CN105058930B - A kind of phosphorus, nitrogen system environmental protection flame retardant polyester film and preparation method thereof - Google Patents
A kind of phosphorus, nitrogen system environmental protection flame retardant polyester film and preparation method thereof Download PDFInfo
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- CN105058930B CN105058930B CN201510511489.3A CN201510511489A CN105058930B CN 105058930 B CN105058930 B CN 105058930B CN 201510511489 A CN201510511489 A CN 201510511489A CN 105058930 B CN105058930 B CN 105058930B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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Abstract
The present invention provides a kind of phosphorus, nitrogen system environmental protection flame retardant polyester film and preparation method thereof, and the film includes sandwich layer and is compound in the upper epidermis and layer of sandwich layer upper and lower surface respectively；The upper epidermis is main to be made up of modified crystal type PET copolymer I, or the upper epidermis is mainly made up of modified crystal type PET copolymer I and crystal type PET homopolymers；The sandwich layer is mainly made up of crystal type PET homopolymers；The layer is main to be made up of modified crystal type PET copolymer II and crystal type PET homopolymers；The modified crystal type PET copolymer I is the crystal type PET copolymer being modified with phosphorus-nitrogen containing flame retardant, nano-inorganic substance and naphthalenedicarboxylic acid, and the modified crystal type PET copolymer II is the crystal type PET copolymer being modified with nano-inorganic substance.The fire retardant mylar heatproof that the present invention is provided can reach 140 DEG C, good flame retardation effect.
Description
Technical field
The invention belongs to macromolecule membrane technical field, more particularly to a kind of phosphorus, nitrogen system environmental protection flame retardant polyester film and its
Preparation method.
Background technology
At present, the application of polyester film is more and more extensive, with the progress and the popularization of environmental protection concept of society, fire-retardant film
Development be increasingly taken seriously.Polyester flame-retardant film has concurrently excellent fire-retardant in addition to being had the advantage that with general thin
Performance and electric property, in top grade decoration, decoration and the application in the field such as electronics, electrical industry, to polyester film anti-flammability
Can and durothermic requirement also more and more higher.
In current fire retardant mylar technology, typically fire retardant mylar, Yi Zhongshi are prepared using three kinds of modes
Fire retardant makes master batch with section by blending extrusion, then with polyester slice according to certain ratio mixture manufacturing, but it is this
The fire-retardant film that mode is manufactured, fire retardant is poor with the compatibility of section, and the film forming and performance impact to polyester film are larger；
A kind of is in polyester film surface polymeric coating layer of the coating with fire-retardant group, this mode complex process, high cost；In addition
One kind is to add reactive flame retardant in building-up process of cutting into slices to be grafted in macromolecular, and this fire-retardant mode fire retardant will not be analysed
Go out, work well, but the fire-retardant film temperature tolerance of traditional response type manufacture is poor, and strand is broken in the case of a high temperature
Bad, fire retardant is separated out, and flame retardant effect is destroyed.While the temperature tolerance of the existing fire retardant mylar in market is at 105~120 DEG C,
Temperature tolerance has much room for improvement.
The content of the invention
The present invention is to make up the deficiencies in the prior art, there is provided a kind of heatproof can reach 140 DEG C, good flame retardation effect it is fire-retardant
Polyester film and this kind of preparation method of film.
The present invention is to reach its purpose, and the technical scheme of use is as follows：
A kind of phosphorus, nitrogen system environmental protection flame retardant polyester film, including sandwich layer and the upper epidermis of sandwich layer upper and lower surface is compound in respectively
And layer；The upper epidermis is main to be made up of modified crystal type PET copolymer I, or the upper epidermis is main by modified crystallization
Type PET copolymer I and crystal type PET homopolymers are constituted；The sandwich layer is mainly made up of crystal type PET homopolymers；The following table
Layer is main to be made up of modified crystal type PET copolymer II and crystal type PET homopolymers；The modified crystal type PET copolymer I is
The crystal type PET copolymer being modified with phosphorus-nitrogen containing flame retardant, nano-inorganic substance and naphthalenedicarboxylic acid, the modified crystal type PET is total to
Polymers II is the crystal type PET copolymer being modified with nano-inorganic substance.
Further, in upper epidermis modified crystal type PET copolymer I and the mass percent of crystal type PET homopolymers
Respectively 60~100%, 0~50%；The matter of modified crystal type PET copolymer II and crystal type PET homopolymers in layer
Amount percentage is respectively 10~50%, 50~90%.
Preferably, the modified crystal type PET copolymer I is prepared according to the method for comprising the following steps：Phosphorus nitrogen system is fire-retardant
Agent, nano-inorganic substance, terephthalic acid (TPA), M-phthalic acid, 1,4- naphthalenedicarboxylic acids, 2,6- naphthalenedicarboxylic acids, ethylene glycol are according to quality
Compare 3.0-6.0：0.5-1.0：30-40：2-20：4-15：10-20：20-40 mixes, in 0.1~0.15MPa, temperature 255~270
DEG C condition carries out 100~150min of esterification；Then contracted under the conditions of 30~50Pa of vacuum, 275~290 DEG C of temperature
Poly- reaction, the reaction time is 5~8h.
Preferably, the modified crystal type PET copolymer II is prepared according to the method for comprising the following steps：Nano inorganic
Thing, terephthalic acid (TPA), M-phthalic acid, ethylene glycol are according to mass ratio 0.5-1.0：60-70：2-10：20-40 mixes, 0.1~
100~150min of esterification is carried out under the conditions of 0.15Mpa, 255~270 DEG C of temperature；It is then 30~50pa, anti-in vacuum
Answer temperature to carry out polycondensation reaction under conditions of 275~285 DEG C, the reaction time is 3-4h.
Preferably, crystal type PET homopolymers used can specifically use big bright PET chips, such as Yi Hua companies production
Polyester slice 5011 of FG600 Huo Sanfang lanes company production etc.；Or, the crystal type PET homopolymers can be also used according to including
Crystal type PET homopolymers obtained in the method for following steps：The terephthalic acid (TPA) of 60~66wt%, the isophthalic of 1.5~2.5wt%
The mixture of dioctyl phthalate, the ethylene glycol of 30~35wt%, under conditions of 0.05~0.15Mpa, 255~265 DEG C of reaction temperature
Esterification is carried out, the reaction time is 110~130min；Then vacuum be 30~50Pa, reaction temperature be 275~280
Polycondensation reaction is carried out under conditions of DEG C, the reaction time is 3-4h.
Preferably, the phosphorus-nitrogen containing flame retardant be selected from biphenyl acid phosphate ester diethylamine, N-N solutions of dimethyl phosphoryl bases urea,
At least one in phenyl-phosphonic acid hexichol azo ester；The nano-inorganic substance is nanometer sodium metasilicate, Nano-meter SiO_22, nano-calcium carbonate
With at least one in nano imvite.
Preferably, the particle diameter of the nano-inorganic substance is 100~700nm, is more highly preferred to, the grain of the nano-inorganic substance
Footpath is 300~500nm.
Further, the intrinsic viscosity of the crystal type PET homopolymers is 0.62~0.68dl/g, the modified crystal type
The intrinsic viscosity of PET copolymer I is 0.65~0.70dl/g, and the intrinsic viscosity of the modified crystal type PET copolymer II is
0.62~0.68dl/g.
Preferably, the density of the fire retardant mylar is 1.40~1.45g/m2, thickness is 23~50 μm；The upper table
The thickness of layer is 2.5~5 μm.
Second aspect present invention provides a kind of phosphorus for preparing as described above, the method for nitrogen system environmental protection flame retardant polyester film,
Comprise the following steps：
1) using modified crystal type PET copolymer I as upper epidermis raw material, or with crystal type PET copolymer I and the crystallization of being modified
The mixture of type PET homopolymers as upper epidermis raw material, through pre-crystallized, dried process after, at a temperature of 260~290 DEG C melt
Melt, extruded with single screw extrusion machine；
2) mixture using be modified crystal type PET copolymer II and crystal type PET homopolymers is used as layer raw material, through pre-
After crystallization, dried process, melted at a temperature of 260~285 DEG C, extruded with single screw extrusion machine；
3) using crystal type PET homopolymers as core layer raw material, through pre-crystallized, dried process after, in 260~285 DEG C of temperature
The lower melting of degree, is extruded with single screw extrusion machine；
4) the upper epidermis raw material of melting extrusion, core layer raw material and layer raw material are molded through compound die coextrusion head, are made
Top layer raw material, layer raw material are compound in the upper and lower surface of core layer raw material respectively, and slab is rapidly cooled at 20~35 DEG C, will
Slab is first through 60~90 DEG C of preheatings, then carries out longitudinal stretching at 90~100 DEG C, and primary diaphragm is then cooled down to obtain at 25~50 DEG C,
Draw ratio is 2.7~3.5, by longitudinal stretching after primary diaphragm preheated again at 100~125 DEG C after, then 100~140
DEG C carry out cross directional stretch and obtain basement membrane, draw ratio is 3.4~4 times, and the basement membrane obtained after stretching is disappeared through cooling, cutting, electrostatic
Except and wind to obtain fire retardant mylar.
The technical scheme that the present invention is provided has the advantages that：
The fire-retardant rank of fire retardant mylar prepared by the present invention can reach V0 grades, and temperature tolerance can reach 140 DEG C, highest
Up to 280 DEG C, definition, transmitance are good.
Fire retardant mylar prepared by the present invention is a kind of fire-retardant film that can be used for high-grade decoration and electron trade, thereon
Using specifically modified crystal type PET copolymer I, layer and sandwich layer use specific materials on top layer, and its is resistance to for obtained film
Warm nature is good, can reach more than 140 DEG C, and with permanent fire retardant characteristic.The upper and lower top layer component of the fire-retardant film contains spy respectively
Fixed modified crystal type copolymer I, II, preferably adds crystal type PET homopolymers on upper and lower top layer, and obtained film has
High transmission rate.
Specific embodiment
Technical scheme is described further with reference to embodiment：
Embodiment 1
A kind of fire retardant mylar, is prepared as follows：
1) using modified crystal type PET copolymer I that fusing point is 270 DEG C as upper epidermis raw material, through vacuum drum it is pre-crystallized,
After dried process, into single screw extrusion machine, melted at 290 DEG C, the upper epidermis raw material of the molten condition of extrusion is through pre-filtering
Device, measuring pump, main filter, into die head；
2) with the modified crystal type PET copolymer II that fusing point is 258 DEG C and the crystal type PET homopolymers that fusing point is 260 DEG C
According to the mixture of the content than mixing of 20wt%, 80wt% as layer raw material, mixture is pre-crystallized, dry through vacuum drum
After dry treatment, into single screw extrusion machine, the melting extrusion at 278 DEG C, the mixture of the molten condition of extrusion through prefilter,
Measuring pump, main filter, into die head；
3) using crystal type PET homopolymers that fusing point is 260 DEG C as core layer raw material, through fluid bed is pre-crystallized, dried process
Afterwards, into single screw extrusion machine, the melting extrusion at a temperature of 275 DEG C, the polymer of the molten condition of extrusion through prefilter,
Measuring pump, main filter, into die head；
4) the upper epidermis raw material of melting extrusion, core layer raw material and layer raw material are molded through compound die coextrusion head, are made
Top layer raw material, layer raw material are compound in the upper and lower surface of core layer raw material respectively, and it is slab to cool down aftershaping through 28 DEG C of chilling rollers,
To cool down after the slab that obtains first preheats through 82 DEG C, then longitudinal stretching will be carried out at 92 DEG C and obtain primary diaphragm, draw ratio will be
3.20, by longitudinal stretching after primary diaphragm preheat again at 120 DEG C after, then carry out cross directional stretch at 125 DEG C and obtain basement membrane,
Draw ratio is 3.70.The basement membrane that will be obtained obtains fire retardant mylar through cooling, cutting, static elimination and winding.
After testing, its flame retardant grade of prepared fire retardant mylar is V0 grades, and temperature tolerance reaches 140 DEG C.Fire-retardant film
Thickness is 50 μm, and the thickness of sandwich layer is 40 μm, and upper table thickness is 5 μm, and following table thickness is 5 μm.
Modified crystal type PET copolymer I used is prepared as follows in the present embodiment：The phosphorus of mass fraction 5%
Nitrogenated flame retardant, mass fraction be 1.0% particle diameter be the nano silicon of 200-700nm, the terephthalic acid (TPA) of 35wt%,
The M-phthalic acid of 2wt%, the 1,4- naphthalenedicarboxylic acids of 4.2wt%, the 2,6- naphthalenedicarboxylic acids of 20wt%, the ethylene glycol of 32.8wt%
Mixture, carry out esterification under the conditions of 0.1Mpa, 260 DEG C of reaction temperature, react 120min；It is in vacuum then
, to carry out polycondensation reaction under conditions of 285 DEG C, the reaction time is 5-8h for 50pa, reaction temperature.Obtained modified crystal type PET is total to
The intrinsic viscosity of polymers I is 0.65~0.70dl/g.Phosphorus-nitrogen containing flame retardant used is specially phenyl-phosphonic acid two in the present embodiment
Benzeneazo ester, it is also possible to biphenyl acid phosphate ester diethylamine or N-N solutions of dimethyl phosphoryl base ureas.Nano silicon used
Can be substituted with nanometer sodium metasilicate, nano-calcium carbonate or nano imvite.
Modified crystal type PET copolymer II used is prepared as follows in the present embodiment：According to mass ratio 1：64：
2：Particle diameter is the nano silicon of 400-700nm by 32.8, terephthalic acid (TPA), M-phthalic acid, ethylene glycol mix,
Esterification is carried out under conditions of 0.1Mpa, 260 DEG C of reaction temperature, 120min is reacted；It is then 50pa, reaction temperature in vacuum
Spend to carry out polycondensation reaction under conditions of 278 DEG C, the reaction time is 3-4h.The spy of obtained modified crystal type PET copolymer II
Property viscosity be 0.62~0.68dl/g.Nano silicon in preparation process can also use nanometer sodium metasilicate, nano-calcium carbonate
Or nano imvite is substituted.
Crystal type PET homopolymers used in the present embodiment is prepared as follows：The terephthalic acid (TPA) of 64wt%,
The mixture of the M-phthalic acid of 2wt%, the ethylene glycol of 34wt%, is esterified under the conditions of 0.1Mpa, 260 DEG C of reaction temperature
Reaction, reacts 120min；Then vacuum be 50pa, reaction temperature be 278 DEG C under conditions of carry out polycondensation reaction, during reaction
Between be 3-4h.The intrinsic viscosity of obtained crystal type PET homopolymers is 0.62~0.68dl/g.Crystallization used in the present embodiment
Polyester slice 5011 that the FG600 Huo Sanfang lanes company that type PET homopolymers can also be produced with Yi Hua companies produces etc..
Embodiment 2
A kind of fire retardant mylar, is prepared as follows：
1) with modified crystal type PET copolymer I that fusing point is 270 DEG C and crystal type PET homopolymers according to 90wt%,
The content of 10wt% than mixing as upper epidermis raw material, through vacuum drum is pre-crystallized, after dried process, into Single screw extrusion
Machine, the melting extrusion at 290 DEG C, the mixture of the molten condition of extrusion through prefilter, measuring pump, main filter, into mould
Head；
2) with the modified crystal type PET copolymer II that fusing point is 258 DEG C and the crystal type PET homopolymers that fusing point is 260 DEG C
According to the mixture of the content than mixing of 20wt%, 80wt% as layer raw material, mixture is pre-crystallized, dry through vacuum drum
After dry treatment, into single screw extrusion machine, the melting extrusion at 278 DEG C, the mixture of the molten condition of extrusion through prefilter,
Measuring pump, main filter, into die head；
3) using crystal type PET homopolymers that fusing point is 260 DEG C as core layer raw material, through fluid bed is pre-crystallized, dried process
Afterwards, into single screw extrusion machine, the melting extrusion at a temperature of 275 DEG C, the polymer thing of the molten condition of extrusion is through pre-filtering
Device, measuring pump, main filter, into die head；
4) the upper epidermis raw material of melting extrusion, core layer raw material and layer raw material are molded through compound die coextrusion head, are made
Top layer raw material, layer raw material are compound in the upper and lower surface of core layer raw material respectively, and it is slab to cool down aftershaping through 28 DEG C of chilling rollers,
To cool down after the slab that obtains first preheats through 82 DEG C, then longitudinal stretching will be carried out at 92 DEG C and obtain primary diaphragm, draw ratio will be
3.20, by longitudinal stretching after primary diaphragm preheat again at 120 DEG C after, then carry out cross directional stretch at 125 DEG C and obtain basement membrane,
Draw ratio is 3.70.The basement membrane that will be obtained obtains fire retardant mylar through cooling, cutting, static elimination and winding.
After testing, its flame retardant grade of prepared fire retardant mylar is V1 grades, and temperature tolerance reaches 140 DEG C.Fire-retardant film
Thickness is 50 μm, and the thickness of sandwich layer is 40 μm, and upper table thickness is 5 μm, is 5 μm after layer.
Modified crystal type PET copolymer I used, modified crystal type PET copolymer II, crystal type PET in the present embodiment
Homopolymers is prepared according to the method for embodiment 1, be will not be repeated here.
Embodiment 3
A kind of fire retardant mylar, is prepared as follows：
1) with modified crystal type PET copolymer I that fusing point is 270 DEG C and crystal type PET homopolymers according to 70wt%,
The content of 30wt% than mixing as upper epidermis raw material, through vacuum drum is pre-crystallized, after dried process, into Single screw extrusion
Machine, the melting extrusion at 290 DEG C, the mixture of the molten condition of extrusion through prefilter, measuring pump, main filter, into mould
Head；
2) with the modified crystal type PET copolymer II that fusing point is 258 DEG C and the crystal type PET homopolymers that fusing point is 260 DEG C
According to the mixture of the content than mixing of 20wt%, 80wt% as layer raw material, mixture is pre-crystallized, dry through vacuum drum
After dry treatment, into single screw extrusion machine, the melting extrusion at 278 DEG C, the mixture of the molten condition of extrusion through prefilter,
Measuring pump, main filter, into die head；
3) using crystal type PET homopolymers that fusing point is 260 DEG C as core layer raw material, through fluid bed is pre-crystallized, dried process
Afterwards, into single screw extrusion machine, the melting extrusion at a temperature of 275 DEG C, the polymer thing of the molten condition of extrusion is through pre-filtering
Device, measuring pump, main filter, into die head；
4) the upper epidermis raw material of melting extrusion, core layer raw material and layer raw material are molded through compound die coextrusion head, are made
Top layer raw material, layer raw material are compound in the upper and lower surface of core layer raw material respectively, and it is slab to cool down aftershaping through 28 DEG C of chilling rollers,
To cool down after the slab that obtains first preheats through 82 DEG C, then longitudinal stretching will be carried out at 92 DEG C and obtain primary diaphragm, draw ratio will be
3.20, by longitudinal stretching after primary diaphragm preheat again at 120 DEG C after, then carry out cross directional stretch at 125 DEG C and obtain basement membrane,
Draw ratio is 3.70.The basement membrane that will be obtained obtains fire retardant mylar through cooling, cutting, static elimination and winding.
After testing, its flame retardant grade of prepared fire retardant mylar is V1 grades, and temperature tolerance reaches 140 DEG C.Fire-retardant film
Thickness is 50 μm, and the thickness of sandwich layer is 40 μm, and upper table thickness is 5 μm, is 5 μm after layer.
Modified crystal type PET copolymer I used, modified crystal type PET copolymer II, crystal type PET in the present embodiment
Homopolymers is prepared according to the method for embodiment 1, be will not be repeated here.
The technical scheme is that improved in prior art basis and obtained, not specified part in text is this
Common knowledge or conventional technical means that art personnel are known, no longer repeat this one by one.
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not done to the present invention, therefore
All contents without departing from technical solution of the present invention, any simply repair according to technical spirit of the invention to made for any of the above embodiments
Change, equivalent variations and modification, still fall within the range of technical solution of the present invention.
Claims (8)
1. a kind of phosphorus, nitrogen system environmental protection flame retardant polyester film, it is characterised in that be compound in following table on sandwich layer including sandwich layer and respectively
The upper epidermis and layer in face；
The upper epidermis is main to be made up of modified crystal type PET copolymer I, or the upper epidermis is main by modified crystal type PET
Copolymer I and crystal type PET homopolymers are constituted；Method systems of the modified crystal type PET copolymer I according to comprising the following steps
It is standby：Phosphorus-nitrogen containing flame retardant, nano-inorganic substance, terephthalic acid (TPA), M-phthalic acid, 1,4- naphthalenedicarboxylic acids, 2,6- naphthalenedicarboxylic acids, second
Glycol is according to mass ratio 3.0-6.0：0.5-1.0：30-40：2-20：4-15：10-20：20-40 mix, 0.1~0.15MPa,
255~270 DEG C of conditions of temperature carry out esterification, 100~150min of esterification；Then in 30~50Pa of vacuum, temperature
Polycondensation reaction is carried out under the conditions of 275~290 DEG C, the reaction time is 5~8h；
The sandwich layer is made up of crystal type PET homopolymers；The crystal type PET homopolymers is big bright PET chips；Or it is described
Crystal type PET homopolymers is prepared according to the method for comprising the following steps：The terephthalic acid (TPA) of 60~66wt%, 1.5~2.5wt%
M-phthalic acid, the mixture of the ethylene glycol of 30~35wt%, in 0.05~0.15Mpa, 255~265 DEG C of reaction temperature
Under the conditions of carry out esterification, the reaction time is 110~130min；Then vacuum be 30~50Pa, reaction temperature be 275
Polycondensation reaction is carried out under conditions of~280 DEG C, the reaction time is 3-4h；
The layer is main to be made up of modified crystal type PET copolymer II and crystal type PET homopolymers；
The modified crystal type PET copolymer II is the crystal type PET copolymer being modified with nano-inorganic substance.
2. phosphorus according to claim 1, nitrogen system environmental protection flame retardant polyester film, it is characterised in that the modified knot in upper epidermis
The mass percent of crystal formation PET copolymer I and crystal type PET homopolymers is respectively 60~100%, 0~50%；In layer
The mass percent of modified crystal type PET copolymer II and crystal type PET homopolymers is respectively 10~50%, 50~90%.
3. phosphorus according to claim 1, nitrogen system environmental protection flame retardant polyester film, it is characterised in that the modified crystal type PET
Copolymer II is prepared according to the method for comprising the following steps：Nano-inorganic substance, terephthalic acid (TPA), M-phthalic acid, ethylene glycol are pressed
According to mass ratio 0.5-1.0：60-70：2-10：20-40 mixes, and ester is carried out in 0.1~0.15MPa, 255~270 DEG C of conditions of temperature
Change reaction, 100~150min of esterification；Then polycondensation is carried out under the conditions of 30~50Pa of vacuum, 275~285 DEG C of temperature
Reaction, the reaction time is 3-4h.
4. phosphorus according to any one of claims 1 to 3, nitrogen system environmental protection flame retardant polyester film, it is characterised in that the phosphorus nitrogen
Flame retardant be selected from biphenyl acid phosphate ester diethylamine, N-N solutions of dimethyl phosphoryl bases urea, phenyl-phosphonic acid hexichol azo ester in extremely
Few one kind；The nano-inorganic substance is nanometer sodium metasilicate, Nano-meter SiO_22, in nano-calcium carbonate and nano imvite at least one
Kind.
5. phosphorus according to any one of claims 1 to 3, nitrogen system environmental protection flame retardant polyester film, it is characterised in that the nanometer
The particle diameter of inorganic matter is 100~700nm.
6. phosphorus according to any one of claims 1 to 3, nitrogen system environmental protection flame retardant polyester film, it is characterised in that the crystallization
The intrinsic viscosity of type PET homopolymers is 0.62~0.68dl/g, and the intrinsic viscosity of the modified crystal type PET copolymer I is
The intrinsic viscosity of 0.65~0.70dl/g, the modified crystal type PET copolymer II is 0.62~0.68dl/g.
7. phosphorus according to any one of claims 1 to 3, nitrogen system environmental protection flame retardant polyester film, it is characterised in that described fire-retardant
The density of polyester film is 1.40~1.45g/m2, thickness is 23~50 μm；The thickness of the upper epidermis is 2.5~5 μm.
8. a kind of phosphorus prepared as described in any one of claim 1~7, the method for nitrogen system environmental protection flame retardant polyester film, its feature
It is to comprise the following steps：
1) using modified crystal type PET copolymer I as upper epidermis raw material, or with crystal type PET copolymer I and the crystal type of being modified
The mixture of PET homopolymers as upper epidermis raw material, through pre-crystallized, dried process after, at a temperature of 260~290 DEG C melt
Extrusion；
2) using the mixture of be modified crystal type PET copolymer II and crystal type PET homopolymers as layer raw material, through pre- knot
After brilliant, dried process, the melting extrusion at a temperature of 260~285 DEG C；
3) using crystal type PET homopolymers as core layer raw material, through pre-crystallized, dried process after, at a temperature of 260~285 DEG C
Melting extrusion；
4) the upper epidermis raw material of melting extrusion, core layer raw material and layer raw material are molded through compound die coextrusion head, make upper epidermis
Raw material, layer raw material are compound in the upper and lower surface of core layer raw material respectively, cool down to obtain slab, and slab is carried out into longitudinal stretching, horizontal stroke
To basement membrane is obtained after stretching, basement membrane is through cooling, cutting, static elimination and winds to obtain fire retardant mylar.
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| CN112297557A (en) * | 2020-10-29 | 2021-02-02 | 天津万华股份有限公司 | Flame-retardant polyester film and preparation method thereof |
| CN115958866A (en) * | 2023-03-16 | 2023-04-14 | 江苏康辉新材料科技有限公司 | Flame-retardant PET film suitable for laser coding and preparation method and application thereof |
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| CN103627150A (en) * | 2013-11-21 | 2014-03-12 | 浙江南洋科技股份有限公司 | Preparation method of polyether material, polyether film and preparation method thereof |
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Denomination of invention: A phosphorus and nitrogen based environmentally friendly flame retardant polyester film and its preparation method Effective date of registration: 20230714 Granted publication date: 20170531 Pledgee: Guangzhou Xinxi Technology Co.,Ltd. Pledgor: SHUYE ENVIRONMENTAL TECHNOLOGY Co.,Ltd. Registration number: Y2023980048456 |
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