CN103467932B - PET fire-retardant film master batch and preparation method thereof, PET fire-retardant film goods - Google Patents

PET fire-retardant film master batch and preparation method thereof, PET fire-retardant film goods Download PDF

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CN103467932B
CN103467932B CN201310361459.XA CN201310361459A CN103467932B CN 103467932 B CN103467932 B CN 103467932B CN 201310361459 A CN201310361459 A CN 201310361459A CN 103467932 B CN103467932 B CN 103467932B
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retardant film
master batch
pet
antioxidant
fire
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CN103467932A (en
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杨柏容
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Shenzhen City Huazhifei Technology Co ltd
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Abstract

The invention discloses a kind of PET fire-retardant film master batch, its raw material includes TDE, antimony oxide, bisphenol-A pair, 1010 antioxidant, 168 antioxidant, diffusing oil, Firebrake ZB and PBT;Also disclose preparation method and the PET fire-retardant film goods of this PET fire-retardant film master batch.The formula design uniqueness of the present invention, rationally, add antimony oxide and play halogen antimony cooperative flame retardant with TDE, PBT solves the compatibility and toughness as carrier, bisphenol-A is double plasticising and cooperative flame retardant, antioxidant plays and reduces carrier and matrix in the oxidation of high temperature process and degraded, diffusing oil plays raising dispersibility and the compatibility, Firebrake ZB cooperative flame retardant improves into carbon and particularly presses down cigarette anti-drip melt effect, use the PET fire-retardant film goods that this PET fire-retardant film master batch prepares, good toughness, tensile strength is high, good flame retardation effect (up to V0 level), low cost, preparation technology is simple, it is easily achieved, it is beneficial to wide popularization and application.

Description

PET fire-retardant film master batch and preparation method thereof, PET fire-retardant film goods
Technical field
The invention belongs to fire-retardant film technical field, be specifically related to a kind of PET fire-retardant film master batch and preparation method thereof, PET fire-retardant film goods.
Background technology
PET fire-retardant film is at home or even the world is all a new technique and technical barrier.The most truly hinder Combustion V0 level and also every mechanical property is the most excellent, only Mitsubishi.Its technology is in area of security monopoly position, its product Price is high.Domestic also in research ester exchange mode, phosphate ester is introduced in PET molecular skeleton, but practical operation is got up the most not Convenient, of a high price, and it is difficult to the V0 level of real meaning, so present stage is difficult to extend.
People attempt with the convenient and practical additive flame retardant of tradition, but there is the compatibility, dispersibility, interface characteristics and hold Property difference and the toxicity problem to operative employee for a long time, particularly poor toughness is without Practical significance.In order to solve these problems, people use Fire-retardant master granule, has people to make carrier with PE, PP, EVA, but the problem that all there are poor compatibility and poor toughness.To this end, people use PET makees carrier, but the PET fire-retardant film made, and poor toughness is without Practical significance.Then people find various toughener, some Toughener adds, and makes its product become fragile on the contrary, and some toughener adds, and makes moderate progress, but effect is little, cost Too high, there is no practical value.Additionally when using fire-retardant master granule, its adding proportion is difficult to hold, and adding proportion is little, it is desirable to master batch The auxiliary agent content such as fire retardant are many, and not only doing master batch, to add man-hour highly difficult, and when film processed, dispersibility incompatibility Difference, film product is fire-retardant uneven, and adding proportion is big, and master batch is many containing carrier, the oxidative degradation when processing master batch of a lot of carriers, Make the film done more crisp, poor practicability.
Summary of the invention
For above-mentioned deficiency, one of the object of the invention is, it is provided that a kind of environmental protection, nontoxic, the compatibility and good dispersion, The PET fire-retardant film master batch of the PET fire-retardant film of good toughness and good flame retardation effect can be produced.
The two of the object of the invention are, it is provided that a kind of preparation method preparing above-mentioned PET fire-retardant film master batch, this preparation side The technique of method is simple, it is easy to accomplish, production efficiency is high, is effectively increased production efficiency.
The three of the object of the invention are, it is provided that a kind of PET fire-retardant film system using above-mentioned PET fire-retardant film master batch to make Product, the good toughness of these PET fire-retardant film goods, tensile strength are high, good flame retardation effect
For achieving the above object, technical scheme provided by the present invention is: a kind of PET fire-retardant film master batch, its raw material Including following components in percentage by weight:
TDE 27~35,
Antimony oxide 10~15,
Bisphenol-A double 0.1~0.5%,
1010 antioxidant 0.5~2%,
168 antioxidant 0.1~0.5%,
Diffusing oil 0.2~0.6%,
Firebrake ZB 0.5~2%,
PBT 48~58%.
A kind of preparation method of above-mentioned PET fire-retardant film master batch, it comprises the following steps:
(1) preparing material, raw material includes following components in percentage by weight:
TDE 27~35,
Antimony oxide 10~15,
Bisphenol-A double 0.1~0.5%,
1010 antioxidant 0.5~2%,
168 antioxidant 0.1~0.5%,
Diffusing oil 0.2~0.6%,
Firebrake ZB 0.5~2%,
PBT 48~58%;
(2) by TDE, antimony oxide, bisphenol-A pair, 1010 antioxidant, 168 antioxidant, diffusing oil and boron Acid zinc is put into and is heated in batch mixer;
(3) starting batch mixer of heating to carry out stirring evenly drying action, until drying, and stirring;
(4) pouring, through the PBT dried in advance, batch mixer of heating into, until stirring, then making plastic cement with extruder Granule, prepares PET fire-retardant film master batch goods.
As a modification of the present invention, in described step (2) first with a little coupling agent to antimony oxide and Firebrake ZB Do surface to process, to increase the intermiscibility between antimony oxide, Firebrake ZB and carrier and matrix.
As a modification of the present invention, the temperature of the batch mixer of heating of described step (3) is set as 90~110 degree, stirs Even drying time is 10~30 minutes.
As a modification of the present invention, the PBT of described step (4) first passes through 120~150 degree, 100~140 minutes in advance Drying and processing.
As a modification of the present invention, the extruder of described step (4) is double screw extruder.
A kind of PET fire-retardant film goods made using above-mentioned PET fire-retardant film master batch, its raw material includes following heavy The component of amount percentage ratio:
PET fire-retardant film master batch 27~35,
PET 65~73.
As a modification of the present invention, the raw material of described PET fire-retardant film master batch includes following percentage by weight Component:
TDE 27~35,
Antimony oxide 10~15,
Bisphenol-A double 0.1~0.5%,
1010 antioxidant 0.5~2%,
168 antioxidant 0.1~0.5%,
Diffusing oil 0.2~0.6%,
Firebrake ZB 0.5~2%,
PBT 48~58%.
Replace PP, PE, EVA, PET using high intensity PBT as carrier, solve toughness and the compatibility, and keep PET film Dominance and characteristic.Using PBT as carrier, both having solved the compatibility of master batch and PET, the toughness of PET fire-retardant film, also keeps again The dominance of PET film and characteristic.
The invention have the benefit that the present invention provides the formula of PET fire-retardant film master batch to design unique, reasonable, with PBT For carrier, solve toughness and the compatibility, and keep dominance and the characteristic of PET film, add antimony oxide and decabrominated dipheny second Alkane plays the purpose of halogen antimony cooperative flame retardant, and bisphenol-A double (diphenyl phosphoester) has the purpose of plasticising and cooperative flame retardant, 1010 antioxygens Agent and 168 antioxidant play and reduce carrier and matrix aoxidizing and the purpose of degraded in high temperature process, and diffusing oil plays raising point Dissipating property and compatibility purpose, Firebrake ZB cooperative flame retardant improves into carbon and particularly presses down cigarette anti-drip melt effect, uses this PET fire-retardant film The PET fire-retardant film goods that master batch prepares, good toughness, tensile strength are high, good flame retardation effect (up to V0 level);The present invention provides The technique of preparation method is simple, be easily achieved, low cost, and preparation efficiency is high, and the PET fire-retardant film master batch quality prepared is good, profit In wide popularization and application.
Below in conjunction with embodiment, the invention will be further described.
Detailed description of the invention
Embodiment 1: a kind of PET fire-retardant film master batch that the present embodiment provides, its raw material includes following percentage by weight Component: TDE 27, antimony oxide 12.7, bisphenol-A double 0.5%, 1010 antioxidant 0.5%, 168 antioxidant 0.2%, diffusing oil 0.6%, Firebrake ZB 0.5%, PBT58%.
The preparation method of a kind of above-mentioned PET fire-retardant film master batch, it comprises the following steps.
(1) preparing material, raw material includes following components in percentage by weight: TDE 27, antimony oxide 12.7, bisphenol-A double 0.5%, 1010 antioxidant 0.5%, 168 antioxidant 0.2%, diffusing oil 0.6%, Firebrake ZB 0.5%, PBT58%.
(2) by TDE, antimony oxide, bisphenol-A pair, 1010 antioxidant, 168 antioxidant, diffusing oil and boron Acid zinc is put into and is heated in batch mixer;Antimony oxide and Firebrake ZB are first done surface with a little coupling agent by described step (2) Reason, to increase the intermiscibility between antimony oxide, Firebrake ZB and carrier and matrix.
(3) starting batch mixer of heating to carry out stirring evenly drying action, until drying, and stirring;Adding of described step (3) The temperature of temperature batch mixer is set as 90~110 degree, and stirring evenly drying time is 10~30 minutes.
(4) pouring, through the PBT dried in advance, batch mixer of heating into, until stirring, then making plastic cement with extruder Granule, prepares PET fire-retardant film master batch goods.The PBT of described step (4) first passes through 120~150 degree, 100~140 minutes in advance Drying and processing.
The extruder of described step (4) is preferably double screw extruder, and extrusion effect is more preferable.
A kind of PET fire-retardant film goods made using above-mentioned PET fire-retardant film master batch, its raw material includes following heavy The component of amount percentage ratio: PET fire-retardant film master batch 29, PET72.
The raw material of described PET fire-retardant film master batch includes following components in percentage by weight: TDE 27, Antimony oxide 12.7, bisphenol-A double 0.5%, 1010 antioxidant 0.5%, 168 antioxidant 0.2%, diffusing oil 0.6%, Firebrake ZB 0.5%, PBT58%.
Embodiment 2: a kind of PET fire-retardant film master batch that the present embodiment provides and preparation method thereof, PET fire-retardant film system Product, it is substantially the same manner as Example 1, and difference is that the component of PET fire-retardant film master batch and percentage by weight are different, and The component of PET fire-retardant film goods and percentage by weight are different.
Wherein component and the percentage by weight of PET fire-retardant film master batch is: TDE 35, antimony oxide 10, bisphenol-A double 0.1%, 1010 antioxidant 2%, 168 antioxidant 0.5%, diffusing oil 0.3%, Firebrake ZB 1.1%, PBT51%.
A kind of PET fire-retardant film goods made using above-mentioned PET fire-retardant film master batch, its raw material includes following heavy The component of amount percentage ratio is: PET fire-retardant film master batch 27, PET73.
Embodiment 3: a kind of PET fire-retardant film master batch that the present embodiment provides and preparation method thereof, PET fire-retardant film system Product, it is substantially the same manner as Example 1, and difference is that the component of PET fire-retardant film master batch and percentage by weight are different, and The component of PET fire-retardant film goods and percentage by weight are different.
Wherein component and the percentage by weight of PET fire-retardant film master batch is: TDE 33.7, three oxidations two Antimony 15, bisphenol-A double 0.2%, 1010 antioxidant 0.8%, 168 antioxidant 0.1%, diffusing oil 0.2%, Firebrake ZB 2%, PBT48%.
A kind of PET fire-retardant film goods made using above-mentioned PET fire-retardant film master batch, its raw material includes following heavy The component of amount percentage ratio is: PET fire-retardant film master batch 35, PET65.
Embodiment 4: a kind of PET fire-retardant film master batch that the present embodiment provides and preparation method thereof, PET fire-retardant film system Product, it is substantially the same manner as Example 1, and difference is that the component of PET fire-retardant film master batch and percentage by weight are different, and The component of PET fire-retardant film goods and percentage by weight are different.
Wherein component and the percentage by weight of PET fire-retardant film master batch is: TDE 31, antimony oxide 13, bisphenol-A double 1%, 1010 antioxidant 0.3%, 168 antioxidant 0.3%, diffusing oil 0.4%, Firebrake ZB 1%, PBT53%.
A kind of PET fire-retardant film goods made using above-mentioned PET fire-retardant film master batch, its raw material includes following heavy The component of amount percentage ratio is: PET fire-retardant film master batch 32, PET68.
Above-described embodiment is only the preferable embodiment of the present invention, and the present invention can not enumerate out whole embodiment party Formula, the technical scheme of one of all employing above-described embodiments, or the equivalent variations done according to above-described embodiment, all protect in the present invention In the range of protecting.
It is unique, reasonable that the present invention provides the formula of PET fire-retardant film master batch to design, and adds antimony oxide and decabrominated dipheny Ethane plays the purpose of halogen antimony cooperative flame retardant, and PBT solves the compatibility and toughness as carrier, and bisphenol-A is double plasticising and collaborative resistance The purpose of combustion, 1010 antioxidant and 168 antioxidant play the purpose reducing the oxidation in high temperature process of carrier and matrix with degraded, Diffusing oil plays raising dispersibility and compatibility purpose, and Firebrake ZB cooperative flame retardant improves into carbon and particularly presses down cigarette anti-drip melt effect.
Using the PET fire-retardant film goods that this PET fire-retardant film master batch prepares, good toughness, tensile strength are high, flame retardant effect Good (up to V0 level).Replace PP, PE, EVA, PET using high intensity PBT as carrier, solve toughness and the compatibility, and keep PET The dominance of thin film and characteristic.Using PBT as carrier, the compatibility of master batch and PET, the again toughness of PET fire-retardant film were both solved, also Keep dominance and the characteristic of PET film.
The technique of the preparation method that the present invention provides is simple, be easily achieved, low cost, and preparation efficiency is high, the PET resistance prepared Combustion film master batch quality is good.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula changes and revises.Therefore, the invention is not limited in detailed description of the invention disclosed and described above, to the present invention's Some modifications and changes should also be as falling in the scope of the claims of the present invention.Although additionally, this specification using Some specific terms, but these terms are merely for convenience of description, the present invention does not constitute any restriction.Such as the present invention Described in above-described embodiment, use same or similarity method and component and other master batch of obtaining and preparation method thereof, goods, All in scope.

Claims (3)

1. a PET fire-retardant film master batch, it is characterised in that its raw material includes following components in percentage by weight:
TDE 27~35,
Antimony oxide 10~15,
Double (diphenyl phosphoester) 0.1~0.5% of bisphenol-A,
1010 antioxidant 0.5~2%,
168 antioxidant 0.1~0.5%,
Diffusing oil 0.2~0.6%,
Firebrake ZB 0.5~2%,
PBT 48~58%.
2. the preparation method of PET fire-retardant film master batch described in a claim 1, it is characterised in that it comprises the following steps:
(1) preparing material, raw material includes following components in percentage by weight:
TDE 27~35,
Antimony oxide 10~15,
Double (diphenyl phosphoester) 0.1~0.5% of bisphenol-A,
1010 antioxidant 0.5~2%,
168 antioxidant 0.1~0.5%,
Diffusing oil 0.2~0.6%,
Firebrake ZB 0.5~2%,
PBT 48~58%;
(2) by TDE, antimony oxide, bisphenol-A double (diphenyl phosphoester), 1010 antioxidant, 168 antioxidant, Diffusing oil and Firebrake ZB are put into and are heated in batch mixer;
(3) starting batch mixer of heating to carry out stirring evenly drying action, until drying, and stirring;
(4) pouring, through the PBT dried in advance, batch mixer of heating into, until stirring, then making plastic grains with extruder, Prepare PET fire-retardant film master batch goods;
Antimony oxide and Firebrake ZB are first done surface with a little coupling agent by described step (2) process, to increase by three oxidations two The compatibility between antimony, Firebrake ZB and carrier and matrix;
The temperature of the batch mixer of heating of described step (3) is set as 90~110 degree, and stirring evenly drying time is 10~30 minutes;
The PBT of described step (4) first passes through 120~150 degree, the drying and processing of 100~140 minutes in advance;
The extruder of described step (4) is double screw extruder.
3. the PET fire-retardant film goods using PET fire-retardant film master batch described in claim 1 to make, it is characterised in that its Raw material includes following components in percentage by weight:
PET fire-retardant film master batch 27~35,
PET 65~73;
The raw material of described PET fire-retardant film master batch includes following components in percentage by weight:
TDE 27~35,
Antimony oxide 10~15,
Double (diphenyl phosphoester) 0.1~0.5% of bisphenol-A,
1010 antioxidant 0.5~2%,
168 antioxidant 0.1~0.5%,
Diffusing oil 0.2~0.6%,
Firebrake ZB 0.5~2%,
PBT 48~58%.
CN201310361459.XA 2013-08-20 2013-08-20 PET fire-retardant film master batch and preparation method thereof, PET fire-retardant film goods Expired - Fee Related CN103467932B (en)

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CN106280322A (en) * 2016-09-26 2017-01-04 高团结 PET fire-retardant film master batch and preparation method thereof, PET fire-retardant film goods

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* Cited by examiner, † Cited by third party
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DE10007672A1 (en) * 2000-02-19 2001-08-23 Mitsubishi Polyester Film Gmbh White-opaque, flame-retardant, UV-stabilized film with low transparency made of a crystallizable thermoplastic
JP4385228B2 (en) * 2005-03-28 2009-12-16 Dic株式会社 Flame retardant masterbatch and molded product using the same
CN101003634A (en) * 2007-01-16 2007-07-25 北京理工大学 Method for manufacturing agglomerate of decabromodiphenyl ethane and antimony trioxide
CN101456962A (en) * 2008-12-29 2009-06-17 黄华昌 High-content red phosphorus flame-retardant master batch
CN102321347A (en) * 2010-10-15 2012-01-18 深圳市科聚新材料有限公司 High creepage trace index polyester composite and preparation method thereof

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Address before: No. 8, Liao Jia group, Nanhua village, Changle Township, Changle Township, Shaoyang County, Shaoyang, Hunan

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