Methyl acetate (CAS 79-20-9; EC 201-185-2; C₃H₆O₂) is a fast-evaporating ester solvent used in coatings, adhesives, printing inks, nail-care preparations and industrial cleaning formulations. The following Methyl Acetate REACH & CLP Compliance: Classification, SDS and Labelling Checklist consolidates the classification, safety data sheet, label and packaging obligations under Regulation (EC) No 1907/2006 and Regulation (EC) No 1272/2008. Methyl acetate is placed on the EU market as a registered substance at tonnages above 1000 tonnes per year, and the registration dossier must include exposure scenarios for identified uses, physicochemical hazard endpoints, toxicological summaries, derived no-effect levels and predicted no-effect concentrations. The substance is not listed as a substance of very high concern and is not subject to authorisation under Annex XIV.

What distinguishes harmonised classification from self-classification for methyl acetate?

The harmonised CLP entry for methyl acetate appears at Index 607-021-00-X in Annex VI to Regulation (EC) No 1272/2008. It assigns Flam. Liq. 2 H225, Eye Irrit. 2 H319 and STOT SE 3 H336. A manufacturer or importer cannot reduce those categories for the corresponding hazard classes, but may add categories where data support a more severe outcome or an additional hazard not covered by the Annex VI entry. Methyl acetate is not assigned a specific concentration limit in Annex VI; mixture classification therefore uses the generic CLP Annex I concentration limits—10% or greater for Eye Irrit. 2 H319 and 20% or greater for STOT SE 3 H336—unless testing or bridging principles justify a different outcome. Flammable liquid category 2 does not translate directly to a simple concentration threshold because mixture flammability is determined by flash point, boiling point and the contribution of other flammable constituents.

The label for pure methyl acetate requires both GHS02 and GHS07. The overall signal word is Danger because Flam. Liq. 2 carries the danger signal word; Eye Irrit. 2 and STOT SE 3 carry the warning signal word individually. The hazard statements H225, H319 and H336 must appear in the official language of the Member State where the substance or mixture is marketed. Under CLP Article 31, the label must be firmly affixed to one or more surfaces of the immediate packaging and must remain legible during storage. A supplier may add supplementary hazard information only where it does not contradict or distract from the harmonised elements; statements such as “low-toxicity solvent” that imply a lower hazard than the harmonised classification are prohibited under CLP Article 17.

SDS Section 2 and 3 integrity under Regulation (EU) 2020/878

Safety data sheets for methyl acetate placed on the EU market must conform to the 16-section structure in Annex II of REACH as amended by Commission Regulation (EU) 2020/878. Section 1 must list the exact product identifier and the supplier’s emergency telephone number; the UFI is not required for the pure substance but is mandatory for hazardous mixtures containing methyl acetate after notification to the ECHA poison centre portal under CLP Annex VIII. Section 2 must reproduce the harmonised classification elements and any additional self-classification arising from impurities. Section 3 must state the assay range, the CAS and EC identifiers, and the classified impurities in the technical grade. For commercial methyl acetate, typical impurities may include methanol, methyl formate and acetone; each impurity must be assessed for its own CLP classification because the final label is determined by the classified constituents above the applicable cut-off limits.

Section 4 must identify first-aid measures for inhalation, skin contact, eye contact and ingestion. Inhalation of high vapour concentrations may produce central nervous system depression consistent with STOT SE 3 H336; the SDS should instruct removal to fresh air and medical follow-up if symptoms persist. Section 5 must list alcohol-resistant foam, dry chemical, carbon dioxide and water spray as suitable extinguishing media; direct water jet is unsuitable for methyl acetate fire control. Section 6 must require small spills to be collected with non-sparking tools, ventilated to below the lower explosion limit, and prevented from entering drains. Section 7 must separate storage from handling conditions. Storage in a cool, ventilated area away from ignition sources is required; transfer lines and containers must be grounded and bonded to limit electrostatic discharge below the ignition energy of the solvent vapour.

Section 8 must include applicable national occupational exposure limits, biological limit values, DNELs and PNECs from the REACH registration dossier. Where a Member State does not list methyl acetate, the SDS should still report the registrant’s DNELs for inhalation and dermal exposure and the derived no-effect level for the critical toxicological endpoint. Section 9 is a frequent audit point: the physical hazard block must include the flash point, initial boiling point, flammability limits, vapour density and vapour pressure. A compliance review of Section 9 must verify that values are tied to standard methods. The closed-cup flash point is reported in supplier safety data sheets as -13 °C using a method such as ISO 3679; the boiling point is 56.9 °C at 101.3 kPa; the vapour density is approximately 2.55 relative to air; and the flammability limits in air are approximately 3.2% v/v to 15.5% v/v. Reporting a flash point without the test method creates a Section 9 compliance gap under Annex II of REACH.

Section 10 must identify hazardous reactions: methyl acetate hydrolyses in the presence of strong acids or strong bases to methanol and acetic acid, and the reaction may be exothermic under high pH. Section 11 must summarise the toxicological endpoints supporting STOT SE 3 and should not use qualitative statements such as “low toxicity” without citing the supporting study data. Section 12 must present aquatic toxicity and degradation data; methyl acetate is not classified as hazardous to the aquatic environment and is expected to be readily biodegradable under OECD 301 series tests, but the SDS must still report the measured or modelled endpoints from the registration dossier. Section 13 must route waste to solvent recovery or controlled incineration; disposal to sewer or unprotected land is not permitted. Section 14 must list UN 1233, Class 3, Packing Group II, and the appropriate ADR/RID transport identification. Section 15 must include CLP classification and any relevant Seveso III inventory thresholds for H225. Section 16 must record the previous SDS revision date and the changes made to classification or composition.

When methyl acetate appears as an impurity or residual solvent in a downstream article

Methyl acetate is not included on the REACH Candidate List of substances of very high concern, and it is not subject to authorisation under Annex XIV or to a restriction under Annex XVII for the common solvent applications. Therefore, Article 33 communication and Article 7 notification for substances in articles do not apply solely because an article contains residual methyl acetate below the 0.1% w/w SVHC threshold, because methyl acetate is not an SVHC. However, if an article contains a liquid mixture with methyl acetate in a reservoir, such as a marker, cleaning wipe or adhesive pen, the liquid mixture itself is a hazardous mixture under CLP and must be classified, labelled and, where marketed as a mixture, notified to poison centres under CLP Annex VIII. The presence of residual methyl acetate in a cured polymer article may be controlled separately by volatile organic compound emission standards applicable to construction products or indoor furnishings; downstream users should check the relevant EN or ISO method for the intended end-use.

Exposure scenario boundaries and downstream user obligations under REACH Annex I

Registrants of methyl acetate at quantities above 10 tonnes per year per registrant must append an exposure scenario to the SDS when the substance is classified as hazardous. The exposure scenario should identify use descriptors such as sector of use, environmental release category, process category and article category. Typical solvent-transfer and application tasks in coatings and adhesives may fall under PROC 8a, PROC 8b, PROC 7, PROC 10 and PROC 28. A downstream user must check whether its own use is covered by the exposure scenario; if the operational conditions or risk management measures cannot be met, the downstream user must prepare a downstream user chemical safety report or request an updated exposure scenario from the supplier under Article 37 of REACH. The scenario may specify closed-system transfer, local exhaust ventilation, leakage-free connections, and dermal protection selected according to EN 374. Where spray application is proposed, the scenario should state the minimum ventilation rate and the required respiratory protection assignment factor under national workplace safety law. Published data for methyl acetate-specific spray exposure controls are limited; therefore, industrial users should verify the registrant’s scenario against their measured personal inhalation exposure data.

Because the lower flammability limit of methyl acetate is approximately 3.2% v/v, drum transfer at ambient temperature can create a flammable headspace before the operator detects a strong odour. Bulk transfer should be carried out with conductive hoses, pumps suitable for Zone 1 or Zone 2 areas classified according to EN 60079-10-1, and continuous bonding to earth with resistance below 10⁶ Ω as measured under IEC 61340-5-1. Splash loading and top-fill lines increase static charge generation and should be replaced by bottom-loading or sub-surface filling. Personnel must use non-sparking tools and antistatic footwear; plastic containers should be avoided unless certified for use in flammable atmospheres.

In a formulated coating or adhesive, if methyl acetate is present at 10% or more, the mixture carries Eye Irrit. 2 H319 under the generic concentration limit. At 20% or more, the mixture carries STOT SE 3 H336. Where multiple volatile solvents are present, flammability classification is based on flash point and boiling point rather than on the methyl acetate concentration alone. Suppliers should document the mixture classification algorithm in the product file because the generic concentration limits apply only to the additive approach; bridging principles or physical testing may justify a less severe classification under CLP Annex I.

For pure methyl acetate, CLP Annex II does not require tactile warnings of danger or child-resistant fastenings because the substance is not classified in the specific acute toxicity, aspiration, mutagenicity, carcinogenicity, reproductive toxicity or respiratory sensitisation categories that trigger those packaging obligations. Packaging must still retain the liquid and be compatible with the ester. High-density polyethylene and steel are generally acceptable, but the supplier should verify permeation and stress-cracking data for the selected packaging under the intended storage duration. A supplier compliance audit should compare the label hazard codes against the SDS Section 2 and the transport marking; inconsistency between the product identifier in Section 1 and the Article 31 label is a legally visible defect.