ASTM D7767-11(2018)
(Test Method)Standard Test Method to Measure Volatiles from Radiation Curable Acrylate Monomers, Oligomers, and Blends and Thin Coatings Made from Them
Standard Test Method to Measure Volatiles from Radiation Curable Acrylate Monomers, Oligomers, and Blends and Thin Coatings Made from Them
SIGNIFICANCE AND USE
5.1 This test method is an extension of Test Method D5403. While Test Method D5403 specifies that a test specimen be cured by exposure to UV or EB as prescribed by the supplier of the material, most radiation curable monomers and oligomers provided as raw materials to formulators are not designed to be used alone but rather as blends of monomers and oligomers so that there are no “supplier prescribed” exposure conditions. Test Method D5403 is not appropriate for the measurement of volatiles from thin radiation-curable coatings because supplier prescribed cure conditions include both a thickness and an exposure specification which are difficult or impossible to achieve in a test lab. Furthermore, inks form a special class of thin radiation curable coatings because they are formulated with known interferences (for example, pigments). As a result, Test Method D5403 does not provide a method for measuring volatiles from monomers and oligomers used as raw materials in the formulation of radiation curable coatings nor does it provide a method for measuring volatiles from thin radiation curable coatings such as inks.
5.2 This test method provides a means to measure the volatile content of individual acrylate monomers, oligomers, and blends commonly used to formulate radiation curable coatings such as printing inks. Such coatings comprise liquid or solid reactants that cure by polymerizing, crosslinking, or a combination of both and are designed to be applied as thin coatings in the absence of water or solvent and to be cured by exposing to ultraviolet radiation. There is currently no direct method for measuring the volatiles from the individual materials used or thin coatings made from them.
5.3 This test method also provides a means to measure the volatiles from acrylate monomers, oligomers, and blends cured using ultraviolet radiation from which an estimate for the volatiles from a thin coating cured using ultraviolet radiation comprising these acrylate monomers, o...
SCOPE
1.1 This test method describes a means to determine the percentage of processing, potential, and total volatiles from radiation curable acrylate monomers, oligomers, and blends. The results can be used to estimate the volatiles from thin radiation curable coatings that cannot otherwise be measured with the restriction that those coatings are not subjected to a pre-exposure water or solvent drying step. It also provides a means to determine the volatiles of thin radiation curable coatings in the absence of known interferences such as pigments in inks.
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.4 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
General Information
Relations
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D7767 − 11 (Reapproved 2018)
Standard Test Method to
Measure Volatiles from Radiation Curable Acrylate
Monomers, Oligomers, and Blends and Thin Coatings Made
from Them
This standard is issued under the fixed designation D7767; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
1.1 This test method describes a means to determine the 2.1 ASTM Standards:
percentage of processing, potential, and total volatiles from D5403 Test Methods for Volatile Content of Radiation Cur-
radiation curable acrylate monomers, oligomers, and blends. able Materials
The results can be used to estimate the volatiles from thin E145 Specification for Gravity-Convection and Forced-
radiation curable coatings that cannot otherwise be measured Ventilation Ovens
with the restriction that those coatings are not subjected to a E177 Practice for Use of the Terms Precision and Bias in
pre-exposure water or solvent drying step. It also provides a ASTM Test Methods
means to determine the volatiles of thin radiation curable E691 Practice for Conducting an Interlaboratory Study to
coatings in the absence of known interferences such as Determine the Precision of a Test Method
pigments in inks. 2.2 Other Document:
EPA Method 24 Determination of Volatile Matter Content,
1.2 The values stated in SI units are to be regarded as
WaterContent,Density,VolumeSolids,andWeightSolids
standard. No other units of measurement are included in this
of Surface Coatings
standard.
1.3 This standard does not purport to address all of the
3. Terminology
safety concerns, if any, associated with its use. It is the
3.1 Definitions:
responsibility of the user of this standard to establish appro-
3.1.1 cure, n—conversion of a coating from its application
priate safety and health practices and determine the applica-
state to its final use state measured by tests generally related to
bility of regulatory limitations prior to use.This standard does
end use performance and mutually agreeable to supplier and
not purport to address all of the safety concerns, if any,
purchaser.
associated with its use. It is the responsibility of the user of this
3.1.2 electron beam (EB) curing, n—conversionofacoating
standard to establish appropriate safety, health, and environ-
from its application state to its final use state by means of a
mental practices and determine the applicability of regulatory
mechanism initiated by electron impingement generated by
limitations prior to use.
equipment designed for that purpose.
1.4 This international standard was developed in accor-
3.1.3 pigment, n—an insoluble substance added to a formu-
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the lation to modify the visual appearance of a coating made from
the formulation.
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
3.1.4 potential volatiles, n—the percentage loss in specimen
Barriers to Trade (TBT) Committee.
weightuponheatingat110°Cfor60minafterradiationcuring.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
This test method is under the jurisdiction of ASTM Committee D01 on Paint contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
and Related Coatings, Materials, andApplications and is the direct responsibility of Standards volume information, refer to the standard’s Document Summary page on
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials. the ASTM website.
Current edition approved June 1, 2018. Published June 2018. Originally AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments,
approved in 2011. Last previous edition approved in 2011 as D7767 – 11. DOI: 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http://
10.1520/D7767-11R18. www.access.gpo.gov.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7767 − 11 (2018)
3.1.5 processing volatiles, n—the percentage loss in speci- combination of both and are designed to be applied as thin
men weight under process conditions that are designed to coatings in the absence of water or solvent and to be cured by
simulate actual industrial cure processing conditions. exposing to ultraviolet radiation. There is currently no direct
method for measuring the volatiles from the individual mate-
3.1.6 retained weight, n—the mass of specimen remaining
rials used or thin coatings made from them.
after exposing to the UV source, heating in an oven, or both.
3.1.7 thin, adj—less than 15 micrometres in thickness. 5.3 This test method also provides a means to measure the
volatiles from acrylate monomers, oligomers, and blends cured
3.1.8 total volatiles, n—the percentage loss in specimen
using ultraviolet radiation from which an estimate for the
weight under process conditions that are designed to simulate
volatiles from a thin coating cured using ultraviolet radiation
actualindustrialcureprocessingconditionsandafterheatingat
comprising these acrylate monomers, oligomers, and blends
110°C for 60 min.
can be calculated. A common exposure step involving a
3.1.9 ultraviolet (UV) curing, n—conversion of a coating
specified amount of ultraviolet radiation in a specific spectral
from its application state to its final use state by means of a
range using a common photoinitiator is called for.
mechanism initiated by ultraviolet radiation in the range from
200 to 400 nm generated by equipment designed for that
5.4 This test method further provides a means to measure
purpose.
the volatiles from thin radiation-curable coatings such as inks
in the absence of known interferences such as pigments. A
3.1.10 UVA, n—the region of the electromagnetic spectrum
common exposure step involving a specified amount of ultra-
comprising wavelengths falling in the range between 320 and
violet radiation in a specific spectral range using a common
390 nm.
photoinitiator is called for.
4. Summary of Test Method
5.5 If desired, volatile content can be determined as two
4.1 Adesignated quantity of an acrylate-functional material
separate components: processing volatiles and potential vola-
(test specimen) is weighed in a container lid before and after a
tiles. Processing volatiles are a measure of volatile loss during
UV exposure step sufficient to ensure a thorough cure of the
the actual cure process. Potential (or residual) volatiles are a
test specimen to obtain the percent solids retained. The
measure of volatile loss that might occur upon aging or under
calculated percentage weight loss is attributed to process
extreme storage conditions. These volatile content measure-
volatiles. The test specimen and container lid are weighed
mentsmaybeusefultotheproducerofamaterial,aformulator
again after heating for 60 min at 110 6 5°C to obtain the
using such materials, or to environmental interests for deter-
percent solids retained.Any additional weight loss is attributed
mining and reporting emissions.
to potential volatiles.The total volatiles for a test specimen are
5.6 The validity of this test method for non-acrylated
the difference between the initial sample mass and the retained
radiation-curable chemistries such as methacrylates, thiol-ene,
mass after exposing and heating divided by the initial mass.
vinyl ethers, and epoxies cured using ultraviolet radiation has
5. Significance and Use
not been verified. Use of an electron beam to cure the acrylate
monomers, oligomers, and blends or thin coatings made from
5.1 This test method is an extension ofTest Method D5403.
them, including inks, has not been verified using this method
While Test Method D5403 specifies that a test specimen be
and cannot be assumed.
cured by exposure to UV or EB as prescribed by the supplier
of the material, most radiation curable monomers and oligom-
6. Interferences
ers provided as raw materials to formulators are not designed
to be used alone but rather as blends of monomers and
6.1 The degree to which the results of this procedure
oligomers so that there are no “supplier prescribed” exposure
accurately measure the volatiles emitted is absolutely depen-
conditions. Test Method D5403 is not appropriate for the
dent upon proper cure during the test procedure. Although
measurement of volatiles from thin radiation-curable coatings
overcure will have little or no effect upon measured volatiles,
because supplier prescribed cure conditions include both a
undercure may lead to erroneously high values. To minimize
thickness and an exposure specification which are difficult or
variability in the cure conditions, an ultraviolet source provid-
impossible to achieve in a test lab. Furthermore, inks form a
ing a given irradiance in a specific spectral region and an
specialclassofthinradiationcurablecoatingsbecausetheyare
exposure energy is specified as is a photoinitiator and concen-
formulated with known interferences (for example, pigments).
tration.
As a result, Test Method D5403 does not provide a method for
6.2 The presence of strong ultraviolet absorbing non-
measuringvolatilesfrommonomersandoligomersusedasraw
acrylate species such as pigments and ultraviolet blockers can
materials in the formulation of radiation curable coatings nor
interfere with the ability of this test procedure to accurately
does it provide a method for measuring volatiles from thin
measure volatiles. These additives are designed to absorb,
radiation curable coatings such as inks.
reflect, luminesce, or scatter visible or ultraviolet radiation.
5.2 This test method provides a means to measure the
Suchadditivesinterferewiththepropercureofmaterialstested
volatile content of individual acrylate monomers, oligomers,
using this method and are to be avoided.
and blends commonly used to formulate radiation curable
coatings such as printing inks. Such coatings comprise liquid 6.3 Photoinitiators are strong ultraviolet absorbers but their
or solid reactants that cure by polymerizing, crosslinking, or a presence is required for proper curing.
D7767 − 11 (2018)
FIG. 1 Photo of Fiber Alignment Relative to Metal Lid During Exposure
7. Apparatus 8.2 Identify the approximate center of the illuminated area
with a mark which will later assist in positioning of a container
7.1 Container Lids, metal can lids having an OD of 35 mm
lid with a test specimen.A25 mm filter paper disk taped to the
and a height of 14 mm with a 25 mm diameter protrusion
work area surface works well for this.Aproper setup is shown
which, when inverted, creates a 0.6 mm deep, 25 mm diameter
4 in Fig. 1.
well.
NOTE 1—Placement of a mark is best accomplished with the shutter
7.2 Forced Draft Oven, Type IIA or IIB as specified in open. Wear appropriate eye protection before opening the shutter and
placing the mark.
Specification E145.
8.3 Centertheopticalwindowoftheradiometeronthemark
7.3 Ring Stand, a device designed to support items using
(8.2). Using the ultraviolet radiation source (7.5) set at 100 %
various clamps.
power with the fiber (8.1) and radiometer optical window (7.6)
7.4 Versatile Clamp, a 3-pronged clamp with adjustable
properly aligned, open the shutter and measure the UVA peak
closure for holding items.
irradiance at the sample plane. If necessary, adjust the fiber
7.5 Ultraviolet Radiation Source, the focused output from a
heighttoachieveaUVApeakirradianceof115 615mW/cm .
short-arc 200W Xe/Hg bulb delivered by a quartz fiber guide.
Once positioned, the fiber should not be moved relative to the
mark (8.2).
7.6 Radiometer, a device able to measure irradiance and
energy in the UVA spectral region.
8.4 Position the radiometer window (7.6) on the mark (8.2)
and measure the UVA energy after an 80 s exposure. If
7.7 Balance, an instrument capable of weighing a mass to
necessary, adjust the exposure time to achieve a UVA target
the nearest 0.1 mg.
energy of 9.0 6 0.2 joules/cm . This determination should be
7.8 Gloves, personal protective wear for handling chemi-
repeated daily to verify proper exposure conditions.
cals.
9. Procedure
7.9 Forceps or Tongs,ameanstohandleaspecimenwithout
direct contact in order to minimize mass transfer.
9.1 Dissolve 2.0 % by weight of ethyl-2,4,6-
trimethylbenzoyphenylphosphinate (TPO-L) photoinitiator in
7.10 Spreading Tool, a small metal or PTFE spatula or a
the material to be tested. Mix thoroughly to ensure homoge-
wooden applicator stick for spreading resin.
neity. Store the test specimen in a dark container.
8. Preparation of Apparatus
9.2 Precondition the container lids for 30 min at 110 6 5°C
8.1 The tip of the quartz fiber guide shall be positioned
and store in a desiccator prior to use.
normal to the center of a container lid (7.1) at a height of
9.3 Weigh a preconditioned container lid (7.1) to 0.1 mg
approximately 80 to 85 mm from the container lid to provide
(A). Use gloves, forceps, or tongs to handle the container lid.
an illuminated circular area of approximately 40 to 45 mm in
9.4 Place the container lid upside down on the balance pan
diameter in the plane on which the container lid (7.1) sets in
and add 0.2 6 0.02 g of the test specimen (9.1) to the recessed
order to approximate uniform irradiance of the test specimen.
area. Spread the test specimen using a spreading tool to ensure
uniform coverage of the recessed area. Do not allow the test
Metal can lids for this method can be obtained from SKS Bottle & Packaging
specimen to contact any surface of the container lid outside of
(Watervliet, NY).
therecessedarea.Weighthecontainerlidwithtestspecimento
This test method was developed using an LC-8 SpotCure source from
0.1 mg (B).
Hamamatsu Corporation (Bridgewater, NJ).
Power Puck II from EIT (Sterling, VA). NOTE 2—It is helpful to hold the container lid with one hand using
D7767 − 11 (2018)
gloves, forceps, or tongs while spreading the test specimen with the
where:
spreading tool in the other. The elapsed time between spreading and
A = weight of container lid, g
weighing should be no greater than 60 s. If the sample to be tested
B = weight of container lid plus test specimen, g
contains any reactive diluent with a vapor pressure at room temperature
C = weightofcontainerlidplustes
...
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