ACS Publications C&EN CAS Join ACS  LogIn

TOPICS  MAGAZINE  COLLECTIONS  VIDEOS JOBS    

CONSUMER PRODUCTS MOST POPULAR IN

BUSINESS

These new textile dyeing methods could C&EN’s Global Top 50 chemical
companies

make fashion more sustainable Kintai Therapeutics launches to tackle

the interface between the gut, immune
system, and brain

Large and small suppliers vow to help a resource-intensive, cost-sensitive industry change
Meet the exosome,with
the rising star in
SHARE
the times drug delivery

by Melody M. Bomgardner Watch out, CRISPR. The RNA editing

 JULY 15, 2018 | APPEARED IN VOLUME 96, ISSUE 29
race is on

These new textile dyeing methods could

 make fashion more sustainable

Arrakis reels in $75 million to drug RNA

 with small molecules





4/5 FREE ARTICLES LEFT THIS MONTH Chemistry matters. Join us to get the news you need. SEE MY OPTIONS or LOG IN

I
Credit: Intech Digital | High-resolution color patterns can be printed directly onto cotton using pigment inks rather than dyes to reduce the use of water and chemicals.

n early June, Dalton Cheng realized something

IN BRIEF
big was afoot. Cheng, who is head of technology
for the textile printing firm Intech Digital, heard Shoppers looking for their next
from customers that Chinese government authorities in great outfit make their selections on
Jiangsu province had shut down massive factories that
the basis of color, cut, style, and
produce synthetic dyes used by the textile industry.
price. They may not know that dyeing
It was just the latest in a series of actions that started in clothes requires massive amounts of
the summer of 2017, when tens of thousands of China’s water, energy, and chemicals. Those
factories were forced to close and undergo
chemicals are released in wastewater
environmental inspections.
from dye houses and textile mills in
Overall, as much as 60% of China’s denim-dyeing places such as China, India, and
chemical capacity has been shuttered, Cheng says, Bangladesh. Reports of rivers with
equal to roughly 30% of global capacity. And that’s why
unnatural hues have inspired
his phone was ringing. Intech, headquartered in Hong
Kong, might be in a position to help apparel industry government crackdowns and
customers out of a critical supply bind. sustainability pledges from
international apparel brands. But
Intech’s specialty is digital printing on textiles, including
changing this $3 trillion industry will
cotton and other cellulosic fabrics like rayon. Printing
textiles with pigments rather than dyes uses very little require innovation that can be scaled
water, Cheng says, and produces much less waste than up and adopted without cost or
traditional methods. disruption for manufacturers. Read
on to learn about greener ways to
Digital printing is one example from a growing list of new,
color clothes that may soon be
more sustainable fabric-coloring technologies from both
major suppliers and smaller chemical and biotech start- available from your favorite retailer.
ups. The companies see business opportunity in tackling
dyeing’s wasteful water and
energy practices and its reliance on toxic chemicals that can give rivers
shocking hues and harm human health.
Sign up for C&EN's must-read
weekly newsletter But the barriers facing those working to promote a more sustainable
textile technology are quite high. The industry’s sheer scale makes it hard
to have an impact: Textiles are a $3 trillion-per-year business that
Email Address Subscribe » employs nearly 60 million workers worldwide, according to economic
research firm Euler Hermes and FashionUnited, an industry information
Contact us to opt out anytime
resource.

It’s also a manufacturing industry under pressure. Price competition is fierce, and profits are
shrinking thanks to volatile raw material costs and rising wages. Despite public commitments by
apparel brands to become more sustainable, suppliers contacted by C&EN say their customers will
not buy anything that could raise the cost of a finished garment by as little as a penny.

The factory shutdowns have disrupted the textile supply chain, says Holger Schlaefke, global
marketing manager at Huntsman’s textile effects segment. Huntsman, Archroma, and DyStar are
the world’s largest suppliers of dyes and textile chemicals.

Credit: Lu Guang/Greenpeace
Greenpeace's Detox My Fashion campaign brought attention to pollution and health hazards of dye and other
chemicals used in textile manufacturing, including at this plant in Tianjin, China.

“Shutdowns are a concern for companies like Huntsman and also for retailers,” Schlaefke says. “You
can imagine retailers have contracted with a fabric-producing mill—they negotiated six months ago
and agreed on a price—but suddenly that price is not certain anymore. It’s not a crisis, but it makes
business a little more complicated for everyone.”

The largest impact of the factory shutdowns has been in the supply and price of so-called disperse
dyes, which are used to color synthetic fibers like polyester, a specialty of Chinese producers,
Schlaefke says. Availability of reactive dyes, which are used on cotton, was also reduced, though
manufacturers in cotton-rich India are likely to take up the slack.

In India as well, the government is taking steps to reel in the textile industry to save precious water
resources. “In India, a trend is huge investment in wastewater treatment for liquid discharge,”
Schlaefke says. It’s now common for factories to reuse 90% of their water.

While both cotton and polyester are normally colored with synthetic dyes,
dyeing cotton is a more water- and heat-intensive process. The surface of cotton fibers is negatively
charged and doesn’t readily react with negatively charged dye compounds.

Even with an assist from salts and alkali added to the dye solution, cotton takes up only about 75%
of the dye. To ensure colorfastness, dyed fabric or yarn is washed over and over again in hot water,
creating large amounts of wastewater.

All told, about 200 L of water is used to produce 1 kg of fabric. A review of wastewater treatment
steps found that textile effluent contains high concentrations of dyes and chemicals, including
chromium, arsenic, copper, and zinc. Dyes and chemicals released into waterways also block
sunlight and increase biological oxygen demand (J. Chem. Eng. Process Technol. 2014, DOI:
10.4172/2157-7048.1000182).

Learn the textile industry's lingo

Bleeding and crocking: Two components of colorfastness. Bleeding happens when dye comes
off a fabric in contact with liquid. Crocking occurs when a dye on a dry fabric rubs off on another
dry fabric.

Colorfastness: The ability of a dye to preserve the original color during industrial processing and
subsequent customer use. The American Association of Textile Chemists & Colorists provides
several dozen test methods to ensure colorfastness of dye products.

Digital textile printing: Directly printing colors and patterns onto fabric using design software,
large-format printers, and specialty inks made with pigments or dyes. Digital printing is an
alternative to standard screen printing, which uses a constrained color palette and requires
separate stencils and production steps for each color.

Dye: Soluble chemicals that contain chromophores, or color-containing compounds. Dyes are
mixed with other additives in a color solution. They can be derived from natural sources, such as
plants, but are more commonly human made. Different classes of dyes are used for different fibers
and stages of the textile production process.

Direct dye: A class of dye that can be applied directly to cotton or other cellulosic fabrics such as
rayon, silk, and wool. Direct dyes are applied in a neutral or alkaline bath of hot water. They do not
require mordant or fixatives for fastness; instead, they attach with hydrogen bonds and van der
Waals forces. Direct dyes are soluble salts of complex sulfonic acids, including diazo or polyazo
chemicals.

Disperse dye: A category of nonionic dyes used to color synthetic yarns and fabrics such as
polyester. These organic chemicals, mostly monoazo dyes, are nonsoluble and rely on dispersing
agents to spread the color molecules in water.

Reactive dye: A class of colored synthetic organic chemicals that attach to textile fibers via a
chemical reaction that forms a covalent bond. Reactive dyes are the most permanent of all dye
types and are the most common type of dye used on cotton and other cellulose fibers. They are
categorized by their functional group, such as dichlorotriazine or vinyl sulfone.

Dye exhaustion or dye fixation: The mass of dye taken up by the yarn or fabric divided by the
total initial mass of dye in the water bath. Once the dyeing process reaches equilibrium, a portion
of the dye remains in the dye bath and becomes part of the dye process wastewater. The
exhaustion ratio depends on the quality of the dye and the characteristics of the fiber.

Leveling agent: Used in disperse dyeing to regulate or slow the uptake of dye onto synthetic
fibers to ensure that the color level is uniform. Leveling agents are often nonionic surfactants that
increase the solubility of the dye and slow adsorption.

Mordant: Also called a dye fixative, a substance used to chemically bond a dye to natural fibers to
ensure fastness. Mordant chemicals include alum, caustic soda, and metal salts. The mordant
forms a coordination complex with the dye, increasing its molecular weight and making it
insoluble.

Pigment: Insoluble materials, usually in powder form, that add color to inks, paints, plastics,
cosmetics, and foods. When used on textiles, they require binders or other additives to attach to
the fibers. Pigments can be derived from minerals but can also be made synthetically. Because
they are not soluble in water, they can last longer than dyes.

To reduce this burden, Huntsman has developed a line of dyes for cotton called Avitera that bonds to
the fiber more readily. According to the company, the colors require one-quarter to one-third less
water and one-third less energy. Three reactive groups are attached to the dye formula’s
chromophore—or color-providing molecule—compared with the one or two reactive groups common
for cotton dyes. Thanks to these extra reactive groups, the dye step lasts about four hours,
compared with seven hours for conventional dyes.

Still, it takes a lot of legwork to sell customers on a new suite of dyes. “It can be hard to show cost
savings when the savings comes from water use or energy,” Schlaefke says. Different regions and
countries have different cost structures, he says. For example, Bangladesh is now the biggest
cotton-producing country, “and as we know, they have no shortage of water,” he notes.

Another way to improve the bond between dyes and cotton fibers is a process called cationization. In
North Carolina, textile industry veteran Tony Leonard is taking that approach. Leonard is the
inventor and technical director behind ColorZen, a start-up that has developed a cotton
pretreatment step.
 

T
“
here are beautiful
colors in the ocean,
in insects—you can crack
open a wide palette of
colors.”
--- David Nugent, cofounder, Colorifix

“With conventional cotton dyeing, salt is used to negate the charge on the surface of the cotton,”
Leonard explains. “ColorZen technology uses a quaternary ammonium compound to permanently
attach a positively charged amino site on the cellulose molecule.” That makes for a natural
attraction between dye and fiber, he says.

ColorZen treats raw cotton fiber right from the field after the seeds are removed. “North Carolina is
still the heart of the cotton and textile industry here in the United States, and there are ready
supplies of baled U.S. cotton here that our customers are tapping into,” Leonard notes. After
treatment, cotton is spun into yarn at customer facilities.

Leonard contends that ColorZen’s pretreatment makes the dyeing process faster while using 90%
less water, 75% less energy, and 90% fewer auxiliary chemicals. It also cuts out almost half the dye
compared with processes that call for salts in the dye bath.

The company has a partnership with the manufacturing technology firm Jabil to help it scale up its
plant in Mebane, N.C. It is also in a program run by the apparel start-up incubator Fashion for Good.
Leonard says the company is developing a supply chain by educating dye houses, spinners, and
retailers about ColorZen’s benefits.

Even the best pretreatment process can’t eliminate the health effects of the dyes and the chemicals
used to make them. That’s the focus of many of the textile industry’s eco-certification programs.

“With advances in measurement instruments, we’re seeing more evidence of contaminants and
degradation products than ever before,” observes John Frazier, technical director at Hohenstein
Institute America, a textile research organization. Hohenstein developed Oeko-Tex, a series of
standards and tools for certifying nontoxic textiles. The first version of the standard was called Oeko-
Tex 100 for the number of chemicals it tracked. Oeko-Tex certification is now up to more than 300
chemicals.

The industry needs to both develop “better chemistry and ensure there is less water going out the
back,” Frazier says. He says he’s seeing “a ton of innovation happening. It’s very exciting.”

Schlaefke says Huntsman’s Avitera dyes were formulated to be free from p-chloroaniline (PCA), a
hazardous chemical used as an intermediate in the manufacture of azo dyes and pigments. “What
we see now is a bit more retailers are looking at PCA,” he notes. Currently, brands including REI and
Levi Strauss & Co. restrict the use of PCA along with a list of other amines from colorants.

Synthetic indigo, used to make blue jeans blue, is an example of a dye that can release unreacted
chemicals downstream of manufacturing. A small number of Chinese manufacturers produce most
of the world’s indigo using aniline as a key raw material. Indigo is unlike most dyes in that in its
unreduced form it is not soluble. So companies like Archroma upgrade it into easier-to-use,
prereduced solutions that are more water soluble.

The company became concerned after seeing published reports that about 400 metric tons of
aniline per year escapes the dyeing process from 70,000 metric tons of indigo. Two-thirds of the
escaped chemical ends up in wastewater, on workers, and in the air, while one-third stays on the
denim that goes to stores, says James Carnahan, Archroma’s global sustainability manager for
textiles.

Archroma developed a technology for prereducing indigo to prevent aniline from carrying through as
a contaminant. Finished textiles colored with the dye contain a nondetectable amount of aniline,
whereas competitor dyes can contain up to 2,000 ppm of the chemical, according to Archroma.

Brands’ awareness of aniline contamination is growing, and the compound has started to appear on
lists that brands send to manufacturers restricting the chemicals they can use.

Carnahan acknowledges differing views about how big a problem aniline is in the textile industry. It
has a better reputation than the category 1 carcinogenic amines that cleave off of azo dyes and were
an early target for elimination by clothing brands. “Aniline is category 2, instead—which is not good,
though,” Carnahan says.

Of course, in the beginning, indigo came from a plant, not a factory. The very first pair of modern-
style blue jeans, made by Levi Strauss, debuted in 1873. That was about 25 years before chemists
developed the synthetic route to indigo dye—with its unappetizing starting materials of aniline,
formaldehyde, and hydrogen cyanide.

The ambition at Stony Creek Colors is to return to those early days. Founder Sarah Bellos says a
complete life-cycle review of the production and use of synthetic indigo provides plenty of reasons to
look again at indigo from plants.

Stony Creek is developing varieties of leguminous indigo

plants that can provide a high-yield, high-profit crop for Environmental hit
Tennessee farmers looking for an alternative to tobacco. Dyeing cotton has more impact
The company is selling all the dye it can make; its goal is
than dyeing other fibers.
to expand U.S. indigo production to 6,000 hectares in
the next five years. That could displace 2.8% of global
synthetic indigo production.
Cotton
The indigo molecule itself is exactly the same as the
Dyeing: Warm temperature, long
synthetic version, with one small difference: “Synthetic
indigo has a tighter crystal formation that makes it more process time, requires addition of
difficult to reduce,” Bellos says. Dye houses can reduce large amounts of salt and alkali
natural indigo in bacterial fermentation vats or use fixatives
more common reducing systems, she adds.
Dye fixation: Poor, 75%
Other start-ups have also turned to biology—in particular,
engineered microbes—to reduce the use of chemicals in Washing: Long, energy- and water-
textile dyes. U.K.-based Colorifix and the French firm Pili
intensive process using multiple
say microbes can produce high-performance, renewable
dyes suitable for mainstream textiles. All that is required baths, with at least one at boiling
to scale up are fermentation tanks and sugar. temperature

The idea for Colorifix came out of a biological sensor

program in Nepal and Bangladesh. David Nugent and Polyester
colleagues were in the region to test drinking water wells
for arsenic. They asked local village governments what Dyeing: Hot temperature, short
other substances in their water concerned them. “We process time, no fixatives required
got a large list of chemicals,” Nugent recalls. “When we
asked, ‘Where do they come from?’ the answer we got Dye fixation: Good, 99% or more
was textiles, again and again.”
Washing: Shorter process requiring
The team was already using color made by
less energy, water, and chemicals
microorganisms to act as a sensor for water
contaminants. Soon, Nugent says, it became clear the than cotton. Uses alkali and chemical
researchers could engineer them to produce natural reducing agent.
colors, including anthocyanins and carotenoids.

“Once you start looking at how nature makes colors, you Viscose (rayon)
see a lot of similarities in the sequences of the proteins
and enzymes,” Nugent says. With more resources, he’d Dyeing: Warm temperature, long
like to go prospecting to find new molecules. “There are process time, requires less salt and
beautiful colors in the ocean, in insects—you can crack alkali than cotton
open a wide palette of colors.”
Dye fixation: Fair, 85–90%
Not all the colors that engineered microbes can make
meet textile industry requirements for lightfastness and Washing: Similar to cotton but
temperature stability. Chlorophyll, the secret to nature’s
shorter process, possibly due to less
abundance of green, can turn an unstylish brown in
factory conditions, Nugent says. unfixed dye to be removed

But microbes that produce stable colors can be adopted

by dye houses with very little change to their normal Wool
processes. First the microbes go into a solution like a
regular dye and get embedded in the textile fiber. Then Dyeing: Warm temperature, simple
they are given nutrients that cause them to grow. When process
heat is applied, the organisms’ membranes burst. That
causes the color to chemically attach to the fiber with Dye fixation: Good, 95% or more
help from metal ions and salts in the microbes’
cytoplasm. Washing: Generally a relatively
simple wash-off procedure
Nugent says the process works like a very efficient
reactive dye that requires only a single finish wash. He  
claims a water savings of 90% and an energy savings of
20% over standard processes. Colorifix is setting up pilot Source: Natural Resources Defense Council
operations in Italy and France; partner dye houses first
have to get a certification to work with genetically
modified microbes.

Pili got its start as a biology outreach program. “We were doing workshops with kids, growing
bacteria and making colors with them, painting with them,” Chief Science Officer Guillaume
Boissonnat recalls. In 2015, he and his partners realized they could make industrially useful colors
that way.

Biology is more efficient than the chemical industry at making dye structures, Boissonnat argues.
“Dyes are usually the aromatic molecules from heavy fractions of petroleum. We have made some
calculations that show to produce 1 kg of dye, you need 100 kg of petroleum, 1,000 L of water, and
10 kg of other chemicals.”

But the major portion of water used for textile dyeing comes after dyeing, when fabrics, particularly
cotton, have to be washed over and over again to remove unfixed dye. Instead, manufacturers can
skip dyes and use pigments. As at Intech Digital, the enabling technology for that move is large-scale
printers that take the place of dyeing vats. The printers use special versions of ink-jet printheads
designed to work with textile inks.

The use of digital textile printing is growing rapidly, thanks in large part to demand from fast-fashion
purveyors, says Tim Check, a textile product manager at Epson, which makes printers, printheads,
and inks for textiles. Check says retailers such as H&M or Zara demand short runs of styles to
appear in stores in as little as two weeks, rather than the traditional design schedule of huge runs
delivered after several months.

Patterned textiles for such garments were historically made by screen printing, which is expensive to
set up, requires custom templates for each color, and uses a limited set of hues. Digital printers,
which give designers almost unlimited choices, are taking over some of that market.

“The big reason we’re really excited is it’s having huge growth, well over 20% per year,” Check says.
But that increase is from a small base of about 2–3% of total textile output.

Digital printing on polyester uses a two-step dye sublimation process that is almost waterless. The
pattern is first printed on transfer paper; heat then turns the color into a cloud of gas, which bonds
with the softened polyester.

This process doesn’t work for cotton, silk, and other natural fabrics, Intech’s Cheng points out. For
them, his firm offers a new specialty ink made with powdered, insoluble pigments plus a polymer-like
binder designed to make the color stick.

Epson’s Check says the digital printing approach can allow apparel manufacturers to operate in
regions closer to their customers, such as in North America. “All you need is a printer and a heat
system to fix the ink. That means you can do that here in the U.S. without the environmental
concerns or cost of managing wastewater,” he says.
 

T
“
he textile industry,
including retail, is
very, very competitive,
and in the end, cost
matters.”
--- Holger Schlaefke, global marketing manager, Huntsman’s textile
effects segment

Huntsman’s Schlaefke agrees that digital printing is a trend that could have an impact on how much
and what types of colorants are used. “The market is moving in the right direction for printing,” he
says.

Since Huntsman sells both traditional dyes and specialty inks, it stands to gain whichever way the
wind blows. Schlaefke says the segment’s growth will depend in large part on how economical the
machines become.

“The textile industry, including retail, is very, very competitive, and in the end, cost matters,”
Schlaefke says. He points out that a penny of additional cost adds up to a lot of money when a
company is making millions of garments.

For companies that have strong chemistry capabilities, being able to help textile customers meet
sustainability goals lends a competitive edge. “If you only see it as a threat and you are getting
worried, I think you won’t survive in the long run,” Schlaefke says.

But nothing is straightforward in the textile industry. While China cracks down with environmental
inspections, and wages in the country rise, the industry is moving to countries, including Bangladesh
and Vietnam, with fewer environmental controls. Innovators with greener dyeing technology will have
to work hard to keep their progress from unraveling.

Chemical & Engineering News

ISSN 0009-2347
Copyright © 2019 American Chemical Society

YOU MIGHT ALSO LIKE...

SUSTAINABILITY POLLUTION
U.S. textile makers Cleaning the clothing Cutting Out Textile
look for a revival industry Pollution

COMMENTS
Charley Liberko
(July 19, 2018 10:25 AM)
Dyes are one of the oldest areas of research in organic chemistry and it is interesting that there is still more to
learn. This is a great story but it left me hungry to know more about the chemical structures of the dyes. Chemists
communicate through chemical structures and I would like to encourage C&EN to include more structures in their
articles.
Reply »

Joe Atkinson
(July 22, 2018 2:54 PM)
I strongly second Charley Liberko's request for structures. "A picture is worth a thousand words" and nowhere
more so than in chemistry.
Reply »

Paul C Li，
(July 23, 2018 10:16 AM)
All technical headaches described in papers have very little difficulties for us to get them done one after another in
whatever you want to make。 A series of pluripotent intermediate is available on demand to get the job done， I
am confident。The chemistry and engineer job work with regulatory agency conscious with cost and performance
is in place。
Reply »

LEAVE A COMMENT
Name

Email*

Comments by first-time contributors will be reviewed prior to appearing on the site. This review is done by humans and not
always immediately. You may be laudatory or critical, but please stay on topic and be respectful of the author and your
fellow readers. We reserve the right to remove any comments that are profane, obscene, abusive, or otherwise
inappropriate. Email addresses are required so that we can verify you are not a robot overlord and in case we need to
contact you about your comment privately. They will not appear on the site.

Submit
*Required to comment
 

ABOUT FOLLOW US
About Us  Join ACS

Advertise Renew Membership

Contact C&EN ACS Network

Sign up for C&EN's must-read weekly newsletter

Email Address Subscribe »

Contact us to opt out anytime

Copyright © 2019 American Chemical Society. All Rights Reserved. Help Site Map Privacy Policy Terms of Use