JP2014122362A - Halogen-free flame retardant tpu composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polyurethane (TPU) composite that is a halogen-free flame retardant (HFFR).SOLUTION: Halogen-free TPU compositions comprise, in weight percent based on the weight of the composition: A. 1 to 99 wt.% of TPU, B. 1 to 50 wt.% of tris(2-butoxyethyl)phosphate (TBEP), C. 1 to 70 wt.% of metal hydrate, and D. 1 to 70 wt.% of organic phosphate ester other than tris(2-butoxyethyl)phosphate. These compositions exhibit better smoke suppression than conventional organic phosphate flame retardant TPU compositions such as those based on resorcinol bis(diphenyl phosphate) (RDP) and bisphenol-A bis(diphenyl phosphate) (BPADP) in the absence of TBEP.

Description

The present invention relates to thermoplastic polyurethane (TPU) composites. In one aspect, the present invention relates to a TPU complex that is a halogen-free flame retardant (HFFR), while in another aspect, the invention is a halogen-free flame retardant, and tris (2-butoxy) It relates to a TPU complex comprising ethyl) phosphate (TBEP) or oligomers thereof, organic phosphate esters and metal hydrates.

TPU elastomers can have a wide range of flexibility. They are from injection molding to extrusion molding,
And it can be manufactured by various methods up to blow molding. They also provide the performance advantages of transparency, abrasion resistance, chemical and hydrocarbon resistance, and load retention and tensile strength. They therefore cover many applications that require flame retardancy.

Conventional flame retardants used in TPU compositions are halogen-based, ie they contain bromine, chlorine, and the like. However, flame retardants that do not contain halogen are still preferred due to the ever-present concerns regarding the environment and safety, but these can cause problems with TPU compositions. Conventional readily available halogen-free flame retardants, such as flame retardants based on organic phosphates, such as resorcinol bis (diphenyl phosphate) (RDP) and bisphenol-A bis (diphenyl phosphate) (BPADP), provide good smoke suppression Does not result in a flame retardant TPU composition. What continues to be interesting in the TPU industry is
It is a halogen-free TPU composition that exhibits both good smoke suppression and flame retardancy.

In one embodiment, the present invention provides (A) TPU, in particular polyether polyurethane,
(B) TBEP or TBEP oligomer, (C) a metal hydrate, and (D) an HFFR TPU composition comprising an organic phosphate ester. In one embodiment, HF
The FR TPU composition may further comprise one or more additives or fillers such as anti-drip agents such as triglycidyl isocyanurate (TGIC), antioxidants, UV stabilizers, processing aids and / or metal oxides. For example, titanium dioxide.

In one embodiment, the present invention provides the following, in weight percent units, based on the weight of the composition:
A. 1-99 wt% TPU,
B. 1 to 50 wt% TBEP,
C. 1-70 wt% metal hydrate, and D. HFFR TPU composition containing 1-70 wt% organic phosphate ester.
In one embodiment, the HFFR TPU composition is further based on the weight of the composition, in weight percent:
E. 0.1 to 10 wt% anti-drip agent,
F. 0.1-5 wt% additive, and G. Contains one or more of 0.1 to 10 weight percent filler.

In one embodiment, the HFFR TPU composition of the present invention is applied to insulation or other exterior products for wires or cables, or to automobiles, building and construction materials, synthetic leather, appliances, textiles, furniture and Fabricated into various parts or components for use in the manufacture of information technology devices. These various products can be made by one or more completely different methods including extrusion, forming and molding.
The present invention includes the following:
1. Based on the weight of the composition, in weight percent, the following:
A. 1 to 99% by weight of thermoplastic polyurethane (TPU),
B. 1-50% by weight of tris (2-butoxyethyl) phosphate (TBEP),
C. 1-70 wt% metal hydrate, and D. 1 to 70% by weight of an organic phosphate ester other than tris (2-butoxyethyl) phosphate,
Here, a halogen-free TPU composition comprising a total percentage of all components of 100% by weight.
2. The composition of item 1, wherein the TPU is at least one of a polyether-based and a polyester-based polyurethane and is present in an amount of 15-80% by weight.
3. Item 1. The composition of item 1 or 2, wherein the metal hydrate is at least one of aluminum trihydroxide (ATH) and magnesium hydroxide and is present in an amount of 10 to 60% by weight.
4). The organic phosphate ester is resorcinol bis (diphenyl phosphate) (
4. A composition according to any one of items 1 to 3, which is at least one of RDP) and bisphenol-A bis (diphenyl phosphate) (BPADP) and is present in an amount of 5 to 60% by weight.
5. 5. A composition according to any one of items 1 to 4, wherein TBEP is present in an amount of 2 to 30% by weight.
6). 6. A composition according to any one of items 1 to 5, further comprising at least one of an anti-drip agent, an antioxidant, a UV stabilizer, a processing aid and a filler.
7). 7. A composition according to any one of items 1 to 6, wherein the anti-drip agent is triglycidyl isocyanurate and is present in an amount of 0.1 to 10% by weight.
8). 8. The composition of any one of items 1 to 7, further comprising at least one of ethylene vinyl acetate (EVA), polyethylene, polypropylene, ethylene- or propylene copolymer and styrenic block copolymer.
9. An article comprising the composition of any one of items 1 to 8.
10. The article of claim 9 in the form of a wire or cable jacket.

Definitions Unless stated to the contrary, contextual implications or conventions in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of the present disclosure. For the purposes of US patent practice, the contents of any referenced patents, patent applications, or publications are specifically disclosed (to the extent not inconsistent with any definition specifically given in this disclosure). And in their entirety with respect to general knowledge in the field (or equivalent US versions thereof are also incorporated by reference as well).

Numerical ranges in this disclosure are approximate ranges, and thus may include values outside the ranges unless otherwise specified. The numerical range includes from the lower value to the upper value in increments of one unit as long as there is a separation of at least 2 units between any lower value and any upper value,
Includes all values. By way of example, if the composition, physical or other properties, such as molecular weight, weight percentage, etc. are between 100 and 1,000, all individual values such as 100, 10
1, 102, etc., and sub-ranges such as 100-144, 155-170, 197-2
00 is clearly listed. For ranges containing values that are less than 1 or containing fractions greater than 1 (eg, 1.1, 1.5, etc.), 1 unit is 0.0001, 0,.
It is considered to be 001, 0.01 or 0.1. For ranges containing a single digit less than 10 (eg 1-5), one unit is typically considered to be 0.1. These are merely examples of what is specifically intended, and all possible combinations of numerical values from the lowest value listed to the highest value should be considered as clearly described in this disclosure.
Numerical ranges are given within the present disclosure with respect to the amount of components in the composition, among other things.

Terms such as “wire” refer to a single strand of conductive metal, such as copper or aluminum, or a single strand of optical fiber.

A term such as “cable” means at least one wire or optical fiber in a chassis, eg, an insulation coating or a protective outer jacket. Typically, the cable is 2
Two or more wires or optical fibers are typically joined together in a common insulation coating and / or protective jacket. Individual wires or fibers inside the chassis may be exposed, covered, or insulated. The combination cable may contain both electrical wires and optical fibers. Cables and the like can be designed for low voltage, medium voltage and high voltage applications. Typical cable designs are illustrated in US Pat. Nos. 5,246,783, 6,496,629, and 6,714,707.

  Terms such as “composition” mean a mixture or blend of two or more components.

The term “polymer” (such as) is a macromolecular compound prepared by reacting (ie, polymerizing) the same or different types of monomers. “Polymer” includes homopolymers and interpolymers.

“Interpolymer” means a polymer prepared by the polymerization of at least two different monomers. This general term includes copolymers commonly used to refer to polymers prepared from two different monomers, and polymers prepared from more than two different monomers, such as terpolymers, tetrapolymers, etc. .

Terms such as “free of halogen” mean that the composition of the present invention is free or substantially free of halogen, ie, as measured by ion chromatography (IC) or similar analytical methods. , Containing less than 2000 mg / kg of halogen. Halogen content less than this amount can be found in many products made from the compositions of the present invention,
For example, it may not be important to the effectiveness of the wire or cable coating.

Thermoplastic polyurethane (TPU)
The thermoplastic polyurethane used in the practice of the present invention is a reaction product of a polyisocyanate (typically a di-isocyanate), one or more polymeric diols and optionally one or more bifunctional chain extenders. is there. “Thermoplastic” as used herein has the ability to (1) extend beyond its original length and substantially return to its original length when released;
(2) Describes a polymer that softens when exposed to heat and substantially returns to its original state when cooled to room temperature.

式中、Ｒはアルキレン、シクロアルキレン、またはアリーレン基である。これらのジ−
イソシアネートの代表的な例は、米国特許第４，３８５，１３３号明細書、同第４，５２
２，９７５号明細書、および同第５，１６７，８９９号明細書に記載されている。好適な
ジ−イソシアネートの非限定例としては、４，４’−ジ−イソシアナトジフェニル−ｌ−
メタン、ｐ−フェニレンジ−イソシアネート、１，３−ビス（イソシアナトメチル）−シ
クロヘキサン、１，４−ジ−イソシアナト−シクロヘキサン、ヘキサメチレンジ−イソシ
アネート、１，５−ナフタレンジ−イソシアネート、３，３’−ジメチル−４，４’−ビ
フェニルジ−イソシアネート、４，４’−ジ−イソシアナト−ジシクロヘキシルメタン、
２，４−トルエンジ−イソシアネート、および４，４’−ジ−イソシアナト−ジフェニル
メタンが挙げられる。 The TPU may be prepared by a prepolymer, pseudo-prepolymer, or one-shot method. Isocyanates form hard segments in TPU and may be aromatic, aliphatic, or cycloaliphatic isocyanates and combinations of two or more of these compounds. One non-limiting example of a structural unit derived from di-isocyanate (OCN-R-NCO) is represented by formula (I):

In the formula, R is an alkylene, cycloalkylene, or arylene group. These dice
Representative examples of isocyanates are described in U.S. Pat. Nos. 4,385,133 and 4,52.
No. 2,975 and No. 5,167,899. Non-limiting examples of suitable di-isocyanates include 4,4′-di-isocyanatodiphenyl-1-
Methane, p-phenylene di-isocyanate, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,4-di-isocyanato-cyclohexane, hexamethylene di-isocyanate, 1,5-naphthalene diisocyanate, 3,3 '-Dimethyl-4,4'-biphenyl di-isocyanate, 4,4'-di-isocyanato-dicyclohexylmethane,
2,4-toluene di-isocyanate and 4,4′-di-isocyanato-diphenylmethane.

The polymeric diol forms a soft segment in the resulting TPU. The polymeric diol can have a molecular weight (number average) in the range of, for example, 200 to 10,000 g / mol. More than one polymeric diol can be used. Non-limiting examples of suitable polymeric diols include polyether diols (resulting in “polyether TPU”),
Polyester diols ("polyester TPU" is obtained), hydroxy-terminated polycarbonate ("polycarbonate TPU" is obtained), hydroxy-terminated polybutanediene, hydroxy-terminated polybutadiene-acrylonitrile copolymer, dialkylsiloxane and Alkylene oxides such as ethylene oxide,
These include hydroxy-terminated copolymers of propylene oxide, natural oil diols, and any combination thereof. One or more of the aforementioned polymeric diols may be an amine-terminated polyether and / or an amino-terminated polybutadiene.
It may be mixed with acrylonitrile copolymer.

Bifunctional chain extenders can be aliphatic linear and branched diols having from 2 to 10 (including the beginning and end) carbon atoms in the chain. Examples of such diols include 1,4-cyclohexanedimethanol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, Hydroquinone bis- (hydroxyethyl) ether, cyclohexylenediol (1,4-, 1,3-, and 1,2-isomers), isopropylidenebis (cyclohexanol), diethylene glycol, dipropylene glycol, ethanolamine, N -Methyl-diethanolamine and the like, and mixtures of any of these. As described above, in certain cases, to the extent that the thermoplasticity of the resulting TPU is not compromised,
A minor amount (less than about 20 equivalent percent) of a bifunctional extender may be replaced with a trifunctional extender, examples of such extenders being glycerol, trimethylolpropane, and the like.

Chain extenders are polyurethanes in an amount determined by the selection of specific reactant components, the desired amount of hard and soft segments, and an index sufficient to give good mechanical properties, such as modulus and tear strength. Incorporated into. The polyurethane composition is, for example, 2 to
25, preferably 3-20, more preferably 4-18% by weight of chain extender constituents.

In some cases, small amounts of monohydroxyl or monoamino functional compounds often referred to as “chain terminators” may be used to control molecular weight. Examples of such chain terminators are propanol, butanol, pentanol and hexanol. When used, the chain terminator is typically 0.1 to 2% of the total reaction mixture leading to the polyurethane composition.
Present in traces of weight percent.

The equivalent ratio of polymeric diol and this extender can vary significantly depending on the desired hardness for the TPU product. In general, the equivalent ratio is within each range of about 1: 1 to about 1:20, preferably about 1: 2 to about 1:10. At the same time, the overall ratio of isocyanate equivalents to equivalents of active hydrogen-containing material is 0.90: 1 to 1.10: 1, preferably 0.95: 1.
Within the range of ˜1.05: 1.

In one embodiment, the TPU is at least one of a polyether-based or polyester-based polyurethane. TPU compositions based on polyether-based polyurethanes are preferred.

Non-limiting examples of suitable TPUs include PELLETHANE® thermoplastic polyurethane elastomer, EST, available from Lubrizol Corporation.
ANE (registered trademark) thermoplastic polyurethane, TECOFLEX (registered trademark) thermoplastic polyurethane, CARBOTHAN (registered trademark) thermoplastic polyurethane, TECOPHIL
IC (R) thermoplastic polyurethane, TECOPLAST (R) thermoplastic polyurethane and TECOTHANE (R) thermoplastic polyurethane (all Nove
on), ELASTOLLAN® thermoplastic polyurethanes and other thermoplastic polyurethanes available from BASF, and Bayer, Huntsman
, Commercially available thermoplastic polyurethanes available from the Lubrizol Corporation and Mercinsa.

The TPU component of the composition of the present invention can include one or more thermoplastic polyurethanes, and optionally includes one or more additional thermoplastic halogen-free polymers, such as ethylene vinyl acetate. (EVA), polyethylene, polypropylene, ethylene- or propylene copolymer, styrenic block copolymer, and the like, but are not limited thereto. These other polymers can be dispersed discontinuously or co-continuously with the TPU resin phase of the composition.

When present, the other polymer is typically 0.1 to 50 wt%, more typically 0.1 to 15 wt%, based on the combined amount of TPU components and other polymers, Even more typically it is present in an amount of 0.1 to 10% by weight.

The TPU is typically at least 1%, more typically at least 15%, even more typically at least 2% by weight (% by weight) of the halogen-free TPU composition.
It is included at 5% by weight. The TPU is typically included at 99 wt% or less of the halogen-free TPU composition, more typically 80 wt% or less, and even more typically 65 wt% or less.

Tris (2-butoxyethyl) phosphate (TBEP)
TBEP is a flexible and rigid polyurethane and polyisocyanurate foam,
Known bright colored, high boiling, non-flammable, low viscosity and low acidity for use in unsaturated polyester resins, polyvinyl chloride, adhesives, elastomers, cellulose acetate, nitrocellulose, epoxy resins and other resins Is a flame retardant additive. TBEP is
It may exist as a single molecule or as an oligomer, ie as a polymer-like material having only a few repeating units. The oligomeric form of TBEP is generally 2 per molecule.
Having an average of two or more phosphate and / or phosphonate ester units.

TBEP is typically included at least 1%, more typically at least 2%, and even more typically at least 3% by weight of the halogen-free TPU composition. TBEP is typically included at 50 wt% or less, more typically 30 wt% or less, even more typically 15 wt% or less of the halogen-free TPU composition.

Metal Hydrate Suitable metal hydrates for use in the practice of the present invention include aluminum trihydroxide (A
Including, but not limited to, TH or aluminum trihydrate), and magnesium hydroxide (also known as magnesium dihydroxide). The metal hydrates may be natural or synthetic and they can be used alone or in combination with other inorganic flame retardants such as calcium carbonate, silica, etc. either alone and / or typically in small amounts.

The metal hydrate is typically at least 1% by weight of the halogen-free TPU composition,
More typically at least 10% by weight, even more typically at least 20% by weight. The metal hydrate is typically included at 70 wt% or less, more typically 60 wt% or less, even more typically 55 wt% or less of the halogen-free TPU composition.

Organic Phosphate Esters Organic phosphate esters useful in the practice of the present invention include aromatic and aliphatic phosphate esters and polymers thereof. Examples of aliphatic phosphate ester flame retardants include trimethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, monoisodecyl phosphate and 2-acryloyloxyethyl acid phosphate. Examples of aromatic phosphate esters include trixylenyl phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate and diphenyl-2-methacryloyloxyethyl phosphate. As aromatic bis (phosphate ester), resorcinol bis (
Diphenyl phosphate) (RDP), resorcinol bis (dixylenyl phosphate), resorcinol bis (dicresyl phosphate), hydroquinone bis (dixylenyl phosphate), bisphenol-A bis (diphenyl phosphate) (BPADP) and tetrakis (2,6 -Dimethylphenyl) 1,3-phenylenebisphosphate. These phosphate esters can be used alone or in combination with each other. Preferred organic phosphate esters include RDP and BPADP.

The organic phosphate ester is typically at least 1%, more typically at least 5%, even more typically at least 1% by weight of the halogen-free TPU composition.
It is contained at 0% by weight. Organic phosphate esters are typically halogen free T
70 wt% or less of the PU composition, more typically 60 wt% or less, even more typically 2 wt%
It is contained at 0% by weight or less.

Anti-Drip Agent In one embodiment, the halogen-free TPU composition of the present invention further comprises an anti-drip agent. Examples include, but are not limited to, one or more triglycidyl isocyanurates, epoxidized novolac resins, and fluororesins such as polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, tetrafluoroethylene and perfluoro Examples thereof include fluorinated carbon resins of alkyl vinyl ethers and polyvinylidene fluoride.

When present, the anti-drip agent is typically at least 0.1%, more typically at least 0.2%, and even more typically at least 0% of the TPU composition free of halogens. 4% by weight. When present, the anti-drip agent is typically 10% by weight or less, more typically 8% by weight or less of the halogen-free TPU composition,
Even more typically it is contained at 5 wt% or less.

Additives and Fillers The halogen-free TPU compositions of the present invention can optionally contain additives and / or fillers. Typical additives include antioxidants, processing aids, colorants, UV stabilizers (including UV absorbers), antistatic agents, nucleating agents, slip agents, plasticizers,
Examples include, but are not limited to, lubricants, viscosity control agents, tackifiers, antiblocking agents, surfactants, extender oils, acid scavengers, and metal deactivators. When present, these additives are typically used in conventional manner and conventional amounts, for example from 0.01 wt% to 10 wt%, based on the total weight of the composition.

Typical fillers include various metal oxides such as titanium dioxide, metal carbonates such as magnesium carbonate and calcium carbonate, metal sulfides and sulfates such as molybdenum disulfide and barium sulfate, metal borates such as barium borate, meta -Barium borates, zinc borates and metals-zinc borates, metal anhydrides such as aluminum anhydride, clays such as diatomaceous earth, kaolin and montmorillonite,
Examples include, but are not limited to, huntite, celite, asbestos, soil minerals, and lithopone. When present, these fillers are typically used in conventional manner and conventional amounts, for example from 5% to 50% by weight based on the weight of the composition.

Suitable UV light stabilizers include hindered amine light stabilizers (HALS) and UV light absorber (UVA) additives. Representative HALS that can be used in the composition include T
INUVIN XT850, TINUVIN622, TINUVIN (registered trademark) 770
, TINUVIN® 144, SANDUVOR® PR-31, and Chimassorb 119FL, but are not limited to these. TINUVI
N® 770 is bis- (2,2,6,6-tetramethyl-4-piperidinyl)
Sebacate, having a molecular weight of about 480 grams / mole, Ciba, Inc. (Currently part of BASF) and retains two secondary amine groups. TINU
VIN® 144 is bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) -2-n-butyl-2- (3,5-di-tert-butyl-4-hydroxy (Benzyl) malonate has a molecular weight of about 685 grams / mole, contains a tertiary amine, Ci
It is also available from ba. SANDUVOR® PR-31 is propanedioic acid, [(4-methoxyphenyl) -methylene] -bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, about 529 It has a molecular weight of grams / mole and contains a tertiary amine, Clariant Chemicals (India) Ltd. Is available from Chimassorb 119FL or Chimassorb 119 is 1
0% by weight of dimethyl succinate polymer with 4-hydroxy-2,2,6,6, -tetramethyl-1-piperidineethanol and 90% by weight of N, N ′ ″-[1,2
-Ethanediylbis [[[4,6-bis [butyl (1,2,2,6,6-pentamethyl-
4-piperidinyl) amino] -1,3,5-trizin-2-yl] imino] -3,1-
Propanediyl]] bis [N′N ″ -dibutyl-N′N ″ -bis (1,2,2,6,
6-pentamethyl-4-piperidinyl)]-1 is available from Ciba, Inc. Commercially available. Typical UV absorber (UVA) additives include benzotriazole types such as C
iba, Inc. Tinuvin 326 and Tinuvin 328 commercially available from
Is mentioned. Blends of HAL and UVA additives are also effective.

Examples of antioxidants include hindered phenols such as tetrakis [methylene (3,
5-di-tert-butyl-4-hydroxyhydro-cinnamate)] methane, bis [(
β- (3,5-di-tert-butyl-4-hydroxybenzyl) -methylcarboxyethyl)] sulfide, 4,4′-thiobis (2-methyl-6-tert-butylphenol), 4,4′-thiobis ( 2-tert-butyl-5-methylphenol), 2,2′-
Thiobis (4-methyl-6-tert-butylphenol), and thiodiethylenebis (3,5-di-tert-butyl-4-hydroxy) hydrocinnamate, phosphites and phosphonites such as tris (2,4-di- tert-butylphenyl) phosphite and di-tert-butylphenyl-phosphonite, thio compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, various siloxanes, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline, n, n′-bis (1,4-dimethylpentyl-p-phenylenediamine), alkylated diphenylamine, 4,4′-bis (α, α- Dimethylbenzyl) diphenylamine, diphenyl-p-ph Nirenjiamin, mixed di - aryl -p- phenylenediamine, and other hindered amine antidegradants or stabilizers include, but are not limited to. Antioxidants can be used, for example, in amounts of 0.1 to 5% by weight, based on the weight of the composition.

Examples of processing aids include metal salts of carboxylic acids such as zinc stearate or calcium stearate, fatty acids such as stearic acid, oleic acid, or erucic acid, aliphatic amides such as stearamide, oleamide, erucamide, or N, N′-ethylene bis-stearamide, polyethylene wax, polyethylene oxide wax, ethylene oxide polymer, copolymer of ethylene oxide and propylene oxide, vegetable wax, petroleum wax, nonionic surfactant, silicone fluid and polysiloxane. It is not limited.

Compounding / Production Compounding of the compositions of the present invention can be done by standard means known to those skilled in the art. Examples of compounding equipment are closed batch mixers, such as Banbury or bowling closed mixers. Alternatively, continuous single or twin screw mixers can be used, such as Farrel continuous mixers, Werner and Pfleiderer twin screw mixers or Buss kneading continuous extruders. The type of mixer utilized and the operating conditions of the mixer will affect the properties of the composition, such as viscosity, volume resistance and extruded surface smoothness.

The compounding temperature of TPU with flame retardant and optional additive package is typically 120-220 ° C, more typically 160-200 ° C. The various components of the final composition can be added to each other or simultaneously in any order and compounded, but typically the TPU is combined with one or more flame retardants prior to compounding with the additive. First compounded.

In some embodiments, the additive is added as a premixed masterbatch. Such a masterbatch can contain additives, either separately or together, in small amounts of TPU or TP.
When U is used in combination with another resin, such as polyethylene or polypropylene, it is generally formed by dispersing with a small amount of other resin. The masterbatch is conveniently formed by a melt compounding process.

Articles of Manufacture In one embodiment, the halogen-free TPU composition of the present invention is applied to a cable in a known manner (eg, US Pat. No. 5,246) in a known amount, such as a chassis or insulating layer. , 783 and 4,144,202)). Typically, the polymer composition is prepared in a reactor-extruder equipped with a cable coating die and after compounding the components of the composition, the composition is drawn when the cable is drawn through the die. Extruded on the cable. The chassis is then typically subjected to a curing period, which occurs at a temperature from ambient temperature to below the melting point of the composition until the article reaches the desired degree of crosslinking. Curing can be initiated in a reactor-extruder.

Other articles of manufacture that can be prepared from the polymer compositions of the present invention, particularly under high pressure and / or high humidity conditions, include fibers, ribbons, sheets, tapes, pellets, tubes, pipes, plugging materials, seals, gaskets, foams, Footwear and bellows. These articles can be manufactured using known equipment and techniques.

The TPU composition of the present invention exhibits the desired flame resistance without the use of halogenated flame retardants, thus eliminating environmental and health concerns for composition combustion. The TPU composition of the present invention is also a conventional organic phosphate flame retardant TPU composition such as RDP in the absence of TBEP.
Or better smoke suppression compared to compositions based on BPADP.

The invention is more fully described through the following examples. Unless otherwise noted, all parts and percentages are by weight.

Specific Embodiments Materials The TPU used in these examples is PELLETHANE® 2103-
90AE and ESTANE® 58219, both of which are polyether thermoplastic polyurethanes, Lubrizol Advanced Materia
available from ls. Prior to use, the TPU sample is pre-dried at 90 ° C. under vacuum for at least 4 hours. TBEP is Zhangjiagang Shunchang Che
obtained from mical. FYROFLEX® RDP is obtained from Supresta. BPADP is available from Adeka Palmarole, grade name ADKSTA
Obtained as BFP600 and used as received. Aluminum trihydrate H42
M is obtained from Showa Kako and pre-dried at 100 ° C. for 6 hours under vacuum.

The Dow Chemical Co with an epoxide equivalent weight of 176-181
DEN438, a solvent-free epoxidized novolak available from many, is used as an anti-drip agent. TGIC and Ciba from FangRuiDa
AD-001 (polytetrafluoroethylene in styrene / acrylonitrile copolymer resin) from Specialty Chemicals is used as an anti-drip agent. Antioxidants include IRGANOX® 168 and 1010, and IR
GAFOS® 126 and MD1024 (all Ciba Special
y Chemicals). UV stabilizers are also Ciba Specialt
y TINUVIN 866 from Chemicals. Color masterbatch
Made by Clariant, titanium dioxide is R103 from DuPont.

Test 1. Indoor imitation VW-1
Wire strips for the simulated VW-1 test are prepared by compression molding. A single copper conductor with a diameter of 0.5 mm is placed in the center of each notch. Hot presser temperature is 185
Set to ° C. The preheating time is about 3 minutes, and then pressurization is performed under 13 MPa for 2 minutes. The plate specimen is cooled to room temperature and a strip sample (203 having a single copper conductor in the center)
mm × 2.5 mm × 2 mm). Samples are slowly cooled prior to flame retardant (FR) testing at least 24 hours at 23 ° C. ± 2 ° C. and 50 ± 2% relative humidity.

The simulated VW-1FR test is performed in a UL-94 chamber. The sample is clamped so that the longitudinal axis is vertical by applying a 50 gram fill to the bottom. 1
Fasten one paper flag (2 x 0.5 cm) to the top of the wire. The distance from the bottom of the flame to the bottom of the flag (the highest point of the burner oracle) is 18 cm. The flame is applied continuously for 45 seconds. Afterflame time (AFT), uncarbonized wire length (UCL) and percentage of uncarbonized flag area (uncarbonized flag) are recorded during and after combustion. Four or five specimens are tested for each sample. Any of the following phenomena will result in a “fail” score.
1. The cotton under the sample ignited,
2. The flag burned out,
3. A drip due to flame occurs.
2. Corn calorimeter test

This test is performed using Fire Test Technology (FTT) with FTT2000 in accordance with ISO 5660-2: 2002 (ASTME-1354). Plate specimen (100mm x 1
00 mm × 3.2 mm) is used to test with a heat flux of 35 kW / m ² . The nominal duct flow rate was 24 l / s. The sampling interval is 5 seconds with a separation of 25 mm.

Compounding The compositions reported in Table 1 are prepared in a laboratory Haake from Thermo Scientific with the model type RHEOMIX® 600 OS. The drive system is HAAKE POLYLAB DRIVE RHEODRIVE7. The mixing temperature is set to 170 ° C.

At a mixer rotation speed (roller type rotor) of 30 revolutions per minute (rpm), TPU is added to the mixing balls and mixed for 2 minutes to obtain a homogeneous molten state. TBEP, metal hydrate, phosphate ester, anti-drip agent and additives are uniformly premixed and added to the mixing bowl. The feed process takes about 2 minutes, followed by mixing at 70 rpm for 5 minutes. After mixing, the composite is removed from the mixing bowl and allowed to cool naturally to ambient temperature.

Test Composition The TPU composition of Comparative Example 1 comprises an organic phosphate ester (RDP) and a metal hydrate and no TBEP. Comparative Example 2 contains metal hydrate and TBEP but does not have an organic phosphate ester. Examples 1 and 2 of the present invention include all three flame retardant components, namely, organic phosphate ester, TBEP and metal hydrate.

Examples 1 and 2 of the present invention are ATH / RDP / TBEP TPU composites. The results show that both Examples 1 and 2 of the present invention pass the mimic VW-1 test robustly. In addition, the specific light reduction area (SEA) results from the corn calorimeter (CC) test also show that Examples 1 and 2 of the present invention have significantly lower SE compared to Comparative Example 1 (478.4 m ² / g).
A (respectively 296.9m ² / g and 336.8m ² / g). The composition of the present invention comprises TB
It shows a much better smoke suppression effect than the comparative formulation without EP. Thus, the results also show that increasing TBEP loading reduces SEA. Comparative Example 2 is RDP
It is an ATH / TBEP-based TPU complex that does not have any. This example is very low SEA
(242.4 m ² / g), which was disqualified for the VW-1 test.

Twin Screw Extruder Compounding and Cable Testing Epoxidized novolac is premixed in liquid phosphate (BPADP and / or TBEP). Then, in a 50 liter high speed mixer, the filler (ATH, TiO ₂
) And additives (anti-drip agent, antioxidant, etc.) and 1800 rp
m for another 1 minute. The premixed blend is then removed for the next operation.

The premixed blend and TPU resin is then 190 ° C. barrel temperature, 40 mm
And a twin screw with a power of about 60 kg / hr under a screw diameter of 38.6 and an L / D of 38.6. Finally, pellets are obtained and dried at less than 120 ° C. for 6 hours.

The composition as described above is then tested as reported in Table 2. All reported data is based on a full cable with an outer diameter of 6.8 mm. The TPU compound is for the jacketing material, and the insulating layer used here is The Dow Chemical.
1 DFDA1648 available from Company. In particular, the smoke density test is EN5.
Passing this test according to 0268-2 means that the smoke density (transparency) exceeds 60%.

The flame retardant package of Comparative Example 3 contains BPADP and ATH but does not have TBEP. The flame retardant packages of Examples 3 to 5 of the present invention are BPADP, ATH and TB
Includes EP.

As shown in Table 2, smoke density performance is improved when 2 wt% TBEP is added (Example 3 of the present invention versus Comparative Example 3). Smoke density performance is further improved to pass the criteria (> 60%) with increasing TBEP dose (Examples 4 and 5 of the invention). However, the tensile elongation of Example 5 of the present invention is significantly reduced. This problem can be solved by lowering the ATH loading and thus adjusting the BPADP and TBEP contents simultaneously (Example 5 of the present invention). Thus, Example 5 of the present invention shows good smoke density performance and balanced mechanical properties. The flame retardant performance is very robust to pass VW-1 for all the formulations in Table 2.

While the invention has been described in specific detail throughout the preceding description of the preferred embodiment,
This detail is mainly for illustrative purposes. Many variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention as set forth in the following claims.

Throughout the preceding description of the preferred embodiment, the present invention has been described with specific details, which are mainly for illustrative purposes. Many variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention as set forth in the following claims.
Specific examples of the present invention provided by the above disclosure include the following inventions.
[1] A halogen-free TPU composition, based on the weight of the composition, in units of% by weight:
A. 1 to 99% by weight of thermoplastic polyurethane (TPU),
B. 1-50% by weight of tris (2-butoxyethyl) phosphate (TBEP),
C. 1-70 wt% metal hydrate, and
D. 1 to 70% by weight of an organic phosphate ester other than tris (2-butoxyethyl phosphate),
Where the total percentage of all components is 100% by weight
A composition comprising
[2] The composition according to [1], wherein the TPU is at least one of polyether-based and polyester-based polyurethane and is present in an amount of 15 to 80% by weight.
[3] The composition according to [2], wherein the metal hydrate is at least one of aluminum trihydroxide (ATH) and magnesium hydroxide and is present in an amount of 10 to 60% by weight.
[4] The organic phosphate ester is at least one of resorcinol bis (diphenyl phosphate) (RDP) and bisphenol-A bis (diphenyl phosphate) (BPADP) and is present in an amount of 5 to 60% by weight. ] The composition as described in.
[5] The composition according to [4], wherein the TBEP is present in an amount of 2 to 30% by weight.
[6] The composition according to [5], further comprising at least one of an anti-drip agent, an antioxidant, a UV stabilizer, a processing aid and a filler.
[7] The composition according to [6], wherein the anti-drip agent is triglycidyl isocyanurate and is present in an amount of 0.1 to 10% by weight.
[8] The composition according to [7], further comprising at least one of ethylene vinyl acetate (EVA), polyethylene, polypropylene, ethylene- or propylene copolymer, and styrenic block copolymer.
[9] An article comprising the composition according to [1].
[10] The article according to [9] in the form of a wire or cable coating.

Claims (10)

A halogen-free TPU composition, based on the weight of the composition, in weight percent units,
Less than:
A. 1 to 99% by weight of thermoplastic polyurethane (TPU),
B. 1-50% by weight of tris (2-butoxyethyl) phosphate (TBEP),
C. 1-70 wt% metal hydrate, and D. 1 to 70% by weight of an organic phosphate ester other than tris (2-butoxyethyl phosphate),
Wherein the total percentage of all components is 100% by weight. The composition of claim 1, wherein the TPU is at least one of a polyether-based and a polyester-based polyurethane and is present in an amount of 15-80 wt%. The composition of claim 2, wherein the metal hydrate is at least one of aluminum trihydroxide (ATH) and magnesium hydroxide and is present in an amount of 10 to 60 wt%. The organic phosphate ester is resorcinol bis (diphenyl phosphate) (
4. A composition according to claim 3, which is at least one of RDP) and bisphenol-A bis (diphenyl phosphate) (BPADP) and is present in an amount of 5 to 60% by weight.   5. A composition according to claim 4, wherein the TBEP is present in an amount of 2 to 30% by weight. 6. The composition of claim 5, further comprising at least one of an anti-drip agent, an antioxidant, a UV stabilizer, a processing aid and a filler. The composition of claim 6, wherein the anti-drip agent is triglycidyl isocyanurate and is present in an amount of 0.1 to 10% by weight. 8. The composition of claim 7, further comprising at least one of ethylene vinyl acetate (EVA), polyethylene, polypropylene, ethylene- or propylene copolymer and styrenic block copolymer.   An article comprising the composition of claim 1.   The article of claim 9 in the form of a wire or cable coating.