Identification and assessment of alternatives to selected phthalates

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10 � Danish manufacturers and importers of toys and childcare articles; � Surveys of plasticisers in toys and childcare articles marketed in the Netherlands, Germany, Austria and Switzerland; � Direct contact to major manufacturers of plasticisers. These data sources have been supplemented with information from the literature and manufacturers' web sites. As consequence of the prohibition of DEHP, DBP and BBP in toys and childcare articles and the prohibition of DINP, DIDP and DNOP in toys and childcare articles which can be placed in the mouth by children, experience exist in substitution of the phthalates for these products. Dutch surveys of plasticisers in toys demonstrate that DEHP and DBP a few years ago could be found in a significant percentage of all samples. In accordance with the fact that the major uses of BBP are in flooring and non-polymer applications (e.g. adhesives) BBP was only found in a few of the toy samples and the surveys of plasticisers used in toys would not give any indication of which plasticisers are applied as alternatives to BBP. Table 0.1 lists plasticisers used in toys and childcare products. The substances reported by Danish manufacturers have specifically been used by the manufacturers as substitutes for phthalates, whereas some of the plasticisers reported in the surveys of plasticisers in toys and childcare products from other EU countries may in fact not have substituted a former use of phthalates. Three of non-phthalate plasticisers were found in a significant percentage of the samples in both surveys and are reported by all responding Danish manufacturers of toys as used as alternatives to phthalates: DINCH, DEHT and ATBC. All three are marketed as general plasticiser alternatives to DEHP. Among the non-phthalate plasticisers there seems not to be one substance that can make a one-to-one substitution for all applications of each phthalate. Which substitutes are suitable depends on the actual processing conditions and the desired properties of the final product. Finding the right plasticiser for a given application is often a complex process, as many technical criteria have to be met simultaneously. Comprehensive testing of the performance of the polymer/plasticiser system is often required. By way of example one Danish manufacturer reports that the development led to the use of a mixture of ATBC, DINCH and DEHT, which could be blended in a variety of combinations to achieve softened PVC that performed to the required standards with the existing production setup. On request a number of manufacturers of plasticisers have provided information on their market experience with possible alternatives to DEHP, BBP and DBP. Unfortunately the manufacturers of DINCH and DEHT, widely used in toys, did not provide detailed information, and the assessment of these substances has mainly been based on information from the manufacturers' websites and the literature. Both substances are marketed as general plasticisers for PVC. Based on information on the plasticisers found in toys and childcare articles and initial information from manufacturers, a gross list of 25 potential nonphthalate alternatives was compiled and from this list 10 plasticisers were selected for further assessment.
Benzoates (represented in Table 0.2 by DGD and "Mix of DGD, DEGD, TGD") have been the main alternative to BBP, because they provide both suitable processing conditions and properties of the final products and have quite similar price. BBP is mentioned as a critical component in seals for insulating double glazing and it cannot be ruled out that niche applications of BBP and DBP exist where alternatives are not suitable. Table 0.1 Plasticisers found in toys and childcare articles Group of plasti- Chemical name Abbreviation CAS no. Occurrence in toys and childcare articles ciser Reported by Survey in the Survey in Ger- Danish manu- Netherlands many, Austria facturers 2007, % of and Switzerland /suppliers *2 samples 2007, % of samples Phthalates Diisononyl phthalate DINP 28553-12-0 Only non- 49% 10% 68515-48-0 phthalatesreported Diisodecyl phthalate DIDP 26761-40-0 271-091-4 _"_ 15% 2% Diisodecyl phthalate DIBP 84-69-5 _"_ 2% 2% Cyclohexanes Di-isononyl-cyclohexane- 1,2dicarboxylate DINCH 166412-78-8 X 25% 48% Terephthalates Di (2-ethyl-hexyl) terephthalate DEHT, DOTP 6422-86-2 X 7% 10% Sulphonates Sulfonic acids, C10 – C18-alkane, phenylesters ASE 91082-17-6 X *3 *3 Other alkyl esters Trimethyl pentanyl diisobutyrate TXIB 6846-50-0 14% 11% Citrates Acetyl tributyl citrate ATBC 77-90-7 X 9% 10% Aliphatic dibasic esters Mixed alkyl aryl esters Diisononyl adipate DINA 33703-08-1 x 6% 4% Bis(2-ethylhexyl) adipate DEHA 103-23-1 4% 2% Diisobutyl adipate DiBA 141-04-8 0.6% Dioctyl sebacate DEHS 122-62-3 0.6% Mixed diesters neopentylglycolbenzoate/2-ethylhexanoate Mixed triesters 1,1,1-trimethylolpropane-benzoate/2-ethylhexanoate Hexanoic acid, 2-ethyl, mixed triesters with benzoic acid and trimethylopropane NPG-EHA-BA 7% TPG-EHA-BA 2% LG-flex BET 610787-76-3 x *3 *3 Polyesters Polyadipate PA 3% Epoxy esters and epoxidized oils Epoxidized soy bean oil ESBO 8013-07-8 1% Alkyl acetyl esters Tert-butyl acetate *1 TBAC 540-88-5 11% Alkylphenols Nonylphenol *1 25154-52-3 18% Trimellates Tri-(2-ethylhexyl)-trimellitate TEHTM (TOTM) 3319-31-1 1% *1 These substances are usually not mentioned as plasticisers in plastics, but may serve other purposes in the plastics. It has not been confirmed that the substances are actually used as plasticiser in the plastics. *2 "X" indicates that the substance is reported by all manufactures. "x" indicates that the substance is reported by one manufacturer only. *3 It is not clear from the report whether the surveys have screened for these alternatives. Experience in the use of alternative plasticiser exists for all major applications of DEHP, DBP, and BBP. Experience for 6 of the selected plasticisers, for which detailed information was obtained is shown in Table 0.2. Note that the alternatives typically do not substitute for the phthalates 1:1; often are more substances used in combination. 11
Page 1 and 2: Identification and assessment of al
Page 3 and 4: Table of Contents PREFACE 7 SUMMARY
Page 5: 6 ASSESSMENT OF ALTERNATIVE FLEXIBL
Page 8 and 9: 8 The study has been guided by a St
Page 12 and 13: Application Table 0.2 Alternatives
Page 14 and 15: 14 and DIDP), whereas ASE, DINA , D
Page 16 and 17: 16 Carcinogenicity has only been ev
Page 18 and 19: 18 � Danske producenter og import
Page 20 and 21: Tabel 0.2 Alternativer til DEHP, BB
Page 22 and 23: 22 pris (10-50% højere)end DEHP og
Page 24 and 25: 24 3 Data-sammenfatninger, som ikke
Page 27 and 28: Abbreviations and acronyms ASE Sulf
Page 29: 1 Introduction 1.1 Data collection
Page 32 and 33: 32 to mix with the resin by process
Page 34 and 35: 34 Figure 2.3 Use of plasticisers f
Page 36 and 37: 36 � Coated fabric; - Upholstery
Page 38 and 39: 38 Table 2.4 Estimated DEHP tonnage
Page 40 and 41: 40 in printing inks by CEPE/EuPIA (
Page 42 and 43: 42 The end-product uses of BBP are
Page 45 and 46: 3 Identified alternatives to DEHP,
Page 47 and 48: Aliphatic dibasic esters, adipates
Page 49 and 50: Hundreds of substances have plastic
Page 51 and 52: Table 3.4 Non-phthalate plasticiser
Page 53 and 54: Table 3.6 Indentified non-phthalate
Page 55 and 56: Table 3.8 Plasticisers identified i
Page 57 and 58: Substances Diisononyl phthalate DIN
Page 59 and 60: Substances Table 3.13 Alternatives
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3.6 Alternatives plasticisers selec
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Group of plasticiser Chemical name
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3.7 Alternative flexible polymers B
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68 ASE was negative in Ames test, I
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70 not associated with any evidence
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72 Table 4.2 Summary of environment
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74 It has a rather low water solubi
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76 Repeat dose, genotoxicity, carci
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78 on standard conversion factors.
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80 4.6.2 Human health assessment DE
Page 82 and 83:
82 Repeat dose, genotoxicity, carci
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84 manometric respirometric method.
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86 rats dosed at 750 and 1,000 mg/k
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88 An inhalation study was conducte
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90 TXIB has low acute toxicity by t
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92 All substances have been tested
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Name of substance 94 CAS No. Acute
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Name of substance DINCH 166412-78-
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98 4.11.2 Environmental assessment
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100 4.11.3 Health and environmental
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102
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104 Table 5.1 Applications of ASE a
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106 ASE was reported as used for to
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108 Note that Vertellus has indicat
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110 blended in a variety of combina
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112 Table 5.8 Applications of COMGH
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114 rameters indicating a potential
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116 Key characteristics DGD is a co
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118 Table 5.14 Applications of DGD
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120 Table 5.16 Technical key parame
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122 Table 5.17 Applications of DEHT
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124 Table 5.20 key characteristics
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126 Table 5.21 Technical key parame
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128 Table 5.23 key characteristics
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130 Table 5.24 Applications of GTA
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132 Application and market experien
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134 5.11 Summary and discussion of
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Table 5.30 Alternatives to DEHP, BB
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138 Substance Phthalates and other
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140 The overall conclusion can be d
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142 publication Nordic Ecolabelling
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144
Page 146 and 147:
146 Christensen, C.L., L. Høibye a
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148 Nilsson, N.H., J. Lorenzen and
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150
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152 Trimellitates These materials a
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154
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156
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158 Diethylene glycol dibenzoate, D
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172 Dipropylene glycol dibenzoate,
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1 ESIS 182 Dipropylene glycol diben
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184 Di-isononyl-cyclohexane-1,2dica
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200 Di (2-ethyl-hexyl) terephthalat
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214 Sulfonic acids, C10 - C18-alkan
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CAS No. 102-76-1 222 Glycerol Triac
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Atmospheric OH rate constant cm 3 /
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226 Glycerol Triacetate, GTA Commer
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228 Glycerol Triacetate, GTA Metabo
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230 Glycerol Triacetate, GTA Mongre
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232 Glycerol Triacetate, GTA Reprod
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234 Glycerol Triacetate, GTA Dog Th
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Other aquatic organisms - 236 Glyce
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238 Glycerol Triacetate, GTA Abioti
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Physical-chemical - Emission - Expo
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242 Trimethyl pentanyl diisobutyrat
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254 Acetyl tributyl citrate, ATBC c
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256 Acetyl tributyl citrate, ATBC 1
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258 Acetyl tributyl citrate, ATBC C
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Inhalation - Dermal - 260 Acetyl tr
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262 Acetyl tributyl citrate, ATBC M
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264 Acetyl tributyl citrate, ATBC M
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266 Acetyl tributyl citrate, ATBC G
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268 Acetyl tributyl citrate, ATBC T
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270 Acetyl tributyl citrate, ATBC T
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272 Acetyl tributyl citrate, ATBC A
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Physical-chemical - Emission - Expo
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276 Diisononyl adipate, DINA Physic
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Atmosphere - Dermal - Observations
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280 Diisononyl adipate, DINA Reprod
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1 ESIS 2 IUCLID dataset 3 EPA HPV p
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12-(Acetoxy)-stearic acid, 2,3-bis(
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