Final Report Summary - BIOBEAUTY (Development of a bioplastic package for organic cosmetic creams - BIOBEAUTY -)
Executive Summary:
The global market for natural and organic cosmetics has never been more promising than today. Europe, being the main cosmetic market worldwide, is a prime target market for companies wishing to explore organic beauty. A critical success factor for natural cosmetics is product positioning, especially as these products come into direct competition with conventional brands in supermarkets, department stores and pharmacies. Market winners will be those companies that can successfully differentiate their products from competing ones. The need for complete product differentiation for organic cosmetic lines requires a bio package that offers the same environmental credentials as the product that it contains.
Environmental concerns such as plastic waste disposal (Directive 94/62/EC) and depletion of non-renewable resources together with the current trend towards greener formulations and sustainable credentials are a challenging opportunity for the development of alternatives to petroleum-based materials. Moreover, the limitations that bioplastics present in their performance provide a well-defined need for a technological solution. Most of the materials used in cosmetic packaging industries today are non-degradable such as Polypropylene and Poly(methyl methacrylate) pots, low and high density polyethylene and even ABL (aluminium barrier laminate) tubes. One of the main environmental problems we are facing today is therefore plastic packaging waste and its disposal. In 2010, 14.3 million tonnes of post-consumer plastics ended up in landfills in Europe. Packaging has become a central focus of waste reduction and bio-assimilation efforts as proper waste management is important to protect human health and the environment. The greatest environmental benefits that the project delivers are landfill waste reduction and the bio-sourced origin of the material.
The main aim of BIOBEAUTY project is to develop biopackaging for organic and eco product lines that offers the same environmental credentials as the product that it contains through a combination of nanotechnology and active packaging. It will be based on an environmentally friendly biomaterial such as a Poly(lactic acid) (PLA) bionanocomposite and a natural active agent with antioxidant properties. The incorporation of nanoclays to the biocomposite is to improve the barrier properties of the PLA, while the incorporation of natural antioxidants in the packaging is to delay the degradation of cosmetic creams.
The safety of each component, nanoclay and natural antioxidant active agent will be tested through in vitro toxicological studies. The package solutions are a PLA tube and a PLA pot. The processing technology for the development of the containers is extrusion moulding for the development of the PLA tube and injection moulding for the development of the PLA pot.
No commercial solution exist that meet both biodegradable and antioxidant cosmetic product requirements. This brings a big opportunity for SMEs both cosmetics manufacturers and polymer and packaging manufacturers to receive a commercial and economic return on their investment.
Project Context and Objectives:
The global market for natural and organic cosmetics has never been more promising than today. Market leaders as well as start-up companies are equally successful while major international brands are becoming more and more actively engaged in reaching their market potential.
An opportunity and at the same time a handicap is that the whole cosmetic market is becoming greener, including products that only claim to be natural. In the EU, the organic regulation (834/2007 of 28 June 2007 repealing 2092/91) does not currently include cosmetic products. Consequently, there are no legal requirements for using the terms ‘natural’ and ‘organic’ in these products, thus leading to different levels of “naturalness” and a tremendous amount of “green-washing”.
Thus, environmental concerns such as plastic waste disposal and depletion of non-renewable resources together with the current trend towards greener formulations and sustainable credentials are a challenging opportunity for the development of alternatives to petroleum-based materials with an emphasis on reducing environmental impact. Moreover, the limitations that bioplastics present in their performance, as compared to traditional plastics, provide a well-defined need for a technological solution.
The supply side is highly fragmented with over 400 European companies involved in producing natural and organic cosmetics. Most are small producers, with very few companies having a trans-regional presence.
However, high growth rates are attracting new entrants, which include large cosmetic companies that are launching natural and organic products. These companies can invest large quantities of money in R&D activities and marketing, whereas SMEs working with organic cosmetics do not have the knowledge, technological capabilities or R&D infrastructure to invest in a sustainable package by themselves.
A critical success factor for natural cosmetics is product positioning, especially as these products come into direct competition with conventional brands in supermarkets, department stores and pharmacies. Market winners will be those companies that can successfully differentiate their products from competing ones, such as organic cosmetics and sustainable solutions.
Therefore, there is a need for RTD research activities and institutional financial support in order to provide the conditions for relevant technological development that will make a difference in organic cosmetic SME competitiveness.
There are 450 million Europeans using beauty and personal care products every day, and the European market for beauty and personal care products was €71.2 billion in Europe in 2011.
A Eurobarometer report from the European Commission dated June 2011 reports that 72% of interviewed Europeans would be willing to pay more for environmentally-friendly products.
If in a market that generates €71.2 billion a year, 72% of consumers are willing to pay more for environmentally-friendly products, there is potentially a €51.26 billion market share for sustainable beauty and personal care products.
The current market situation, according to calculations by the British market researcher Organic Monitor which specialises in organic issues and sustainability, is that the worldwide market for natural beauty care is worth $9 billion (€7.1 billion). This report also highlights that the global market is dominated by the EU and the US. Furthermore, this is forecast to grow at an annual growth of 5%. If products with lower levels of natural compounds are included, sales estimates go up to $16 billion (€12.6 million). Large growth potential is forecast particularly for the emerging countries. The BRIC countries of Brazil, Russia, India and China are among the promising regions with which manufacturers of natural cosmetics are currently occupied. The incorporation of these new countries into the natural cosmetics sector is a clear threat to European SMEs in the coming years.
Within Europe, Germany is the most mature market for natural cosmetics. The range of certified natural cosmetics in Germany registered sales of €815 million in 2011 and achieved a market share of 6.5%. The German sector has increased sales by 50% alone since 2006, according to consumer researcher Gesellschaft für Konsumforschung (GfK).
Within beauty and personal care, organics are predominantly found in personal care products as their appeal is based on nourishment and long-term care. The appeal of products that are less damaging to long-term health means that consumers are most likely to buy into organic products in categories such as skin care, hair care, sun care and bath and shower.
However, organic cosmetic brands find it difficult to provide a consistent packaging for their “natural and organic” product lines. These products have fewer preservatives than traditional cosmetics and therefore a shorter shelf life. The package, however, must provide adequate protection for a proper shelf life.
The need for complete product differentiation for organic cosmetic lines requires a biopackage that offers the same environmental credentials as the product that it contains.
Skin cosmetic creams with eco/organic lines do not currently have truly bio-based packaging, which meet the requirements for their product lines. Therefore, by overcoming this limitation the consortium SMEs will have a significant competitive advantage, and fulfil the demands of an educated and conscientious consumer.
The main aim of BIOBEAUTY project is to develop biopackaging for organic and eco product lines that offers the same environmental credentials as the product that it contains through a combination of nanotechnology and active packaging. It will be based on an environmentally friendly biomaterial such as a Poly(lactic acid) (PLA) bionanocomposite and a natural active agent with antioxidant properties. The incorporation of nanoclays to the biocomposite is to improve the barrier properties of the PLA, while the incorporation of natural antioxidants in the packaging is to delay the degradation of cosmetic creams.
The safety of each component, nanoclay and natural antioxidant active agent will be tested through in vitro toxicological studies.
The package solutions are a PLA tube and a PLA pot. The processing technology for the development of the containers is extrusion moulding for the development of the PLA tube and injection moulding for the development of the PLA pot.
Cosmetic skin treatment creams contain both aqueous and anhydrous phases. They are emulsions that contain two phases (water and oil), which are incompatible with each other and use an emulsifier to reduce the interfacial tension between the two phases and provide an input of shearing energy. Due to their lipid content, these products are sensitive to oxidation mechanisms and therefore require packaging with good barrier properties.
Poly(lactic acid) is aliphatic polyester made up of lactic acid (2-hydroxy propionic acid) building blocks. Because PLA is compostable and derived from renewable sources such as starch and sugar, it has been considered as one of the solutions to alleviate solid waste disposal problems and to lessen the dependence upon non-renewable resources for packaging materials.
However, PLA lacks the mechanical, thermal and barrier properties of conventional polymers. A package for cosmetic skin creams requires these properties in order to protect the product. To overcome these limitations, organomodified clays and active agents will be used to develop a new active bionanocomposite material that can provide adequate quality and shelf life.
Layered silicate clays will be organically modified to compatibilise and facilitate their dispersion in the PLA matrix. Quaternary alkylammonium cations will be used for the cation exchange that creates the modification.
The properties of clay nanocomposites are highly dependent on how well the clay disperses in the polymer matrix which will depend on the exfoliation of the clay. Clay exfoliation involves the isolation of clay nanoplatelets in the polymer matrix, leading to a layered nanocomposite. With this structure best improvements are achieved. Considering the chemical compatibility of the clay and the matrix, and the processing conditions, the exfoliation and dispersion of the clays will be optimised.
According to the actual Cosmetic Directive (EC) 1223/2009 the SMEs must fulfil a Cosmetic Safety Report, prior to placing the product in the market. In this sense, the toxicological studies are critical to ensure the safety of the nanocomposite and its components prior to their widespread use. The physico-chemical properties of nanomaterials are fundamental to their toxicity. Accordingly, particle attributes such as size, shape, composition, charge etc. are able to influence nanomaterial toxicity. This information can be used within the safe and intelligent design of nanomaterials. Due to diversity of nanomaterials under production and use it is essential to develop predictive in vitro models that are able to screen nanomaterial toxicity using cells that represent primary or secondary sites of nanomaterial toxicity. Promoting the development of alternatives to animal testing is required to minimise animal use which is necessary from both a financial, time and ethical perspective. The area of nanotoxicology first emerged in the early 2000s and there has been an exponential increase in the number of hazard and exposure studies concerned with evaluating nanomaterial safety (risk). Although there is an absence of standardised tests that enable an evaluation of nanomaterial toxicity, it has been frequently observed that nanomaterials cause toxicity via oxidative and pro-inflammatory responses. The ability of nanomaterials to induce cytotoxicity is often utilised to benchmark the toxicity of particles, and identify sub-lethal concentrations of nanomaterial to assess the mechanistic drivers of any observed effects. In BioBeauty project, compounding and packaging material toxicity will be evaluated in order to obtain a safe packaging.
The incorporation of a natural antioxidant agent to the package will compensate for the possibly less effective barrier properties of the package. Furthermore, it will provide the system with a controlled and continuous infeed of antioxidant that will protect the product from deterioration. This release mechanism can extend the product’s shelf life by maintaining the levels of antioxidant over its shelf life. The main advantage of active packaging is that it offers an extended shelf life for the packaged product by adjusting its kinetics. It can also be adjusted to match the exact needs of the product. Expected shelf life of the proposed biopackage is 1.5-year.
The main aim of the project is the development of a biopackage for organic cosmetic lines that offers the same environmental credentials as the product that it contains. This packaging solution has three components (PLA biopolymer, nanoclay, natural antioxidant) and the combination of these components is what provides the performance that is required for cosmetic products.
To achieve this overall aim specific scientific and technological objective will have to be reached:
1. Generation of knowledge on nanoclay modification, tailored for biodegaradable thermoplastic polyesters.
2. Understanding of the mechanisms of release of the active components from the packaging materials to the cosmetic matrix.
3. Increase knowledge about the combination of nanoclays and active compounds to evaluate synergies between them.
4. Increase knowledge about security protocols of nanomaterials intended for packaging cosmetic sector.
5. Improved Oxygen gas barrier properties of PLA using layered nanocomposites.
6. Adjustment of the adequate control release of antioxidant agents.
7. Adjustment of processing parameters of materials and strategy to add antioxidant agents and nanoclays to the PLA matrix.
8. Optimised performance of the new packages in the filling and closing machines at the industrial cosmetic manufacturer.
9. Assessment of the toxicity of the packaging.
8. Conservation of the organic skin cream in the proposed package for at least 1 year.
9. No excess in the final price.
10. Increase market share
Project Results:
The technical work performed during the project of execution of the project, include the research and development activities carried out within the WP2, WP3, WP4, WP5 and WP6.
WP2 has been completely executed. This WP has dealt with the selection of natural antioxidants, based on evaluation tests performed through different procedures. These test will assess its effectiveness, safety and stability.
The first task within this WP was a preliminary selection that included 10 natural antioxidant extracted by VITIVA from plants. In addition, some commercial antioxidants were selected in order to obtain a target value of antioxidant capacity to achieve with the natural ones. The tests carried out included:
A) Concentration of the active compounds.
B) Thermal stability.
C) Antioxidant capacity of the antioxidants samples – DPPH.
D) Oxidative stability of the oily phase incorporating the antioxidants – Rancimat Tests.
E) Oxidative stability of the cosmetic products incorporating the antioxidants
F) Incorporation of the antioxidants into the polymer matrix.
G) Thermal properties of the materials incorporating antioxidants – DSC.
H) Mechanical properties of the materials incorporating antioxidants.
I) Release of active compounds into a cosmetic simulant from the polymeric matrices selected.
J) Chemical stability of antioxidant extracts in IPA at 30 ºC
K) Antioxidant activity of the released fraction from the materials into IPA.
It is important to highlight that the release tests revealed a slow release kinetics of the active compounds, which led us to the final conclusion that encapsulation process was not needed.
The samples with the best properties were: A6, A7, A9, A1 and A10. These samples showed even better performance in terms of antioxidant capacity than commercial antioxidants. These samples were selected for the toxicological studies in which toxicity test has been performed to screen the safety of the antioxidant compounds assessed using in vitro skin cell models.
Regarding the toxicological results, A6 did not show any irritation potential at the concentration tested (40 ppm). However, lower incorporation level (<4%) is recommended to ensure tests are relevant and to minimise any potential for toxicity. Based on results of sensitisation studies, samples that are less reactive (e.g. A9, A10, A1) and which produced less/no cytokines could be a safer choice (e.g. A7, A8 and A9). In particular sample A9 meets both these criteria and thus selection of such an antioxidant would lower sensitisation potential. In addition, this sample also showed very good anti-oxidative capacity.
WP3 has been completely finished. This WP has dealt with the development of modified clays for PLA packaging applications. The final objective is to obtain a nanocomposite material to be used in the final packaging, which cause a reduction in the oxygen permeability values.
The first Step was the selection of the clays and organomodifiers suitable to produce the organo-modified clays for PLA. From this study, sodium montmorillonite was selected as raw clay and different modifiers (quats) were selected from a list of approved substances for cosmetic applications according to the European cosmetic regulation (EC) No 1223/2009, and taken into account availability at industrial scale and price. Finally, 4 modifiers were selected HDTA, DTMA, DMOA, TMSA. The modified clays were developed at laboratory scale for subsequent characterization. Different modifier contents and procedures have been used (aqueous media and a mixture of aqueous/ethanol media). In total, 40 modified clays in powder form were developed. Also polymer nanocomposites have been obtained to be able to make a good decision of the clay selection.
Once all the organoclays have been obtained they have been characterised in order to determine the effectiveness of the modification reaction by means of quantification of the modifier present in the organoclay as well as the increase of the interlayer distance propitiated by the intercalation of the long chain alkylammonium compounds between the clay platelets. Apart from these analyses, the dispersion of the clay in the polymeric matrix of PLA was evaluated to know the interaction between the clay and the polymer chains. After characterization, it was concluded that samples prepared with the modified clays exchanged with TMSA and HDTA, are the most suitable for our application and the results were collected in Deliverable 3.1.
After being selected the routes of modification of the nanoclays, assessments focused on potential hazards associated with dermal exposure, as the primary concern of consumer exposure to the nanoclays and modifiers were evaluated and described in Deliverable 3.2. A total of four different quaternary ammonium salts (HDTA, DTMA, DMOA and TMSA) were screened for irritation potential in preliminary tests. However, following results from modification efficiency studies, DTMA and DMOA did not meet the selection criteria and thus only nanoclays modified using HDTA and TMSA were tested in the hazard assessment.
Hypothetical exposure assessments were devised in order to predict what concentrations of nanoclays may be reached in a worst case and a more realistic exposure scenario.
Following a detailed hazard assessment results have revealed that while there is no evident hazard associated with the use of unmodified raw nanoclays, their modification increases their hazard potential. There was also no evidence of sensitisation found for unmodified and modified nanoclays. Hazard assessments performed on the HDTA and TMSA modified clays allowed investigations on the potential contribution of modifier to any observed effects to be performed. Based on the hazard potential, N116_1HDTA_H20 was the most appropriated for use in the nanocomposite development. Furthermore, the migration of (N116_1HDTA_H20) into the cosmetic at concentrations up to 0.4% (worst case scenario) should not produce adverse effects according to lack of cytotoxicity towards keratinocytes, no irritation seen using EpiDermTM models and no evidence of sensitisation potential.
WP4 has been completely executed. This WP has been focused on the development of nanocomposites with the organoclays obtained at WP3 (N116_1TMSA and N116_8HDTA), and scaled in this WP4 as well as the antioxidant selected from WP2 (AOX8 from VITIVA). The characterization of nanocomposites has been evaluated with the aim of confirming a good interaction between the polymer matrix and the clay platelets, and therefore to obtain high improvement in barrier properties. These all results have been included in the Deliverable 4.1.
In this deliverable the characterization of organoclays scaled (pilot scale), confirm the same properties achieved at the laboratory, regarding yield of reaction, washing effectiveness and increase of interlayer distance (50 % reaction yield and 20 Å of interlayer space). Once obtained the different batches of both organoclays, nanocomposites with two different grades of PLA (PLA3052D for pots and PLA2003 for tubes) were processed by using a microcompounding system and injected samples were obtained to be characterized, confirming its effect, especially on barrier properties.
Besides this, samples with different concentrations of organoclay and the antioxidant selected were also processed and characterized with the aim of observing the interaction between them. Then, it was concluded that both organoclays (N116_8HDTA and N116_1TMSA) at 4% with the AOX8, had a negative impact on the processability of the samples, probably due to the degradation of polymer and the consequent loss of properties, making possible the selection of those materials and at maximum concentration of 2% for obtaining of the biopackages in the WP5. As conclusions, 4 compositions were selected as the most promising to obtain our biopackages (1. PLA+2%N116_1TMSA+2%AOX8, 2. PLA+2%N116_8HDTA+2%AOX8, 3. PLA+4%N116_1TMSA and 4. PLA+4%N116_8HDTA and the same with 20% of PBS for tubes, since PBS was necessary for their processability).
On the other side, also as a part of the work involved in this WP, the study of the release kinetics of antioxidant system from the different packaging materials were studied and the results were collected in Deliverable 4.2. Two types of packages have been considered; a PLA pot and a PLA tube. In a first instance, the release of antioxidant activity was experimentally determined to estimate the diffusion coefficients of each material composition.
In both cases, the active packaging materials were able to release antioxidant activity to the cosmetic simulants. In addition, the kinetics associated to each material were different; the inclusion of additives, such as plasticizers and other polymers, increased the diffusivity of antioxidant activity from 10-11 to 10-9 cm2/s. In this sense, in function of the specific requirements of the cosmetics in terms of release of antioxidant activity from the packages, the selection of a given additive and concentration to be incorporated into the PLA matrices can be carried out.
However, the composition for pots and tubes was selected based on processability requirements; PLA3052 + 2% AOX8 and PLA2003 + 20%PBS + 2% AOX8, respectively.
The active performance of these two packaging formulations was assessed by simulation considering the obtained experimental diffusion coefficients and assuming different scenarios in function of the equilibrium constant and degradation/consumption rate of the antioxidant system in the cosmetic. In this sense, materials incorporating 2% of antioxidant should be suitable to provide antioxidant preservation of the cosmetic even for a longer shelf-life and even for the largest degradation rate (250%), although equilibrium constant should be lower than 40.
In the case of the biodegradability evaluation, tests were finally carried out with the packages developed in WP5, with the compositions selected as the most promising from the results of characterization.
Then, the compostability of samples was analysed according to EN 13432:2000 with some modifications. The main conclusions are:
- Chemical composition of packages materials was suitable for composting.
- Disintegration test after 90 days showed a percentage of disintegration higher than 90%, therefore, the samples are considered disintegrable according EN 13432:2000.
- Biodegradation of the samples was more than 90% in comparison with the reference material (cellulose) what means that the samples are biodegradable according EN 13432:2000.
- Compost quality was not influenced by the presence of the packaging materials as confirmed by physico-chemical analyses and also by plant toxicity tests in Lepidium sativum and Hordeum vulgare, ensuring that compost from packaging materials are suitable to support plant growth.
This study was performed directly on the prototypes developed at WP5, and the results are fully described in Annex 1, and submitted directly to the project officer.
The potential hazards that may arise from the use of these PLA based nanocomposites for cosmetic packaging applications have been described in Deliverable 4.3. It has been focused on assessment of the dermal toxicity of components which may migrate from the PLA nanocomposites into the cosmetic formulations.
An experimental approach was designed to test the biocompatibility of the nanocomposites and their potential to release migration extracts that could be cytotoxic or phototoxic towards human HaCaT keratinocyte skin cells or cause skin irritation in the EpiDermTM human skin model, according to OECD TG 439. Overall findings from these studies provide valuable information to show that the PLA nanocomposites developed within the BioBeauty project can be used safely in the cosmetic packaging industry and meet regulatory requirements.
WP5 has been completely executed. The selected formulations after the characterization in the WP4 of the nanocomposites, were used for the preparation of the compound at pilot scale, the processing of the packages, and the evaluation of tubes and pots to select the final composition. In this work, the process parameters for each formulation were optimized for obtaining the tube and the pot, before carrying out the industrial scaled up. Compounding and processing conditions for each format are collected in Deliverable 5.1 and 5.2. While the tube was obtained by extrusion moulding, the pot was done by injection moulding, as well as its cap. In the case of the development of tube prototypes, some considerations were taken into account. As a result of trials at ETS-BUGNON facilities, different processing solutions were proposed to overcome processing issues with antioxidants due to its low melt strength. The most promising was the production of a bilayer tube prototype (PLA+CLAY / PBS+Antioxidant), however it is not available at ETS-BUGNON. Another option was to produce injection moulded pieces based on PBS to be subsequently introduced in the developed PLA tube prototypes. This has been considered as the viable solution. For this purpose, new compounds based on formulations of PBS and antioxidant have been developed.
Once optimized the parameters in the respective processing equipment, they were characterized according to mechanical, barrier, thermal and optical properties as well as the thickness uniformity.
Taking into account the results, for the semi-industrial trials to obtain the pots, were selected the samples with the compositions PLA3052+4%N116_8HDTA and PLA+2%N116_8HDTA+2%AOX8, while in the case of the tubes was the formulation PLA2003+20%PBS+4%N116_8HDTA.
Parallel to the characterization, HWU carried out the hazard assessment of the packaging prototype with their respective formulations, which results are collected in Deliverable 5.3. As a result of the different tests, it was observed a lack of skin irritation from cosmetic formulations in contact with prototype packaging material for 1 month at 40 °C, what suggested that there is likely to be no skin irritation hazard associated with the use of the packaging.
The phototoxic potential associated with the use of the natural antioxidant constituent (polyphenols (UV) from green tea, carnosic acid and oleuropein) in AOX8 and the reduction in viability in the EpiDermTM in vitro skin model upon application of cosmetic formulations, that have been in contact with packaging incorporating 2 % wt/wt antioxidant, suggest a possible phototoxic hazard associated with the use of AOX8. This hazard can be reduced by lowering the incorporation level of AOX8 (<2% wt/wt (0.156 % wt/wt recommended)) in the packaging or removing the polyphenols (UV) from green tea, carnosic acid and oleuropein constituents from AOX8. Importantly, whilst the studies performed within the BioBeauty project have focused on performing a comprehensive assessment of the potential dermal toxicity of the packaging material, hazards at other target sites may also need to be investigated
Finally, shelf life study of the cosmetic product was evaluated with the final packages developed in the WP6, whose results are collected in Deliverable 6.2.
WP6 has been completely executed. The packages selected to be developed at semi-industrial scale were those whose better properties were obtained in the WP5 (Pots: PLA+4%N116_8HDTA, PLA+2%N116_8HDTA+3%AOX8; Tubes: PLA+20%PBS+4%N116_8HDTA with a sheet composed of PBS+2%AOX8 and PBS+3%AOX8). First of all, for the production of the different packages at semi-industrial scale in the facilities of the industrial partners, it was necessary to scale the production of PLA nanocomposite compound as well as the PBS+AOX8 compound.
The production of the compounds mentioned before was carried out by Martin Snijder Holding. As starting conditions (collected in Deliverable 6.1) the processing parameters previously determined in pilot scale trials have been used, and then adjusted to optimize final compounding process.
For the processing of samples, previous knowledge suggested to evaluate low screw speeds, while keeping processing temperatures as low as possible to avoid polymer degradation.
No further modification in compound formulations was considered as a result of technical evaluation. Therefore, it was considered that the production of tube prototypes carried out at ETS-BUGNON in WP5 represented an industrial processing of final packages, and it was not necessary to produce again these prototypes in this work package.
The production of final PLA based pots was carried out at Miniland facilities. The process is based on the injection of both halves of pot (body and thread), on the same step.
To perform the final industrial processing trials of PLA pots it has been considered to start with the processing parameters optimized previously in WP5, and then adjust it until producing the package under the best conditions.
In the same way it was done with compounds based on PLA 3052D, the two compounds based on PBS previously processed by MSH, were crystallized prior injection moulded processing.
These crystallized compounds have been injected at Miniland facilities, in order to produce circular pieces providing active properties from the antioxidant present in its formulations.
Once processed on previous stages, prototypes were evaluated through an industrial scale filling process. After the tubes were arranged through the automatic tube feeding device, next step was to place them into the cup seats.
Once filled, table will continue its rotation and rapidly bring the tubes to different work stations for sealing. Once sealed, final station prints code and date tubes are and trimmed to remove tail excess.
Procedure for pot filling is analogous to tubes. Filling is achieved through a volumetric dosing unit. Once filled, pots continue its rotation and continues to capping station. Caps are usually fed from hopper using an inclined chute.
This pot type has a screw cap without sealing. Therefore, tightening force is critical to ensure the integrity of the container (scheme of the filling process were described in Deliverable 6.1).
To study the integrity of the packages, molecular weight (Mw) of PLA pots and tubes was studied along time in order to know the effect and tendency that cosmetic cream produced in the final material. For that, it was studied the Mw of the PLA in several periods of time (0, 8, 15, 35, 56 and 70 days) in pots and tubes which were maintained at 40 °C including the cosmetic cream inside. Results were collected in Deliverable 6.2 and it was appreciated a decrease in the Mw along time. Moreover, this decrease is more significant in the case of the pots not containing AOX. In the case of PLA tubes without clays, they showed almost a constant Mw along time. However, in the case of PLA containing clays, there is a clear decrease in the Mw, especially for the case of PLA reinforced with clay 1 which showed a decrease of 36% at day 70 versus day 0.
Apart from the stability of the packages, shelf life of cosmetic products filled in the new packages have been evaluated though lipid oxidation according to TBARS method during the accelerated oxidation experiment, whose results are detailed in Deliverable 6.2.
In the case of Alissi Bronte cosmetics, it could be observed that cosmetics remained quite stable in terms of oxidation up to day 20. From that time, the cosmetics packed in the different packaging systems underwent different degrees of oxidation over time.
The best packaging composition identified was the PLA containing 2% A8 and clay 2 at 2% followed by the same material containing clay 2 and no antioxidant. The other materials based on clay 1 also reduced the oxidation of the cosmetic in comparison with PLA without clays and A8 although in a lower degree than materials based on clay 1. Moreover, both materials showed no significant differences among them independently of the percentage of clay.
On the other hand, the Alan Coar cosmetics underwent oxidation from day 15 after packing. The analysis of variance did not identify significant differences among the packaging compositions. Therefore, the possible effect of the addition of clays to the PLA matrix on improving the barrier properties to oxygen was not significant for the tubes. At least, this possible improvement was not reflected on the oxidative stability of the cosmetics.
Finally, the impact of the cosmetic matrix on the release kinetics (i.e. D and K) of the packaging systems as well as the antioxidant protection of the cosmetic over time have been evaluated and described in Deliverable 6.2.
The release of the active substances from the active materials based on PLA 3052 was studied by measuring the release of antioxidant activity along time (up to 120 days) using the cosmetic from Alissi Bronte. The experimental test was designed to promote the release of the antioxidant up to an equilibrium is reached after a sufficient period of time.
PBS showed a clear faster release of antioxidant activity in comparison with PLA. In this sense, PBS showed a total release by day 30. The release of antioxidant from the PLA materials was slower although PLA incorporating clay 2 seemed to show a higher degree of release.
On the other hand, the release rate of antioxidant activity released along the time from the packaging materials was determined as an apparent diffusion coefficient (D).
The D-values obtained shown the faster release rate for PBS, about 2 orders of magnitude higher than PLA containing 20%PBS and 2% clay 2. The system based on PLA containing 20%PBS without clays shown D-values one order of magnitude lower than PLA with clay 2. The D value for the system of PLA containing clay 1 could not be determined since no release was observed. In this case, the D-value would be lower than 10-16 cm2/s.
The release of the active substances from the active materials based on PLA 2003 was also studied by measuring the release of antioxidant activity over time using the cosmetic product from Alan Coar. In this case, all the active materials showed some release of antioxidant activity along time. The active packaging material based on PBS and A8 without any clay released its antioxidant activity from day 0 until day 50. At that time, the system seemed to reach an equilibrium condition between the content released to the cosmetic and the content retained in the packaging material. From day 50 up to day 120, no more release of antioxidant activity was observed even when 2 – 3 mg A8 per gram of packaging material was still left inside the biopolymeric matrix.
The materials based on PLA also showed some release but in a lower degree than PBS.
The material based on PLA containing 20%PBS and 2% clay 1 did not show a significant release of antioxidants to the cosmetic. The D value would be lower than 10-16 cm2/s. The D-values obtained show the fastest release rate for PBS, although in this case the difference with some of the PLA 2003 based materials (PLA containing clay 2 and PLA containing PBS and no clays) is not so high. These materials showed D-values in the order of 10-11 and 10-12 cm2/s. However, the main difference among PBS and PLA materials comes from the equilibrium constant (20 vs. more than 100). These values show PBS as a material with a higher release degree.
In comparison with the results obtained in the deliverable 4.2 there was a clear impact of the cosmetic matrix on the release rate of the antioxidant incorporated into the packaging materials, either in the diffusion rate or as a consequence of reaching an equilibrium condition.
The results obtained from a mathematical simulation of the antioxidant release for the active packaging solutions for Alissi Bronte cosmetics shown that a high content of antioxidant should be incorporated to the PLA pots (around 3.5%). This high amount will probably modify the rheological properties of the PLA matrix thus making it not processable by injection moulding in addition to a possible modification of the thermal or mechanical properties of the pot. Therefore, for this cosmetic could be more convenient to incorporate the antioxidant by means of a disk made of PBS placed at the bottom of the pot.
Considering the 2 possibilities for the PBS disk, it seems to be more feasible to keep the content of antioxidant at 2% and manufacture disks with at least 1 mm thickness.
In the case of the release simulation for the active packaging solutions for Alan Coar cosmetics, the results obtained shown that a high content of antioxidant should be incorporated to the PLA tubes (above 5%). This high amount will probably modify the rheological properties of the PLA matrix thus making it not processable by extrusion in addition to a possible modification of the thermal or mechanical properties of the tubes. Therefore, for this cosmetic could be more convenient to incorporate the antioxidant by means of a sheet made of PBS placed inside the package in direct contact with the cosmetic.
Considering the two possibilities for the PBS sheet, it seems to be more feasible to keep the content of antioxidant at 2% and manufacture disks with at least 2 mm thickness.
Potential Impact:
The expected final results in BIOBEAUTY project is to develop a biopackaging for organic and eco product lines that offers the same environmental credentials as the product that it contains through a combination of nanotechnology and active packaging. In concrete, the final products to be obtained will be based on an environmentally friendly biomaterial such as a Poly (lactic acid) (PLA) bionanocomposite and a natural active agent with antioxidant properties to obtain a PLA active tube and a PLA active pot for cosmetic skin treatment creams. The incorporation of nanoclays to the biocomposite will improve the barrier properties of the PLA, while the incorporation of natural antioxidants in the packaging is to delay the degradation of cosmetic creams. The safety of each component, nanoclay and natural antioxidant active agent will be tested through in vitro toxicological studies.
The processing technology for the development of the containers are extrusion moulding for the development of the PLA tube and injection moulding for the development of the PLA pot.
Taking into account that the new packages will reduce the content of antioxidants in the cosmetic formulations and promote the use of biodegradable materials for organic cosmetic applications, the following potential impacts will be obtained at European level:
Political – Protecting and promoting the health and safety of European people is a key priority for the EU. Article 168 of the Treaty on the functioning of the European Union sets out the objectives of EU health policy and the underlying legal basis for it. In addition, for the EU, with its limited crude oil and natural gas resources, the increased use of biomass will be indispensable in the midterm.
Societal – Consumers around the world are becoming increasingly aware of the need for and benefits of socially responsible behaviour. The objective of social responsibility is to contribute to sustainable development. The development of a bio-based and compostable package for organic cosmetics contributes to a greener and safer environment.
Commercial – The possibility of using biodegradable antioxidant packaging materials for cosmetic products brings the opportunity to the European cosmetic SMEs of expanding their business beyond local and national frontiers. This will make stronger the exporting position of Europe in the global market.
Scientific & Technological knowledge – According to the Woodrow Wilson Project on Emerging Nanotechnologies (PEN), the number of registered nanotechnology products increased by nearly 1900% between 2005 and 2009. Of these 1015 registered products, 137 are classified as nanotechnology products for cosmetic use. One reason for this high proportion could be that the cosmetic industry focuses on final products, i.e. the high value-added segment. Therefore, nanotechnology in cosmetics is currently growing at a fast pace in research and development worldwide. In addition, active packaging solutions are being extensively studied in the food sector and valuable scientific and technological knowledge is being generated in this field.
Environmental – The greatest environmental benefits that the project delivers are landfill waste reduction and the bio-sourced origin of the material. In 2010, 14.3 million tonnes of post-consumer plastic waste ended up in landfills in Europe. The increase in biodegradable packaging in the cosmetic industries could significantly reduce the amount of waste disposal in these sites.
Finally, several materials for disseminating the project, as well as the main results and the European funds provided by the Research for SMEs project programme were developed.specifically information of the project was disseminated through different channels along the project lifetime and some of them can still be found via internet:
· Specific project website at www.biobeautyproject.eu.
· Brochure.
· Press releases available in electronic portals.
· Promotional material with the project’s logo to be shown in trade fairs, conferences, meetings with future customers, etc.
· Poster with the results of the project to be shown in trade fairs as FACHPACK 2015, EMPACK 2015 and CEP Packaging 2016.
· News in social media as Facebook.
· Specific video about the project (available at www.biobeautyproject.eu).
List of Websites:
Public website address:
http://biobeautyproject.eu/
Relevant contact details:
Coordinator:
INSTITUTO TECNOLOGICO DEL EMBALAJE, TRANSPORTE Y LOGISTICA
Calle Albert Einstein, 1. Parque Tecnológico.
Paterna (Spain)
Administrative contact: Oana Ciuca
Technical contact: Maria Jorda
Tel.: +34 961820000
Fax: +34 961820001
Participants:
HWU
Nano-Saftey Research Group,
School of Life Sciences,
William Perkin Building (Lab 3.18)
Heriot-Watt University
Edinburgh (EH14 4AS), UK
Contact: Mona Conolly / Teresa Fernandes
Tel: +44 (0) 131 451 4442
VITIVA (now FRUTAROM)
Nova vas pri Markovcih 98
2281 Markovci (Slovenia)
Contact: Majda Hadolin Kolar, PhD
Tel: +386 2 7888 738
Martin Snidjer Holding (MSH)
Kraailand 18
3828 HS Hoogland
The Netherlands
Contact: Martin Snijder
ETS BUGNON
5 bis avenue des Grabilles
74500 LUGRIN
Contact: Sylvie GRANGEOT
Tél. : +33(0)4 50 76 00 18
Fax : +33(0)4 50 76 05 82
MINILAND NEW CONCEPTS
Parque Ind. La Marjal I ·
C/ de La Patronal, 8 y 10 · 03430 · ONIL ·
(Alicante) · SPAIN ·
Contact: German Sempere
Tel. +34 965 564 950
ALAN COAR
C / Alcalde Albors, 16
46018 Valencia ESPAÑA
Contact: Alfonso Copoví
Telephone: +34 963 844 276
ALISSI BRONTE
Calle Uruguay parcela 18/1,
Polígono industrial oeste.
30169 San Ginés. Murcia
Contact: Marta Moral / Mariano Sánchez
Telephone: +34 968884311
The global market for natural and organic cosmetics has never been more promising than today. Europe, being the main cosmetic market worldwide, is a prime target market for companies wishing to explore organic beauty. A critical success factor for natural cosmetics is product positioning, especially as these products come into direct competition with conventional brands in supermarkets, department stores and pharmacies. Market winners will be those companies that can successfully differentiate their products from competing ones. The need for complete product differentiation for organic cosmetic lines requires a bio package that offers the same environmental credentials as the product that it contains.
Environmental concerns such as plastic waste disposal (Directive 94/62/EC) and depletion of non-renewable resources together with the current trend towards greener formulations and sustainable credentials are a challenging opportunity for the development of alternatives to petroleum-based materials. Moreover, the limitations that bioplastics present in their performance provide a well-defined need for a technological solution. Most of the materials used in cosmetic packaging industries today are non-degradable such as Polypropylene and Poly(methyl methacrylate) pots, low and high density polyethylene and even ABL (aluminium barrier laminate) tubes. One of the main environmental problems we are facing today is therefore plastic packaging waste and its disposal. In 2010, 14.3 million tonnes of post-consumer plastics ended up in landfills in Europe. Packaging has become a central focus of waste reduction and bio-assimilation efforts as proper waste management is important to protect human health and the environment. The greatest environmental benefits that the project delivers are landfill waste reduction and the bio-sourced origin of the material.
The main aim of BIOBEAUTY project is to develop biopackaging for organic and eco product lines that offers the same environmental credentials as the product that it contains through a combination of nanotechnology and active packaging. It will be based on an environmentally friendly biomaterial such as a Poly(lactic acid) (PLA) bionanocomposite and a natural active agent with antioxidant properties. The incorporation of nanoclays to the biocomposite is to improve the barrier properties of the PLA, while the incorporation of natural antioxidants in the packaging is to delay the degradation of cosmetic creams.
The safety of each component, nanoclay and natural antioxidant active agent will be tested through in vitro toxicological studies. The package solutions are a PLA tube and a PLA pot. The processing technology for the development of the containers is extrusion moulding for the development of the PLA tube and injection moulding for the development of the PLA pot.
No commercial solution exist that meet both biodegradable and antioxidant cosmetic product requirements. This brings a big opportunity for SMEs both cosmetics manufacturers and polymer and packaging manufacturers to receive a commercial and economic return on their investment.
Project Context and Objectives:
The global market for natural and organic cosmetics has never been more promising than today. Market leaders as well as start-up companies are equally successful while major international brands are becoming more and more actively engaged in reaching their market potential.
An opportunity and at the same time a handicap is that the whole cosmetic market is becoming greener, including products that only claim to be natural. In the EU, the organic regulation (834/2007 of 28 June 2007 repealing 2092/91) does not currently include cosmetic products. Consequently, there are no legal requirements for using the terms ‘natural’ and ‘organic’ in these products, thus leading to different levels of “naturalness” and a tremendous amount of “green-washing”.
Thus, environmental concerns such as plastic waste disposal and depletion of non-renewable resources together with the current trend towards greener formulations and sustainable credentials are a challenging opportunity for the development of alternatives to petroleum-based materials with an emphasis on reducing environmental impact. Moreover, the limitations that bioplastics present in their performance, as compared to traditional plastics, provide a well-defined need for a technological solution.
The supply side is highly fragmented with over 400 European companies involved in producing natural and organic cosmetics. Most are small producers, with very few companies having a trans-regional presence.
However, high growth rates are attracting new entrants, which include large cosmetic companies that are launching natural and organic products. These companies can invest large quantities of money in R&D activities and marketing, whereas SMEs working with organic cosmetics do not have the knowledge, technological capabilities or R&D infrastructure to invest in a sustainable package by themselves.
A critical success factor for natural cosmetics is product positioning, especially as these products come into direct competition with conventional brands in supermarkets, department stores and pharmacies. Market winners will be those companies that can successfully differentiate their products from competing ones, such as organic cosmetics and sustainable solutions.
Therefore, there is a need for RTD research activities and institutional financial support in order to provide the conditions for relevant technological development that will make a difference in organic cosmetic SME competitiveness.
There are 450 million Europeans using beauty and personal care products every day, and the European market for beauty and personal care products was €71.2 billion in Europe in 2011.
A Eurobarometer report from the European Commission dated June 2011 reports that 72% of interviewed Europeans would be willing to pay more for environmentally-friendly products.
If in a market that generates €71.2 billion a year, 72% of consumers are willing to pay more for environmentally-friendly products, there is potentially a €51.26 billion market share for sustainable beauty and personal care products.
The current market situation, according to calculations by the British market researcher Organic Monitor which specialises in organic issues and sustainability, is that the worldwide market for natural beauty care is worth $9 billion (€7.1 billion). This report also highlights that the global market is dominated by the EU and the US. Furthermore, this is forecast to grow at an annual growth of 5%. If products with lower levels of natural compounds are included, sales estimates go up to $16 billion (€12.6 million). Large growth potential is forecast particularly for the emerging countries. The BRIC countries of Brazil, Russia, India and China are among the promising regions with which manufacturers of natural cosmetics are currently occupied. The incorporation of these new countries into the natural cosmetics sector is a clear threat to European SMEs in the coming years.
Within Europe, Germany is the most mature market for natural cosmetics. The range of certified natural cosmetics in Germany registered sales of €815 million in 2011 and achieved a market share of 6.5%. The German sector has increased sales by 50% alone since 2006, according to consumer researcher Gesellschaft für Konsumforschung (GfK).
Within beauty and personal care, organics are predominantly found in personal care products as their appeal is based on nourishment and long-term care. The appeal of products that are less damaging to long-term health means that consumers are most likely to buy into organic products in categories such as skin care, hair care, sun care and bath and shower.
However, organic cosmetic brands find it difficult to provide a consistent packaging for their “natural and organic” product lines. These products have fewer preservatives than traditional cosmetics and therefore a shorter shelf life. The package, however, must provide adequate protection for a proper shelf life.
The need for complete product differentiation for organic cosmetic lines requires a biopackage that offers the same environmental credentials as the product that it contains.
Skin cosmetic creams with eco/organic lines do not currently have truly bio-based packaging, which meet the requirements for their product lines. Therefore, by overcoming this limitation the consortium SMEs will have a significant competitive advantage, and fulfil the demands of an educated and conscientious consumer.
The main aim of BIOBEAUTY project is to develop biopackaging for organic and eco product lines that offers the same environmental credentials as the product that it contains through a combination of nanotechnology and active packaging. It will be based on an environmentally friendly biomaterial such as a Poly(lactic acid) (PLA) bionanocomposite and a natural active agent with antioxidant properties. The incorporation of nanoclays to the biocomposite is to improve the barrier properties of the PLA, while the incorporation of natural antioxidants in the packaging is to delay the degradation of cosmetic creams.
The safety of each component, nanoclay and natural antioxidant active agent will be tested through in vitro toxicological studies.
The package solutions are a PLA tube and a PLA pot. The processing technology for the development of the containers is extrusion moulding for the development of the PLA tube and injection moulding for the development of the PLA pot.
Cosmetic skin treatment creams contain both aqueous and anhydrous phases. They are emulsions that contain two phases (water and oil), which are incompatible with each other and use an emulsifier to reduce the interfacial tension between the two phases and provide an input of shearing energy. Due to their lipid content, these products are sensitive to oxidation mechanisms and therefore require packaging with good barrier properties.
Poly(lactic acid) is aliphatic polyester made up of lactic acid (2-hydroxy propionic acid) building blocks. Because PLA is compostable and derived from renewable sources such as starch and sugar, it has been considered as one of the solutions to alleviate solid waste disposal problems and to lessen the dependence upon non-renewable resources for packaging materials.
However, PLA lacks the mechanical, thermal and barrier properties of conventional polymers. A package for cosmetic skin creams requires these properties in order to protect the product. To overcome these limitations, organomodified clays and active agents will be used to develop a new active bionanocomposite material that can provide adequate quality and shelf life.
Layered silicate clays will be organically modified to compatibilise and facilitate their dispersion in the PLA matrix. Quaternary alkylammonium cations will be used for the cation exchange that creates the modification.
The properties of clay nanocomposites are highly dependent on how well the clay disperses in the polymer matrix which will depend on the exfoliation of the clay. Clay exfoliation involves the isolation of clay nanoplatelets in the polymer matrix, leading to a layered nanocomposite. With this structure best improvements are achieved. Considering the chemical compatibility of the clay and the matrix, and the processing conditions, the exfoliation and dispersion of the clays will be optimised.
According to the actual Cosmetic Directive (EC) 1223/2009 the SMEs must fulfil a Cosmetic Safety Report, prior to placing the product in the market. In this sense, the toxicological studies are critical to ensure the safety of the nanocomposite and its components prior to their widespread use. The physico-chemical properties of nanomaterials are fundamental to their toxicity. Accordingly, particle attributes such as size, shape, composition, charge etc. are able to influence nanomaterial toxicity. This information can be used within the safe and intelligent design of nanomaterials. Due to diversity of nanomaterials under production and use it is essential to develop predictive in vitro models that are able to screen nanomaterial toxicity using cells that represent primary or secondary sites of nanomaterial toxicity. Promoting the development of alternatives to animal testing is required to minimise animal use which is necessary from both a financial, time and ethical perspective. The area of nanotoxicology first emerged in the early 2000s and there has been an exponential increase in the number of hazard and exposure studies concerned with evaluating nanomaterial safety (risk). Although there is an absence of standardised tests that enable an evaluation of nanomaterial toxicity, it has been frequently observed that nanomaterials cause toxicity via oxidative and pro-inflammatory responses. The ability of nanomaterials to induce cytotoxicity is often utilised to benchmark the toxicity of particles, and identify sub-lethal concentrations of nanomaterial to assess the mechanistic drivers of any observed effects. In BioBeauty project, compounding and packaging material toxicity will be evaluated in order to obtain a safe packaging.
The incorporation of a natural antioxidant agent to the package will compensate for the possibly less effective barrier properties of the package. Furthermore, it will provide the system with a controlled and continuous infeed of antioxidant that will protect the product from deterioration. This release mechanism can extend the product’s shelf life by maintaining the levels of antioxidant over its shelf life. The main advantage of active packaging is that it offers an extended shelf life for the packaged product by adjusting its kinetics. It can also be adjusted to match the exact needs of the product. Expected shelf life of the proposed biopackage is 1.5-year.
The main aim of the project is the development of a biopackage for organic cosmetic lines that offers the same environmental credentials as the product that it contains. This packaging solution has three components (PLA biopolymer, nanoclay, natural antioxidant) and the combination of these components is what provides the performance that is required for cosmetic products.
To achieve this overall aim specific scientific and technological objective will have to be reached:
1. Generation of knowledge on nanoclay modification, tailored for biodegaradable thermoplastic polyesters.
2. Understanding of the mechanisms of release of the active components from the packaging materials to the cosmetic matrix.
3. Increase knowledge about the combination of nanoclays and active compounds to evaluate synergies between them.
4. Increase knowledge about security protocols of nanomaterials intended for packaging cosmetic sector.
5. Improved Oxygen gas barrier properties of PLA using layered nanocomposites.
6. Adjustment of the adequate control release of antioxidant agents.
7. Adjustment of processing parameters of materials and strategy to add antioxidant agents and nanoclays to the PLA matrix.
8. Optimised performance of the new packages in the filling and closing machines at the industrial cosmetic manufacturer.
9. Assessment of the toxicity of the packaging.
8. Conservation of the organic skin cream in the proposed package for at least 1 year.
9. No excess in the final price.
10. Increase market share
Project Results:
The technical work performed during the project of execution of the project, include the research and development activities carried out within the WP2, WP3, WP4, WP5 and WP6.
WP2 has been completely executed. This WP has dealt with the selection of natural antioxidants, based on evaluation tests performed through different procedures. These test will assess its effectiveness, safety and stability.
The first task within this WP was a preliminary selection that included 10 natural antioxidant extracted by VITIVA from plants. In addition, some commercial antioxidants were selected in order to obtain a target value of antioxidant capacity to achieve with the natural ones. The tests carried out included:
A) Concentration of the active compounds.
B) Thermal stability.
C) Antioxidant capacity of the antioxidants samples – DPPH.
D) Oxidative stability of the oily phase incorporating the antioxidants – Rancimat Tests.
E) Oxidative stability of the cosmetic products incorporating the antioxidants
F) Incorporation of the antioxidants into the polymer matrix.
G) Thermal properties of the materials incorporating antioxidants – DSC.
H) Mechanical properties of the materials incorporating antioxidants.
I) Release of active compounds into a cosmetic simulant from the polymeric matrices selected.
J) Chemical stability of antioxidant extracts in IPA at 30 ºC
K) Antioxidant activity of the released fraction from the materials into IPA.
It is important to highlight that the release tests revealed a slow release kinetics of the active compounds, which led us to the final conclusion that encapsulation process was not needed.
The samples with the best properties were: A6, A7, A9, A1 and A10. These samples showed even better performance in terms of antioxidant capacity than commercial antioxidants. These samples were selected for the toxicological studies in which toxicity test has been performed to screen the safety of the antioxidant compounds assessed using in vitro skin cell models.
Regarding the toxicological results, A6 did not show any irritation potential at the concentration tested (40 ppm). However, lower incorporation level (<4%) is recommended to ensure tests are relevant and to minimise any potential for toxicity. Based on results of sensitisation studies, samples that are less reactive (e.g. A9, A10, A1) and which produced less/no cytokines could be a safer choice (e.g. A7, A8 and A9). In particular sample A9 meets both these criteria and thus selection of such an antioxidant would lower sensitisation potential. In addition, this sample also showed very good anti-oxidative capacity.
WP3 has been completely finished. This WP has dealt with the development of modified clays for PLA packaging applications. The final objective is to obtain a nanocomposite material to be used in the final packaging, which cause a reduction in the oxygen permeability values.
The first Step was the selection of the clays and organomodifiers suitable to produce the organo-modified clays for PLA. From this study, sodium montmorillonite was selected as raw clay and different modifiers (quats) were selected from a list of approved substances for cosmetic applications according to the European cosmetic regulation (EC) No 1223/2009, and taken into account availability at industrial scale and price. Finally, 4 modifiers were selected HDTA, DTMA, DMOA, TMSA. The modified clays were developed at laboratory scale for subsequent characterization. Different modifier contents and procedures have been used (aqueous media and a mixture of aqueous/ethanol media). In total, 40 modified clays in powder form were developed. Also polymer nanocomposites have been obtained to be able to make a good decision of the clay selection.
Once all the organoclays have been obtained they have been characterised in order to determine the effectiveness of the modification reaction by means of quantification of the modifier present in the organoclay as well as the increase of the interlayer distance propitiated by the intercalation of the long chain alkylammonium compounds between the clay platelets. Apart from these analyses, the dispersion of the clay in the polymeric matrix of PLA was evaluated to know the interaction between the clay and the polymer chains. After characterization, it was concluded that samples prepared with the modified clays exchanged with TMSA and HDTA, are the most suitable for our application and the results were collected in Deliverable 3.1.
After being selected the routes of modification of the nanoclays, assessments focused on potential hazards associated with dermal exposure, as the primary concern of consumer exposure to the nanoclays and modifiers were evaluated and described in Deliverable 3.2. A total of four different quaternary ammonium salts (HDTA, DTMA, DMOA and TMSA) were screened for irritation potential in preliminary tests. However, following results from modification efficiency studies, DTMA and DMOA did not meet the selection criteria and thus only nanoclays modified using HDTA and TMSA were tested in the hazard assessment.
Hypothetical exposure assessments were devised in order to predict what concentrations of nanoclays may be reached in a worst case and a more realistic exposure scenario.
Following a detailed hazard assessment results have revealed that while there is no evident hazard associated with the use of unmodified raw nanoclays, their modification increases their hazard potential. There was also no evidence of sensitisation found for unmodified and modified nanoclays. Hazard assessments performed on the HDTA and TMSA modified clays allowed investigations on the potential contribution of modifier to any observed effects to be performed. Based on the hazard potential, N116_1HDTA_H20 was the most appropriated for use in the nanocomposite development. Furthermore, the migration of (N116_1HDTA_H20) into the cosmetic at concentrations up to 0.4% (worst case scenario) should not produce adverse effects according to lack of cytotoxicity towards keratinocytes, no irritation seen using EpiDermTM models and no evidence of sensitisation potential.
WP4 has been completely executed. This WP has been focused on the development of nanocomposites with the organoclays obtained at WP3 (N116_1TMSA and N116_8HDTA), and scaled in this WP4 as well as the antioxidant selected from WP2 (AOX8 from VITIVA). The characterization of nanocomposites has been evaluated with the aim of confirming a good interaction between the polymer matrix and the clay platelets, and therefore to obtain high improvement in barrier properties. These all results have been included in the Deliverable 4.1.
In this deliverable the characterization of organoclays scaled (pilot scale), confirm the same properties achieved at the laboratory, regarding yield of reaction, washing effectiveness and increase of interlayer distance (50 % reaction yield and 20 Å of interlayer space). Once obtained the different batches of both organoclays, nanocomposites with two different grades of PLA (PLA3052D for pots and PLA2003 for tubes) were processed by using a microcompounding system and injected samples were obtained to be characterized, confirming its effect, especially on barrier properties.
Besides this, samples with different concentrations of organoclay and the antioxidant selected were also processed and characterized with the aim of observing the interaction between them. Then, it was concluded that both organoclays (N116_8HDTA and N116_1TMSA) at 4% with the AOX8, had a negative impact on the processability of the samples, probably due to the degradation of polymer and the consequent loss of properties, making possible the selection of those materials and at maximum concentration of 2% for obtaining of the biopackages in the WP5. As conclusions, 4 compositions were selected as the most promising to obtain our biopackages (1. PLA+2%N116_1TMSA+2%AOX8, 2. PLA+2%N116_8HDTA+2%AOX8, 3. PLA+4%N116_1TMSA and 4. PLA+4%N116_8HDTA and the same with 20% of PBS for tubes, since PBS was necessary for their processability).
On the other side, also as a part of the work involved in this WP, the study of the release kinetics of antioxidant system from the different packaging materials were studied and the results were collected in Deliverable 4.2. Two types of packages have been considered; a PLA pot and a PLA tube. In a first instance, the release of antioxidant activity was experimentally determined to estimate the diffusion coefficients of each material composition.
In both cases, the active packaging materials were able to release antioxidant activity to the cosmetic simulants. In addition, the kinetics associated to each material were different; the inclusion of additives, such as plasticizers and other polymers, increased the diffusivity of antioxidant activity from 10-11 to 10-9 cm2/s. In this sense, in function of the specific requirements of the cosmetics in terms of release of antioxidant activity from the packages, the selection of a given additive and concentration to be incorporated into the PLA matrices can be carried out.
However, the composition for pots and tubes was selected based on processability requirements; PLA3052 + 2% AOX8 and PLA2003 + 20%PBS + 2% AOX8, respectively.
The active performance of these two packaging formulations was assessed by simulation considering the obtained experimental diffusion coefficients and assuming different scenarios in function of the equilibrium constant and degradation/consumption rate of the antioxidant system in the cosmetic. In this sense, materials incorporating 2% of antioxidant should be suitable to provide antioxidant preservation of the cosmetic even for a longer shelf-life and even for the largest degradation rate (250%), although equilibrium constant should be lower than 40.
In the case of the biodegradability evaluation, tests were finally carried out with the packages developed in WP5, with the compositions selected as the most promising from the results of characterization.
Then, the compostability of samples was analysed according to EN 13432:2000 with some modifications. The main conclusions are:
- Chemical composition of packages materials was suitable for composting.
- Disintegration test after 90 days showed a percentage of disintegration higher than 90%, therefore, the samples are considered disintegrable according EN 13432:2000.
- Biodegradation of the samples was more than 90% in comparison with the reference material (cellulose) what means that the samples are biodegradable according EN 13432:2000.
- Compost quality was not influenced by the presence of the packaging materials as confirmed by physico-chemical analyses and also by plant toxicity tests in Lepidium sativum and Hordeum vulgare, ensuring that compost from packaging materials are suitable to support plant growth.
This study was performed directly on the prototypes developed at WP5, and the results are fully described in Annex 1, and submitted directly to the project officer.
The potential hazards that may arise from the use of these PLA based nanocomposites for cosmetic packaging applications have been described in Deliverable 4.3. It has been focused on assessment of the dermal toxicity of components which may migrate from the PLA nanocomposites into the cosmetic formulations.
An experimental approach was designed to test the biocompatibility of the nanocomposites and their potential to release migration extracts that could be cytotoxic or phototoxic towards human HaCaT keratinocyte skin cells or cause skin irritation in the EpiDermTM human skin model, according to OECD TG 439. Overall findings from these studies provide valuable information to show that the PLA nanocomposites developed within the BioBeauty project can be used safely in the cosmetic packaging industry and meet regulatory requirements.
WP5 has been completely executed. The selected formulations after the characterization in the WP4 of the nanocomposites, were used for the preparation of the compound at pilot scale, the processing of the packages, and the evaluation of tubes and pots to select the final composition. In this work, the process parameters for each formulation were optimized for obtaining the tube and the pot, before carrying out the industrial scaled up. Compounding and processing conditions for each format are collected in Deliverable 5.1 and 5.2. While the tube was obtained by extrusion moulding, the pot was done by injection moulding, as well as its cap. In the case of the development of tube prototypes, some considerations were taken into account. As a result of trials at ETS-BUGNON facilities, different processing solutions were proposed to overcome processing issues with antioxidants due to its low melt strength. The most promising was the production of a bilayer tube prototype (PLA+CLAY / PBS+Antioxidant), however it is not available at ETS-BUGNON. Another option was to produce injection moulded pieces based on PBS to be subsequently introduced in the developed PLA tube prototypes. This has been considered as the viable solution. For this purpose, new compounds based on formulations of PBS and antioxidant have been developed.
Once optimized the parameters in the respective processing equipment, they were characterized according to mechanical, barrier, thermal and optical properties as well as the thickness uniformity.
Taking into account the results, for the semi-industrial trials to obtain the pots, were selected the samples with the compositions PLA3052+4%N116_8HDTA and PLA+2%N116_8HDTA+2%AOX8, while in the case of the tubes was the formulation PLA2003+20%PBS+4%N116_8HDTA.
Parallel to the characterization, HWU carried out the hazard assessment of the packaging prototype with their respective formulations, which results are collected in Deliverable 5.3. As a result of the different tests, it was observed a lack of skin irritation from cosmetic formulations in contact with prototype packaging material for 1 month at 40 °C, what suggested that there is likely to be no skin irritation hazard associated with the use of the packaging.
The phototoxic potential associated with the use of the natural antioxidant constituent (polyphenols (UV) from green tea, carnosic acid and oleuropein) in AOX8 and the reduction in viability in the EpiDermTM in vitro skin model upon application of cosmetic formulations, that have been in contact with packaging incorporating 2 % wt/wt antioxidant, suggest a possible phototoxic hazard associated with the use of AOX8. This hazard can be reduced by lowering the incorporation level of AOX8 (<2% wt/wt (0.156 % wt/wt recommended)) in the packaging or removing the polyphenols (UV) from green tea, carnosic acid and oleuropein constituents from AOX8. Importantly, whilst the studies performed within the BioBeauty project have focused on performing a comprehensive assessment of the potential dermal toxicity of the packaging material, hazards at other target sites may also need to be investigated
Finally, shelf life study of the cosmetic product was evaluated with the final packages developed in the WP6, whose results are collected in Deliverable 6.2.
WP6 has been completely executed. The packages selected to be developed at semi-industrial scale were those whose better properties were obtained in the WP5 (Pots: PLA+4%N116_8HDTA, PLA+2%N116_8HDTA+3%AOX8; Tubes: PLA+20%PBS+4%N116_8HDTA with a sheet composed of PBS+2%AOX8 and PBS+3%AOX8). First of all, for the production of the different packages at semi-industrial scale in the facilities of the industrial partners, it was necessary to scale the production of PLA nanocomposite compound as well as the PBS+AOX8 compound.
The production of the compounds mentioned before was carried out by Martin Snijder Holding. As starting conditions (collected in Deliverable 6.1) the processing parameters previously determined in pilot scale trials have been used, and then adjusted to optimize final compounding process.
For the processing of samples, previous knowledge suggested to evaluate low screw speeds, while keeping processing temperatures as low as possible to avoid polymer degradation.
No further modification in compound formulations was considered as a result of technical evaluation. Therefore, it was considered that the production of tube prototypes carried out at ETS-BUGNON in WP5 represented an industrial processing of final packages, and it was not necessary to produce again these prototypes in this work package.
The production of final PLA based pots was carried out at Miniland facilities. The process is based on the injection of both halves of pot (body and thread), on the same step.
To perform the final industrial processing trials of PLA pots it has been considered to start with the processing parameters optimized previously in WP5, and then adjust it until producing the package under the best conditions.
In the same way it was done with compounds based on PLA 3052D, the two compounds based on PBS previously processed by MSH, were crystallized prior injection moulded processing.
These crystallized compounds have been injected at Miniland facilities, in order to produce circular pieces providing active properties from the antioxidant present in its formulations.
Once processed on previous stages, prototypes were evaluated through an industrial scale filling process. After the tubes were arranged through the automatic tube feeding device, next step was to place them into the cup seats.
Once filled, table will continue its rotation and rapidly bring the tubes to different work stations for sealing. Once sealed, final station prints code and date tubes are and trimmed to remove tail excess.
Procedure for pot filling is analogous to tubes. Filling is achieved through a volumetric dosing unit. Once filled, pots continue its rotation and continues to capping station. Caps are usually fed from hopper using an inclined chute.
This pot type has a screw cap without sealing. Therefore, tightening force is critical to ensure the integrity of the container (scheme of the filling process were described in Deliverable 6.1).
To study the integrity of the packages, molecular weight (Mw) of PLA pots and tubes was studied along time in order to know the effect and tendency that cosmetic cream produced in the final material. For that, it was studied the Mw of the PLA in several periods of time (0, 8, 15, 35, 56 and 70 days) in pots and tubes which were maintained at 40 °C including the cosmetic cream inside. Results were collected in Deliverable 6.2 and it was appreciated a decrease in the Mw along time. Moreover, this decrease is more significant in the case of the pots not containing AOX. In the case of PLA tubes without clays, they showed almost a constant Mw along time. However, in the case of PLA containing clays, there is a clear decrease in the Mw, especially for the case of PLA reinforced with clay 1 which showed a decrease of 36% at day 70 versus day 0.
Apart from the stability of the packages, shelf life of cosmetic products filled in the new packages have been evaluated though lipid oxidation according to TBARS method during the accelerated oxidation experiment, whose results are detailed in Deliverable 6.2.
In the case of Alissi Bronte cosmetics, it could be observed that cosmetics remained quite stable in terms of oxidation up to day 20. From that time, the cosmetics packed in the different packaging systems underwent different degrees of oxidation over time.
The best packaging composition identified was the PLA containing 2% A8 and clay 2 at 2% followed by the same material containing clay 2 and no antioxidant. The other materials based on clay 1 also reduced the oxidation of the cosmetic in comparison with PLA without clays and A8 although in a lower degree than materials based on clay 1. Moreover, both materials showed no significant differences among them independently of the percentage of clay.
On the other hand, the Alan Coar cosmetics underwent oxidation from day 15 after packing. The analysis of variance did not identify significant differences among the packaging compositions. Therefore, the possible effect of the addition of clays to the PLA matrix on improving the barrier properties to oxygen was not significant for the tubes. At least, this possible improvement was not reflected on the oxidative stability of the cosmetics.
Finally, the impact of the cosmetic matrix on the release kinetics (i.e. D and K) of the packaging systems as well as the antioxidant protection of the cosmetic over time have been evaluated and described in Deliverable 6.2.
The release of the active substances from the active materials based on PLA 3052 was studied by measuring the release of antioxidant activity along time (up to 120 days) using the cosmetic from Alissi Bronte. The experimental test was designed to promote the release of the antioxidant up to an equilibrium is reached after a sufficient period of time.
PBS showed a clear faster release of antioxidant activity in comparison with PLA. In this sense, PBS showed a total release by day 30. The release of antioxidant from the PLA materials was slower although PLA incorporating clay 2 seemed to show a higher degree of release.
On the other hand, the release rate of antioxidant activity released along the time from the packaging materials was determined as an apparent diffusion coefficient (D).
The D-values obtained shown the faster release rate for PBS, about 2 orders of magnitude higher than PLA containing 20%PBS and 2% clay 2. The system based on PLA containing 20%PBS without clays shown D-values one order of magnitude lower than PLA with clay 2. The D value for the system of PLA containing clay 1 could not be determined since no release was observed. In this case, the D-value would be lower than 10-16 cm2/s.
The release of the active substances from the active materials based on PLA 2003 was also studied by measuring the release of antioxidant activity over time using the cosmetic product from Alan Coar. In this case, all the active materials showed some release of antioxidant activity along time. The active packaging material based on PBS and A8 without any clay released its antioxidant activity from day 0 until day 50. At that time, the system seemed to reach an equilibrium condition between the content released to the cosmetic and the content retained in the packaging material. From day 50 up to day 120, no more release of antioxidant activity was observed even when 2 – 3 mg A8 per gram of packaging material was still left inside the biopolymeric matrix.
The materials based on PLA also showed some release but in a lower degree than PBS.
The material based on PLA containing 20%PBS and 2% clay 1 did not show a significant release of antioxidants to the cosmetic. The D value would be lower than 10-16 cm2/s. The D-values obtained show the fastest release rate for PBS, although in this case the difference with some of the PLA 2003 based materials (PLA containing clay 2 and PLA containing PBS and no clays) is not so high. These materials showed D-values in the order of 10-11 and 10-12 cm2/s. However, the main difference among PBS and PLA materials comes from the equilibrium constant (20 vs. more than 100). These values show PBS as a material with a higher release degree.
In comparison with the results obtained in the deliverable 4.2 there was a clear impact of the cosmetic matrix on the release rate of the antioxidant incorporated into the packaging materials, either in the diffusion rate or as a consequence of reaching an equilibrium condition.
The results obtained from a mathematical simulation of the antioxidant release for the active packaging solutions for Alissi Bronte cosmetics shown that a high content of antioxidant should be incorporated to the PLA pots (around 3.5%). This high amount will probably modify the rheological properties of the PLA matrix thus making it not processable by injection moulding in addition to a possible modification of the thermal or mechanical properties of the pot. Therefore, for this cosmetic could be more convenient to incorporate the antioxidant by means of a disk made of PBS placed at the bottom of the pot.
Considering the 2 possibilities for the PBS disk, it seems to be more feasible to keep the content of antioxidant at 2% and manufacture disks with at least 1 mm thickness.
In the case of the release simulation for the active packaging solutions for Alan Coar cosmetics, the results obtained shown that a high content of antioxidant should be incorporated to the PLA tubes (above 5%). This high amount will probably modify the rheological properties of the PLA matrix thus making it not processable by extrusion in addition to a possible modification of the thermal or mechanical properties of the tubes. Therefore, for this cosmetic could be more convenient to incorporate the antioxidant by means of a sheet made of PBS placed inside the package in direct contact with the cosmetic.
Considering the two possibilities for the PBS sheet, it seems to be more feasible to keep the content of antioxidant at 2% and manufacture disks with at least 2 mm thickness.
Potential Impact:
The expected final results in BIOBEAUTY project is to develop a biopackaging for organic and eco product lines that offers the same environmental credentials as the product that it contains through a combination of nanotechnology and active packaging. In concrete, the final products to be obtained will be based on an environmentally friendly biomaterial such as a Poly (lactic acid) (PLA) bionanocomposite and a natural active agent with antioxidant properties to obtain a PLA active tube and a PLA active pot for cosmetic skin treatment creams. The incorporation of nanoclays to the biocomposite will improve the barrier properties of the PLA, while the incorporation of natural antioxidants in the packaging is to delay the degradation of cosmetic creams. The safety of each component, nanoclay and natural antioxidant active agent will be tested through in vitro toxicological studies.
The processing technology for the development of the containers are extrusion moulding for the development of the PLA tube and injection moulding for the development of the PLA pot.
Taking into account that the new packages will reduce the content of antioxidants in the cosmetic formulations and promote the use of biodegradable materials for organic cosmetic applications, the following potential impacts will be obtained at European level:
Political – Protecting and promoting the health and safety of European people is a key priority for the EU. Article 168 of the Treaty on the functioning of the European Union sets out the objectives of EU health policy and the underlying legal basis for it. In addition, for the EU, with its limited crude oil and natural gas resources, the increased use of biomass will be indispensable in the midterm.
Societal – Consumers around the world are becoming increasingly aware of the need for and benefits of socially responsible behaviour. The objective of social responsibility is to contribute to sustainable development. The development of a bio-based and compostable package for organic cosmetics contributes to a greener and safer environment.
Commercial – The possibility of using biodegradable antioxidant packaging materials for cosmetic products brings the opportunity to the European cosmetic SMEs of expanding their business beyond local and national frontiers. This will make stronger the exporting position of Europe in the global market.
Scientific & Technological knowledge – According to the Woodrow Wilson Project on Emerging Nanotechnologies (PEN), the number of registered nanotechnology products increased by nearly 1900% between 2005 and 2009. Of these 1015 registered products, 137 are classified as nanotechnology products for cosmetic use. One reason for this high proportion could be that the cosmetic industry focuses on final products, i.e. the high value-added segment. Therefore, nanotechnology in cosmetics is currently growing at a fast pace in research and development worldwide. In addition, active packaging solutions are being extensively studied in the food sector and valuable scientific and technological knowledge is being generated in this field.
Environmental – The greatest environmental benefits that the project delivers are landfill waste reduction and the bio-sourced origin of the material. In 2010, 14.3 million tonnes of post-consumer plastic waste ended up in landfills in Europe. The increase in biodegradable packaging in the cosmetic industries could significantly reduce the amount of waste disposal in these sites.
Finally, several materials for disseminating the project, as well as the main results and the European funds provided by the Research for SMEs project programme were developed.specifically information of the project was disseminated through different channels along the project lifetime and some of them can still be found via internet:
· Specific project website at www.biobeautyproject.eu.
· Brochure.
· Press releases available in electronic portals.
· Promotional material with the project’s logo to be shown in trade fairs, conferences, meetings with future customers, etc.
· Poster with the results of the project to be shown in trade fairs as FACHPACK 2015, EMPACK 2015 and CEP Packaging 2016.
· News in social media as Facebook.
· Specific video about the project (available at www.biobeautyproject.eu).
List of Websites:
Public website address:
http://biobeautyproject.eu/
Relevant contact details:
Coordinator:
INSTITUTO TECNOLOGICO DEL EMBALAJE, TRANSPORTE Y LOGISTICA
Calle Albert Einstein, 1. Parque Tecnológico.
Paterna (Spain)
Administrative contact: Oana Ciuca
Technical contact: Maria Jorda
Tel.: +34 961820000
Fax: +34 961820001
Participants:
HWU
Nano-Saftey Research Group,
School of Life Sciences,
William Perkin Building (Lab 3.18)
Heriot-Watt University
Edinburgh (EH14 4AS), UK
Contact: Mona Conolly / Teresa Fernandes
Tel: +44 (0) 131 451 4442
VITIVA (now FRUTAROM)
Nova vas pri Markovcih 98
2281 Markovci (Slovenia)
Contact: Majda Hadolin Kolar, PhD
Tel: +386 2 7888 738
Martin Snidjer Holding (MSH)
Kraailand 18
3828 HS Hoogland
The Netherlands
Contact: Martin Snijder
ETS BUGNON
5 bis avenue des Grabilles
74500 LUGRIN
Contact: Sylvie GRANGEOT
Tél. : +33(0)4 50 76 00 18
Fax : +33(0)4 50 76 05 82
MINILAND NEW CONCEPTS
Parque Ind. La Marjal I ·
C/ de La Patronal, 8 y 10 · 03430 · ONIL ·
(Alicante) · SPAIN ·
Contact: German Sempere
Tel. +34 965 564 950
ALAN COAR
C / Alcalde Albors, 16
46018 Valencia ESPAÑA
Contact: Alfonso Copoví
Telephone: +34 963 844 276
ALISSI BRONTE
Calle Uruguay parcela 18/1,
Polígono industrial oeste.
30169 San Ginés. Murcia
Contact: Marta Moral / Mariano Sánchez
Telephone: +34 968884311
