP was further reviewed in a background

document prepared in support of its inclusion in Annex XIV (ECHA 2009), again drawing on the

EU RAR together with data submitted by COWI, IOM and Entec and RCOM.

Since DBP met the criteria in Article 57(c) and, according to available information, it was possible

to determine a toxicological threshold, it was noted that if the risks to human health from the use of

the substance arising from its toxicity to reproduction were to be demonstrated to be adequately

controlled in accordance with Section 6.4 of Annex I and that this was documented in the

applicant’s chemical safety report (CSR), an authorisation would be granted in accordance with

Article 60(2) (‘adequate control route’); if not, an authorisation would be granted in accordance

with Article 60(4) (‘socio-economic route’).

Alongside the Authorisation process, the Danish authorities submitted in 2011 a proposal for a

restriction (together with the justification and background information documented in an Annex XV

dossier) on the placing on the market and use of certain articles containing four classified phthalates

(DEHP, benzyl butyl phthalate (BBP), dibutyl phthalate (DBP) and diisobutyl phthalate (DIBP)) in

articles that are intended for indoor use, or in articles that come into contact with skin or mucous

membranes, on the grounds of the aforementioned Toxic to Reproduction, Category 1B CLP

classification.

The Annex XV report conforming to the requirements of the REACH Regulation was made

publicly available by ECHA on 16/09/2011. The final opinions of the ECHA Committees (i.e. the

Committee for Risk Assessment (RAC), and the Committee for Socio-Economic Analysis (SEAC))

were reached, by consensus, on 12/06/2012 and 05/12/2012, respectively. These are summarised

below:

“RAC considers that the proposed restriction is not justified because the available data do

not indicate that currently (2012) there is a risk from combined exposure to the four


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phthalates. The regulatory requirements and consequent reduction in use are further

reducing the risk, as will the authorisation requirements imposed on these phthalates in the

next few years” (ECHA, 2012c).

and

“Taking into account RAC’s conclusions that the proposed restriction is not justified

because the available data do not indicate that currently (2012) there is a risk from

combined exposure to the four phthalates and that the regulatory requirements and

consequent reduction in use are further reducing the risk, as will the authorisation

requirements imposed on these phthalates in the next few years, SEAC has no basis to

support the proposed restriction” (ECHA, 2012c).

This Application for Authorisation takes into consideration and expands upon the discussions held

at the time of the scrutiny of the Danish restriction proposal. It must be noted, however, that the

scope of this Application is significantly different as it covers only the industrial use of DBP in

closed system.

1.1.2. The role of plasticizers

A plasticiser is a substance which when added to a material, usually a plastic, produces a product

which is flexible, resilient and easier to handle. They are an important additive to ceramic slurry

and the majority of ceramic sheet products are plasticised. In modern applications plasticisers are

produced by complete solubility in a toluene/ethanol solvent mix with an acid such as phthalic

anhydride, adipic acid, terephthalic acid, trimellitic mellitate, etc. They are developed to satisfy

demanding technical and economic requirements and, due to their technical performance, versatility

and cost- effectiveness, phthalate-based plasticisers are the most widely used type within the EU

and globally.

Plasticisers are liquids of low or negligible volatility or low molecular weight solids and, in addition

to the processability, end-product softness, flexibility and extensibility (Sen, 2008) of a material,

they deliver a series of other concomitant effects. These include lowering of the glass transition

temperature (Tg) and softening temperature, reduction of strength, and increased impact resistance.

A plasticiser acts by lowering the intermolecular forces between the polymer chains and should be

compatible with the polymer or exudation will occur (Sen, 2008).

1.2. Summary of Issues Considered When Determining the Approach to the AoA

The key factors considered by the applicant, when determining how to assess substance function

and, hence, the overall feasibility and suitability of potential alternatives are summarised below.

Importantly, for an alternative to be suitable it must be technically and economically

feasible from the applicant’s (DEZA, a.s. and downstream users perspective). In terms

of technical feasibility, it must be technically possible for the applicant to manufacture

the alternative taking into account their existing plant or the potential for investment in

new plant, taking into account any constraints on moving to a new technology as a result

of patent restrictions or the availability of the precursor raw materials in sufficient

quantities. In addition, manufacture of the alternative must be economically feasible for

the applicant (especially for downstream users), taking into account requirements for

returns on new investments and the size of the downstream market for an alternative

plasticiser.


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The size of the downstream market will be determined by the technical and economic

feasibility of alternatives for downstream users. These aspects therefore must be

considered from the perspective of the applicant’s supply chain, as well as in terms of

more general considerations.

In terms of assessing the substance’s function, the technical requirements for the use of

an alternative plasticiser in an industrial setting have been combined with the

performance requirements of the substance. This increases the complexity of the

technical criteria each alternative must meet before it is considered a feasible alternative.

The scope of what a company further down the supply chain are limited a potentially

feasible alternative considered as technically or economically feasible from the

perspective of the applicant as well.

2. ANALYSIS OF SUBSTANCE FUNCTION

2.1. Background of the use of DBP in the manufacture of ceramic sheets and printing pastes

Plasticizers containing phthalates, such as DBP, are commonly used in small amounts (≤ 6%) for

the fabrication of ceramic components. This plasticizer is used to make ceramic sheets and printing

pastes from which the ceramic sensor elements for lambda sensor elements are produced. With

DBP it is possible to produce tapes which are more flexible, allowing it to be handled in

manufacturing operations with less mechanical damage. After the ceramic article is fabricated, it

undergoes a lengthy high temperature firing process (>1200°C) that eliminates all the organic

materials including the plasticizer. Because of the temperatures required to eliminate the organics,

phthalate is thermally decomposed, so no phthalate compound is discharged to the atmosphere.

Likewise, the final ceramic product after firing contains no phthalate.

The final products - ceramic sheets and printing pastes are used also for the manufacturing of

capacitors.

Capacitors are devices that store energy in the form of an electric field. They can also be used to

filter signals of different frequencies. The capacitance value is an indicator of how much electrical

charge the capacitor can hold.

This trend is attributed to the fact that large-scale high density multilayer ceramic capacitors relies

on the performance of ceramic types and high reliable multilayer ceramic capacitors are easily

realized using ceramic sheets and printing pastes. Conductive layers of multilayer ceramic

substrates are made by printing and connected through fine through holes. Chip capacitors made by

laminating green sheets need fine printing technique. The firing shrinkage of ceramic sheets

depends not only on the characteristics of ceramic powder but rather on the void generated in the

green sheets in the manufacturing process. When insufficient mixing causes non-uniform

distribution of ceramic powder, many voids are created because the ceramic powder in green sheets

remains as an agglomerated particle. These voids lower the density of green sheets and increase the

firing shrinkage, resulting in less dimensional reproducibility. Therefore, in order to obtain high

precision ceramics, it is important, other than quality of ceramic materials and powder

characteristics, to use green sheets to uniform mixture of ceramic powder, binder and solvent,

having little void in it. Using this technique, agglomerated particles can be pulverized to primary

particles without mechanical destruction. This technique is available to manufacture good quality

ceramic sheets with little pore (Ueyama at all, 1986).


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2.2. Descriptions of the use of DBP

Current use of DBP is in the manufacture of ceramic sheets and printing pastes for production of

capacitors and lambda sensor elements. The principle of manufacture by downstream user is

described in confidential annex.

Additional confidential information is presented in: Confidential Annex AoA Use3, Section 2: 2.1,

pages 1 - 3.

According to literature research is described the principle of manufacture in non-confidential part of

AoA, mentioned below.

Figure 1: Description of production ceramic chip capacitors-part 1 (Johanson Dielectrics)

Figure 2 Description of production ceramic chip capacitors-part 2 (Johanson Dielectrics)


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According to literature research were also published another types of this manufacture, see figure

below.

Figure 3: Description of production ceramic chip capacitors (Lee, 2008)

Frequently ceramic multilayer capacitor materials are based upon BaTiO3. Many titanates have the

perovskite structure. Titanates show a phase transformation at the temperature about 125°C. Above

this temperature the material is cubic and paraelectric. Below this temperature the material is

tetragonal and ferroelectric. In almost all cases substitutions are made to control the Curie

temperature. Also additives are used which modify the dielectric and electric behaviour. The

dielectric permittivity versus temperature is highly dependent on the microstructure, that is, main

composition, second phases and grain size (distribution) of the material. It is probably superfluous

to state that these materials have been largely optimized with respect to their functional behaviour

without considering their structural behaviour. Finally, it is important to note that the tetragonal and

cubic phases have different thermo-physical properties, e.g. thermal expansion coefficient, specific

volume and elastic constants (With, 1993).

One of the most critical material processing parameters is the degree of homogeneous mixing of

additives in the slurry. The binder distribution in the ceramic sheet is investigated to produce high

density, defect free layers. The degree of surface roughness is becoming a more serious problem

with thinner dielectric sheets. The roughness of 5 µm thick sheets must be controlled to less than

0.5 µm to provide a smooth contact surface with the inner nickel electrodes. This is very important


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factor in avoiding the concentration of electric field at asperities, where the charge emission from

the electrode is accelerated, resulting in short failure. For the same reason, the nickel metal powder

for the electrode paste must also be very fine, typically less than 0.5 µm and well dispersed in the

paste (Sakabe, 1997).

Figure 4: The principle of ceramic slurry preparing

The process of making ceramic capacitors involves following steps (Lee at all, 2006; Johanson

Dielectrics, 2013)

Manufacture of Dielectric Paste

Ceramic powder is mixed with binder and solvents to create the slurry; this makes it easy to process

the material.

Barium titanate and other metal oxides are dispersed into a toluene/ethanol solvent blend and mixed

thoroughly (step1) to produce low viscosity slurry. In step 2, high molecular weight binders are

added to increase the viscosity of the slurry and approximately 5-6% by weight, of DBP is added to

add plasticity. DBP has the correct properties to:

a) Dissolve effectively into the slurry mixture and

b) Provide the correct level of plasticity to allow further processing.

Sheet Formation

The slurry is poured onto conveyor belt inside a drying oven, resulting in the dry ceramic tape. This

is then cut into square pieces called sheets. The thickness of the sheet determines the voltagerating

of the capacitor.

Figure 5: Manufacture dielectric paste and sheet formation (TDK, 2008)


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Internal Electrode Printing

The electrode ink is made from a metal powder that is mixed with solvents and ceramic material to

make the electrode ink. The electrodes are now printed onto the ceramic sheets using a screen

printing process. This is similar to a t-shirt printing process. After that the sheets are stacked to

create a multilayer structure.

Sheet Layering and Pressing

Pressure is applied to the stack to fuse all the separate layers, this created a monolithic structure.

This is called a bar.

Figure 6: Electrode printing and sheet layering (TDK, 2008)

Cutting Multilayer Sheets and Chip Formation

The bar is cut into all the separate capacitors. The parts are now in what is called a ‘green’ state.

The smaller the size, the more parts there are in a bar.

Sintering

The parts are fired in kilns with slow moving conveyor belts. The temperature profile is very

important to the characteristics of the capacitors.


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Figure 7: Cutting and sintering

Application of Terminal Electrode Paste, Baking and Plating

The termination provides the first layer of electrical and mechanical connection to the capacitor.

Metal powder is mixed with solvents and glass frit to create the termination ink. Each terminal of

the capacitor is then dipped in the ink and the parts are fired in kilns. Using an electroplating

process, the termination is plated with a layer of nickel and then a layer of tin. The nickel is a

barrier layer between the termination and the tin plating. The tin is used to prevent the nickel from

oxidizing.

Inspection and Packaging

The parts are tested and sorted to their correct capacitance tolerances. At this point the capacitor

manufacturing is complete. The parts could be packaged on tape and reel after this process or

shipped as bulk.

Figure 8: Application of terminal electrode, inspection and packaging (TDK, 2008)

The structure of final ceramic capacitor is viewed below:

Figure 9: The structure of ceramic capacitor (With, 1993; He, 2004)

After the ceramic article is fabricated, it undergoes a lengthy high temperature firing process that

eliminates all the organic materials including plasticizer. Because of the temperatures required to


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eliminate the organics, any phthalate is thermally decomposed, so no phthalate compounds are

discharged to the atmosphere. Likewise, the final ceramic product after firing contains no DBP.

Off-gases from the clean-rooms where the phthalates are handled during manufacturing are cooled,

and the organics are separated from the air.

Gases from production equipment - ovens, dryers, etc. are burned in the incinerator.

The use of ceramic capacitors is very large, especially in automotive industry.

One of the most uses is in manufacture of oxygen sensors. An oxygen sensor (or lambda sensor) is

an electronic device that measures the proportion of oxygen (O2) in the gas or liquid being

analyzed. The original sensing element is made with a thimble-shaped zirconia ceramic coated on

both the exhaust and reference sides with a thin layer of platinum and comes in both heated and

unheated forms.

The planar-style sensor entered the market in 1998 (pioneered by Bosch) and significantly reduced

the mass of the ceramic sensing element as well as incorporating the heater within the ceramic

structure. This resulted in a sensor that started sooner and responded faster. The most common

application is to measure the exhaust gas concentration of oxygen for internal combustion engines

in automobiles and other vehicles.

It is necessary to mention that TechNavio's analysts forecast the Global Multilayer Ceramic

Capacitor market 2011-2015 to grow at a CAGR (Compounded Annual Growth Rate) of 17.23

percent over the period 2011-2015. One of the key factors contributing to this market growth is the

increasing demand for MLCCs in smartphones. The availability of cost-effective MLCCs is also

contributing to the growth of the Global Multilayer Ceramic Capacitor market.

2.3. Conditions of DBP use

The following table summarises the role of DBP in the manufacture of ceramic types and provides

an overview of how the substance has to be used in the manufacture of ceramic types.


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Table 1. Parameters for DBP use in the manufacture of ceramic types

Task(s)

performed

by the

substance

Plasticizer to make an intermediate ceramic slurry

Physical

form of

product

Liquid

Concentratio

n of

substance in

the product

DBP is used as a processing aid and is not detectable routine manufacturing quality control

methods in the final product

Critical

properties

and quality

criteria it

must fulfil

Key properties of DBP include:

1. Boiling point

2. Solubility in organic solvents

3. Vapour pressure at the temperatures used

4. Thermal stability

The most important effect is the behaviour of the tapes and pastes in the process. The diluents

influence the green and sinter density of the tapes. In the same way, the type and amount of

porosity is influenced. The diluents system must be the same in pastes and tapes and

influences the behaviour of the tapes, the printing shrinkage during the several printing steps

(up to 30). Too much porosity leads to less mechanical stability à insufficient life time. To

much more to less sinter shrinkage leads to bad functional values.

Function

conditions

(frequency of

use and

quantity

used)

Continuous use; Exposure Scenario covers daily exposures up to 8 hours per shift; operation

365/days/y

Consumption of DBP is variable, depending on the slurry output of the plant. Design

conditions allow for a consumption of < 6% (maximal use of DBP < 20 tonne/year)

Process and

performance

constraints

Temperature at which the lean solvent is introduced into the absorption step is below 75°C,

ideally 30-40 °C, to minimize overhead losses of the solvent

Conditions

under which

the use of the

substance

could be

eliminated

Use of DBP could only be eliminated if a suitable substitute could be used or the plant using

DBP converted to an alternative ceramic type manufacturing technology. The functionality of

DBP cannot be eliminated, the ceramic type manufacturing needs to have plasticizer of this

property. The only known potential alternative substances which currently find commercial

application are not suitable. Currently available alternative technologies are considered far

inferior in technical, commercial, economic and environmental impact terms.

Customer

requirements

associated

with the use

of the

substance

DBP user: for the user of DBP, the critical properties referred to above apply.

Ceramic type user: DBP is not incorporated into sintered ceramic type and is not detectable

according to routine manufacturing quality control testing. Thus the use of DBP in the

manufacture of ceramic type is of no consequence to downstream users.

Industry

sector and

legal

requirements

for technical

acceptability

that must be

met and

function

must deliver

Downstream industry is largely oblivious to use of DBP as it is generally absent from the

final product and does not affect its performance.


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2.3.1. Technical requirements for DBP and alternative substances

The technical requirements are described in confidential annex.

Additional confidential information is presented in: Confidential Annex AoA Use 3, Section 2: 2.2,

page 4.

3. IDENTIFICATION OF POSSIBLE ALTERNATIVES

3.1. Description of efforts made to identify possible alternatives

3.1.1. Research and development

Activities of downstream users of DBP

As downstream users formulate their products for a particular function and thus choose an

appropriate plasticiser to achieve that effect, they are not tied to a particular substance unless it is

the only one that is suitable in terms of its customers’ requirements and/or provides qualities that

other substances do not.

There is, therefore, an incentive for flexible slurry compounders to trial alternative substances in

order to leverage potential improvements in product properties or savings in processing or purchase

price. Developing more cost-effective compounds for their customers should provide a relative

market advantage. Downstream users therefore are not allied to a particular substance and hence

manufacturer (the applicants in this case).

It is clear from the responses to the consultation carried out to support this application that most

companies that carry out formulating and compounding activities have tried and tested a range of

plasticisers. It is also clear that those companies that produce ceramic sheets and printing pastes

have also tested alternatives to DBP. As a result, these downstream users have a good

understanding of whether the alternatives that they have tested (and perhaps others that they have

researched) are capable of delivering the properties that they or their customers require.

In the past was processed a development of change DBP for alternative substance, which could be

technically suitable, more information in confidential annex.

Additional confidential information is presented in: Confidential Annex AoA Use 3, Section 3:

3.1.1.1, pages 4 - 5.

In recent months one of DBP downstream users has indicated an alternative material, which is

compatible with their solvent, more information in confidential annex. The alternative material was

not yet tested in real production, so it is unknown whether it could replace DBP in short period.


3.1.1.2, pages 5 - 6.

3.1.2. Data searches

A literature review by compiler was undertaken for potential alternatives. The open literature has

been searched for information on both potential alternative substances of manufacture of ceramic


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types using keywords as “ceramic types”, “ceramic green sheet” and “ceramic chip capacitors”.

Once some information had been collected, the data searches were expanded to include additional

relevant keywords.

Information was sought on:

the identities of potential alternative substances (including acronyms, EC numbers and CAS

numbers for substances, where available);

information on technical parameters of alternative technologies, in particular information

from those licensing or using the available technologies; and

information on the technical feasibility, economic feasibility and human health and

environmental impacts profile of alternative substances and technologies.

The table below provides the main sources of information used, although as new leads were being

found a much larger number of individual Internet sites were visited when looking for information.

Table 2. Key information sources used in the identification of potential alternatives

Source Details Description

Google https://www.google.com Search engine

Science direct http://www.sciencedirect.com Scientific articles

Google Books http://www.google.com/advanced_book_search Books

With regards to the characteristics and properties of potential alternative substances, a range of

specialist websites have been systematically consulted. The following Table gives an overview of

some of the most important information sources that were used in the preparation of this analysis of

alternatives.

Table 3. Key information sources used in the collection of information on the properties of potential alternatives

Source Details Description

Google https://www.google.com Search engine

Scirus http://www.scirus.com Scientific search

engine

Science direct http://www.sciencedirect.com Scientific articles

ESIS http://esis.jrc.ec.europa.eu Chemical substance

inventory

ChemIDPlus http://chem.sis.nlm.nih.gov/chemidplus Chemical substance

inventory

US EPA Substance

Registry Services

http://semanticommunity.info/EPA/EPA_Substance_Registry_System Chemical substance

inventory

TOXNET http://toxnet.nlm.nih.gov Human health and

environmental data

ChemSpider http://www.chemspider.com Properties of

chemical substances

ChemNet http://www.chemnet.com Properties of

chemical substances

Chemical Book http://www.chemicalbook.com Properties of

chemical substances

TRC http://www.trc-canada.com/index.php Properties of

chemical substances

NIOSH http://www.cdc.gov/NIOSH Properties of

chemical substances

ECHA http://echa.europa.eu/web/guest/information-on-chemicals/registered-

substances

Properties of

chemical substances

Pubchem http://pubchem.ncbi.nlm.nih.gov Properties of

chemical substances

Sigma-aldrich http://www.sigmaaldrich.com Properties of

chemical substances

https://www.google.com/

http://www.sciencedirect.com/

http://www.google.com/advanced_book_search

https://www.google.com/

http://www.scirus.com/

http://www.sciencedirect.com/

http://esis.jrc.ec.europa.eu/

http://chem.sis.nlm.nih.gov/chemidplus

http://semanticommunity.info/EPA/EPA_Substance_Registry_System

http://toxnet.nlm.nih.gov/

http://www.chemspider.com/

http://www.chemnet.com/

http://www.chemicalbook.com/

http://www.trc-canada.com/index.php

http://www.cdc.gov/NIOSH

http://echa.europa.eu/web/guest/information-on-chemicals/registered-substances

http://echa.europa.eu/web/guest/information-on-chemicals/registered-substances

http://pubchem.ncbi.nlm.nih.gov/

http://www.sigmaaldrich.com/


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The core of the literature research was undertaken in the period May 2013 – June 2013.

3.1.3. Consultations

Consultation with the manufacturer of DBP

DEZA was asked to indicate whether it manufacturers any of the identified potential alternatives

that are either commercially proven or at the research and development stage. The company has

provided information on:

whether it manufactures any of the substances identified;

whether specific plans exist to start the manufacture of any substance;

if DEZA was theoretically able to start the manufacture of any substance, what tonnage

could potentially be placed on the market; and

if DEZA was unable to manufacture any substance, what were the key reasons and

difficulties behind this.

A questionnaire was prepared and submitted to DEZA in 2.5.2013 aimed at collecting the

information described above.

Consultation with current user of DBP

Consultation had been undertaken with - in confidential annex.


3.1.2, page 7.

Written questionnaires: a questionnaire was originally used for the collection of information. This

was prepared by compiler and submitted to users in 2.5.2013. The aim of the questionnaire was to

collect information on:

the use of DBP in the manufacture of ceramic types and the downstream applications;

the importance of DBP in this use;

the most important disadvantageous characteristics of DBP;

the most important advantageous characteristics of DBP;

the alternative substance(s) possible for substitute;

the technical suitability and economic feasibility of alternative substances.

Responses started being submitted 3.6.2013 and several additional questions were subsequently

added as the questionnaire evolved into a living document that facilitated the exchange of

information between compiler and companies (mentioned above).

Face-to-face meetings: several meetings were held with DEZA in preparation of this work on the

Application for Authorisation.

Email corresponding: when necessary, email conversations were held.

3.2. List of potential alternatives

The table presents alternative substances which are commonly referred to in the literature but are

only a few out of the thousands of potential alternatives investigates by current users. Although this

cannot be considered to be a shortlist of the best or most suitable potential alternatives, it provides a

useful overview of the families of substances that might be considered as possible for the selection

of suitable alternatives, i.e. phthalates, adipates.


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Table 4. Identities and REACH registration status of alternative substances

Alternative substance CAS No. EC No. REACH registered

2,2,4-trimethyl 1,3-pentanediol diisobutyrate 6846-50-0 229-934-9 Yes

Acetyl tributyl citrate 77-90-7 201-067-0 Yes

Alkylsulphonic phenylester 91082-17-6 293728-5 Yes

Butylated hydroxytoluene 128-37-0 204-881-4 Yes

Di - isobutyl phthalate 84-69-5 201-553-2 Yes

Di – isononyl adipate 33703-08-1 251-646-7 Yes

Di - isononyl phthalate 28553-12-0 249-079-5 Yes

Di (isononyl) cyclohexan 1,2-dicarboxylate 166412-78-8 431-890-2 Yes

Di(2-ethyl hexyl) adipate 103-23-1 203-090-1 Yes

Di(2-ethylhexyl) phosphate 298-07-7 206-056-4 Yes

Di-butyl adipate 105-99-7 203-350-4 Yes

Di-butyl sebacate 109-43-3 203-672-5 Yes

Diethylene benzyl benzoate 120-55-8 204-407-6 Yes

Diisobutyl adipate 141-04-8 205-450-3 No

Dioctyl adipate 123-79-5 204-652-9 No

Dioctyl sebacate 122-62-3 204-558-8 Yes

Dioctyl terephthalate 6422-86-2 229-176-9 Yes

Dipropylene Glycol Dibenzoate 27138-31-4 248-258-5 Yes

Epoxidized soybean oil 8013-07-8 232-391-0 Yes

Glycerides, Castor-oil-mono-, hydrogenated, acetates 736150-63-3 451-530-8 Yes

Glyceryl triacetate 102-76-1 203-051-9 Yes

O-toluene sulfonamide 88-19-7 201-808-8 Yes

Tri(2-ethylhexyl) phosphate 78-42-2 201-116-6 Yes

Tri-2-ethylhexyl trimellitate 3319-31-1 222-020-0 Yes

For each of the selected potential alternatives listed in Table below boiling point, flash point values

and solubility are presented. On the other hand, for solubility in slurry, a relative value in

comparison to DBP is generally given. The data in the Table have largely been provided by

literature research.

The following points must be noted:

values given in red colour indicate that the selected potential alternative substance does not

meet the relevant technical performance criterion;

for vapour pressure, for which a specific threshold has not been set, only values that are well

above the vapour pressure of DBP are marked in red colour;

the Table also contains (on the ride side) commentary on specific shortcomings of the

selected substances.

The Table clearly demonstrates that each of the selected solvents under investigation fail one or

more of the technical criteria established for DBP and therefore cannot be considered technically

feasible and, hence, realistic alternatives, at least at the present time.


15

Table 5. Comparison of selected potential alternative substances against key technical comparison criteria

Solvent

name

CAS

No EC No

Boiling

point

(°C)

Vapour

pressure

(kPa)

Flash

point

(°C)

Solubility

in organic

solvents

Comments

Dibutyl

phthalate

84-74-2 201-

557-4 340

9.7 * 10-6

at 20°C 191 Yes

Optimal combination of

properties from physical-

chemical perspective

Dibutyl

sebacate

109-43-

3

203-

672-5 344.5

4.69 * 10-6

at 25°C 178 Yes

Not optimal only within flash

point.

Di(2-

ethylhexyl)

adipate

103-23-

1

203-

090-1 417 3*10

-7 196 Yes

Optimal only within solubility

and flash point.

Diisononyl

phthalate

28553-

12-0

249-

079-5 341 6 * 10

-5 236 Yes

Optimal only within boiling

point and solubility.

DINCH

166412

-78-8

431-

890-2 397 2.2*10

-7 224 Yes

Optimal only within

solubility.

Di-isobutyl

adipate

141-04-

8

205-

450-3 280 0.00563 ?? Yes Optimal only within solubility

DOTP

6422-

86-2

229-

176-9 375 <0.001 212 Yes Optimal only within solubility

Di-butyl

adipate

105-99-

7

203-

350-4 183 0.021 113 Yes Optimal only within solubility

Dibutyl phthalate: CSR

Dibutyl sebacate: HSDB: http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~Wxy7yi:1

Chemspider.com

http://www.chemicalbook.com/ChemicalProductProperty_EN_CB8737502.htm

Di(2-ethylhexyl) adipate: ECHA Dissemination Portal

http://apps.echa.europa.eu/registered/data/dossiers/DISS-a134506c-6383-58e2-e044-00144f67d031/DISS-

a134506c-6383-58e2-e044-00144f67d031_DISS-a134506c-6383-58e2-e044-00144f67d031.html

Ministry of Economy, Trade and Industry http://www.meti.go.jp/english/report/downloadfiles/gED0311e.pdf

Diisononyl phthalate: ECHA Dissemination Portal

http://apps.echa.europa.eu/registered/data/dossiers/DISS-828e025b-9dd6-1b22-e044-00144fd73934/AGGR-

cb83eb9f-a441-4d41-9102-00d52b67b510_DISS-828e025b-9dd6-1b22-e044-00144fd73934.html#AGGR-cb83eb9f-

a441-4d41-9102-00d52b67b510

Australian Government Internet site:

http://www.nicnas.gov.au/Consultations/Draft%20PEC%20Assessment%20Report_DINP.pdf

Di-butyl adipate: NIOSH http://www.cdc.gov/niosh/ipcsneng/neng1705.html

IUCLID http://esis.jrc.ec.europa.eu/doc/IUCLID/data_sheets/105997.pdf

NIOSH http://www.cdc.gov/niosh/ipcsneng/neng1705.html

IUCLID http://esis.jrc.ec.europa.eu/doc/IUCLID/data_sheets/105997.pdf

National Centre for Biotechnology Information http://www.ncbi.nlm.nih.gov/pubmed/16835133

http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~Wxy7yi:1


http://apps.echa.europa.eu/registered/data/dossiers/DISS-a134506c-6383-58e2-e044-00144f67d031/DISS-a134506c-6383-58e2-e044-00144f67d031_DISS-a134506c-6383-58e2-e044-00144f67d031.html


http://www.meti.go.jp/english/report/downloadfiles/gED0311e.pdf

http://apps.echa.europa.eu/registered/data/dossiers/DISS-828e025b-9dd6-1b22-e044-00144fd73934/AGGR-cb83eb9f-a441-4d41-9102-00d52b67b510_DISS-828e025b-9dd6-1b22-e044-00144fd73934.html#AGGR-cb83eb9f-a441-4d41-9102-00d52b67b510




http://www.cdc.gov/niosh/ipcsneng/neng1705.html

http://esis.jrc.ec.europa.eu/doc/IUCLID/data_sheets/105997.pdf



http://www.ncbi.nlm.nih.gov/pubmed/16835133


16

4. SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES

The use of DBP is this case is unique, so no potential alternative can be disclosed to the public. The

number of companies producing the same or similar articles worldwide is very low, so even

disclosure of the name of alternative can harm downstream users of Applicant and could break the

position of these companies on the market

4.1. ALTERNATIVE 1

Alternative 1 is described in confidential annex.

Additional confidential information is presented in: Confidential Annex AoA Use 3, Section 4.1:

4.1.1 – 4.1.6, pages 8 – 15.

4.2. ALTERNATIVE 2



4.2.1 – 4.2.6, pages 15 - 18.

4.3. ALTERNATIVE 3



4.3.1 – 4.3.6, pages 19 – 21.

4.4. ALTERNATIVE 4



4.4.1 – 4.4.6, pages 22 – 24.

4.5. ALTERNATIVE 5




17

4.5.1 – 4.5.6, pages 25 - 27.

4.6. ALTERNATIVE 6



4.6.1 – 4.6.6, pages 28 – 31.

Overview table of desired properties for potential alternatives

Desired property Range, figure Comment

Physical state, melting point,

boiling point

Liquid, working temperature:

-35°C to 200°C

Handling and transport in winter

in country of origin, transit and

target destination for low limit

Process operation for high limit

Density (at 20°C) 0,98 – 1,1 g/cm3 Handling, pumping, analysis

Vapour pressure (20°C) Lower than 10e-5 kPa Safety requirement

Flash point >180°C Safety requirement

Affinity to metallic oxide powders

and precious metal powders

Process requirement

Solubility in organo metallic

substances

Process requirement

Water solubility 10,7 – 12,1 mg/L Needed for processing of the

mixture

Long-term stability at 20°C More than 6 months Needed for storage, handling

Note: all properties should be met for one potential alternative

5. OVERALL CONCLUSIONS ON SUITABILITY AND AVAILABILITY OF POSSIBLE

ALTERNATIVES FOR USE 3

Six commercially proven alternatives have been considered in this analysis: the alternative

substances.


18

5.1. Conclusion on the technical feasibility of commercially proven alternatives

Six commercially proven alternatives cannot be considered technically feasible for downstream

users, some of them also not for applicant. In terms of technical feasibility for the downstream user

they are not useful because of deficiency in the process. The deficiencies are described in

confidential annex.


page 32.

Technically, neither of eight alternatives can match the performance of DBP-based ceramic sheet

and the need for prolonged, complex and costly plant modifications render these alternatives

technically unfeasible and unrealistic for the applicant and the downstream user, particularly given

that the CSR has demonstrated that risks to workers health are adequately controlled.

5.2. Conclusion on the economic feasibility of commercially proven alternatives

Six commercially proven alternatives are not available to the downstream users of DBP (the

manufactured of ceramic sheets and printing pastes) from the perspective of technical feasibility.

The refused authorisation would have impacts for downstream users in loss of production, loss of

annual turnover etc.

From the perspective of the downstream user, the economic impact of loss DBP in production is

summarised in confidential annex.


pages 32 - 33.

The estimated annualised costs represent a very substantial proportion of the turnover of the

downstream users. Under either alternative, the cost of conversion is prohibitive, thus rendering

these alternatives economically unfeasible and entirely unrealistic, particularly since exposure of

workers to DBP is strictly controlled below the effects threshold.

5.3. Conclusion on risk reduction potential of commercially proven alternatives

In terms of risk reduction, it is important to consider the key premise of this Application for

Authorization: exposure of workers at the DEZA and downstream user’s plant is kept well below

the effect threshold. Adequate control of risk is demonstrated in the CSR, thus there is no

unacceptable risk for the endpoint of concern (reproductive toxicity). Therefore, the replacement of

DBP by an alternative substance would not confer any discernible benefit to workers health.

The information on alternative substances was taken from REACH registration dossiers. These

substances are not dangerous for human health and environment. The externalities of the release

because of using alternative substances were not established.

5.4. Overall conclusion

It is clear that DEZA and downstream users of DBP for the manufacture of ceramic sheets and

printing pastes for production of capacitors and lambda sensor elements would have very little

incentive to switch to either of the two commercially proven alternatives. These alternatives:

would not confer any discernible benefit to workers health as the risks from exposure to

DBP are adequately controlled as demonstrated in CSR;


19

can be detrimental to the quality of ceramic sheets product;

would require plant conversions which modification of the plant, would require very long

downtime of 48 months. It is estimated that additional 24 months would be required for

obtaining agreement of the company owners/ shareholders, drawing up of engineering plans,

cost estimation and raising capital and another 24 months to get EIA, certification of the

product etc.;

would be accompanied by much poorer economics that would make the manufacture of

ceramic types unprofitable.

In general terms, alternative substances cannot be considered to be available. Some of them could

not be produced by the Applicant. From the downstream user’s perspective, alternative substances

are unlikely to be available at the required tonnage.

The availability of commercially unproven alternatives has not been examined in detail. DEZA was

asked about its ability to manufacture and supply any of the theoretical alternative substances that

have been identified in the open literature. In general terms, DEZA manufacturers some phthalates

and adipates but has no knowledge or expertise in the manufacture of potential alternatives that

belong to other group of substances. Downstream users are not currently involved in the

manufacture or import of any of the identified potential alternative substances. It is expected that

availability will vary amongst the substances.

Making the commercially proven alternatives suitable is considered impossible with the current

level of knowledge. Indeed, it is considered unwise to invest time, effort and funds in attempting to

make the alternative. Any effort concentrated on them would be a backward step towards inefficient

processes with worse economics, which the applicant and the downstream users would not consider.

It is more realistic and practical to focus instead on the development of a suitable new alternative,

which even if commercially unproven at present, it can be properly researched and adapted to the

downstream technology of manufacture of ceramic types.

Downstream user is committed continuing its research and development work with the aim of

identifying and developing technical suitable and economically feasible alternatives which can be

obtained from the market in sufficient quantities.


20

APPENDIXES

Annex 1: List of data sources

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http://www.alibaba.com/trade/search?fsb=y&IndexArea=product_en&CatId=&SearchText=dibutyl+sebacate

http://www.alibaba.com/trade/search?fsb=y&IndexArea=product_en&CatId=&SearchText=dibutyl+sebacate

http://www.alibaba.com/trade/search?fsb=y&IndexArea=product_en&CatId=&SearchText=diisononyl+phthalate

http://www.alibaba.com/trade/search?fsb=y&IndexArea=product_en&CatId=&SearchText=diisononyl+phthalate

http://www.alibaba.com/trade/search?fsb=y&IndexArea=product_en&CatId=&SearchText=dotp

http://www.alibaba.com/trade/search?fsb=y&IndexArea=product_en&CatId=&SearchText=dotp

http://uk.alibaba.com/product/128210284-BASF-Hexamoll-Dinch-Plasticizer.html

http://worldaccount.basf.com/wa/NAFTA~en_US/Catalog/ChemicalsNAFTA/doc4/BASF/PRD/30085336/.pdf?title=&asset_type=msds/pdf&language=EN&validArea=CA&urn=urn:documentum:ProductBase_EU:09007af8802bb3e4.pdf



http://www.bdl-cee.com/home/diisobutyl-adipate-baleni-500mlcas-no.141-04-8

http://www.bdl-cee.com/home/diisobutyl-adipate-baleni-500mlcas-no.141-04-8

http://press.bosch.cz/detail.asp?f_id=177

http://www.bosch.com/media/com/sustainability/sustainability_new/downloads/GB_2012_EN.pdf

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21

Chemical Book. (2010) Diisononyl adipate. Retrieved July 30, 2013, from


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2&ExecuteSearch=true&fc=true&lang=cs

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4b55-b106-76dda4989dd6

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00144f67d031/DISS-a134506c-6383-58e2-e044-00144f67d031_DISS-a134506c-6383-

58e2-e044-00144f67d031.html




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http://echa.europa.eu/documents/10162/13640/justif_draft_annex_xiv_recom_en.pdf

http://echa.europa.eu/documents/10162/13637/authorisation_application_en.pdf

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http://echa.europa.eu/documents/10162/58050be8-f7be-4b55-b106-76dda4989dd6





22

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00144f67d249/DISS-9c7eba3b-31b2-3fd1-e044-00144f67d249_DISS-9c7eba3b-31b2-3fd1-

e044-00144f67d249.html

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df

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