[+/-] : Antimony market summary Jul 23-27

BEIJING (Asian Metal) 30 Jul 07 – Antimony market kept fluctuating during the week as it is still unclear when closed mines and smelters in Hunan may restart.

The closures of smelters did not attract more buyers to come back to the market. As demand remains weak, antimony ingot producers continue reducing offers to stimulate consumer buying at the beginning of the week. Some major smelters cut offers to around RMB40,500/t (USD5,350/t) ex works and small smelters in Lengshuijiang district decreased quotations to RMB37,500-38,000/t (USD4,954-5,020/t) VAT excluded.

However, as inquires did not pour in as expected, producers gave up their attempt of attracting buyers by reducing price. “No matter how low we quote, market demand will continue to be very weak in this slack season. Furthermore, as we have been out of production for nearly a month, we don’t have many stocks on hand. Therefore, we do not bother to offer and decide to hold on till consumers come back to the market,” producers said. Therefore, many producers ceased quoting or raised offers again, waiting for consumers’ return.

Similar to Chinese local market, the export market of antimony ingot has also been swinging. Some buyers received lower offers of USD5,300-5,350/t FOB for antimony ingot at the beginning of week whereas the offers bounced back to USD5,400-5,500/t FOB late in the week. However, neither Chinese export market nor spot market in Europe saw much business due to both fluctuating prices and absence of westerners.

The antimony trioxide market in China still keeps sluggish and prices decrease a little on weak demand. Some suppliers who concluded deals at around RMB37,000/t (USD4,888/t) ex works in the previous week reported that it is hard to sell at RMB36,500/t (USD4,822/t) ex works. Producer sources reported that many consumers prefer to use low-grade antimony oxide due to the low price.

However, the export price for antimony trioxide keeps firm prompted by the effort of major suppliers. According to market sources, traders offer Twinkling Star antimony trioxide at as high as USD4,950-5,000/t FOB and other materials with famous brand such as Muli and Huachang are also offered at USD4,850-4,900/t FOB. However, limited deals were concluded in the week.


We can supply any quantity and any kind of Antimony products from stock.would you please inform us how many you need and your target price, then we will confirm ASAP. We are sincerely hope to do business with you and establish long term business relationship with your respectable company.

Look forward to hearing from you soon.

Best regards,

Sam Xu
Contact me:
MSN: xubiao_1996@hotmail.com
GMAIL: samjiefu@gmail.com
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[+/-] : European antimony consumers leaving market

BEIJING (Asian Metal) 30 Jul 07 – From this Monday, one of the major European antimony trioxide producers in Europe also left the market for holiday. As most manufacturers left, antimony market will continue to be quiet.

A major European consumer told Asian Metal that he thinks the situation in China has almost no effect to the European market, as July is the quietest time of the year. Even with no environmental control in Hunan province, there will still be regular equipment maintenance for most of the suppliers.

The source claimed that after Chinese suppliers closed in Hunan, the consumer received offers of standard grade two antimony ingot at around USD200/t higher than the offers they received at end of June, but the new offers were still lower than the prices talked by others. “I have never received price higher than USD5,650/t CIF Rotterdam, most offers were still under USD5,400/t CIF Rotterdam.”

The source holds that most the deals talking in the market are the material traded between traders with no end-users involved. He expects market continues to be quiet in August, and recovers in early September.

A UK trader bought one container grade two antimony ingot with 60ppm bismuth content at USD5,480/t in warehouse Rotterdam. According to the source, material with less than 50ppm bismuth content is offered at USD5,500/t in warehouse Rotterdam. “My customer asked for material urgently, so I have to buy material in the warehouse already.”

The source said that the market is very quiet in general, and will remain quiet in the following several weeks.



We can supply any quantity and any kind of Antimony products from stock.would you please inform us how many you need and your target price, then we will confirm ASAP. We are sincerely hope to do business with you and establish long term business relationship with your respectable company.

Look forward to hearing from you soon.

Best regards,

Sam Xu
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[+/-] : Antimony Introduction

Antimony is the element with interesting history and interesting properties; element which have been used widely for a long time; element which is important not only for the development of science and technical sphere but for cultural one also. The historians consider that first productions of antimony appeared in Ancient East about 5 thousand years ago.

The history of antimony and its name Along with gold, mercury, copper and other six elements the antimony is considered to be prehistoric. Name of its discoverer didn’t reach our ears. It is only known that, for example, in Babylon as far back as 3 thousand years B.C. vessels were made of it. Latin name of the element “stibium” is met in the works of Plinius Maior. However Greek “στιβι”, from which this name came from, was referred not to antimony itself initially, but to its most spread mineral – sulphide of antimony.

In the countries of ancient Europe only this mineral was known. In the middle of the century people learned how to melt “antimony regulus”, which was considered to be semimetal. The outstanding scientist of the medieval metallurgical science, Agricola, wrote: “If while the alloying some portion of antimony is added to lead the type-metal alloy will be formed. It is used for making the type applied by those who publish the books”. Thus the history of application of element # 51 in the printing works counted many centuries.

Firstly, the properties and methods of getting the antimony, its compounds and alloys were described in details in the famous book “Triumphal chariot of antimony”, issued in 1604 in Europe. Name “antimonium”, given by the author to natural sulphureous antimony here came from Greek ανεμον – “flower” (by appearance of joins of acicular crystals of antimony sulphide, reminding the flowers of composites).

Name “antimonium” in our country and abroad was referred to this mineral only for a long time. And metal antimony was called antimony regulus at that time - regulus antimony. In 1789 Lavoisier included the antimony in the list of elementary substances and give name antimonie to it that still remains the French name of element # 51. English and German names - antimony, Antimon – are close to it.

But there is also an another version according to which the superior of abbey in Stalgauzen, noticed the great state and weight increase of pigs, licking “dark substance with metallic luster” and decided to mix it with the food of his monks. Forty monks died with terrible tortures. From that time the substance acquired the name “antimonium”, i.e. remedy against monks (see details in Y.Gashek. “Stone of life”).

Russian name of this element – “surma” – came from Turkish word “surme”, that is translated as “rubbing” or “darkening the eyebrows”. Right up to XIX in Russia there was a colloquialism “to antimony the eyebrows”, though they “antimonied” them not always with antimony compounds. Only one of them - black modification of trisulfide antimony – was applied as paint for eye-brows. This very substance was designated by word, that later became Russian name of element # 51.

Why do we need antimony? Metal antimony is applied rarely because of its brittleness. However since the antimony increases the hardness of the other metals (tin, lead) and is not oxidized at normal conditions, the metallurgists add it to different alloys sometimes. Number of alloys including element # 51 is approximately two hundred. The most distinguished alloys of antimony are hard lead (or antimony lead), typographical metal, bearing metals.

Bearing metals are the alloys of antimony with tin, lead and copper, sometimes zinc and bismuth are added to them. These alloys are rather easily melted; they are used for the manufacturing of the bearing insert. The most spread alloys of this group are babbits, they contain from 4 to 15 % of antimony. The babbits are applied in the machine tool building, in railway and motor transport. The bearing metals feature sufficient hardness, high attrition resistance, high corrosion-resistance.

The antimony belongs to small number of metals which expand at the consolidation. Due to this property of the antimony the typographical metal – alloy of lead (82 %), tin (3 %) and antimony (15 %) – fills the molds while making the types very well; the molded from this metal strings give accurate prints. The antimony gives hardness, impact stability and strength to the typographical metal.

The lead alloyed with the antimony (from 5 to 15 %) is known as antimony lead of hard lead. The adding 1% Sb to the lead already increases its hardness. Hard lead is used in chemical machine building and in the manufacturing of tubes in which corrosive liquids are transported. The coatings for telegraph, telephone and electrical cables, electrodes, accumulator plates are also made of it. By the way, the manufacturing of the accumulator plate is one of the most principal directions of element # 51 application. The antimony is added to the lead, used for the manufacturing of shrapnel and bullets.

The antimony compounds are widely used in technics. Trisulfide antimony is used in the production of matches and pyrotechnics. Most of the antimony materials are also obtained from this compound. Pentasulfide antimony is applied for the caoutchouc vulcanization. “Medical” rubber, containing Sb2S5, has specific red color and high elasticity. Heat-resistant antimony trioxide is used in the production of fireproof paints, construction materials, fabrics, conveyer belts, enamel.

Intermetallic compounds of the antimony with aluminum, gallium, indium possess semiconducting properties. The antimony is used for the improving of the properties of one of the most important semiconductor – germanium.

Hydrated potassium antimonyl (emetic stone) is used for the production of preparations for the curing of stomach diseases. Such compounds as ethylstibamine, sodium gluconate antimonyl (Pentostam) and N-Methylglucamin antimonate (Glucantime) are applied for curing the leishmaniasis.

Many antimony compounds may act as the pigments in the paints. So the antimponial acid potassium (K2O · 2Sb2O5) is widely used in the production of ceramics. Meta-antimonial acid sodium (NaSbO3) called leikonin is used for coating the cooking battery and in the production of the enamel and white milk glass. The famous paint “Neapolitan yellow” is nothing but antimonial acid yellow lead. It is applied in the painting as oil-base paint and for colouring the ceramics and porcelain. Even metallic antimony in a form of fine-dyspersated powder is used as paint. This powder is base of famous paint “iron black”.

In a word, the antimony is one of the ancient metals, known by the mankind and today it is still needed to us.


We can supply any quantity and any kind of Antimony products from stock.would you please inform us how many you need and your target price, then we will confirm ASAP. We are sincerely hope to do business with you and establish long term business relationship with your respectable company.

Look forward to hearing from you soon.

Best regards,

Sam Xu
Contact me:
MSN: xubiao_1996@hotmail.com
GMAIL: samjiefu@gmail.com
SKPYE:jiefu1996


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[+/-] : Global antimony market to reach 169,000 mt by 2010

Antimony trioxide is a major compound used in flame retardant formulations in plastic, textile, paint, and rubber industries. Worldwide antimony market is characterized by slow growth and a significant decline in prices in the past few years. Decline in demand forced several producers to cut down production and diversify their business. Price control measures taken by China, the largest producer of antimony, are likely to show a considerable impact on the market.

China is the leading antimony producer accounting for over 85% of global antimony and antimony trioxide market mine production, as stated by Global Industry Analysts, Inc. Other major producers include South Africa, Bolivia, Russia, Tajikistan, and Kyrgyzstan. Antimony trioxide is a major compound used in flame retardant formulations in plastic, textile, paint and rubber industries. Tajikistan is projected to be the fastest growing region with a CAGR of about 4.5% over the ten-year analysis period. Global antimony demand is primarily derived from the flame retardant sector that consumes 60-65% of the global antimony and 90% of global antimony trioxide produce. Plastics sector in Asia also forms a key consumer of antimony. As much as 80% of the Japanese output of antimony trioxide is consumed by the flame retardant sector. Antimony trioxide demand is forecast to surpass antimony metal demand.

Key players dominating the global antimony and antimony trioxide market include Gredmann Group, Hsikwangshan Twinkling Star, Metorex, Nanning Antimony Product Factory, SICA, United States Antimony Corporation, and Guangdong JIEFU



We can supply any quantity and any kind of Antimony products from stock.would you please inform us how many you need and your target price, then we will confirm ASAP. We are sincerely hope to do business with you and establish long term business relationship with your respectable company.

Look forward to hearing from you soon.

Best regards,

Sam Xu
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[+/-] : China's Muli expects to output 6,000 mt antimony trioxide in 2007

Hong Kong (Platts)--23Jul2007

China's Yunnan Muli Antimony Mine is on target to produce about 6,000
mt/year of antimony trioxide in 2007, a company official said Monday. The
company will also produce about 3,000 mt of antimony ingots this year.

"Our antimony ingot output is used as raw material to produce antimony
trioxide. But this is not enough for our trioxide production and we have to
source more ingot from other local producers in China," the official said. He
added that the company has its own antimony mine.

"The supply of antimony products in China will only get tighter as
recently more producers in the Hunan region had to stop production due to the
country's rising environmental concerns," he said. This would probably lead to
higher prices for antimony products, he added.

Muli is offering antimony trioxide at present at Yuan 38,500 ($5,090)/mt
FOB Huangpu, the official said. It sells 70% of its antimony trioxide products
overseas and the rest in the domestic market.

Production costs had become higher for Chinese producers following the
cancellation of the 5% export rebate on antimony trioxide with effect from
July 1, the official said. "I expect the prices are likely to rise further
later this year," he added.



We can supply any quantity and any kind of Antimony products from stock.would you please inform us how many you need and your target price, then we will confirm ASAP. We are sincerely hope to do business with you and establish long term business relationship with your respectable company.

Look forward to hearing from you soon.

Best regards,

Sam Xu
Contact me:
MSN: xubiao_1996@hotmail.com
GMAIL: samjiefu@gmail.com
SKPYE:jiefu1996


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[+/-] : Australia AGD's antimony output at less than half of expectation

Tokyo (Platts)--24Jul2007

Australian miner has produced 160-200 mt/month of antimony
concentrate since late March, which is less than half of the initially
expected volume, an official of the company said on Tuesday.

Australian miner, a UK-based Cambrian Mining group company, operates an
antimony/gold mining field and an antimony concentrate plant in the
Costerfield region in the Australian state of Victoria. The company's initial
target was to produce 60,000 mt/year of antimony and gold ores from the mine
field and produce 5,500 mt/year of antimony concentrate, by treating the ore
at the concentrate plant built in the mine field. The plant became operational
in late March of this year. Its current production capacity is 200 mt/month,
treating 2,000-3,000 mt/month of ores, according to the AGD official in charge
of Costerfield operations.

The 200 mt/month (2,400 mt/year) concentrate production is less than half
of the company's initial target of 5,500 mt/year.

The official said there have been restrictions limiting the output level
but once various conditions are met, his company plans to expand production.

In 2006, AGD signed a contract to supply the Costerfield antimony
concentrate to a Chinese trading house Hunan. The Costerfield official said all of his antimony concentrate
are being shipped to China and not to other destinations. AGD is committed to
supply the Chinese buyers for a period of three years, he added.


We can supply any quantity and any kind of Antimony products from stock.would you please inform us how many you need and your target price, then we will confirm ASAP. We are sincerely hope to do business with you and establish long term business relationship with your respectable company.

Look forward to hearing from you soon.

Best regards,

Sam Xu
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MSN: xubiao_1996@hotmail.com
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[+/-] : Indium market summary Jul 16-20

BEIJING (Asian Metal) 23 Jul 07 – Indium market is stable this week, with most participants watching the market. The prices of indium 99.99%min are at RMB4,100-4,400/kg (USD542-582/kg) and USD600-640/kg for domestic sales and exports respectively in China, unchanged compared with last week.

The price of indium 99%min is at RMB3,300-3,500/kg (USD437-463/kg) VAT included this week, stable compared with that last week. Many crude indium smelters halted production for months, holding their stockpiles for higher prices. In combination of reluctance to sell and low demand for crude indium, there are not many conclusions in the spot market.

Refined indium smelters are trapped with low demand from foreign buyers, especially Japanese ITO manufacturers. Because Japanese consumers shift their purchases to South Korea, Canada and other regions, reducing demand from Chinese spot market. Only long-term contract supply is going on, with a little indium contracted to Japan in the spot market.

Japanese ITO manufacturers depend on long-term contracts, recycled indium and inventories to meet their demand, seldom buying indium from the spot market. Therefore, market players believe that the indium market may have to wait its chance to go up until next year.

The price of indium 99.99%min is stable at USD660-700/kg in Europe, with many sources putting that the market may lose its chance to rebound within this year. Although the price is stable, there is not much business going, especially during the summer vacation.




We can supply any quantity and any kind of Antimony products from stock.would you please inform us how many you need and your target price, then we will confirm ASAP. We are sincerely hope to do business with you and establish long term business relationship with your respectable company.

Look forward to hearing from you soon.

Best regards,

Sam Xu
Contact me:
MSN: xubiao_1996@hotmail.com
GMAIL: samjiefu@gmail.com
SKPYE:jiefu1996


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[+/-] : Antimony trioxide market stagnant

BEIJING (Asian Metal) 24 Jul 07 – As no major consumers in the market now, the rising antimony price has not attracted more deals in the market, and remaining consumers are waiting for the price to fall.

A German trader told Asian Metal that antimony market is very quiet in Europe and the offered price he received for 99.5%min Twinkling Star antimony trioxide is USD5,250/t CIF Rotterdam. However, no consumers are interested in such price now.

“Plus, my customers want me to guarantee the material with at least 99.6%min antimony oxide content and with other specific.” According to him, the offers from other source can provide him the specified material at around USD5,000/t CIF Rotterdam, which is also a very high price.

Market is very slow at the moment, the trader thinks it will recover when people come back form holiday, “at beginning or middle of September, depending on where is in Germany.”

An Indian trader received offers from Chinese suppliers at around USD5,050/t CIF Nhava Sheva for regular 99.5%min antimony trioxide, “but the consumers are asking price at around USD4,800/t CIF India, so no one is interested to buy the material now.”

He thinks price is likely to drop if the market keeps dull in India, and rebounds at the same time as the European market.


Pls let us know if you are interesting in it. with any question, ask me freely.Tks you.
Sam Xu
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[+/-] : Hunnan Nonferrous raises $154.81 mln from share placement

Hong Kong-listed Hunan Nonferrous Metals Corporation Ltd. intends to raise a total of HKD 1.21 billion($154.81 million) through a share placement on the Hong Kong Stock Exchange, according to a company announcement released on Tuesday.

According to the announcement, Hunan Nonferrous will issue 272.12million H-shares at a per-share-price of HKD 4.93 ($0.63), increasing the total number of company H-shares by approximately 20 percent.

The shares to be issued include 247.38 million new H-shares and 24.74million H-shares, converted from the same number of domestic state-owned shares, through the National Social Security Fund Council of China, according to the announcement.

"The share placement was completed by the close of trade yesterday," a Hunan Nonferrous general affairs department official, surnamed Xu, said today.

"The fund raised from the placement will be used to finance several overseas mining rights acquisitions concerning lead, zinc, tungsten and antimony," Xu said.

However, he declined to comment on any acquisition plan details. Hunan Nonferrous suspended stock trading on July 10 and resumed trading yesterday.

Hunan Nonferrous is China's largest comprehensive base metals producer and owns the world's largest tungsten and antimony mines

Pls let us know if you are interesting in it. with any question, ask me freely.Tks you.
Sam Xu
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[+/-] : Tell Me Why

Declan Galbraith是英国最畅销的童声歌手之一。他的歌声清彻迷人，高音清亮，极富感染力……

　　“如果天使会唱歌，那个天使一定是——declan galbraith。” 在没有听到这个年仅12岁的英国小男孩的音乐之前，您可能会不以为然，但当他那美得残酷的高音震撼着你的heart时，你会明白， 他的声音是用心去听得，而不仅仅是你的耳朵。

In my dream,children sing
　　A song of love for every boy and girl
　　The sky is blue and fields are green:
　　And laughter is the language of the world
　　Then i wake and all i see
　　Is a world full of people in need 　
　　Chorus:
　　Tell me why(why) does it have to be like this?
　　Tell me why (why) is there something i have missed?
　　Tell me why (why) cos i don t understand
　　When so many need somebody
　　We don t give a helping hand Tell me why?
　　Everyday i ask myself
　　What will i have to do to be a man?
　　Do i have to stand and fight
　　To prove to everybody who i am?
　　Is that what my life is for
　　To waste in a world full of war?

　　chorus:
　　(children)tell me why?(declan)tell me why?
　　(children)tell me why?(declan)tell me why?
　　(together) just tell me why, why, why?
　　chorus:
　　chorus chant:
　　Tell me why (why,why,does the tiger run)
　　Tell me why(why why do we shoot the gun)
　　Tell me why (why,why do we never learn)

　　Can someone tell us why we let the forest burn?

　　(why,why do we say we care)
　　Tell me why(why,why do we stand and stare)
　　Tell me why(why,why do the dolphins cry)

　　Can some one tell us why we let the ocean die?
　　(why,why if we re all the same)
　　Tell me why(why,why do we pass the blame)
　　Tell me why (why,why does it never end)

　　Can some one tell us why we cannot just be friends?
　　Why,why

 

Pls let us know if you are interesting in it. with any question, ask me freely.Tks you.
Sam Xu
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GMAIL: samjiefu@gmail.com
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[+/-] : Fire retardant plasticized polyvinyl chloride compositions containing triphosphate plasticizer, aluminum hydroxide and antimony trioxide filler

Soft or plasticized polyvinyl chloride compositions with good chemical, mechanical and electrical properties characterized by their fire-retardant and flame-resistant properties comprising polyvinyl chloride with a content of a triphosphate plasticizer, aluminum hydroxide and antimony trioxide compounds. The compositions are particularly suitable for use in electrical conductors as sheathings and/or insulation.

BACKGROUND OF THE INVENTION

Soft or plasticized polyvinyl chloride compositions are used for many purposes in industry. However, the plasticization of the PVC results in a clear deterioration of the flame resistance of the polyvinyl chloride. For this reason it has been tried repeatedly to make polyvinyl chloride compositions more fire resistant, particularly less inflammable, by either adding flame-retarding plasticizers or by the incorporation of additional flame-retarding substances (see, for example, Published German applications Nos. DOS 19 26 412, 19 31 697; and 24 59 957). Such plasticizers and additives, however, caused in the past, a deterioration of the mechanical, chemical and/or electrical properties of these plasticized polyvinyl chloride compositions, and the flame resistance was not always satisfactory.

OBJECTS OF THE INVENTION

An object of the present invention is the development of a soft or plasticized polyvinyl chloride with good chemical, mechanical and electrical properties together with good fire-retardant and flame-resistant properties.

Another object of the present invention is the production of a plasticized polyvinyl chloride composition with flame-resistant properties consisting essentially of

(a) for every 100 parts by weight of a vinyl chloride polymer selected from the group consisting of polyvinyl chloride, copolymers of vinyl chloride with up to 10% of monomers copolymerizable with vinyl chloride, and mixtures thereof,

(b) from 1 to 7 parts by weight of conventional stabilizers against decomposition,

(c) from 20 to 100 parts by weight of a plasticizer mixture of from 50% to 100% by weight of the mixture of at least one phosphoric acid triester having the formula ##STR1## wherein R is a member selected from the group consisting of alkyl having from 2 to 10 carbon atoms, chloroalkyl having from 2 to 10 carbon atoms, phenyl, C.sub.1-4 -alkylphenyl and di-C.sub.1-4 -alkylphenyl, and from 0 to 50% by weight of the mixture of chlorinated paraffins containing from 30% to 60% chlorine content, based on the total possible chlorine substitution,

(d) from 15 to 100 parts by weight of aluminum hydroxide filler,

(e) from 2 to 10 parts by weight of a flameretarding substance selected from the group consisting of antimony trioxide and complexes of antimony trioxide and silica,

(f) from 0 to 10 parts by weight of conventional flame inhibitors selected from the group consisting of zinc boron salts and tri-polybromoalkyl phosphates with 2 to 5 carbon atoms in the alkyl, each with 2 to 4 bromine atoms, and mixtures thereof where the total amount of flame inhibitors and retarding substances does not exceed 15 parts by weight, and

(g) from 0 to 10 parts by weight of auxiliary substances selected from the group consisting of lubricants, pigments, light protecting agents, processing aids, conventional fillers and conventional plasticizers.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION

The subject of the present invention are soft or plasticized polyvinyl chloride compositions containing

(a) 100 parts by weight of polyvinyl chloride

(b) 1 to 7 parts by weight of stabilizer

(c) 20 to 100 parts by weight of plasticizer

(d) 15 to 100 parts by weight of filler, characterized in that they contain, as a plasticizer one or more phosphoric esters with, optionally, chlorine substituted alkyl radicals with 2 to 10 carbon atoms and/or, optionally, substituted phenyl radicals, as a filler aluminum hydroxide, and as a flame-retarding substance antimony trioxide or complex antimony compound in amounts of 2 to 10 parts by weight.

Broadly, therefore, the present invention relates to a plasticized polyvinyl chloride composition comprising

(a) 100 parts by weight of polyvinyl chloride,

(b) 1 to 7 parts by weight of conventional stabilizers against decomposition,

(c) 20 to 100 parts by weight of a plasticizer phosphoric acid ester with an alcohol moiety selected from the group consisting of alkyl having 2 to 10 carbon atoms, chlorine substituted alkyl having 2 to 10 carbon atoms, phenyl and lower alkyl substituted phenyl,

(d) 15 to 100 parts by weight of aluminum hydroxide filler, and

(e) 2 to 10 parts by weight of a flame-retarding substance selected from the group consisting of antimony trioxide and complex antimony compounds.

More particularly, the invention relates to a plasticized polyvinyl chloride composition with flame-resistant properties consisting essentially of

(a) for every 100 parts by weight of a vinyl chloride polymer selected from the group consisting of polyvinyl chloride, copolymers of vinyl chloride with up to 10% of monomers copolymerizable with vinyl chloride, and mixtures thereof,

(b) from 1 to 7 parts by weight of conventional stabilizers against decomposition,

(c) from 20 to 100 parts by weight of a plasticizer mixture of from 50% to 100% by weight of the mixture of at least one phosphoric acid triester having the formula ##STR2## wherein R is a member selected from the group consisting of alkyl having from 2 to 10 carbon atoms, chloroalkyl having from 2 to 10 carbon atoms, phenyl, C.sub.1-4 -alkylphenyl and di-C.sub.1-4 -alkylphenyl, and from 0 to 50% by weight of the mixture of chlorinated paraffins containing from 30% to 60% chlorine content, based on the total possible chlorine substitution,

(d) from 15 to 100 parts by weight of aluminum hydroxide filler,

(e) from 2 to 10 parts by weight of a flame-retarding substance selected from the group consisting of antimony trioxide and complexes of antimony trioxide and silica,

(f) from 0 to 10 parts by weight of conventional flame inhibitors selected from the group consisting of zinc boron salts and tri-polybromoalkyl phosphates with 2 to 5 carbon atoms in the alkyl, each with 2 to 4 bromine atoms, and mixtures thereof, where the total amount of the flame inhibitors and retarding substances does not exceed 15 parts by weight, and

(g) from 0 to 10 parts by weight of auxiliary substances selected from the group consisting of lubricants, pigments, light protecting agents, processing aids, conventional fillers and conventional plasticizers.

The soft or plasticized PVC compositions according to the invention are suitable for all applications where, in addition to the known mechanical properties of plasticized PVC, non-combustibility or difficult flammability are important, such as, in construction, automotive engineering and in electrical installations. As examples of such applications are: as a material for packings and profiles, but particularly as sheathings and/or insulation of electric conductors, such as cables.

By the use of the composition according to the invention, the low flammability of hard PVC can be achieved without the expected loss of the mechanical, chemical and electrical properties (see German Patent DAS No. 23 11 550), compared to the conventionally plasticized and therefore highly inflammable PVC, which would make their use in the above-mentioned fields impossible.

The measure of the inflammability and combustibility of a material frequently used is the oxygen index according to Fenimore and Marin (LOI=low oxygen index, according to ASTM D-2863-70). The LOI indicates at which minimum volume percentage of oxygen in a nitrogen-oxygen mixture, combustion of the specimen can still be maintained.

Another important criterion for the combustion behavior is the flue gas density (according to ASTM D-2843-70). The flue gas density indicates the percentage of the extinction of a light ray through a layer of combustion gases.

A prerequisite for the admissible use of contruction materials is frequently its assignment to a certain combustion class of the German Industrial Specifications DIN 4102. In addition to class A for mineral construction materials, e.g. silicate materials, there are the classes B1 for difficultly flammable, B2 for flammable, and B3 for highly flammable construction materials.

The soft PVC compositions according to the invention far exceed the requirements for combustion class B1, that is, they extinguish within a short period of time when the initial flame is removed and their combustion gases have low temperatures; furthermore, they exceed by far the LOI-limiting value of 27 for self-extinguishing materials, and the flue gas density is likewise considerably reduced.

Hard PVC generally has an oxygen index (LOI) of about 45 to 48, but even this index can be attained by the composition according to the invention. In general, the LOI value of the compositions of the invention is not below 30.

The polyvinyl chloride employed can be any PVC which could be used heretofore for plasticized polyvinyl chloride compositions, in particular, a PVC produced by mass, emulsion, suspension or solution polymerization, particularly with K-values of 60 to 80.

The terms polyvinyl chloride and PVC are understood here also to cover a polyvinyl chloride which contains other polymerizable monomers or which can be diluted or mixed with other polymers. Such other polymers, which can be contained in polyvinyl chloride used according to the invention as starting hard PVC in amounts of up to about 10% by weight, can be homopolymers or copolymers from the same monomer(s) copolymerized with vinyl chloride, which can be polymerized with vinyl chloride in amounts of up to 10% by weight in the PVC to be plasticized. The vinyl chloride polymer preferably can be polyvinyl chloride or copolymers of vinyl chloride with up to 10% of mono-olefinically unsaturated monomers copolymerizable with vinyl chloride. Examples of such mono-olefinically-unsaturated monomers copolymerizable with vinyl chloride are: olefins, particularly alkenes having 2 to 5 carbon atoms such as ethylene; vinyl esters of saturated carboxylic acids, particularly vinyl alkanoates having 1 to 18 carbon atoms in the alkanoate, such as vinyl acetate and vinyl butyrate; vinyl halides such as vinyl bromide and vinylidene chloride; and esters of mono-olefinically unsaturated carboxylic acids, particularly alkyl alkenoates having 1 to 7 carbon atoms in the alkyl and 3 to 5 carbon atoms in the alkenoate, such as ethyl acrylate or methyl methacrylate.

The amounts of the components contained in the soft or plasticized PVC compositions according to the invention relate in each instance to 100 parts by weight of the PVC component (a).

The stabilizers employed in the soft PVC compositions according to the invention are the usual stabilizers against decomposition, particularly by heat, individually or in mixture in amounts of 1 to 7 parts by weight, preferably 2 to 6 parts by weight. Examples of such suitable heat stabilizers are: calcium, barium, zinc and cadmium compounds, particularly with higher fatty acids like stearic acid, and 2-ethylhexanoic acid, and organotin compounds, particularly dialkyltin salts of lower alkanoic acids like dibutyl tin diacetate. For use of the compositions, according to the invention for insulations and sheathings of electrical conductors, lead compounds are preferred as heat stabilizers, individually or in mixture, such as lead sulfates, e.g. di- or tribasic lead sulfates, lead phosphate, lead stearate and lead phthalate. Mixtures of lead compounds and the stearates are preferred.

Suitable plasticizers according to the invention contain one or more phosphoric acid esters, preferably tertiary phosphoric acid esters with, optionally, chlorine-substituted alkyl radicals with 2 to 10 carbon atoms and/or with, optionally, substituted phenyl radicals in amounts of 20 to 100 parts by weight, preferably 30 to 80 parts by weight. Substituted phenyl radicals are particularly alkyl substituted.

The preferred phosphoric acid esters are phosphoric acid triesters having the formula ##STR3## wherein R is a member selected from the group consisting of alkyl having from 2 to 10 carbon atoms, chloroalkyl having from 2 to 10 carbon atoms, phenyl, C.sub.1-4 -alkylphenyl and di-C.sub.1-4 -alkylphenyl. The following triesters can be mentioned: tricresyl phosphate, triphenyl phosphate, cresyldiphenyl phosphate, dicresyl-phenyl phosphate, xylenyldiphenyl phosphate, dixylenyl-phenyl phosphate, tris-(chloroethyl) phosphate, diphenyl-octyl phosphate, phenyldioctyl phosphate, and trioctyl phosphate. If the compositions of the invention contain mixtures of these plasticizers, these mixtures can consist of different, but preferably equal amounts of the individual components.

In a preferred embodiment, the amount of phosphate plasticizer is partly substituted up to 50% of the plasticizer by chlorinated paraffin with a chlorine content of 30% to 60%, preferably about 50%, related to the number of chlorine atoms in the corresponding perchlorinated paraffin. Preferably the portion of the chlorinated paraffin is 20% to 50% by weight of the total plasticizer content.

As fillers, the compositions according to the invention contain aluminum hydroxide, preferably in amounts of 50 to 90 parts by weight. Included in the term aluminum hydroxide, which preferably has particle sizes of up to 2 micrometer, is a substance which is frequently also called aluminum oxide hydrate, aluminum oxyhydrate, alumina hydrate or aluminum hydrate, and which is frequently represented by the following formula: Al(OH).sub.3 or Al.sub.2 O.sub.3. H.sub.2 O. The aluminum hydroxide can contain so-called neutral, but also so-called basic or acid aluminum hydroxide, that is, it can optionally contain aluminates or aluminum salts in amounts up to about 25% by weight. Preferably, however, it is free of such compounds.

Furthermore, the soft PVC compositions according to the invention contain at least one so-called flame inhibitor or flame retarder in a total amount of 2 to 10 parts by weight, preferably 3 to 8 parts by weight. Such flame inhibitors are antimony trioxide and/or complex antimony compounds, preferably antimony trioxide silica complexes. Examples for the latter are "Oncor.RTM. 75RA" and "Oncor.RTM. 75RAZ" by National Lead Inc. New York, USA, two antimony trioxide/silica complexes.

Preferred embodiments can contain, in addition to the antimony compound(s) individually or in mixture additional flame inhibitors, like zinc borate and tri-(bromoalkyl) phosphate with C.sub.2-5 -alkyl radicals, each with 2 to 4 bromine atoms as substituents, preferably tris-(2,3-dibromopropyl) phosphate.

These flame inhibitors can be contained in amounts of 2 to 10 parts by weight, provided the total amount of all flame inhibitors, that is, of antimony compound(s), optionally, zinc borate and, optionally, trialkyl brominated phosphates, does not exceed 15 parts by weight per 100 parts by weight of the PVC component.

In addition, additional substances, as they are usually added to plasticized PVC compositions, can be added to the compositions according to the invention, in amounts of up to 2 parts by weight each, but preferably not more than a total of 10 parts by weight, for example, lubricants, pigments, light protecting agents, processing aids.

Furthermore, up to 10% by weight of the filler and/or of the plasticizer can be replaced by other conventional fillers of plasticizers without any substantial deterioration of the properties.

The soft PVC compositions according to the invention can be produced, like the presently known compositions, that is, by mixing or kneading in suitable apparatus.

The following examples are illustrative of the practice of the invention without being limitative in any respect.

EXAMPLES 1 to 5 and COMPARISON TEST

The following Table shows for various plasticized PVC compositions of the invention the composition (in parts by weight), the oxygen index (LOI value in % by vol.), the flue gas density (% extinction), the shore A hardness, the residual length after combustion (in %) and the flue gas temperature (in .degree.C.). The last two values are determined, similar to DIN 4102, in small combustion chambers with samples of 200.times.40.times.4 mm.sup.3. The conditions of combustion class B1 are a residual length of the sample after selfextinction of at least 15% of the original length, and a combustion gas temperature below 200.degree. C.

TABLE
______________________________________
Examples
Compari-
1 2 3 4 5 son Test
______________________________________
Suspension PVC,
K-value 70 100 100 100 100 100 100
Stabilizer compound.sup.(1)
4 4 4 4 4 4
Diphenyl-cresyl
phosphate 30 30 20 20 20 --
Diphenyl-octyl
30 30 20 20 20 --
phosphate
Aluminum hydroxide
70 70 70 70 70 --
Antimony trioxide
7 3.5 3.5 -- 3.5 --
Oncor.sup.(R) 75 RA
-- -- -- 3.5 -- --
Chlorinated
paraffin 50% -- -- 20 20 20 --
Zinc borate -- 3.5 3.5 3.5 3.5 --
Tris-(2,3-dibromo-
propyl) phosphate
-- -- -- -- 4.5 --
Di-2-ethylhexyl
phthalate -- -- -- -- -- 60
Calcium carbonate
(chalk) -- -- -- -- -- 70
LOI - value (Vol. %)
37.6 42.4 43 44 47 23
Flue gas density
(% extinction)
99 93 87 86 85 100
Shore - A-hardness
87 87 88 87 87 85
Residual length (%)
22.7 27.1 32.4 29 34.9 0
Flue gas temperature
(.degree.C.) 191 169 156 165 154 >700
Combustion class
B 1 B 1 B 1 B 1 B 1 --
______________________________________
Footnote to table:
.sup.(1) The stabilizer compound is composed of 80% by weight tribasic
lead sulfate and 20% by weight of a mixture of equal parts by weight of
lead stearate, calcium stearate and paraffin wax.



The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art or disclosed herein, may be employed without departing from the spirit of the invention or the scope of the appended claims.
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[+/-] : U.S.antimony trioxide market stable

BEIJING (Asian Metal) 6 Jul 07 – Followed the cancellation of antimony trioxide export rebate, Hunan halt antimony production due to environmental protection, Chinese suppliers tried to enhance the price in the world market, but American market participants told Asian Metal that price of antimony trioxide is stable at around USD2.3/lb in warehouse Baltimore.
A U.S. distributor told Asian Metal that the 99.5%min Twinkling Star antimony trioxide is offered at USD2.28-2.3/lb in warehouse Baltimore. He claimed that the price is stable. He had received higher offers from Chinese suppliers, but the consumers are reluctant to accept the higher prices.
A Chinese representative who is located in the East Coast told Asian Metal that price of 99.5% min antimony trioxide is the same as before at USD2.3-2.4/lb d.d.p. The material he represents has its own brand and has the quality the same as Twinkling Star.
The source takes that it is normal to have delay for the American market react to the changes from in the Chinese market. “Because there were already stocks in Baltimore and other warehouses, and the market will be affected only when the current stockpile is consumed.” Plus, it takes more than a month for the material to get to America.
According to the sources, demand in U.S. is steady, and the manufacturers maintain normal productions during the summer.

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[+/-] : European marketers: no antimony offers from Chinese

BEIJING (Asian Meta) 5 Jul 07 – In the passed weekend, most Hunan antimony mines and metal productions have been shut down due to the environmental reason. Some suppliers raised the offers in the domestic market; however, European market participants told Asian Metal that the suppliers are not offering material in Europe now.
A UK trader claimed that he received an offer of 99.65%min standard grade two antimony ingot at USD4,950/t CIF Rotterdam, but the offer was no longer available this Monday, and he had not received any offer of antimony since then.
The source thinks the price now, at around USD5,000-5,100/t CIF Rotterdam, in Europe is not accepted by both consumers and suppliers that consumers are waiting for lower prices and consumers want to sell at higher prices. However, when the demand is as slow as now, the change in supply does not make any difference. “Market will remain quiet.”
An official from a German antimony trioxide consumer is trying to get quotations from his suppliers but find that “the Chinese are reluctant to give an offer now.” He also read the news about what happened in Hunan and he thinks Chinese suppliers are waiting for more news for them to raise the price to the level they desires which is a little difficult, because the consumers are not cooperative.
The official thinks that the price of antimony will only rise when the production will be halt for a long time.
In the past years, there is one news followed another about antimony production or Chinese policies and the Chinese raised the prices each time after the news were released. However, the market is build up on both supply and demand. When there is enough supply and little demand, price will not change easily.
Antimony trioxide price remains at around USD4,650-4,700/t CIF Rotterdam for 99.5%min standard material, but demand is also very slow.

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[+/-] : Environmental control has no effect on European antimony market

BEIJING (Asian Metal) 4 Jul 07 – When Hunan government closed many antimony mines and smelters for environmental control, European market had not been affected due to the weak demand.
A major European market participant told Asian Metal that he had not yet seen any change in the European market and also the offers made from the Chinese suppliers. According to him, the quotation from Chinese are still in the range of USD5,000-5,100/t CIF Rotterdam for 99.65%min standard grade two antimony ingot.
“European market is very quiet now,”the source claimed that there is almost no demand of antimony ingot or antimony trioxide due to two reasons. First, the summer is the general slow season of the year, and second, Chinese government had cancelled the export rebate for antimony trioxide. “Consumers do not want to accept higher price, and they are waiting for lower prices.”
Because of the slow demand, the source thinks the missing material from China will not affect the current slow market. Moreover, “there is a lot of material in Rotterdam warehouse.”
A UK trader told Asian Metal that the lowest offer he received for 99.65%min low bismuth antimony ingot was at USD5,150/t CIF Rotterdam, and the offer was received last week. “Market is quite quiet; there is no demand and no offer so far this week.”
A Belgium trader read about the new environmental control in Hunan province and he thinks world market will be affected as Hunan produces around 40% antimony in Chinese. However, the effect will only reflected in the market if the productions will be halt for a long time and when Europeans are back from holidays.


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[+/-] : Antimony products producers raise offers

BEIJING (Asian Metal) 4 Jul 07 – Due to the series closures of antimony smelters and mining enterprises, antimony products producers begin to raise offers on anticipation of the short supply. Some major producers hold off from offering, waiting for clearer market trend, while small smelters in Lengshuijiang, Hunan start quoting RMB36,500/t (USD4,796/t) VAT excluded, up from RMB34,300-34,500/t (USD4,507-4,534/t) VAT excluded late last week, market sources reported to Asian Metal today.
Despite higher offers, a Hunan-based trader reported that the market is generally quiet at the moment as most consumers are still watching and waiting for further market trend. “Having learnt that most antimony ingot smelters in Hunan were forced to close down, we planned to purchase some antimony ingot lest that the market should go up in the near future. However, small smelters offered us RMB36,000-36,500/t (USD4,731-4,796/t) VAT excluded yesterday against RMB35,000/t (USD4,599/t) VAT excluded seen late last week,” said the source. “We have not decided whether to buy or not.”
Meanwhile, the source revealed that most of the major antimony ingot producers, who also stopped production lately, do not quote at the moment. However, they are likely to offer higher prices soon.
An antimony trioxide consumer from Zhejiang is considering replenishing stocks for fear that the price of antimony trioxide might go up. “Our supplier in Hunan is still running, but they informed us that they may soon increase offers in view of the possible supply shortage of raw material,” said the source.
What consumers worry about is that when smelters will resume production. Many are hesitant to stock large quantities of materials on hand as they don’t know when the market will return to normal.
The source purchased around 10t of antimony trioxide from a Hunan producers ten days ago at RMB35,000/t (USD4,599/t) ex works and is planning to purchase another batch soon.

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[+/-] : Hunan antimony smelters halt on environmental concern

BEIJING (Asian Metal) 3 Jul 07 – With the relevant authority up to its responsibility, almost all antimony ingot and trioxide smelters in Hunan province, the most important antimony production base in China, especially along Zijiang River, are being forced to stop production as pollutants discharge exceeds the tolerable level. Many major smelters, including Hsikwangshan, Zhaizixi, Jiutong have consequently been affected.
Senior officials from Hsikwangshan and Zhazixi, the major antimony trioxide and ingot producers in China, confirmed to Asian Metal that their smelters were asked to halt production late last week until functional anti-pollution facilities are put in place. However, an official from Zhaizixi rationalized it thus: “We usually carry out equipment maintenance in summer, so the closure is just within our plan.”
“All smelters along Zijiang River were forced to shut down due to a toxic spill from those smelters into the river,” said a Yiyang-based antimony ingot producer, whose capacity is 200tpm. No details are confirmed when those smelters can resume production. “But no smelter will be allowed to restart until they pass the environmental assessment currently being conducted,” the source added.
The source revealed that many antimony ingot and trioxide producers have stocks on hand due to the sluggish market. The closures of smelters might prevent the price of antimony products from dipping further. In fact, smelters in Lengshuijiang, one of the most important producing areas in Hunan province, begin offering a higher price of around RMB35,000/t (USD4,599/t) VAT excluded for antimony ingot against RMB34,300-34,500/t (USD4,507-4,534/t) VAT excluded seen last week. Those major smelters, who sold antimony ingot at RMB37,200-37,500/t (USD4,888-4,928/t) ex works, suspended quoting and are waiting for clearer market trend.
Meanwhile, some consumers have opined that the market is unlikely to rise much due to the continuously weak demand. “Not only foreign buyers have little interests to purchase due to the coming summer break, but also Chinese consumers are also inactive in buying. Furthermore, smelters in Guangxi and Guizhou are still in normal operation. Therefore, it is hard for antimony products price to rise by a large scale,” said a Guangdong-based consumer of antimony ingot

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[+/-] : Indian antimony market dips

BEIJING (Asian Metal) 2 Jul 07 – With slow demand in the spot market, Chinese suppliers decreased their offers of antimony in the export market. Indian market participants reported to Asian Metal that the price of antimony ingot they received from Chinese suppliers have lowered from USD5,200/t to currently USD5,100/t CIF India ports.
A Mumbai trader told Asian Metal that the demand of antimony ingot is slow in India, and the price he received from China is at USD5,100/t CIF Nhava Sheva for the standard 99.65%min grade two antimony ingot. He checked with his consumers, and no one showed interest in the material lately.
Although Indians do not take holidays in summer as the Europeans and Americans, consumers also hold off from purchasing when they see price is decreasing. “We might see some buying activity when price drops to USD5,000/t.” That is the price he thinks would be attractive to the Indian consumers.
Another Mumbai trader received offers in the range of USD5,100-5,300/t CIF Nhava Sheva for antimony ingot from Chinese suppliers, and the price range covers all grades from grade two to grade zero. Market is quiet and he had not concluded any deals of antimony in the last three weeks.
“This may be a downward cycle, that Chinese would lower prices to prompt sale, and consumers will hold longer from buying when price is decreasing.” The source thinks the market will remain quiet for a few weeks before it recovers in August.

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[+/-] : Tax rebates removed, cut to curb exports

The government will eliminate or cut tax rebates for more than 2,800 export items from July 1 - in the boldest move yet to rein in exports since it joined the World Trade Organization in 2001.
The affected items account for 37 percent of all export products, the Ministry of Finance announced yesterday.
Export tax rebates for 553 "highly energy-consuming and resource-intensive" products, such as cement, fertilizer and non-ferrous metals, will be eliminated, the ministry said.
Rebates for another 2,268 products, described as "easy to trigger trade frictions", will be slashed from 8-17 percent to 5-11 percent. They include garments, toys, steel products and motorcycles.
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By imposing restrictions on more categories, Washington has ignored China's efforts at enlarging imports from the United States, which will negatively affect the process of balancing two-way trade, Yao Shenhong, a spokesman for the Ministry of Commerce, said yesterday.
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Yesterday's announcement follows the imposition or raising of export tariffs on 142 categories of goods effective June 1. The products include steel billets and non-ferrous metal minerals.
Both steps are part of the policy package designed to control soaring exports and bloating trade surplus.
From January to May, exports surged 27.8 percent year-on-year to $443.5 billion; and the trade surplus rocketed 83.1 percent to $85.7 billion, according to Customs statistics.
The huge surplus has aggravated such problems as trade conflicts with other countries and pressures on China to revalue the renminbi, as well as excessive liquidity at home, the ministry said.
Liu Xueqin, a researcher with the Chinese Academy of International Trade and Economic Cooperation affiliated to the Ministry of Commerce, said: "The new policy will restrain exports because it affects a broad range of products."
Domestic producers say they are already feeling the pressure from the export control measures.
"Our steel companies are at threat (of losing foreign markets). But we can understand the overall significance of the policy," Qi Xiangdong, deputy secretary general of the China Iron & Steel Association, told China Daily.
The association predicted earlier that, as a result of the export disincentives, the country - the world's top steel producer - would this year export no more or even less than last year.
Steel exports totaled 43 million tons in 2006, a growth of 110 percent over 2005.
The finance ministry said the new policy will also help slow down investment in fixed assets and reduce over-capacity; and lead to sustainable development.
Many industrial sectors, such as steel, cement and motorcycles, are believed to have excessive production capacity in relation to domestic demand.

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[+/-] : Flame-retarded ABS formulations with high impact strength

This invention is in the field of thermoplastic synthetic resin formulations, especially ABS (acrylonitrile-butadiene-styrene) resins flame retarded with at least one brominated organic flame retardant, as well as a method for producing the formulations.

BACKGROUND

ABS resins are well known in the synthetic organic polymer art as a class of thermoplastics which offers excellent mechanical properties as well as good processability and chemical resistance. The general characteristics of ABS resins are described, for example, in "Modern Plastics Encyclopedia," McGraw-Hill, New York, N.Y., 1990, pp 90-91. ABS resins are co- or terpolymers which generally comprise a rigid styrene/acrylonitrile continuous phase in combination with a polybutadiene elastomer disperse phase. A graft copolymer in which small amounts of styrene and acrylonitrile are grafted onto butadiene chains may also be present to bridge the rigid phase and the elastomer phase and make them more compatible.

For purposes of the instant invention, an ABS resin is a thermoplastic, the chemical structure of which includes each of the following structural units, however combined: ##STR1## Further, a formulated ABS resin, for all purposes herein, comprises at least about 50 wt % ABS resin. The remainder of the formulated ABS resin comprises various monomeric or polymeric additives which modify the properties of the ABS resin. These additives include, for example, various impact modifiers, stabilizers, processing aids, pigments, flame retardants, synergists, etc. They can be incorporated into the ABS resin in various ways.

Incorporation of the various additives is not a trivial matter, and the properties of the formulated ABS resin can be affected by the manner in which it is done. When the additives are solids, dry-blending can be employed. For example, the solids can be mixed and heated to soften and homogenize the mass, which can then be sheeted, chopped, and pelletized.

A flame retardant, such as a halogenated organic compound, is often incorporated into a formulated ABS resin so as to constitute as much as about 25-30 wt % of the formulation. Such incorporation can adversely affect the properties, other than the flammability, of the formulated ABS resin.

SUMMARY OF THE INVENTION

Consequently, it is one object of this invention to provide a formulated ABS resin in which a halogenated organic flame retardant is incorporated and an impact modifying polymer is added so as to provide a significant net increase in the impact strength of the formulation. It is another objective to build on this improvement by providing a method for incorporating the flame retardant which leads to a still further increase in the impact strength.

In attaining the aforesaid objectives, this invention provides a flame retarded ABS formulation which comprises at least about 50 wt % ABS resin, about 5-30 wt % halogenated flame retardant, about 0-6 wt % flame retardant synergist, and about 8-38 wt % polymeric impact modifier. In preferred embodiments, the polymeric impact modifier is selected, and the flame retardant is incorporated in such a way that the Izod impact strength is dramatically increased.

DETAILED DESCRIPTION

The ABS resin component of the formulated ABS can be selected from the many resins available in commerce. Such resins include GE Cycolac.RTM. resins, Monsanto Lustran.RTM. resins, and Dow Magnum.RTM. resins, for example. The ABS resin component of the formulated ABS resin of this invention comprises at least about 50 wt % of the formulation, and the ABS resin can comprise as much as about 70 wt % of the formulation.

One of the additives which will be present in the formulated ABS resin of this invention is one or more flame retardants, and halogenated flame retardants have been recommended and employed in that application. Halogenated flame retardants especially useful in the practice of this invention are selected from the group consisting of tetrahalobisphenol A, N,N'-bis(tetrahalophthalimide), ethylenebis(tetrahalophthalimide), halogenated polystyrene, and pentahalobenzyl acrylate, in all of which halo is selected from chloro and bromo, and also bis-halophenyl compounds represented by the following structural formula which are solids at ambient temperature: ##STR2## in which formula each X is selected independently from chlorine and bromine; m and n can be the same or different and can range from 1 to 5; Y is selected from oxygen, alkylene, --NR--(where R is selected from hydrogen and hydrocarbyl), alkylenedioxy, aryldioxy, and a chemical bond. Alkylene is preferably lower alkylene, i.e., straight chain or branched C.sub.1 -C.sub.6, such as methylene, ethylene, isopropylene, butylene, t-butylene, and the like, methylene or ethylene being preferred. Hydrocarbyl includes alkylene, especially lower alkylene, but also unsaturated alkylene and aromatic groups such as phenyl and alkylphenyl or halophenyl. Alkylenedioxy includes methylenedioxy, 1,2-dioxyethylene, and the like, while aryldioxy includes dioxyphenyl, for example. In the preferred flame retardants halo and X are bromo. Among the aforesaid flame retardants, the bishalophenyl compounds are preferred, and among these compounds, decabromodiphenyl oxide, decabromodiphenyl ethane, 1,2-bis(tribromophenoxy)ethane, and decabromodiphenyl amine are especially attractive.

In addition to one or more halogenated flame retardants, the formulated ABS resin of this invention optionally includes a flame retardant synergist in an amount ranging from about 2 to about 6 wt %. A number of materials, such as metal oxides, e.g., iron oxide, tin oxide, zinc oxide, aluminum trioxide, alumina, antimony tri- and pentoxide, and boron compounds, e.g., zinc borate; also antimony silicates and ferrocene, are known to enhance the effectiveness of flame retardants, especially halogenated flame retardants. A particularly effective and preferred synergist is antimony trioxide.

In addition to flame retardant, the formulated ABS resin of this invention includes one or more polymeric impact modifiers. It is well known that the addition of certain materials to an ABS resin tends to toughen articles molded therefrom. Among these materials are styrene/butadiene/styrene triblock copolymer, styrene/isoprene/styrene triblock copolymer, styrene/butadiene diblock copolymer, polycaprolactone, functionalized ethylene/propylene copolymers, and poly(haloolefins). A preferred impact modifying material is a halogenated polyolefin resin, such as chlorinated polyethylene. A typical formulated ABS resin containing chlorinated polyethylene and a brominated flame retardant, in addition to the ABS resin, is described in Example 1.

EXAMPLE 1

A. The components indicated in column A, Table 1 were dry-blended by shaking them together for 2 min in a plastic bag. The mixture was then extruded on a Haake-Buchler System 40 Rheometer equipped with a twin-screw extruder head. The extrusion was carried out at 210.degree.-210.degree.-220.degree.-220.degree. C. and 60 rpm. The extruded material was pelletized and dried at 88.degree. C. for 4 hr before injection molding it on a Battenfeld BSKM 100/40 machine at 195.degree. C.

B. The components indicated in column B, Table 1 were combined as follows: The flame retardant, chlorinated polyethylene, processing aid, and one-half the stabilizer were blended in a Brabender mixer at 175.degree. C. and 66 rpm for 2 min. The resultant blend was sheeted on a two-roll mill and chopped into small pieces on a Glouster grinder, affording a masterbatch. An amount of the masterblend appropriate to the desired composition was dry-blended with the remaining ingredients. The combination was then extruded, pelletized, dried, and molded as described in A above. The IZOD impact strength of the extruded materials was measured on 1/8 in. test bars according to the ASTM D256 test method.

TABLE 1
______________________________________
Component A (wt %) B (wt %)
______________________________________
ABS Resin (Dow 69.9 68.9
Magnum .RTM. PG-914)
Impact Modifier; 13.1 13.1.sup.a
Polychloroethylene
(Tyrin .RTM. 3611 of Dow
Chemical Co.)
Flame Retardant; 12.5 12.5.sup.a
Decabromodiphenyl Ethane
(Ethyl Corp.)
Synergist; Sb.sub.2 O.sub.3
4.0 4.0
Processing Aid; 0.5.sup.a
Zinc Stearate
Stabilizer; Dibutyltin
0.5 1.0.sup.a
Maleate (Thermolite .RTM.
13 of Atochem No. Am.)
IZOD Impact Strength
3.6 .+-. 0.1
3.6 .+-. 0.1
(ft-lb/in notch)
______________________________________
.sup.a component of masterbatch



The data in Example 1 show that master batching per se has little or no effect on impact strength of the resultant formulated ABS resin. The effect on IZOD impact strength of including a second impact modifying resin; more specifically, a styrene/butadiene/styrene block copolymer is set forth in Example 2.

EXAMPLE 2

A. The components indicated in column A, Table 2 were combined as explained in Example 1 A.

B. The components indicated in column B. Table 2 were combined as explained in Example 1 B.

TABLE 2
______________________________________
Component A (wt %) B (wt %)
______________________________________
ABS Resin (Dow 64.9 63.9
Magnum .RTM. PG-914)
Impact Modifier; 13.1 13.1.sup.a
Polychloroethylene
(Tyrin .RTM. 3611 of Dow
Chemical Co.)
Impact Modifier; 5.0 5.0.sup.a
Styr/But/Styr Block
Copolymer (Shell
Kraton .RTM. D1102)
Flame Retardant; 12.5 12.5.sup.a
Decabromodiphenyl Ethane
(Ethyl Corp.)
Synergist; Sb.sub.2 O.sub.3
4.0 4.0
Processing Aid; 0.5.sup.a
Zinc Stearate
Stabilizer; Dibutyltin
0.5 1.0.sup.a
Maleate (Thermolite .RTM.
13 of Atochem No. Am.)
IZOD Impact Strength
4.8 .+-. 0.2
9.0 .+-. 0.4
(ft-lb/in notch)
______________________________________
.sup.a component of masterbatch



The data in Example 2 illustrate the improvement in IZOD impact strength of the formulated ABS resin brought about by replacing some of the ABS resin with a styrene/butadiene/styrene block copolymer; i.e., an increase in the IZOD impact strength from 3.6.+-.0.1 in Ex. 1 A to 4.8.+-.0.2 ft-lb/in notch. Moreover, the data illustrate the surprising increase in IZOD impact strength which occurs when the styrene/butadiene/styrene block copolymer is part of the masterbatched ingredients; i.e., from 4.8.+-.0.2 to 9.0.+-.0.4 ft-lb/in notch.

In Example 3, the effects of removing the impact modifying resins, one at a time, from the masterbatch is illustrated.

EXAMPLE 3

In both A and B the components were combined as explained in Example 1 B.

TABLE 3
______________________________________
Component A (wt %) B (wt %)
______________________________________
ABS Resin (Dow 63.9 63.9
Magnum .RTM. PG-914)
Impact Modifier; 13.1.sup.a
13.1
Polychloroethylene
(Tyrin .RTM. 3611 of Dow
Chemical Co.)
Impact Modifier; 5.0 5.0.sup.a
Styr/But/Styr Block
Copolymer (Shell
Kraton .RTM. D1102)
Flame Retardant; 12.5.sup.a
12.5.sup.a
Decabromodiphenyl Ethane
(Ethyl Corp.)
Synergist; Sb.sub.2 O.sub.3
4.0 4.0
Processing Aid; 0.5.sup.a 0.5.sup.a
Zinc Stearate
Stabilizer; Dibutyltin
1.0.sup.a 1.0.sup.a
Maleate (Thermolite .RTM.
13 of Atochem No. Am.)
IZOD lmpact Strength
5.8 .+-. 0.2
7.6 .+-. 0.3
(ft-lb/in notch)
______________________________________
.sup.a component of masterbatch



When the components were combined without master batching, i.e., Example 2 A, the IZOD impact strength was 4.8.+-.0.2 ft-lb/in notch. Although excluding either impact modifier resin from the masterbatch affects IZOD impact strength adversely, this affect is most pronounced when the styrene/butadiene/styrene block copolymer is left out of the masterbatch.

It will be evident to those skilled in the art that considerable variation in the specific nature and relative amounts of the components of the formulated ABS resin of this invention, as well as in the manner in which those components are combined is possible within the contemplation of this invention and that the invention is limited only by reference to the following claims:


Pls let us know if you are interesting in it. with any question, ask me freely.Tks you.
Sam Xu
Sales Engineer
DONGGUAN JIEFU FLAME-RETARDED MATERIALS CO.,LTD
Contact me:
MSN: xubiao_1996@hotmail.com
GMAIL: samjiefu@gmail.com
SKPYE:jiefu1996


Chinese antimony market



DONGGUAN JIEFU FLAME-RETARDED MATERIALS CO.,LTD...
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[+/-] : Polyether-based polyurethane foams including a flame-retardant system containing antimony trioxide

Polyether-based polyurethane foams including as the flame-retardant, an antimony compound, chlorine derived from at least one chlorinated paraffin and alumina trihydrate, and the polyol used to prepare the foams being a diol- or triol-based polyol wherein at least 50% of the hydroxyl end groups are primary hydroxyl end groups, having good flame-retardancy and without any significant fall-off in physical properties as the foams are able to tolerate relatively high levels of the flame retardant.


BACKGROUND OF THE INVENTION

The present invention relates to high-resilience, flexible and semi-flexible, flame-resistant, polyether-based, polyurethane foams and formulations for preparing the same.

In recent years there has been a growing awareness of the need for greater resistance to combustion of seating and trim materials, particularly in applications where a number of people may be at risk at the one time, such as rail carriages, aircraft, buses, boats, public buildings and hospitals where large amounts of combustible materials are present. Polyvinyl chloride foams (PVC) have relatively good performance in fire, but their comfort and recovery properties are poor. Thin liner sheets of special neoprene (polychloroprene) have been used to protect polyurethane seat pads, but when the liner is cut as a result of vandalism, the degree of protection is reduced or eliminated. Since polyurethane is currently by far the most widely used cushioning material, continuing attempts have been made to improve its resistance to combustion, but so far the success achieved has been very limited. Research carried out in all developed countries has been based on the inclusion of a wide range of fire retardant materials in the urethane reaction mixture. However, when the proportion of fire retardant materials is increased beyond quite low levels, the result has been a severe falling off in properties such as compression set so that either the improvement in fire retardance has been minimal, or performance of the foam in service has been unacceptable.

It is the purpose of this invention to produce flexible or semi-flexible foams with very high levels of flame retardance yet with a combination of physical properties equal to the combination of physical properties in the best foams currently available. These foams can be moulded, cut to shape or laid down on a backing material, so affording protection against fire in depth.

Flexible and semi-flexible foams only are within the ambit of this invention. The term "flexible", as understood in the art, indicates the use of polyols the molecular weights of which are between 1000 and 10,000 but usually between 3000 and 6500, and the functionality of which is 2 to 3, reacted with isocyanates having a functonality of two or three, to form the foam. These foams have relatively low crosslink densities. The term "semi-flexible" indicates the additional inclusion of low molecular weight multi-functional reactants to the foam system previously described, (or by other methods well known in the art) to produce foams with relatively high crosslink densities.

Even the evaluation of fire retardance is a vexed question, and innumerable test methods have been developed in attempts to ascertain the behaviour of cellular materials in a fire. It has now become generally recognized that small scale laboratory tests are of limited value and are useful mainly only for process control purposes. A useful way to predict behaviour in an actual fire situation is with a full scale and complete seat assembly with a correspondingly large heat source. Such tests may be made under specified conditions or if not carried out in a conditioned environment the tests may be conducted with different materials at the same time to compare the behaviour of these different materials. The latter tests have in fact been conducted. The heat source consisted of 125 gm of newspaper crumpled into balls and placed in one double sheet of newspaper made up into a box. This total fire load was placed on the foam cushion in contact with the "squab". Two 15".times.15".times.4" pieces of foam, one to act as the "cushion", the other as the squab, were placed on a public transport type seat totally made from metal, as they would be when part of a normal seat construction. That is, the squab was placed against the back of the seat which was of sheet metal, at an angle, and the cushion was placed on the horizontal sheet metal seat in front of and in contact with the squab. The metal seat was enclosed in a hood to prevent draughts which might adversely affect some trials and not others, Observations were made and times recorded at the height of the burning ignition source, at the height of involvement of the foam, and after the finish of the trial. for ease of later reference, such tests are called `the Transport Test`.

As previously suggested it has been difficult in the past to produce a flexible polyurethane which would behave well in the abovementioned tests. ICI state, for instance, in their Technical Service Note No. TS/B/2119/1 Table 16, Page 12 that the cited foams when tested according to ASTM D 1692-59T, method 9, Appendix 1, could only be rated "self-extinguishing" and not "non-burning".

In the formulations quoted by ICI on Page 13 of the abovementioned publication, 7.5 parts of antimony trioxide and 15 parts of a chlorinated paraffin namely Cereclor 56L or 65L, suggest an optimum level (or ceilings) of these flame retardants it is possible to include in the formulation. The polyether employed in all these formulations is Daltocel T56, a polyol which contains in the main secondary hydroxyl end groups.

The prior art discloses various means for imparting flame-retardant properties to polyurethane foams. For example, U.S. Pat. Nos. 3,075,927 and 3,075,928 to Union Carbide Corporation disclose polyurethane foams in which flame-retardance is imparted by a combination of antimony trioxide and a vinyl chloride resin.

In British Pat. No. 1,453,178 to M. & T. Chemicals Inc. the flame-retardance is provided by a composition consisting essentially of antimony trioxide, a halogen-containing polymer such as a vinyl chloride resin, and barium carbonate.

British Pat. No. 1,256,672 to The General Tire & Rubber Company describes polyurethane foams in which flame-retardance is imparted by a combination of a solid halogen-containing polymeric resin such as a vinyl chloride resin, zinc oxide and antimony oxide.

U.S. Pat. No. 3,876,571, again to General Tire, is similar to British Pat. No. 1,256,672, and teaches a chlorinated paraffin replacing up to as much as 80% by weight of the solid halogen-containing polymeric resin in this polyvinyl chloride, zinc oxide ad antimony oxide based flame-retardant combination.

U.S. Pat. No. 3,884,849, once again to General Tire, is similar to U.S. Pat. No. 3,876,571, except that there is also present in the combination a zinc salt of an organic monocarboxylic acid or of an organic mono dithiocarbamic acid and, moreover, the chlorinated paraffin is optional as a replacement for part of the solid halogen-containing polymeric resin. U.S. Pat. No. 3,931,062, a yet further grant to General Tire, is similar to U.S. Pat. No. 3,884,849, except that instead of the zinc salt there is employed an oxide, hydroxide or basic salt of certain Group 2a metals, namely magnesium, calcium, strontium or barium.

U.S. Pat. No. 3,799,897 to Toyo Rubber Chemical Industrial Corporation reveals a flame-proof composition of antimony oxide and chlorinated paraffin for polyurethane foams and to this extent differs from say U.S. Pat. Nos. 3,075,927 and 3,075,928 where a vinyl chloride resin is employed in accompaniment with the antimony oxide.

British Pat. No. 1,456,805 to The Upjohn Company discloses flame-retardant flexible polyurethane foams including a combination of antimony oxide, a polyhalogenated aromatic compound and alumina trihydrate.

British Pat. No. 1,368,931 to General Tire incorporates into the foam composition a combination of a solid halogen-containing polymeric resin such as, for example, a vinyl chloride resin, alumina trihydrate and antimony trioxide. Up to 70% by weight of the polymeric resin can be replaced by a chlorinated paraffin. This specification discloses an improvement in the fire retardant effect arising with an increasing concentration of polymeric resin, antimony trioxide and alumina trihydrate (subject to the limits therein specified). However, in this case those skilled in the art would appreciate that the viscosity of the mixture would be such that it would be probable that many conventional machines currently used in commercial production could not be used without modification. The specification teaches that replacement of part of the halogen-containing polymer with a chlorinated paraffin, still gives "useful" foams having sufficient extinguishing properties. However, this qualification is coupled with the warning that when all of the resin is replaced with chlorinated paraffin, the resulting foams exhibit poor cell character, tend to collapse, show poor charring and are not self-extinguishing.

Workers in this area have faced a particular problem for while it has been possible to make some foams with acceptable fire retardant properties, the physical properties of many of these foams are such that the material is only suitable for purposes such as providing insulation, etc. when the material is encapsulated or otherwise contained. Other foams, while having acceptable physical properties, do not have adequate fire retardant properties. Accordingly, it is desirable to produce a polyurethane foam having adequate fire retardant properties and at the same time having the physical properties necessary for applications such as seat cushioning, particularly in public transport vehicles, and for mattresses, particularly in public hospitals.

Notwithstanding the teaching of the prior art it has been surprisingly discovered that these results may be achieved without the need for incorporating a polymeric resin in the foam. A feature of the present invention is the selection of the polyol. More particularly, the polyol must be a diol- or triol-based polyol wherein at least 50% of the hydroxyl end groups are primary hydroxyl end groups.

SUMMARY OF THE INVENTION

Thus, according to a first aspect of the invention, there is provided a high-resilience, flexible or semi-flexible, flame-retardant, polyether based polyurethane foam which is suitable for moulding. The polyurethane foam is formed by reacting

(a) a diol- or triol-based polyol wherein at least 50% of the hydroxyl end groups are primary hydroxyl end groups with

(b) an isocyanate, a mixture of isocyanates or an isocyanate adduct or prepolymer, in the presence of

(c) an effective amount of a flame-retardant system including (1) a chlorinated paraffin, (2) antimony trioxide and (3) alumina trihydrate.

Accordingly, it is a primary object of the invention to provide an improved polyether based polyurethane foam.

A further object of the invention is to provide a polyether based polyurethane foam including an improved fire retardant system which does not adversely affect the physical properties of the foam.

Another object of the invention is to provide a polyether based polyurethane foam of improved fire retardant properties suitable for moulding.

Still another object of the invention is to provide an improved polyether based polyurethane foam of improved fire retardant properties suitable for use as seat cushioning, particularly in public transport vehicles.

Yet another object of the invention is to provide a method of preparing a polyether based polyurethane foam derived from a diol- or triol-based polyol wherein at least 50% of the hydroxyl end groups are primary hydroxyl end groups and an isocyanate having an improved fire retardant system of a chlorinated paraffin, antimony trioxide and alumina trihydrate.

Still other objects and advantages of the invention will in part be obvious and will in part be apparent from the specification.

The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others, and the composition possessing the features, properties and the relation of constituents which are exemplified in the following detailed disclosure, and the scope of the invention will be indicated in the claims.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

It will be readily appreciated that normally when preparing a polyurethane foam the isocyanate component is kept separate from the remaining reactants until the final mixing of the foam. An exception occurs where a prepolymer, quasi-prepolymer or adduct is first prepared by reacting the isocyanate with a part of the polyol to produce an isocyanate-terminated compound and this compound is then reacted with the remainder of the polyol. Another exception arises where the whole of the isocyanate is reacted with the other components in the presence of a delayed action or heat activated catalyst and the reaction product laid down in the form of a carpet underlay or like material. Generally, however, the system will take the form of a three-part mix comprising

(i) a preblend or masterbatch of polyol, antimony trioxide, a chlorinated paraffin or a mixture of chlorinated paraffins, and alumina trihydrate;

(ii) a further blend including one or more catalysts; and

(iii) an isocyanate.

Polyols used in making the polyurethanes of the present invention are diols or triols, having a molecular weight of from about 2500 to 7500, and at least 50% of the hydroxyl end groups being primary hydroxyl end groups. These polyols are liquids or are capable of being liquified or melted for handling in the polyurethane foaming machine.

Examples of diols or triols well suited to the present invention include linear and branched polyoxypropylene polyols, block copolymers of ethylene oxide and propylene oxide, and polyol grafts of ethylenically unsaturated monomers such as in particular styrene and acrylonitrile on the aforementioned polyols. These polyols will be substantially free from functional groups other than hydroxyl groups and moreover, and as mentioned above, will be in the main tipped with primary hydroxyl groups. In the most preferred embodiments of the invention, at least about 78% of the hydroxyl end groups are primary hydroxyl end groups.

There are a number of suitable polyols available commercially. By way of example only, there is mentioned CP4701 (ex Dow Chemicals), Niax 11-34 (ex Union Carbide Corp). Desmophen 3900 (ex Bayer), Propylan M12 (ex Lankro Chemicals) and Daltocel T 32-75 (ex ICI). "Polymer polyols" are also suitable, i.e. graft polyols containing a proportion of a vinyl monomer, polymerised in situ e.g. Niax 34-28.

Water is usually used in the further blend (ii) as a blowing agent since it liberates carbon dioxide on reaction with excess isocyanate. Alternatively a halogenated hydrocarbon may be used, such as fluorotrichloromethane or methylene chloride. In a further alternative, the blowing agent may be a gas, e.g. air, which is entrained in the system by mechanical means. In some cases a combination of blowing agents may be expedient.

The preferred isocyanate are toluene di-isocyanate (TDI), and polymethylene polyphenyl isocyanate and diphenylmethane di-isocyanate, both of which are known as MDI. Mixtures of these two isocyanates, and mixtures of either of isocyanate with a proportion of a polyol, say CP4701, either separately or together to form an adduct, are also useful. The invention does not preculde the use, however, of other aromatic and aliphatic isocyanates known in the art. The amount of isocyanate required is regulated by the stoichiometry of the reaction, an index of 100 to 105 giving foams with optimum physical property values; but, on either side of these figures, there is scope for making foams having good properties.

The flame-retardant system of the present invention includes about 5 to 20 parts by weight of antimony trioxide, about 15 to 60 parts by weight of a chlorinated paraffin, and about 30 to 80 parts by weight of alumina trihydrate, based on 100 parts by weight of the polyol. Addition of these amounts can easily be tolerated without any significant fall-off in physical properties.

The antimony trioxide will generally be present in the formulation in an amount ranging from 5 to 20 parts by weight, preferably in the range of 8 to 15 parts, and most preferably about 10 parts.

The chlorinated paraffin will usually be present in an amount ranging from 15 to 60 parts by weight, preferably from about 25 to 45 parts and most preferably from about 30 to 40 parts. Alternatively, the paraffin can be expressed in terms of the chlorine content and generally speaking there is present between about 18 and 36 parts, preferably about 20 to 30 parts by weight of chlorine. The term "chlorinated paraffin" as used herein, includes a single chlorinated paraffin, or mixtures thereof.

The chlorinated paraffins usually have a chlorine content of at least 60%, although if a mixture of chlorinated paraffins is used those with less chlorine may be included. The chlorinated paraffins may be either liquid or solid, for example, Cereclor 70L or Cereclor 70. ("Cereclor" is as registered ICI trade mark). In the preferred embodiments of the invention, the chlorinated paraffin is a liquid. These chlorinated paraffins are generally represented by the following emperical formula:

C.sub.n H.sub.[(2n+2)-y] Cl.sub.y

where n usuallyranges from about 10 to 25 and y from about 5 to 25, and preferably n is between about 12 and y is about 11.

Alumina trihydrate, a well-known and readily available material in a finely divided state, may be incorporated into the polyol masterbatch in the same way and at the same time as the antimony compound. Generally, the trihydrate is present in an amount of from 30 to 80 parts by weight, based on 100 parts by weight of the polyol. The efficiency of alumina trihydrate in this flame retardant system is due, it is believed, to a number of factors which are unique in their entirety. It acts as a heat sink in the first instance, and then at about 250.degree. C. the three molecules of water chemically bound in the molecule of alumina trihydrate are evolved as steam thus cooling down the flame front. This enormously assists the otherflame retardants in the system, namely the chlorinated paraffin and the antimony compound. The chlorinated paraffin also breaks down at about 250.degree. C., to liberate hydrogen chloride. It is believed that this hydrogen chloride combines with the antimony trioxide to produce antimony trichloride which is believed to act as a free radical deactivator, thus removing combustible products from the flame front.

Further compounds may be included in the system as required, among them being cross-linking agents, such as low molecular weight (1000 and under) species which will react with isocyanates, exemplified by, but not confined to, polyols, polyamines and amino hydroxy compounds. Tertiary amine and organometallic catalysts, silicone polymers and copolymers and other surfactants, foam stabilisers and bubble modifiers, all known in the polyurethane foam art, may be used. Fillers such as calcium silicate, magnesia, calcium carbonate and barium sulphate may also be included, to confer some special property such as reduced drip on ignition, reduced smoke emission on ignition and sound attenuation.

Normally, foams in accordance with the present invention are cured in an oven the air temperature of which is no greater than 120.degree. C., the mould temperature usually being no greater than 80.degree. C. This is generally referred to as `cold cure` moulding in contrast to `hot cure` moulding where the air temperature is usually 175.degree.-200.degree. C. and the mould temperature about 120.degree. C.

In situations where the flame-retardant properties of the foam are critical, for example in applications in the public transportation or hospital fields, the density of the foam will usually be between about 4.5 and 6.5 pounds per cubic foot. Within this range an optimum balance between the flame-retardant properties of the foam and the physical characteristics of the foam is achieved.

Specific examples of the invention will now be illustrated.

Examples I, II and III are flexible foams, suitable for seating, and Example IV is a semi-flexible foam suitable for automotive headrests. All were prepared using conventional foaming techniques. In each case the formulation was supplied in three streams (A), (B) and (C). All parts are by weight.

EXAMPLE I

______________________________________
Parts
(by weight)
______________________________________
(A) Polyol preblend
CP 4701.sup.1 60.00
NIAX 34-28.sup.2 40.00
CERECLOR 70L.sup.3 35.00
ANTIMONY TRIOXIDE 10.00
ALUMINA TRIHYDRATE.sup.4 50.00
L5307.sup.5 2.00
DIBUTYLTIN DILAURATE (DBTL)
0.03
(B) Catalyst preblend
Water 2.70
NIAX Al.sup.6 0.20
NIAX A4.sup.7 0.30
DABCO 33LV.sup.8 0.35
(C) Isocyanate
80/20 TD180:20/MDI 35.5
______________________________________
.sup.1 Voranol 4701 a primary hydroxyl tipped polyether polyol, formed b
end blocking a polypropylene triol with ethylene oxide to the stage where
the primary hydroxyl content is about 78%; molecular weight about 4700; e
Dow Chemical.
.sup.2 A graft polymer polyol, ex Union Carbide, Hydroxyl number 28.
.sup.3 An ICI chlorinated paraffin having a chlorine content of about 70%
.sup.4 Finely divided, Alcoa (Registered Trade Mark) AS301.
.sup.5 A silicone surfactant, ex Union Carbide.
.sup.6 A proprietary tertiary amine catalyst, ex Union Carbide.
.sup.7 A proprietary tertiary amine catalyst, ex Union Carbide.
.sup.8 A 33% solution of triethylenediamine in a glycol solution.



This formulation has produced a foam having the following physical properties.

______________________________________
TEST RESULT
______________________________________
DENSITY CORE APPARENT 5.3 lb/cu. ft
ILD AS PER ASTM D2406 METHOD A
15".times. 15".times. 4"
@ 25% compression 81 lb
@ 65% compression 258 lb
@ 225% return 67.5 lb
MODULUS 3.18
HYSTERESIS 83.4%
TENSILE STRENGTH
ASTM D2406 SUFFIX T 21.4 lb/sq. in
ELONGATION
ASTM D2406 SUFFIX T 99%
TEAR RESISTANCE
ASTM D2406 SUFFIX G 1.44 lb/in
DRY COMPRESSION SET
ASTM D2406 METHOD B 50%
11.4
75% 9.0
STEAM AUTOCLAVE
ASTM D2406 % change in
compression load deflection
22.0
50% compression set 19.0
DRY HEAT AGE
ASTM D2406 SUFFIX A
% change tensile 9.3
STATIC FATIGUE HEIGHT LOSS
4.4%
LOAD LOSS 20.5%
DYNAMIC FATIGUE HEIGHT LOSS
3.7%
LOAD LOSS 19.1%
FLAMMABILITY
MVSS 302 SE.
______________________________________



EXAMPLE II

______________________________________
Parts
(by weight)
______________________________________
(A) Polyol preblend
CP 5701 60.00
NIAX 34-28 40.00
CERECLOR 70L 40.00
ANTIMONY TRIOXIDE 10.00
ALUMINA TRIHYDRATE 50.00
DBTL 0.03
SILICONE L5307 2.0
(B) Catalyst preblend
WATER 2.7
TRIETHANOLAMINE 2.0
DIMETHYLAMINOETHANOL (DMAE)
0.3
DABCO 33LV 0.45
(C) Isocyanate
TDI 80/20 37.00
______________________________________



EXAMPLE III

______________________________________
Parts (by weight)
______________________________________
(A) Polyol preblend
CP 4701 60.00
NIAX 34-28 40.00
CERECLOR 70L 40.00
ANTIMONY TRIOXIDE 10.00
ALUMINA TRIHYDRATE 50.00
L5307 2.00
DBTL 0.03
(B) Catalyst preblend
WATER 2.7
TRIETHANOLAMINE 2.0
DMAE 0.3
DABCO 33LV 0.45
(C) Isocyanate
CP 4701/TDI prepolymer
free NCO 25% 71.4
______________________________________



EXAMPLE IV

______________________________________
Parts (by weight)
______________________________________
(A) Polyol preblend
CP 4701 100.00
CERECLOR 70L 40.00
ANTIMONY TRIOXIDE 10.00
ALUMINA TRIHYDRATE 50.00
L5307 2.00
(B) Catalyst preblend
WATER 2.5
TRIETHANOLAMINE 4.5
TMBDA 0.15
DABCO 33LV 0.45
(C) Isocyanate
MDI 63.00
______________________________________



EXAMPLE V

The three separate streams of Example I were temperature conditioned by means of heated tanks. The temperature of the main polyol stream was 35.degree. C..+-.1.degree. C. and that of the other two streams was 25.degree. C..+-.1.degree. C.

A "Halco" low pressure polyurethane moulding machine was used to provide the required quantity from each stream. The pumps on the machine were set to give the requuired stream ratio and output. On injection the chemicals were mixed in a low pressure, high shear mixer and deposited into an open mould. A preset timer was adjusted to determine the duration of pour. The mould was fabricated from steel. The mould was designed to produce a test piece measuring 15".times.15".times.4". The mould was constructed so as to contain and constrain the rising and reacting foam into the required final shape. It was provided with vents to let out the air, but as little foam as possible, consistent with a high quality surface finish. The mould at pour was at a temperature of 50.degree..+-.1.degree. C. After pouring the mould was passed through a curing oven (the air temperature of which was approximately 120.degree. C.) for seven and a half minutes. After this time the mould, which was then at a temperature of about 80.degree. C., emerged, was mechanically opened, and the foam moulding stripped. The foam moulding was first crushed between rollers to 10% of its thickness i.e. 90% deflection, and then passed through a postcure oven at 120.degree. C. for 10 minutes.

Meanwhile, the empty mould was recycled back to the pour position being cleaned, sprayed with wax and reheated to 50.degree. C..+-.1.degree. C.

EXAMPLE VI

The Transport Test was carried out on a moulded foam formulated in accordance with the present invention, more specifically that the subject of Example V.

Listed below are the times and actions/observations:

______________________________________
TIME ACTION/OBSERVATION
______________________________________
0.00 Paper lit.
0.30 Paper at maximum conflagration level.
1.30 Foam becomes involved.
2.45 Paper burnt out completely.
3.20 All flames out.
______________________________________



There was very little smoke and fumes, a high char and no dripping.

Accordingly, a high resilience, flexible or semi-flexible, flame-retardant polyether based polyurethane foam is obtained in accordance with the invention. This polyurethane foam exhibits improved flame-retardant properties while maintaining superior physical properties. In this respect, use of a liquid chlorinated paraffin permits increased levels of antimony trioxide to be incorporated into the foam while avoiding viscosity problems during preparation. These polyurethane foams prepared in accordance with the invention are particularly suited to be formed in a cold or warm moulding process and thus are particularly well suited for fabrication of seating for public transport vehicles.

It will thus be seen that the objects set forth above, among those made apparent from the preceding description are efficiently attained and, since certain changes may be made in carrying out the above method and in the composition set forth without departing from the spirit and scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.

Pls let us know if you are interesting in it. with any question, ask me freely.Tks you.
Sam Xu
Sales Engineer
DONGGUAN JIEFU FLAME-RETARDED MATERIALS CO.,LTD
Contact me:
MSN: xubiao_1996@hotmail.com
GMAIL: samjiefu@gmail.com
SKPYE:jiefu1996


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