CN109401275A - A kind of high fire-retardance softness TPU film and preparation method thereof - Google Patents
A kind of high fire-retardance softness TPU film and preparation method thereof Download PDFInfo
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/12—Polyester-amides
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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Abstract
The present invention relates to a kind of high fire-retardance softness TPU films and preparation method thereof, the high fire-retardance softness TPU film includes thermoplastic polyurethane elastomer, fire retardant, filling oil and crosslinking agent, the present invention passes through the weight content of reasonable preparation each component and optimizes the type of each component, a kind of high fire-retardance softness TPU film is prepared, its anti-flammability can reach 94V-0 grades of UL, softness reaches shore 30A or so, has excellent flexibility.
Description
Technical field
The present invention relates to polyurethane fields more particularly to a kind of high fire-retardance softness TPU film and preparation method thereof.
Background technique
TPU elasticity physical efficiency has the flexibility of wide scope.It can be by from being injection molded into the extensive a variety of sides for being expressed into blow molding
Method preparation.It also offers the feature performance benefits of the transparency, wear resistance, chemistry and bearing and tensile strength.Therefore, it covers
The many applications for needing anti-flammability are covered.
Conventional flame retardant used in TPU composition is based on halogen, i.e., it includes bromine, chlorine etc..However, due to eternal
The existing consideration to environment and safety, halogen-free fire retardant receive an acclaim now, but it can choose for the proposition of TPU composition
War.The halogen-free flame-retardant being routinely easy to get is (such as based on organic phosphate (such as resorcinol two (diphenyl phosphoester)
(RDP) and bisphenol-A two (diphenyl phosphoester) (BPADP)) those of) still have many defects.
In addition, being also disclosed in US2003/0166749A1 a kind of fire-retardant other than organic phosphate above-mentioned
Thermo-plastic polyurethane, the fire-retardant thermo-plastic polyurethane include melamine cyanurate as fire retardant, and by being added up to 2
At least one crosslinker component of weight % improves its mechanical performance；The example of published crosslinking agent has trihydroxy methyl third
Alkane, pentaerythrite, amine, 3- isocyanatomethyl -3,5,5- trimethylcyclohexylisocyanate etc..It is disclosed in DE10343121A1
Thermoplastic polyurethane comprising metal hydroxides as fire retardant.The feature of these thermo-plastic polyurethanes first is that molecular weight is special
It is not high, at least 60,000g/mol.The crosslinking of thermo-plastic polyurethane is not described in the specification.In WO2006/121549A1
Disclose the thermo-plastic polyurethane comprising halogen-free flame-retardant, fire retardant includes a kind of organophosphinate component, a kind of organic
Phosphate ester components and a kind of polyalcohol.EP0617079A2 discloses self-extinguishment thermo-plastic polyurethane and its manufacturing method.Resistance used
Combustion agent includes one or more organophosphorus esters and/or one or more Organophosphonates, especially with melamine derivative
Mixing.
The method of the prior art can generate flame-proof thermoplastic polyurethane, however, it inevitably also needs to add phase
Reach sufficiently high flame retardant effect to the filler of fire retardant high level, and the filler of this high additive amount will certainly weaken again
Close the mechanical performance of thermoplastic polyurethane material.
Thus, for issue noted above, that is, how to provide a kind of halogen-free TPU group with good anti-flammability
Object is closed, and how to avoid the filler of high additive amount in TPU composite material, technology urgently to be resolved at present is had become and asks
Topic.
Summary of the invention
It is an object of the present invention to provide a kind of high fire-retardance softness TPU films, wherein the thermoplastic polyurethane bullet obtained
Property body thin film mechanical performance to reach with without be added fire retardant thermoplastic polyurethane elastomer as it is good, in addition, the heat
Plastic polyurethane film has excellent pliability；There is provided a kind of manufacture high fire-retardance softness TPU is thin for another purpose
The preparation method of film.
For this purpose, the invention adopts the following technical scheme:
A kind of high fire-retardance softness TPU film, it includes:
(A) thermoplastic polyurethane elastomer of 20 weight of weight %~70 %；
(B) fire retardant of 20 weight of weight %~30 %；The fire retardant is by tricresyl phosphate (2- butoxyethyl group) ester, metal
Hydroxide, three (xylyl) phosphates, (methoxyl group second) ester of phthalic acid two composition, components by weight percent ratio be (10~
50): (20~30): (1~5): (20~50)；
(C) the filling oil of 5 weight of weight %~30 %；Filling oil by polyol-ester type oil agent, polyesteramide and
Base oil composition, components by weight percent ratio are (0.1~0.5): (2~5): (90~100)；
(D) crosslinking agent of 5 weight of weight %~20 %；
The total amount of component (A), (B), (C) and (D) is 100 weight %.
Preferably, thermo-plastic polyurethane's elastomer has the shore hardness of 45A to 85A, with the survey of GB/T531-1999 method
It is fixed；Further preferably with the shore hardness of 50A to 65A.
Preferably, the metal hydroxides is made of aluminum trihydrate and magnesium hydroxide, and components by weight percent ratio is (1~5):
(5~10).
Preferably, the polyol-ester type oil agent is tricarboxymethyl propane oleate, the trimethylolpropane oleic acid pungent last of the ten Heavenly stems
In acid esters, pentaerythritol oleate or neopentyl glycol dioleate any one or at least two combination.
Preferably, the base oil is hydrorefined mineral oils, further preferably base oil 60N and/or base oil
70N。
Preferably, the crosslinking agent is dissolved at least one of thermoplastic polyurethane elastomer isocyanates, the friendship
The NCO content for joining agent is greater than 5%.
Preferably, the isocyanates is 4, the 4 '-diisocyanate (MDI) of diphenyl methane of carbodiimide modified, into
One step preferred isocyanate content is carbodiimide modified diphenyl of the 25 weight % to 33 weight %, particularly 29.5 weight %
Methane 4,4 '-diisocyanate.
The present invention also provides the preparation methods of foregoing high fire-retardance softness TPU film comprising: by component (A),
(B), (C) and (D) is sent in casting machine after three-level mixes, then through automatic feeding system according to the ratio, is extruded into film, thus
The high fire-retardance softness TPU film is prepared.
Preferably, each zone temperatures of the casting machine are provided that barrel temperature is 140-170 DEG C, strainer temperature 170-
180 DEG C, 170-180 DEG C of elbow temperature connects 170-180 DEG C of temperature, 170-180 DEG C of die head temperature.
The present invention also provides the purposes of foregoing high fire-retardance softness TPU film in the molded part.
Compared with prior art, the present invention at least has the advantages that
High fire-retardance softness TPU film provided by the invention, wherein the machinery of the thermoplastic polyurethane elastomer film obtained
Performance to reach with without be added fire retardant thermoplastic polyurethane elastomer as it is good, can be realized 94V-0 grades of UL it is fire-retardant；
Meanwhile softness can reach shore 30A or so, have excellent pliability.
Specific embodiment
Definition
Unless the contrary indication, in context imply or the prior art convention, all parts and percentages be all with
Poidometer, and all test methods are all existing when the applying date of the application.
Numberical range in the application include wherein with all numerical value of a unit increment and including upper lower limit value, as long as
At least two units can be divided between any upper limit value and any lower limit value, as example, if composition, physics or other properties
(such as molecular weight, weight percent etc.) be 100-1,000, then all single numerical value (such as 100,101,102 etc.) and son
Range (such as 100-144,155-170,197-200 etc.) all clearly includes.For comprising the numerical value less than 1 or comprising being greater than 1
Score numerical value (such as 1.1,1.5 etc.), a unit is considered 0.0001,0.001 or 0.1.For comprising small
In the range (such as 1-5) of 10 unit amount, a unit is typically considered 0.1.These are only the examples specifically indicated,
The all possible combination of numerical value between minimum lower limit and maximum is considered to explicitly point out in this application.Numerical value
Range is provided in this application particularly for the constituent content in composition.
Component (A):
High fire-retardance softness TPU film in the present invention includes at least one thermoplastic polyurethane elastomer, usually can be with
It reacts to obtain by following substances:
A) organic and/or modified organic diisocyanate and
B) relatively high molecular weight, particularly substantially bifunctional polyol and, if appropriate
C) cahin extension agent.
In the present invention, abbreviation TPU is also used to refer to for thermo-plastic polyurethane.They be it is known per se it is substantial linear, can
The polyurethane of thermoplastic processing.In principle, mixture of the invention can be suitable for by any known TPU that conventional method manufactures.
It is preferable to use polyether TPUs as component A.
Here be in relation in the present invention TPU and their constituent a) to details c):
The organic and/or modified organic diisocyanate that can be used is aliphatic, alicyclic or optimization aromatic two is different
Cyanate.The example that can individually refer to is: aliphatic diisocyanate, such as 1, hexamethylene-diisocyanate, 2- methyl pentamethylene
1,5- diisocyanate, the 2- ethylbutylene Isosorbide-5-Nitrae diisocyanate either aliphatic diisocyanate as listed by least two
The mixture of composition；Alicyclic diisocyanate, such as isophorone diisocyanate, hexamethylene Isosorbide-5-Nitrae diisocyanate, 1- first
Base-hexamethylene 2,4- or 2,6- diisocyanate and corresponding isomer mixture, dicyclohexyl methyl hydride 4,4 '-, 2,4 '-and 2,
2 '-diisocyanate and corresponding isomer mixture；Preferred fragrance (cyclo) aliphatic diisocyanates, such as toluene 2,4- diisocyanate,
The mixture being made of toluene 2,4- and 2,6- diisocyanate.
The polyol of suitable higher molecular weight, molal weight are 500 to 8000g/mol, are polyester-diols,
Especially polyetherdiol.One example of compound used therefor is polybutadiene diol, it can generate good when producing cross-linking TPU
Good result.Other polymer containing hydroxyl and ether or ester group on polymer chain can also be with here, such as polyacetals
Class, such as polyformaldehyde, formal class especially not soluble in water such as polytetramethylene glycol formal and poly- hexanediol formal and poly- carbon
Acid esters, especially by diphenyl carbonate and 1,6- hexylene glycol passes through the polycarbonate that ester exchange reaction is produced.Polyol
It should at least be mainly linear, and to carry out isocyanates reaction, polyol should substantially bifunctional knot
Structure.The polyol being previously mentioned can be used as individual component and use, and can also use as a mixture.
Suitable polyether Glycols can be produced with known method, such as alkylene oxide is carried out anionic polymerisation, wherein be used
Alkali metal hydroxide (such as sodium hydroxide or potassium hydroxide) or alkali alcoholate (such as sodium methoxide, sodium ethoxide or potassium ethoxide
Or potassium isopropoxide) it is used as catalyst, and at least one starting containing 2 to 3, preferably 2 reactivity hydrogen atoms is added
Molecule；Or there is the alkylene oxide of 2 to 4 carbon atoms to carry out cationic polymerization alkylene moiety, wherein with lewis acid, such as
Antimony pentachloride, boron fluoride close ether etc. or bleaching earth as catalyst.
The available cahin extension agent that molal weight is generally 60 to 400g/mol, preferably 60 to 300g/mol is that have 2 to 12
A, preferably 2,4 or 6 carbon atoms aliphatic diol, such as ethylene glycol, 1,6- hexylene glycol, diethylene glycol (DEG), dipropylene glycol, especially
It is 1,4- butanediol.However, other suitable compounds are terephthalic acid (TPA) and the glycol formation with 2 to 4 carbon atoms
Diester, such as the hydroxyl of two (1,4-butanediol) esters and hydroquinone of two (ethylene glycol) esters or terephthalic acid (TPA) of terephthalic acid (TPA)
Base alkylene ether is 162 polytetramethylenes for arriving 378g/mol there are also molal weight such as Isosorbide-5-Nitrae-two (3- ethoxy) hydroquinone
Glycol.
In order to adjust the hardness and melt index (MI) of TPU, the dosage of constituent (b) and (c) can be in wider molar ratios
Change within the scope of rate.With the increase of cahin extension agent (c) content, the hardness and melt viscosity of TPU increases, and melt index (MI) then under
Drop.
The preferably described thermo-plastic polyurethane's elastomer of the present invention has the shore hardness of 45A to 85A, with GB/T531-1999 method
Measurement；Preferably with the shore hardness of 50A to 65A.
The amount of component A is based on amount of the mixture in inventive mixture, the usually 20 weight % of weight %~70, such as
It can be 20 weight %, 25 weight %, 30 weight %, 40 weight %, 45 weight %, 50 weight %, 60 weight %, 62 weights
Measure %, 65 weight %, 70 weight %.
Component (B):
Fire retardant of the invention uses the form of mixture, by tricresyl phosphate (2- butoxyethyl group) ester TBEP, metallic hydrogen
Oxide, three (xylyl) phosphates, (methoxyl group second) ester of phthalic acid two composition, components by weight percent ratio be (10~
50): (20~30): (1~5): (20~50).
TBEP is obtainable light color, high-melting-point, non-combustible, low sticky, faintly acid flame-retardant additive on the market, it is known that
For flexible and rigid olyurethane and polyisocyanurate foam, unsaturated polyester resin, polyvinyl chloride, adhesive, elastomer,
In cellulose acetate, NC Nitroncellulose, epoxy resin and other resins.TBEP can be used as unimolecule or oligomer (only has
There is the quasi polymer material of several repetitive units).The usually each molecule of the oligomer form of TBEP has 2 or more average
Phosphate and/or phosphonate unit.
Metal hydroxides
Be suitable for the invention practice in metal hydroxides include but is not limited to: three aluminium hydroxides (also referred to as ATH or
Aluminum trihydrate) and magnesium hydroxide (also referred to as magnesium dihydroxide).What metal hydroxides can be a naturally occurring or synthesize, energy
It is enough to be used alone or combined with usually a small amount of another kind and/or other inorganic fire retardantss (such as calcium carbonate, silica etc.)
It uses.Preferably, the metal hydroxides is made of aluminum trihydrate and magnesium hydroxide, and components by weight percent ratio is (1~5): (5
~10).
The amount of component B is based on amount of the mixture in inventive mixture, the usually 20 weight % of weight %~30, such as
It can be 20 weight %, 21 weight %, 22 weight %, 23 weight %, 24 weight %, 25 weight %, 26 weight %, 28 weights
Measure %, 30 weight %.
Tricresyl phosphate (2- butoxyethyl group) ester, metal hydroxides, three (xylyl) phosphates, phthalic acid
The components by weight percent ratio of two (methoxyl group second) esters is (10~50): (20~30): (1~5): (20~50), such as can be 10:
20:1:20、20:22:4:30、30:25:5:46、50:20:1:20。
Component (C):
The present invention is added to filling oil in the raw material of TPU film, is used cooperatively with fire retardant, can greatly improve this
The flexibility of TPU film, so that it be made to meet the requirement of pliability.
The filling oil is made of polyol-ester type oil agent, polyesteramide and base oil, and components by weight percent ratio is (0.1
~0.5): (2~5): (90~100).
The polyol-ester type oil agent is tricarboxymethyl propane oleate, the pungent decylate of trimethylolpropane oleic acid, season
In penta tetrol oleate or neopentyl glycol dioleate any one or at least two combination.
Preferably, the base oil is hydrorefined mineral oils, preferably base oil 60N and/or base oil 70N.
The amount of component C is based on amount of the mixture in inventive mixture, the usually 5 weight % of weight %~30, such as
Can be 5 weight %, 10 weight %, 20 weight %, 21 weight %, 22 weight %, 23 weight %, 24 weight %, 25 weight %,
26 weight %, 28 weight %, 30 weight %.
Component (D):
The present invention increases crosslinker component in preparing for TPU film in raw material, refer to and be dissolved at least one polyurethane
At least one of isocyanates.
In a preferred embodiment, the NCO content of the crosslinking agent is greater than 5%, for example, may be greater than 6%, 8%,
10% etc..
Here identified NCO content refers to the entirety being made of isocyanates and allophanate.It is by by sample
Product be dissolved in amine-containing dimethylformamide and by mixture in 80 DEG C keep 4 hours and measure.Unreacted excess amine acid
Back titration.The known this method of those skilled in the art, this will not be repeated here.
Isocyanates existing for instant component (D) is well known isocyanates, such as aliphatic, alicyclic and/or fragrant
Race's isocyanates, general there are two isocyanate groups.It can also be with such as MDI polymer with the isocyanates of higher functionality
Or modified isocyanate, such as comprising biuret group and there is the isocyanates of 2 to 10 isocyanate groups, preferably has 2
To 8, the isocyanuric acid ester of particularly preferred 3 isocyanate groups, and/or the pre-polymerization with 2 to 10 isocyanate groups
Object, the isocyanates that can be such as obtained after isocyanates and the compound that can be reacted with it (usually alcohol) reaction.
It is preferable to use MDI, a kind of diphenyl methane 2,2 '-, 2 of carbodiimide modified, 4 '-, and/or 4,4 '-two isocyanides
Acid esters (MDI), and/or it is a kind of be based on diphenyl methane 2,2 '-, 2,4 '-, and/or 4, the pre-polymerization of 4 '-diisocyanate (MDI)
Object, triisocyanate or polyisocyanates, the biuret or isocyanuric acid ester of the especially described isocyanates, especially NCO
Content is that viscosity is 2500 isocyanuric acid esters and/or diisocyanate and three for arriving 4000mPas at 20% to 25% and 23 DEG C
The mixture of isocyanates.
4, the 4 '-diisocyanate (MDI) of diphenyl methane of particularly preferred carbodiimide modified, particularly preferred isocyanates
Content is 4,4 '-two isocyanide of carbodiimide modified diphenyl methane of 25 weight % to 33 weight %, particularly 29.5 weight %
Acid esters (MDI), such as MM103 (BASFSE).
The amount of component D is based on amount of the mixture in inventive mixture, the usually 5 weight % of weight %~20, such as
It can be 5 weight %, 8 weight %, 10 weight %, 12 weight %, 14 weight %, 16 weight %, 18 weight %, 20 weight %.
If appropriate, mixture of the invention also may include additive in addition to component A, B, C and D.Those skilled in the art
The additive that suitable additive known to member is for example selected from auxiliary agent well known by persons skilled in the art and/or additive, such as
Lubricant, inhibitor, the stabilizer for hydrolysis, light, heat or discoloration, dyestuff, pigment, inorganic and/or organic filler and enhancing
Agent and its mixture.Other non-polyurethane homopolymers or copolymer can also be added.Such as it is polyformaldehyde, polyolefin, polyester, poly-
Carbonic ester, polyesterols, acrylonitrile-butadiene-styrene copolymer (ABS), Acrylate-styrene bipolymer-acrylonitrile copolymer
(ASA), styrene-acrylonitrile copolymer (SAN), polyamide or poly- (methyl) acrylate, or the mixture of the above substance.
If there is other additives in mixture, the total amount of all components is 100 weight %.
The present invention also provides a kind of methods for manufacturing the high fire-retardance softness TPU film, this method comprises:
Component (A), (B), (C) and (D) is sent to casting machine after three-level mixes, then through automatic feeding system according to the ratio
In, it is extruded into film, so that the high fire-retardance softness TPU film be prepared.
Wherein, each zone temperatures of the casting machine are provided that barrel temperature is 140-170 DEG C, strainer temperature 170-180
DEG C, 170-180 DEG C of elbow temperature connects 170-180 DEG C of temperature, 170-180 DEG C of die head temperature.
The present invention also provides the mechanograph comprising TPU film of the present invention, such as: roller, sole, motor vehicle coating, hose, cable
Plug, bellows, towing cable, scraping blade, cable cover(ing), gasket, driving belt or damping piece or foil or fiber.
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of high fire-retardance softness TPU film, it includes:
(A) thermoplastic polyurethane elastomer of 50 weight %, the shore hardness of the thermoplastic polyurethane elastomer are 55A；
(B) fire retardant of 30 weight %；The fire retardant by tricresyl phosphate (2- butoxyethyl group) ester, metal hydroxides,
Three (xylyl) phosphates, (methoxyl group second) ester of phthalic acid two composition, components by weight percent ratio are 20:25:3:30；Wherein
Metal hydroxides is aluminum trihydrate and magnesium hydroxide, and components by weight percent ratio is 2:5；
(C) the filling oil of 10 weight %；The filling oil is by tricarboxymethyl propane oleate, polyesteramide and base oil
60N composition, components by weight percent ratio are 0.2:3:95；
(D) crosslinking agent of 10 weight %；The crosslinking agent is carbodiimide modified hexichol of the isocyanate content 30%
Methylmethane 4,4 '-diisocyanate.
The preparation method of the high fire-retardance softness TPU film, comprising:
Component (A), (B), (C) and (D) is sent to casting machine after three-level mixes, then through automatic feeding system according to the ratio
In, each zone temperatures of casting machine be provided that barrel temperature be 140 DEG C, 175 DEG C of strainer temperature, 175 DEG C of elbow temperature,
170 DEG C of temperature, 170 DEG C of die head temperature of connection；It is extruded into film, so that the high fire-retardance softness TPU film be prepared.
Embodiment 2
A kind of high fire-retardance softness TPU film, characterized by comprising:
(A) thermoplastic polyurethane elastomer of 60 weight %；The shore hardness of the thermoplastic polyurethane elastomer is 60A；
(B) fire retardant of 30 weight %；The fire retardant by tricresyl phosphate (2- butoxyethyl group) ester, metal hydroxides,
Three (xylyl) phosphates, (methoxyl group second) ester of phthalic acid two composition, components by weight percent ratio are 10:30:5:20；Wherein
Metal hydroxides is aluminum trihydrate and magnesium hydroxide, and components by weight percent ratio is 2:9；
(C) the filling oil of 5 weight %；The filling oil is made of polyol-ester type oil agent, polyesteramide and base oil,
Its components by weight percent ratio is 0.5:3:100；
(D) crosslinking agent of 5 weight %；The crosslinking agent is carbodiimide modified diphenyl of the isocyanate content 26%
Methane 4,4 '-diisocyanate.
The preparation method of the high fire-retardance softness TPU film, comprising:
Component (A), (B), (C) and (D) is sent to casting machine after three-level mixes, then through automatic feeding system according to the ratio
In, each zone temperatures of casting machine be provided that barrel temperature be 150 DEG C, 175 DEG C of strainer temperature, 175 DEG C of elbow temperature,
175 DEG C of temperature, 175 DEG C of die head temperature of connection；It is extruded into film, so that the high fire-retardance softness TPU film be prepared.
Embodiment 3
A kind of high fire-retardance softness TPU film, characterized by comprising:
(A) thermoplastic polyurethane elastomer of 45 weight %；The shore hardness of the thermoplastic polyurethane elastomer is 75A；
(B) fire retardant of 30 weight %；The fire retardant by tricresyl phosphate (2- butoxyethyl group) ester, metal hydroxides,
Three (xylyl) phosphates, (methoxyl group second) ester of phthalic acid two composition, components by weight percent ratio are 30:22:2:28；Wherein
Metal hydroxides is aluminum trihydrate and magnesium hydroxide, and components by weight percent ratio is 3:8；
(C) the filling oil of 15 weight %；The filling oil is by polyol-ester type oil agent, polyesteramide and base oil group
At components by weight percent ratio is 0.3:3:95；
(D) crosslinking agent of 10 weight %；The crosslinking agent is carbodiimide modified hexichol of the isocyanate content 32%
Methylmethane 4,4 '-diisocyanate.
The preparation method of the high fire-retardance softness TPU film, comprising:
Component (A), (B), (C) and (D) is sent to casting machine after three-level mixes, then through automatic feeding system according to the ratio
In, each zone temperatures of casting machine be provided that barrel temperature be 160 DEG C, 175 DEG C of strainer temperature, 175 DEG C of elbow temperature,
180 DEG C of temperature, 180 DEG C of die head temperature of connection；It is extruded into film, so that the high fire-retardance softness TPU film be prepared.
Embodiment 4
A kind of high fire-retardance softness TPU film, characterized by comprising:
(A) thermoplastic polyurethane elastomer of 55 weight %；The shore hardness of the thermoplastic polyurethane elastomer is 68A；
(B) fire retardant of 28 weight %；The fire retardant by tricresyl phosphate (2- butoxyethyl group) ester, metal hydroxides,
Three (xylyl) phosphates, (methoxyl group second) ester of phthalic acid two composition, components by weight percent ratio are 25:22:2:50；Wherein
Metal hydroxides is aluminum trihydrate and magnesium hydroxide, and components by weight percent ratio is 3:7；
(C) the filling oil of 12 weight %；The filling oil is by polyol-ester type oil agent, polyesteramide and base oil group
At components by weight percent ratio is 0.3:2:100；
(D) crosslinking agent of 5 weight %；The crosslinking agent is carbodiimide modified hexichol of the isocyanate content 29.5%
Methylmethane 4,4 '-diisocyanate.
The preparation method of the high fire-retardance softness TPU film, comprising:
Component (A), (B), (C) and (D) is sent to casting machine after three-level mixes, then through automatic feeding system according to the ratio
In, each zone temperatures of casting machine be provided that barrel temperature be 170 DEG C, 175 DEG C of strainer temperature, 175 DEG C of elbow temperature,
180 DEG C of temperature, 180 DEG C of die head temperature of connection；It is extruded into film, so that the high fire-retardance softness TPU film be prepared.
Comparative example 1
Compared with Example 1, fire retardant tricresyl phosphate therein (2- butoxyethyl group) ester is replaced with into resorcinol (hexichol
Base phosphate), it is other same as Example 1.
Comparative example 2
Compared with Example 1, crosslinking agent therein is omitted, it is other same as Example 1.
Comparative example 3
Compared with Example 1, filling oil therein is omitted, it is other same as Example 1.
The TPU film being prepared in embodiment 1-4 and comparative example 1-3 is tested for the property, result such as 1 institute of table
Show.
Table 1
The TPU film being prepared in the present invention it can be seen from the result of table 1 has high flame retardant, and anti-flammability reaches
To 94V-0 grades of UL, softness reaches shore 30A or so, has excellent flexibility, thus is a kind of high fire-retardance softness TPU
Film.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (8)
1. a kind of high fire-retardance softness TPU film, it includes:
(A) thermoplastic polyurethane elastomer of 20 weight of weight %~70 %；
(B) fire retardant of 20 weight of weight %~30 %；The fire retardant is by tricresyl phosphate (2- butoxyethyl group) ester, metal hydrogen-oxygen
Compound, three (xylyl) phosphates, (methoxyl group second) ester of phthalic acid two composition, components by weight percent ratio is (10~50):
(20~30): (1~5): (20~50)；
(C) the filling oil of 5 weight of weight %~30 %；The filling oil is by polyol-ester type oil agent, polyesteramide and basis
Oil composition, components by weight percent ratio are (0.1~0.5): (2~5): (90~100)；
(D) crosslinking agent of 5 weight of weight %~20 %；
The total amount of component (A), (B), (C) and (D) is 100 weight %.
2. high fire-retardance softness TPU film as described in claim 1, which is characterized in that thermo-plastic polyurethane's elastomer has
The shore hardness of 45A to 85A, with the measurement of GB/T531-1999 method；Preferably with the shore hardness of 50A to 65A.
3. high fire-retardance softness TPU film as claimed in claim 1 or 2, which is characterized in that the metal hydroxides is by three water
Aluminium and magnesium hydroxide composition are closed, components by weight percent ratio is (1~5): (5~10).
4. the high fire-retardance softness TPU film as described in one of claim 1-3, which is characterized in that the polyol-ester type oil
Agent is tricarboxymethyl propane oleate, two oil of the pungent decylate of trimethylolpropane oleic acid, pentaerythritol oleate or neopentyl glycol
In acid esters any one or at least two combination；
Preferably, the base oil is hydrorefined mineral oils, preferably base oil 60N and/or base oil 70N.
5. the high fire-retardance softness TPU film as described in one of claim 1-4, which is characterized in that the crosslinking agent is dissolved in heat
The NCO content of at least one of plastic polyurethane elastomer isocyanates, the crosslinking agent is greater than 5%；
Preferably, the isocyanates is 4, the 4 '-diisocyanate (MDI) of diphenyl methane of carbodiimide modified, further
Preferred isocyanate content is carbodiimide modified diphenyl methane of the 25 weight % to 33 weight %, particularly 29.5 weight %
4,4 '-diisocyanate.
6. the preparation method of the high fire-retardance softness TPU film as described in one of claim 1-5 characterized by comprising by group
Divide (A), (B), (C) and (D) to be sent in casting machine after three-level mixes, then through automatic feeding system according to the ratio, is extruded into thin
Film, so that the high fire-retardance softness TPU film be prepared.
7. preparation method as claimed in claim 6, which is characterized in that each zone temperatures of casting machine are provided that barrel
Temperature is 140-170 DEG C, 170-180 DEG C of strainer temperature, and 170-180 DEG C of elbow temperature connects 170-180 DEG C of temperature, die head temperature
170-180 DEG C of degree.
8. the purposes of high fire-retardance softness TPU film in the molded part as described in one of claim 1-5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111607218A (en) * | 2020-06-04 | 2020-09-01 | 北京浦江兄弟科技有限公司 | Polyurethane flame-retardant film, preparation method and application thereof |
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