Archive for August, 2010

New LNG traders challenge old guard

Monday, August 16th, 2010


THE traditional old-guard of major liquefied natural gas producers, (LNG) which has dominated LNG trade since its inception, is being challenged.

Growing ranks of trading houses and banks, already ingrained in the oil market, are now looking to cement positions in the fast-growing LNG market historically run by a clique of major incumbents.

While some banks tried and failed to penetrate the LNG market a few years ago, the expected increase in LNG production globally and a potential surplus of supply in the coming years, could create a platform on which new players can thrive.

If successful, these new entrants could bring transparency and efficiency to a previously closed market. But they will have to loosen the tight grip that the likes of BP, BG Group, Royal Dutch Shell and others have on the market before real change can come about.


“Traditional producers and their long term buyers want cheap xenical online to control what happens in the market,” said Morten Frisch an independent LNG consultant in East Horsley, England.

“However, with an increasing number of LNG suppliers and buyers active in the market, this is becoming increasingly difficult to achieve.”

The growing LNG market has until now been run by producers and shippers who have supplied LNG under long term contracts straight to customers – mainly utilities – with gas demand of their own. The space for middle men has been narrow.

Even the burgeoning LNG spot market, which has more than doubled to about 20 per cent of total LNG trade over the past ten years, has been dominated by a small group of big players.

But, as global production grows, the old order faces some fresh competition. While banks like Morgan Stanley have been involved in LNG for a number of years, the past year has seen a quickening stream of new players announcing plans to trade cargoes of the gas that is super-cooled into a liquid for transportation by ship.

This week Barclays Capital said it plans to trade physical cargoes while European energy trading house Mercuria also announced its entry into the market.

LNG production is set to grow by 50 per cent from 2009 to 2013, according to the International Energy Agency.

LNG traders have become a precious commodity. New outfits are poaching traders from the established desks of the majors to head up their own teams. Mercuria hired two former BP traders for its new team. Golar LNG head-hunted five of Citi Group’s team when it opened a trading desk earlier this year.

“With a higher number of different classes of market players and an increasing numbers of transactions, we are likely to see increased market-based pricing of LNG developing,” Frisch said.

While the potential is there to increase liquidity and competition in the LNG market, barriers remain, some unique to the LNG market.

Aside from the need to build up contacts in a strongly relationship-based world, new players need access to the specially-designed tankers that carry LNG, a downstream outlet to send the gas and access to the LNG itself.

The size of LNG fleet

has rocketed, from 100 in 1998 to 200 in 2006 and to 300 today, but still the majority of LNG tankers are in the hands of production projects and their shareholders.

According to Keith Bainbridge, partner at shipbrokers RS Platou in London, about 80 percent of the LNG fleet is assigned to production projects. Of the remaining tankers, about 80 percent are in the hands of the majors.

“The big boys are taking all the shipping that’s out there. It’s not a level playing field for the traders,” Bainbridge said.

Without a chartered tanker, or some terminal capacity to send the gas, traders will struggle to find their bids accepted in a spot tender.

“You need shipping, molecules or downstream capacity,” Bainbridge added. “They have to put some investment in and taking some long position.”

In a sign that it can be done, European energy trade Gunvor has burst onto the LNG scene, buying 19 cargoes since it opened its LNG trading desk in January. Gunvor has import capacity in two terminals in Europe, and plans to double that number soon.

Traders believe there is money to be made for new entrants, however thin the margins.

“Greater competition is going to bring the LNG market forward. Whether or not this will make it more like the oil market is a different question,” one LNG trader said. – Reuters

Tackling oil and gas talent conundrum

Sunday, August 15th, 2010


STUTTERING global economic recovery and fluctuating oil prices aside, the fact of the matter is that demand for oil and gas (O&G) will continue to grow and grow at an intense pace. The factors for this growth in demand have already been well documented.

Naturally, the rise in demand will drive the need for enhanced capacity in the industry. This includes core areas of the entire business stream: from exploration to drilling to production, all the way to distribution. In Malaysia alone, it was recently reported that O&G jobs worth some RM88 billion are expected to come on stream over the next four years.

It is indeed good news for the O&G support services sector – companies which make a living out of offering products and services to O&G companies. To take advantage of this growth, participants in O&G services have scrambled to consolidate and merge in a bid to become bigger, more visible and, thus, better positioned to seize opportunities.

While size does matter in the world of O&G, we strongly believe that knowledge, not assets, will be an integral source of future growth in this sector. Herein lies the conundrum: the global O&G industry is seriously short-staffed!


Where have all the people gone?

Just like in any business sector, the O&G industry is governed by business cycles. There are “ups” and then there are “downs”. In the down cycle, when oil prices are low or supply outstrips demand, people are often let go. Unfortunately, in the O&G industry, people who are retrenched do not necessarily return. Understandably, they feel that going back to an industry with a high likelihood of being laid off again in the not too distant future is unpalatable. As such, talent with highly specialised skill sets is often lost in this nature.

The O&G industry is also facing an acute ageing workforce. Globally, more than a third of O&G industry workers are expected to retire by 2012. This means that the industry has to compete for an ever-reducing pool of experienced talent. What’s worse, this pool may not be replenished anytime soon given that the industry is finding it difficult to attract entry-level talent.

Having said this, the availability of entry-level talent with the basic knowledge and skill sets required to start a career in the O&G sector is not the issue here. Admittedly, education institutions across the world churn out many young, capable and driven individuals who have the tools to succeed in this industry. However, the O&G industry is oftentimes associated with dirty, harsh, cramped and, sometimes, dangerous work environment. Also, industry workers will likely have to be away from home for long durations. These factors may not appeal to today’s workforce, more so if there are alternative employment opportunities that offer similar compensation with more comfortable working conditions. As such, qualified prospective talent today is being taken by other industries.

With the global O&G industry shifting into higher gear, after a relatively quiet period over the recent years, the talent conundrum poses the greatest risk to O&G companies. But how can the industry as a whole address this serious predicament?

Focus on talent now!

The shortage of talent in the O&G industry can be addressed if industry participants first acknowledge the fact that human capital is the industry’s most prized asset. Unfortunately, we are where we are today because this is oftentimes not the case.

By realising the importance of human capital and long-term growth, O&G companies will naturally be inclined to grow at a sustained pace. It will do wonders for the industry if

it understands that hiring aggressively during an up cycle and letting people go when times are down is bad for business in the long term.

The way forward for O&G industry participants in the realm of talent is to look at the entire gamut of human capital management. These include strategies to source and recruit talent as well as developing and retaining the existing workforce. Not one component can be stand-alone as we face this talent crisis in the industry.

“Pay them and they will come.” This may online cialis be a common adage for talent sourcing and recruiting, but, unfortunately, it is not that simple. While competitive compensation is a must in any industry, tangible and intangible elements such as career progression plans, personal development paths and employee-friendly corporate culture are factors just as important in attracting talent today.

In addition, continuous training is crucial to developing and retaining talent. This is regardless of whether it is during an industry up cycle or down cycle. Training can be in various forms and formats, ranging from on-the-job-training to classroom training.

A great way for O&G companies to utilise training as a platform to recruit new talent is by collaborating with universities and institutions of higher learning. Via an internship programme, students can apply what they have learnt in the classroom to “real-life” work situations, while experiencing life in the industry first-hand. This will eventually create a ready pool of willing and trained talent for the industry.

In terms of personal development, O&G industry workers will likely stay on if they feel that they are improving their personal value. Towards this end, continuous learning can be an ideal philosophy implemented in O&G companies. Collaborations can be formed between other corporate organisations as well as government or non-government agencies where employees can learn and exchange ideas and knowledge across different stakeholders of the O&G industry.

All in all, it is exciting times for the O&G sector. For companies to succeed and advance, effective integrated human capital management strategies must be a top priority for all industry participants. This is all the more important for the O&G support services sector given that its business model is predicated on a high-quality workforce with specialised industry knowledge. Our people are our fuel for growth and our bottom line depends on them.

# The writer is the president of Scomi Group’s oilfield services division.

DuPont Nomex 111A VS China Aramid

Thursday, August 12th, 2010

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Hunstman Pyrovatex VS China FRC

Thursday, August 12th, 2010

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Construction Of Fire Retardant Winter Coverall – Pyrovatex

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Malaysia gears up on deep-water drive

Wednesday, August 11th, 2010


Malaysia’s state player Petronas Carigali will need three drillships between 2010 and 2015 to support the development of deep-water oil and gas fields, the company’s

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head of deep-water development, Rosli Hamzah said at a conference in Singapore.

News wires  28 July 2010 02:50 GMT

Hamzah said two drillships, Transocean’s Deepwater Expedition and Frontier Phoenix are scheduled to arrive in Malaysian waters in September buy cheap cialis online no prescription and November, respectively.

AmResearch’s Alex Goh said the average day rates for drillships with rated water depth of over 4000 feet are around $425,000.

The drillships’ arrival signal Petronas’ commitment to re-direct capital expenditure to its home market, according to Goh.

Murphy’s Kikeh field off Sabah is the only Malaysian deep-water field that has commenced production.

The supermajor is expected to start up its second deep-water field off Sabah, the Gumusut-Kakap project in 2012 to 2013, Hamzah was cited as saying at the conference.

Two other deep-water discoveries, Shell’s Malikai and the supermajor’s Kebabagan project, jointly operated with Petronas Carigali and ConocoPhillips, have been earmarked for development.

A recent CIMB Research industry review estimates the development of the three discoveries off Sabah, Malikai, Kebabangan and Murphy Oil’s

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Jangas, would cost 13 billion ringgit ($4 billion).

Other deep-water projects off Sabah include Shell-operated Ubah Crest and Pisangan oilfields and Kamunsu gas development. These projects are in the planning stage, Hamzah said.

Oil and gas produced off Sabah will be processed through the Sabah Oil and Gas Terminal to be constructed at Kimanis.

Malaysia has awarded 23 deep-water production sharing contracts so far, but only 16 are active. Seven others have been relinquished, according to Hamzah.

Hamzah also said there are seven new deep-water blocks available in Malaysia.

The South-East Asian country is currently producing around 650,000 barrels per day of oil and 5.8 billion cubic feet per day of gas.

Deep-water oil and gas fields contributes to 4% of the country’s hydrocarbon production, Hamzah said.

Formaldehyde-free flame retardant treatment ( Proban & Pyrovatex )

Tuesday, August 10th, 2010



PROBAN and the PYROVATEX brand materials. The PROBAN technology, from Albright & Wilson, is based on the use of tetrakis-(hydrox

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ymethyl)phosphonium chloride (“THPC”)–based products and an ammoniation chamber. It is described in detail in the following U.S. Pat. Nos. 4,078,101; 4,145,463) 4,311,855 and 4,494,951, all to Albright and Wilson. The PYROVATEX CP methodology, originally developed by Ciba-Geigy ( Now by Huntsman,Germany ), utilizes dimethyl (N-hydroxymethylcarbamoyl-ethyl)phosphonate or a similar methylol-functional phosphorus-containing analogue as the flame retardant agent. Given the market share that PROBAN and PYROVATEX products control in the industry, it is often difficult to understand the widespread tolerance of the negative aspects associated with the use of these products and the various chemistries they employ.

The present invention relates to a formaldehyde-free flame retardant treatment for cellulose-containing materials, such as cotton or cotton blends (e.g., cotton/polyester and cotton/nylon), which is durable to both laundering and dry cleaning operations.

There are currently several different types of chemical finishes that can be applied

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to cellulose-containing materials to impart flame retardant (FR) properties. Of these systems, only a few create finished fabrics that can be laundered and dry-cleaned without losing their FR qualities. These treatments are generally referred to as durable FR finishes. Of these finishes, the most pertinent to the current invention are


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have been several versions of the THPC cross-linking chemistry used over the years. For example, the precondensate-NH3 process (e.g., PROBAN) technology is the most recent of these versions. Although this may be the most durable treatment on the market, this technology involves the use of an ammoniation chamber and strict application conditions to obtain consistent results without significant strength loss to the fabric. In addition to difficult application conditions, the startup costs for implementing this finishing technique and the regulatory issues associated with aimmonia gas make it less than attractive, especially for new arrivals to the market.

In many ways, the PYROVATEX technology suffers from much the same sort of downfalls as the PROBAN technology. Whether it is the original PYROVATEX CP methodology, based on the use of dimethyl (N-hydroxymethylcarbamoyl-ethyl)phosphonate, or other methods using different N-methylol-functional phosphorus-containing analogs, all of the products contain and emit the toxic component formaldehyde (a known carcinogen). In addition to the molecule forming overnight cialis the basis of the PYROVATEX-type approach, a formaldehyde-containing cross-linking resin, such as a N-methylolurea (for example, 1,3-dimethylol-4,5-dihydroxyethyleneurea–”DMDHEU”), N-methylolamide, or N-methylolmelamine, is also required to ensure adequate durability of the chemical finish. These resins are also independently used as durable-press cross-linking agents in the textile industry. The combination of a N-methylol phosphorus-containing analog and a N-methylol cross-linking resin, or the use of either reagent separately, often leads to the release of significant amounts of formaldehyde both during fabric application and throughout the lifetime of the garment. As a result, formaldehyde emission levels are limited and closely regulated throughout the industry. The only reason formaldehyde emissions are still tolerated is due to the lack of an acceptable formaldehyde-free replacement technology.

Given the negative impact of formaldehyde on human health, it has been a primary focus of the cotton apparel and textile finishing industries to create equivalent non-formaldehyde technologies. Accounting for their widespread use, most of the current research effort has been spent on the creation and design of new formaldehyde-free cross-linking agents for cellulose-containing materials. These reagents could be used in many different applications, ranging from use in durable-press finishes to general fixation additives for products such as the PYROVATEX-type FR additives. In the past several years, research efforts have led to the discovery of several new low formaldehyde based systems. These finishes are generally based on the structural modification of DMDHEU, either via substitution or elimination of the pendant methylol functionality. Nevertheless, these new finishing agents have never gained widespread acceptance due to their inadequate performance as cross-linking agents. In general, removal or modification of the most reactive aspect of the DMDHEU molecule has only resulted in the generation of less reactive and less desirable finishing agents.

In addition to modifying DMDHEU, other technologies have also begun to develop. One of the more promising non-formaldehyde systems is based on the use of polycarboxylic acids. These molecules create a cross-linked cellulosic material via the in-situ generation of five-membered cyclic anhydrides and their subsequent reaction with hydroxyl moieties contained within the treated textile. This technology was developed at the United States Department of Agriculture in New Orleans under the direction of Clark Welch and was based on the use of 1,2,3,4-butanetetra-carboxylic acid (BTCA). Representative patents describing this approach are: U.S. Pat. Nos. 4,820,307; 4,936,865; 4,975,209; and 5,221,285.

Since the invention of the BTCA technology, additional investigators have begun to work with polycarboxylic acids to improve their commercial attractiveness. Some of the recent work has focused on the use of polymaleic acid and in some cases citric acid or combinations containing citric acid. Polymaleic acid (PMA) is an inexpensive, commercially available material commonly used as a water treatment chemical. Some aspects of this work are described in PCT International Patent Publication No. WO 98/30387. In addition to PMA, there is a wide range of alternative non-formaldehyde cross-linking resins that can be used in creating durable non-formaldehyde FR treatments for cellulose-containing materials. Many of these resins are currently available and used in the water treatment business for scale-inhibition, some of which even contain small amounts of phosphorus. The utilization of these formaldehyde-free, phosphorus-containing resins may even offer additional advantages over the phosphorus-free cross-linking resins such as PMA. Incorporation of phosphorus species into the cross-linking resin itself may eliminate the need for an external cross-linking catalyst and/or the added phosphorus may result in improved FR properties of the treated cellulose-containing materials. Examples of these resins can be seen in the following U.S. Pat. Nos. 4,046,707; 4,105,551; 4,621,127; 5,376,731; 5,386,038; 5,496,476; 5,705,475; and 5,866,664.


The present invention relates to an aqueous finishing composition for cellulose-containing materials and the materials treated with such a composition. The aqueous finishing composition, in its broadest embodiment, comprises a hydroxyalkyl-functional organophosphorus flame retardant and a non-formaldehyde cross-linking agent, optionally with a cross-linking catalyst also being included therein.


The aqueous finishing composition, which is intended to be used to treat cellulose-containing materials in accordance with the present invention contains two essential components: (1) a hydroxyalkyl-functional organophosphorus flame retardant (excluding N-methylol, ethers thereof, and potentially formaldehyde releasing reagents); and (2) a non-formaldehyde cross-linking agent.

Monomeric, oligomeric (which generally contain from about two to ten repeat units) and polymeric (which generally contain over about ten repeat units) hydroxyalkyl-functional organophosphorus flame retardant additives are intended for use herein.

A reactive oligomeric phosphorus-containing flame retardant of the type that is described in U.S. Pat. No. 3,695,925 to E. D. Weil and U.S. Pat. Nos. 4,199,534, 4,268,633, and 4,335,178 to R. B. Fearing is an example of one of the hydroxyalkyl-functional organophosphorus flame retardants that can be used in accordance with the present invention. A preferred embodiment has the following structure: ##STR1##

where R1 is independently selected from methyl and hydroxyethyl, R2 is independently selected from methyl, methoxy, and hydroxyethoxy, and n is equal to or greater than 1. This embodiment is made by a multistep process from dimethyl methylphosphonate, phosphorus pentoxide, ethylene glycol, and ethylene oxide and is available under the registered trademark FYROL.RTM. 51 from Akzo Nobel Chemicals Inc. The endgroups are principally hydroxyl groups.

Another class of materials for use herein includes water soluble oligomeric alkenylphosphonate materials, examples of which are described in U.S. Pat. Nos. 3,855,359 and 4,017,257, both to E. D. Weil. The presence of alkenyl substituents in these materials provide an additional mechanism for permanence utilizing free radical curing conditions (described in the patents above). A preferred species of this type was available under the trademark PYROL.RTM. 76 from Akzo Nobel Chemicals Inc. and is produced by reacting bis(2-chloroethyl) vinylphosphonate and dimethyl methylphosphonate with the substantial elimination of methyl chloride.

Another type of hydroxyalkyl-functional organophosphorus flame retardant that can be employed are oligomeric phosphoric acid esters that carry hydroxyalkoxy groups as described in U.S. Pat. Nos. 2,909,559, 3,099,676, 3,228,998, 3,309,427, 3,472,919, 3,767,732, 3,850,859, 4,244,893, 4,382,042, 4,458,035, 4,697,030, 4,820,854, 4,886,895, 5,117,033, and 5,608,100.

The flame retardant is generally present at from about 1% to about 60%, preferably from about 10% to about 40%, by weight of the aqueous finishing composition.

The non-formaldehyde cross-linking agent, which is the second essential component of the aqueous finishing composition of the present invention, is generally present at from about 1% to about 40%, by weight, of the total weight of that composition, preferably from about 5% to about 20%.

Polycarboxylic acid cross-linking agents form one type of cross-linking agent for use herein. The polycarboxylic acids effective as cellulose cross-linking agents in regard to this invention include aliphatic, alicyclic and aromatic acids either olefinically saturated or unsaturated with at least three and preferably more carboxyl groups per molecule or with two carboxyl groups per molecule if a carbon-carbon double bond is present alpha, beta to one or both carboxyl groups. An additional requirement is that to be reactive in esterifying cellulose hydroxyl groups, a given carboxyl group in an aliphatic or alicyclic polycarboxylic acid should be separated from a second carboxyl group by no less than two carbon atoms and no more than three carbon atoms. In an aromatic acid, a carboxyl group must be ortho to a second carboxyl group if the first carboxyl is to be effective in esterifying cellulosic hydroxyl groups. It appears from these requirements that for a carboxyl group to be reactive, it should be able to form a cyclic 5- or 6-membered anhydride ring with a neighboring carboxyl group in the polycarboxylic acid molecule. Where two carboxyl groups are separated by a carbon-carbon double bond or are both connected to the same ring, the two carboxyl groups should be in the cis configuration relative to each other if they are to interact in this manner. The aliphatic or alicyclic polycarboxylic acid may also contain an oxygen or sulfur atom in the chain or ring to which the carboxyl groups are attached.

In aliphatic acids containing three or more carboxyl groups per molecule, a hydroxyl group attached to a carbon atom alpha to a carboxyl group does not interfere with the esterification and cross-linking of cellulose by the acid. However, the presence of the hydroxyl group may cause a noticeable yellowing of the material during the heat cure. Such an alpha-hydroxy acid is suitable for durable press finishing of suitably dyed cotton fabric, since the color of the dye conceals the discoloration that may be caused by the presence of the hydroxyl group. Fabric discoloration is similarly observed with an unsaturated acid having an olefinic double bond that is not only alpha, beta to one carboxyl group but also beta, gamma to a second carboxyl group.

The discoloration produced in a white cellulose-containing material by cross-linking it with an alpha-hydroxy acid such as citric acid can be removed by impregnating the discolored material with an aqueous solution containing from 0.5% to 5% by weight of a decolorizing agent selected from the group consisting of magnesium monoperoxyphthalate, sodium perborate, sodium tetraborate, boric acid, sodium borohydride, sodium hypochlorite, and hydrogen chloride. The material is immersed in the solution of decolorizing agent and soaked for 5 to 120 minutes at ambient temperature or if necessary in such a solution warmed to a temperature not exceeding 60° C. The material is subsequently rinsed with water to remove excess chemicals and solubilized colored products, and then is dried.

A particularly preferred polycarboxylic acid cross-linking agent for use herein is 1,2,3,4-butanetetracarboxylic acid.

Another preferred polycarboxylic acid cross-linking agent for use herein is polymaleic acid.

Another embodiment for this component is a hydrolyzed terpolymer of maleic anhydride with vinyl acetate and ethyl acrylate. The molar ratio of maleic anhydride to the combined moles of vinyl acetate and ethyl acrylate is preferably from about 2.5:1 to about 5:1 and the molar amount of vinyl acetate to ethyl acrylate is preferably from about 1:4 to about 4:1, most preferably from about 1:2 to about 2:1. The molecular weight of the terpolymer has an upper limit of about 4,000. A product of this type is available under the trademark BELCLENE 283 from FMC Corporation.

Examples of other specific polycarboxylic acids which fall within the scope of this invention are the following: maleic acid; citraconic acid also called methylmaleic acid; citric acid also known as 2-hydroxy-1,2,3-propanetricarboxylic acid; itaconic acid also called methylenesuccinic acid; tricarballylic acid also known as 1,2,3,-propanetricarboxylic acid; trans-aconitic acid also known as trans-1-propene-1,2,3-tricarboxylic acid; 1,2,3,4-butanetetracarboxylic acid; all-cis-1,2,3,4-cyclopentanetetracarboxylic acid; mellitic acid also known as benzenehexacarboxylic acid; oxydisuccinic acid also known as 2,2′-oxybis-(butanedioic acid); thiodisuccinic acid; the phosphorus-containing polycarboxylic acid resins described in U.S. Pat. Nos. 4,046,707; 4,105,551; 4,621,127; 5,376,731; 5,386,038; 5,496,476; 5,705,475; 5,866,664; and the like.

In the event that adequate cross-linking is not accomplished using the previously mentioned systems, it may be necessary to add a suitable cross-linking catalyst to enhance the reaction between the cellulose-containing material which is to be treated, the hydroxyalkyl-functional organophosphorus flame retardant, and the non-formaldehyde cross-linking agent. This catalyst can be present at up to about 30 wt % of the total weight of the aqueous finishing composition, preferably up to about 10%. Examples of suitable catalyst types to select, as set forth in PCT International Patent Publication No. WO 98/30387 and U.S. Pat. Nos. 4,820,307, 4,936,865, 4,975,209, and 5,221,285 include one or more of the alkali metal salts of the known hypophosphite, phosphite, pyrophosphate, dihydrogen phosphate, phosphate, and hydrogen phosphate species, and such acids as one or more of the polyphosphoric, hypophosphorous, phosphorous, and alkyl phosphinic acids. Alternative basic cross-linking catalysts such as NaHCO3 and Na2 CO3 can also be used.

In some cases, in order to raise the pH of the treating solution to improve compatibility of the bath or additives and/or for improved strength retention, a portion of the polycarboxylic acid may be used in salt form, especially as a water soluble salt. Suitable for this purpose are alkali metal salts of the acid. Alternatively, or in combination with use of the polycarboxylic acid in salt form, the pH of the treating solution may be raised, or the solution partially neutralized, by the addition of a base, preferably a water soluble base, such as an alkali metal hydroxide, ammonium hydroxide, or an amine. The pH may be elevated for such purpose to about 2.3 to about 5, preferably about 2.5 to 4.

The present invention is further illustrated by the Examples that follow.


Flame Retardant (“FR”) Additives Used

Sample Compound #1: Modified FYROL.RTM. 51 Flame Retardant (low OH#)

Sample Compound #2: PEEOP (low OH#)

Sample Compound #3: Modified PEEOP (high OH#)

Sample Compound #4: FYROL.RTM. 51 Flame Retardant (high OH#)

Sample Compound #5: FYROL.RTM. 6 Flame Retardant

Sample Compound #6: FYROL.RTM. 76 Flame Retardant

In the listing given above, “PEEOP” is a poly(ethyl ethyleneoxy) phosphate of the type described in U.S. Ser. No. 08/677,283, having a molecular weight of around 915 (number average)/1505 (weight average), and a typical hydroxyl number of under about 5 mg KOH/g (low hydroxyl number version) and about 150 mg KOH/g (high hydroxyl number version). The modified FYROL.RTM. 51 flame retardant has a hydroxyl number of under about 5 mg KOH/g and the high hydroxyl version of the FYROL.RTM. 51 brand product has a hydroxyl number of about 125 mg KOH/g. The FYROL.RTM. 6 flame retardant has a hydroxyl number of about 440 mg KOH/g whereas the FYROL.RTM. 76 flame retardant has a hydroxyl number of about 100 mg KOH/g.

Polycarboxylic Acid Resins and Other Chemicals Used

Belclene 283: a 35% aqueous solution of the hydrolysis product of a terpolymer (TMPA) of maleic anhydride, vinyl acetate, and ethyl acrylate.

Belclene 200: a 35% aqueous solution of polymaleic acid (PMA).

BTCA: 1,2,3,4-butanetetracarboxylic acid (solid).

NaH2 PO2 (hydrate): used as a cross-linking catalyst.

Equipment Used

Pad Applicator (laboratory size): an instrument used to apply a solution to fabric at a specified level (% wet-pickup).

Curing Oven (laboratory size): an oven that is used to dry and subsequently cure chemically treated fabrics at high temperatures.

Washing Machine (household size): used for laundering (with Tide.RTM. detergent) fabrics before and after chemical treatment and curing.

Fabric Used

Medium weight (about 1am thick), white, prewashed, 100% cotton fabric (12×16 inch samples).

Experimental Details

Preliminary Work:

The cotton fabric was laundered to ensure its cleanliness, and then cut into about 12×16 inch samples for subsequent use. Using water and fabric samples, the pad applicator was set to a wet-pickup of about 75% (additional weight of the liquid divided by the original weight of the dry cloth). A 75% wet-pickup of water translated to about 80% wet-pickup for the chemical solutions.

General Procedure:

The application solutions with and without FR were prepared. Each solution contained a FR (except blanks), polycarboxylic acid, NaH2 PO2, and water. Given a wet-pickup of 80%, the solution concentrations were adjusted to give the desired add-on weights of each chemical.

After preparation, each application solution was used within a period of five hours.

Each solution was then applied to a fabric sample. The fabric was immersed in the solution, fed through the pad applicator, immersed in the solution again, and fed through the pad applicator again to ensure adequate homogeneity throughout the fabric sample.

After application, each fabric sample was placed on a metal frame and inserted into the oven at 80° C. to dry (three to five minutes).

After drying, each sample was placed in the oven again at 180° C. to cure the chemical treatment (one and one half to two minutes).

Each cured sample was then removed from the metal rack and its physical properties recorded. Any observations made while drying and curing the fabric were also recorded.

Informal Ignition Tests:

Each fabric sample was held in a horizontal position and ignited with a propane lighter. The flamability properties of each fabric sample were recorded.

EXPERIMENTAL DATA 1st Trial Application: BELCLENE 283 Resin BTCA Sample Sample Sample Sample Sample Sample Comp. #2 Comp. #4 Comp. #5 Comp. #2 Comp. #4 Comp. #5 Dry Add-On 10% FR#2 10% FR#4 10% FR#5 10% FR#2 10% FR#4 10% FR#5 Weight 4% TMPA 4% TMPA 4% TMPA 4% BTCA 4% BTCA 4% BTCA 2% NaH2 PO2 2% NaH2 PO2 2% NaH2 PO2 2% NaH2 PO2 2% NaH2 PO2 2% NaH2 PO2 Application 26.6 g FR#2 26.6 g FR#4 26.6 g FR#5 26.6 g FR#2 26.6 g FR#4 26.6 g FR#5 Solution 30.4 g 30.4 g 30.4 g 10.7 g BTCA 10.7 g BTCA 10.7 g BTCA Recipe BELCLENE BELCLENE BELCLENE 5.4 g NaH2 PO2 5.4 g NaH2 PO2 5.4 g NaH2 PO2 283 283 283 157.3 g H2 O 157.3 g H2 O 157.3 g H2 O 5.4 g NaH2 PO2 5.4 g NaH2 PO2 5.4 g NaH2 PO2 137.6 g H2 O 137.6 g H2 O 137.6 g H2 O Drying 3 min. @ 3 min. @ 3 min. @ 3 min. @ 3 min. @ 3 min. @ Conditions 80° C. 80° C. 80° C. 80° C. 80° C. 80° C. Curing 1.5 min. @ 1.5 min. @ 1.5 min. @ 1.5 min. @ 1.5 min. @ 1.5 min. @ Conditions 180° C. 180° C. 180° C. 180° C. 180° C. 180° C. Burn Bad – Bad – Bad – Bad – Bad – Bad – (before fabric fabric fabric fabric fabric fabric washing) burned burned burned burned burned burned 2nd Trial Application: Blank Samples (without FR) BELCLENE 283 (TMPA) BTCA BELCLENE 200 (PMA) Dry Add-On 8% TMPA 8% TMPA 8% TMPA Weight 4% NaH2 PO2 4% NaH2 PO2 4% NaH2 PO2 Application 57.1 g BELCLENE 283 57.1 g BELCLENE 283 57.1 g BELCLENE 283 Solution 10.0 g NaH2 PO2 10.0 g NaH2 PO2 10.0 g NaH2 PO2 Recipe 132.9 g H2 O 132.9 g H2 O 132.9 g H2 O Drying 5 min. @ 80° C. 5 min. @ 80° C. 5 min. @ 80° C. Conditions Curing 2 min. @ 180° C. 2 min. @ 180° C. 2 min. @ 180° C. Conditions Burn Test Bad – fabric burned Bad – fabric burned Bad – fabric burned (before wash) Fabric Color Slight off-white White Yellow tint tint Fabric Hand Very hard Hard Very hard Other No smoke No smoke No smoke Observations Sample Sample Sample Sample Sample Sample Comp. #1 Comp. #2 Comp. #3 Comp. #4 Comp. #5 Comp. #6 BELCLENE 283 Resin (TMPA) Dry Add-On 20% FR#1 20% FR#2 20% FR#3 20% FR#4 20% FR#5 20% FR#6 Weight 8% TMPA 8% TMPA 8% TMPA 8% TMPA 8% TMPA 8% TMPA 4% NaH2 PO2 4% NaH2 PO2 4% NaH2 PO2 4% NaH2 PO2 4% NaH2 PO2 4% NaH2 PO2 Application 50.0 g FR#1 50.0 g FR#2 50.0 g FR#3 50.0 g FR#4 50.0 g FR#5 50.0 g FR#6 Solution 57.1 g 57.1 g 57.1 g 57.1 g 57.1 g 57.1 g Recipe BELCLENE BELCLENE BELCLENE BELCLENE BELCLENE BELCLENE 283 283 283 283 283 283 10.0 g 10.0 g 10.0 g 10.0 g 10.0 g 10.0 g NaH2 PO2 NaH2 PO2 NaH2 PO2 NaH2 PO2 NaH2 PO2 NaH2 PO2 82.9 g H2 O 82.9 g H2 O 82.9 g H2 O 82.9 g H2 O 82.9 g H2 O 82.9 g H2 O Drying 5 min. @ 5 min. @ 5 min. @ 5 min. @ 5 min. @ 5 min. @ Conditions 80° C. 80° C. 80° C. 80° C. 80° C. 80° C. Curing 2 min. @ 2 min. @ 2 min. @ 2 min. @ 2 min. @ 2 min. @ Conditions 180° C. 180° C. 180° C. 180° C. 180° C. 180° C. Burn Test Good Good Good Good Bad – Good (before fabric wash) burned Burn Test Acceptable Bad – Good Good Bad – Good (after 1 fabric fabric water wash) burned burned Burn Test — – Acceptable Good — Acceptable (after 5 launderings) Fabric Color Pink color Dark pink Pink color Dark pink Pink color Light pink color color tint Fabric Hand Hard Soft Very hard Very hard Very hard Very hard Other Smoked Solubility No smoke No smoke Smoked No smoke Observations during cure problem-FR during cure BTCA Dry Add-On 20% FR#1 20% FR#2 20% FR#3 20% FR#4 20% FR#5 20% FR#6 Weight 5% BTCA 5% BTCA 5% BTCA 5% BTCA 5% BTCA 5% BTCA 2.5% 2.5% 2.5% 2.5% 2.5% 2.5% NaH2 PO2 NaH2 PO2 NaH2 PO2 NaH2 PO2 NaH2 PO2 NaH2 PO2 Application 50.0 g FR#1 50.0 g FR#2 50.0 g FR#3 50.0 g FR#4 50.0 g FR#5 50.0 g FR#6 Solution 12.5 g BTCA 12.5 g BTCA 12.5 g BTCA 12.5 g BTCA 12.5 g BTCA 12.5 g BTCA Recipe 6.3 g 6.3 g 6.3 g 6.3 g 6.3 g 6.3 g NaH2 PO2 NaH2 PO2 NaH2 PO2 NaH2 PO2 NaH2 PO2 NaH2 PO2 131.2 g H2 O 131.2 g H2 O 131.2 g H2 O 131.2 g H2 O 131.2 g H2 O 131.2 g H2 O Drying 5 min. @ 5 min. @ 5 min. @ 5 min. @ 5 min. @ 5 min. @ Conditions 80° C. 80° C. 80° C. 80° C. 80° C. 80° C. Curing 2 min. @ 2 min. @ 2 min. @ 2 min. @ 2 min. @ 2 min. @ Conditions 180° C. 180° C. 180° C. 180° C. 180° C. 180° C. Burn Test Good Good Good Good Bad – Good (before fabric wash) burned Burn Test Acceptable Bad – Good Good Bad – Good (after 1 fabric fabric water wash) burned burned Burn Test — – Good Good — Good (after 5 launderings) Fabric Color White White White White Slight White yellow tint Fabric Hand Semi-soft Soft Hard Very hard Hard Very hard Other Smoked Solubility No smoke No smoke Smoked No smoke Observations during cure problem-FR during cure BELCLENE 200 (PMA) Sample Comp. Sample Comp. Sample Comp. Sample Comp. #1 #3 #4 #6 Dry Add-On 20% FR#1 20% FR#3 20% FR#4 20% FR#6 Weight 8% PMA 8% PMA 8% PMA 8% PMA 4% NaH2 PO2 4% NaH2 PO2 4% NaH2 PO2 4% NaH2 PO2 Application 50.0 g FR#1 50.0 g FR#3 50.0 g FR#4 50.0 g FR#6 Solution 57.1 g BELCLENE 57.1 g BELCLENE 57.1 g BELCLENE 57.1 g BELCLENE Recipe 200 200 200 200

10.0 g NaH2 PO2 10.0 g NaH2 PO2 10.0 g NaH2 PO2 10.0 g NaH2 PO2 82.9 g H2 O 82.9 g H2 O 82.9 g H2 O 82.9 g H2 O Drying 5 min. @ 80° C. 5 min. @ 80° C. 5 min. @ 80° C. 5 min. @ 80° C. Conditions Curing 2 min. @ 180° C. 2 min. @ 180° C. 2 min. @ 180° C. 2 min. @ 180° C. Conditions Burn Test Good Good Good Good (before wash) Burn Test Acceptable Good Good Good (after 1 water wash) Burn Test — – Good — (after 5 launderings) Fabric Color Yellow tint Yellow tint Yellow tint Yellow tint Fabric Hand Hard Very hard Hard Very hard Other Smoked during No smoke No smoke No smoke Observations cure 3rd Trial Application: Sample Compound #5 BELCLENE 283 BELCLENE 200 (TMPA) BTCA (PMA) Dry Add-On 40% FR#5 40% FR#5 40% FR#5 Weight 8% TMPA 5% BTCA 8% PMA 4% NaH2 PO2 2.5% NaH2 PO2 4% NaH2 PO2 Application 100.0 g FR#5 100.0 g FR#5 100.0 g FR#5 Solution 57.1 g BELCLENE 12.5 g BTCA 57.1 g BELCLENE Recipe 283 6.3 g NaH2 PO2 200 10.0 g NaH2 PO2 81.2 g H2 O 10.0 g NaH2 PO2 32.9 g H2 O 32.9 g H2 O Drying 5 min. @ 80° C. 5 min. @ 80° C. 5 min. @ 80° C. Conditions Curing 2 min. @ 180° C. 2 min. @ 180° C. 2 min. @ 180° C. Conditions Burn Test Bad – fabric Bad – fabric Bad – fabric (after 1 burned burned burned water wash) Fabric Color Yellow tint Yellow tint Yellow tint Fabric Hand Soft Soft Soft Other Smoked during Smoked during Smoked during Observations cure cure cure

Analysis of Selected Fabric Samples

Sample Compound #3 (20% add-on) with TMPA and BTCA (samples–before washing, after one water wash, and after five launderings).

Sample Compound #4 (20% add-on) with TMPA, BTCA, and PMA (samples–before washing, after one water wash, and after five launderings).

Sample Compound #6 (20% add-on) with TMPA and BTCA (samples–before washing, after one water wash, and after five launderings).

Sample Compound #5 (40% add-on) with TMPA, BTCA, and PMA (samples–after one water wash).

Percent Phosphorus Determinations on Selected Fabric Samples Before After 1 After 5 Sample Identification (dry Washing Water launderings add-on weights) (% P) Wash (% P) (% P) 20% FR #3, 5.0% BTCA, 2.5% 2.8 1.9 1.6 NaH2 PO2 20% FR #3, 8.0% TMPA, 4.0% 3.6 2.1 2.1 NaH2 PO2 20% FR #4, 5.0% BTCA, 2.5% 3.4 2.0 2.1 NaH2 PO2 20% FR #4, 8.0% TMPA, 4.0% 4.2 2.7 2.5 NaH2 PO2 20% FR #4, 8.0% PMA, 4.0% 3.9 2.2 2.3 NaH2 PO2 20% FR #6, 5.0% BTCA, 2.5% 3.9 2.6 2.3 NaH2 PO2 20% FR #6, 8.0% TMPA, 4.0% 4.5 1.5 1.5 NaH2 PO2 40% FR #5, 5.0% BTCA, 2.5% — 0.35 — NaH2 PO2 40% FR #5, 8.0% TMPA, 4.0% — 0.37 — NaH2 PO2 40% FR #5, 8.0% PMA, 4.0% — 0.34 — NaH2 PO2 Percent Sodium Determinations on Selected Fabric Samples Sample Identification (dry add-on weights) After 5 launderings (% Na) 20% FR #3, 5.0% BTCA, 2.5% 72 ppm* NaH2 PO2 20% FR #3, 8.0% TMPA, 4.0% 58 ppm* NaH2 PO2 20% FR #4, 5.0% BTCA, 2.5% 55 ppm* NaH2 PO2 20% FR #4, 8.0% TMPA, 4.0% 95 ppm* NaH2 PO2 20% FR #4, 8.0% PMA, 4.0% 92 ppm* NaH2 PO2 20% FR #6, 5.0% BTCA, 2.5% 51 ppm* NaH2 PO2 20% FR #6, 8.0% TMPA, 4.0% 76 ppm* NaH2 PO2 *Numbers are blank corrected (sodium level in blank was ~75 ppm)

As can be seen from the results above, several of the FR/resin application mixtures resulted in FR durability even after five launderings (the maximum number of washings that were used) with detergent. Given the above reported successful runs and the other tested embodiments that did not give the desired results either due to a lack of fire retardant reactivity (insufficient hydroxyl functionality) or to the volatility of the flame retardant additive, one trend became very clear. The presence of OH functionality in the flame retardant additive is needed to achieve the most satisfactory FR durability. Application mixtures containing Sample Compounds #3, #4, and #6 (OH-functional) resulted in the most durable FR treatments recorded.

Based on OH functionality, it seemed very likely that Sample Compound #5 would turn out to be the most durable FR additive evaluated. However, this was not the case during the experiments that were performed. The most likely explanation for this is that the FR additive vaporized during the oven curing stage. This was not surprising since the TGA and DSC analytical results for Compound #5 showed a significant weight loss (TGA & DSC) around 160° C., about twenty degrees below the set curing temperature (180° C.). Volatilization would also explain the large amount of smoke and vapor observed during the curing step of treated fabric. Given these results, the volatility of the selected FR additive(s) also needs to be considered when practicing the invention. Potential FR additives should have a substantially non-volatile, reactive component at the curing temperature to ensure cross-linking takes place before volatilization of the FR additive. The curing temperature is defined as the temperature at which the cross-linking reaction takes place.

In addition to the types of FR additives used, several observations were also made regarding the type of cross-linking resin used. Out of the various characteristics noted during the trials, the color and hand of the fabric samples were the most important. In general, the BTCA resin gave the softest hand and whitest color, both very desirable qualities. PMA and TMPA however gave less preferred results. As a general rule, the hand imparted by both resins was much stiffer than with BTCA, a property likely caused by the higher resin levels used. Either by reducing the add-on of these resins or by using softeners, the hand of the fabrics should improve. Another negative aspect of PMA and TMPA was the color they imparted on the fabric. The PMA-treated fabric developed a slight yellow tint. A quality that may be reduced by lowering the curing temperature and/or the addition of a whitening agent, two techniques commonly used in the industry to remedy this type of problem. In addition to PMA, TMPA also colored the fabric. However, the pink color produced by this resin was much more intense and noticeable.

During these initial trials, all but one of the fabric samples using Sample Compounds #3, #4, and #6 retained 56-68% of the applied phosphorus after one water wash. In addition, the phosphorus that did adhere to the fabric through the first wash seemed to remain there throughout all five launderings.

In addition to percent phosphorus determinations, it was also decided to confirm the level of sodium in the laundered samples. A high level of sodium would reflect badly on the long-term durability of the FR treatments tested. It is a well known fact that the hydrolysis and subsequent ion exchange of sodium into a phosphorus FR treatment from detergent significantly affects the FR performance of the treatment over time (i.e., sodium salts of phosphorus esters make poor FRs). Other than hydrolysis and removal of phosphorus from a fabric, the ion exchange of sodium into a FR treatment is one of the leading causes of FR performance loss after laundering. As the data above shows, all of the laundered samples contained very low levels of sodium, a good indication that the bonded phosphorus is stable to laundering and should retain good FR properties well after five washings.

The foregoing Example should not be construed in a limiting fashion since they are only intended to set forth certain preferred embodiments of the present invention. The scope of protection sought is set forth in the Claims that follow.

* * * * *

Introduction of Proban ( Rhodia Group , UK )

Wednesday, August 4th, 2010

Textile flame retardant solution: the unique guarantee of safety and comfort for protective clothing


PROBAN® is a world leading textile flame retardant solution. PROBAN® canadian phamacy cialis has been developed to give fabrics made from natural fibres reliable flame retardant properties, durable to modern day living and to professional work conditions. Part of the Rhodia range, PROBAN® is a product which provides peace of mind to both industrial and consumer markets.

Customers’ Challenges


Whether you are a supplier of PROBAN® fabrics and garments or responsible for the safety of your employees you want to have the highest confidence in the protection you are offering.

Solutions & Benefits


PROBAN® is a trademarked, quality controlled technological process based on specific chemicals developed by Rhodia. The process takes place at the finishing stage of cotton and cotton blended fabrics and involves various very specific steps – the technology is only available to PROBAN® licensees.

  • Safety First & Quality control

All PROBAN® fabrics are manufactured not only to protect the wearer from fire, but to ensure that they offer flame retardant protection for the lifetime of the article if washing recommendations are followed. Part of the licensee agreement means fabrics are tested for their wash durability after a minimum of 50 wash cycles.

As a leading player in the flame retardant protective wear market, Rhodia has undergone strict quality procedures and is able to provide fabric producer specialists with best quality solutions that meet high fire safety regulations. Licensee’s textile companies are required to submit samples of PROBAN® fabrics at stipulated intervals collected systematically from each production. Through the Quality Control testing carried out by our UKAS accredited laboratory, Rhodia can ensure that PROBAN® fabrics continue to meet fire safety regulations.

  • Durability and Comfort

In addition to putting safety first, PROBAN® provides the best comfort in fabrics. Fabrics finished with PROBAN® process have never been so comfortable, and are now available in t-shirt and sweatshirt fabrics.

  • Unique distribution

PROBAN® is sold on a licensing only basis to textile companies. To obtain a licence, companies must demonstrate they have the

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necessary technical skills and marketing capabilities in line with PROBAN® plans. Rhodia will then supply the technology, chemicals, training and ongoing technical support.



PROBAN® finished fabrics are used in a wide variety of end use applications

Protective clothing:
- Protective wear
- Metal

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- Electrical industries
- Racing drivers’ overalls
- Chemical manufacturing
- Anywhere there is a risk of fire

Furnishing of hospitals, care homes, schools and institutions:
- Fire mattress ticking
- Curtains
- Upholstery

Proban By Rhodia Group, UK .

Wednesday, August 4th, 2010

The Chemical process


PROBAN® in Action


PROBAN® is both a chemical and a quality controlled technological process, treatment takes place at the finishing stage of cotton and cotton blended textile manufacture.

The PROBAN® process involves chemical impregnation. Drying and curing with ammonia gas using Rhodia’s patented licensed technology followed by oxidation and finally neutralisation.

      The process of polymer formation is irreversible. The polymer is completely insoluble and is embedded in the body of the fibre. The polymer can only be removed by powerful oxidising agents, particularly in the presence of metal ions.


PROBAN® Process

  1. Molecules are sufficiently small and linear to penetrate the internal areas of the cotton fibre. Some chemical will be present in the spaces between the fibres.    
  2. Drying removes excess moisture and prepares the fabric for curing.  
  3. Dried fabric is cured with ammonia gas. This causes the small molecules to misoprostol pill cross link and form a polymer. The polymer is then physically trapped and fixed in the core of each fibre.  
  4. A final oxidation and neutralisation treatment completes polymer fixation and removes any residual by-products.  





PROBAN® has an established reputation for offering reliable flame retardant properties to cotton and cotton rich fabrics, built on 50 years experience. PROBAN® was first developed in 1955 to provide protection for children’s sleepwear.

Since then PROBAN® finished fabrics have been developed for use in a

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wide range of applications including Personal Protective wear, upholstery and soft furnishings, mattress ticking and as protective wear for racing drivers.

Recently PROBAN® is contributing to the new concept of multi-layer protection, as it is applied to knitted fabrics used for sweatshirts and t shirts. Wearers can now have several layers of protection from the hardy overalls right down to soft handle t-shirts.


Product lines


The PROBAN® process can be applied to different product lines which can be classified into:

  • Knitted
  • Woven

Both knitted and woven fabrics can be applied to workwear, furnishing and bedding. When choosing a PROBAN® finished product, the following considerations should be made:

Technical aspects such as the way the articles will be laundered

• A cotton/polyester blended fabric is more popular with industrial laundries because it is more economical.

• Fabric containing synthetic fibres will be easier to launder and easier to dry, as synthetic fibres retain less moisture than cellulosic fibres.

• They will last longer.

• The wash dye fastness of synthetic fibres are higher than those of cotton fibres, meaning colours will keep their original tones longer than the fabrics of 100% cotton.

• The crease recovery of a blended fabric is also better than those of 100% cotton. In some conditions PROBAN® cotton/polyester made garments can be dried and worn without having to be ironed.

End use

• PROBAN® fabrics are well adapted to metal industries, electrical utilities and systematically it depends on the FR standards in use in the specific country or industry.


Advantages of PROBAN®

  • Comfort is not modified by PROBAN® finish (air permeability, sweat absorption).
  • Nearly no action on mechanical strengths of finished fabrics.
  • Fabrics can be stored many years without losing

    FR properties.

  • PROBAN® finish does not modify electrostatic properties of untreated fabric.
  • Durability of Flame Retardancy to repeated washes and to dry cleaning is extended to useful lifetime of made up articles, when wash recommendations are respected.
  • FR properties are fast to acid sour, procedure used more and more in industrial laundries at the end of wash cycles for neutralisation of highly alkaline detergent composition used.
  • Cotton rich fabrics can be processed with success.
  • Samples from licensees are systematically FR tested after multiple washes by PROBAN® Quality Control Department.