CN110105723B - Flame-retardant composite film - Google Patents

Flame-retardant composite film Download PDF

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Publication number
CN110105723B
CN110105723B CN201910316849.2A CN201910316849A CN110105723B CN 110105723 B CN110105723 B CN 110105723B CN 201910316849 A CN201910316849 A CN 201910316849A CN 110105723 B CN110105723 B CN 110105723B
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parts
flame retardant
layer
composite film
modified
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CN201910316849.2A
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CN110105723A (en
Inventor
马守宋
杨慧聪
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Jiaxing Kebang Medical Packaging Co ltd
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Jiaxing Kebang Medical Packaging Co ltd
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Classifications

    • 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
    • B32B27/08—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 of synthetic resin
    • 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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3

Abstract

The invention discloses a flame-retardant composite film which is characterized by comprising a modified polyester layer, a composite flame retardant layer and a modified polyethylene layer which are sequentially arranged from outside to inside; the composite flame retardant layer comprises the following components in parts by weight: 35-50 parts of carbamate, 20-30 parts of polyethylene terephthalate, 15-25 parts of a silicon-phosphorus composite flame retardant, 0.5-1.5 parts of an antioxidant and 0.4-1 part of a dispersant; antioxidant and anti-scratching agent are added into the modified polyester layer and the modified polyethylene layer. The composite film disclosed by the invention has good flame retardant performance, and the preparation process of the flame retardant is simple, the production cost is low, and the composite film is suitable for large-scale production.

Description

Flame-retardant composite film
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant composite film.
Background
The composite film is a high polymer material compounded by two or more layers of films made of different materials, and can combine the advantages of various materials together to endow good barrier property, air permeability, strength performance and the like. At present, composite film materials are widely used in the field of packaging, including vegetable packaging, medical instrument packaging and the like, and are in the aspects of life of people; therefore, the composite film has good flame retardant property. Has very important significance for eliminating fire hazard, delaying fire spread, reducing life and property loss and the like.
Disclosure of Invention
The invention aims to provide a multi-layer composite flame-retardant film with good flame-retardant performance.
The technical purpose of the invention is realized by the following technical scheme: a flame-retardant composite film comprises a modified polyester layer, a composite flame retardant layer and a modified polyethylene layer which are sequentially arranged from outside to inside; the composite flame retardant layer comprises the following components in parts by weight: 35-50 parts of carbamate, 20-30 parts of polyethylene terephthalate, 15-25 parts of silicon-phosphorus composite flame retardant, 0.5-1.5 parts of antioxidant and 0.4-1 part of dispersant.
Further, the preparation steps of the silicon-phosphorus composite flame retardant are as follows: adding 5 parts of dimethyl phosphine, 5-5.5 parts of vinyl silane coupling agent and 20-25 parts of acetone solvent into a reaction container under the atmosphere of inert gas, and fully stirring; adding 0.1-0.2 part of azo compound catalyst, reacting for 1-1.5 hours at 70-120 ℃, and removing the solvent by rotary evaporation to obtain the silicon-phosphorus composite flame retardant.
Further, the modified polyester layer is prepared from the following components: 60-130 parts of polyester, 5-10 parts of phosphite ester and 1-1.5 parts of silicon dioxide.
Further, the modified polyethylene layer is prepared from the following components: 50-150 parts of polyethylene, 5-10 parts of phosphite ester and 1-1.5 parts of silicon dioxide.
Further, the polyester is a polyester composed of at least one of polypropylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and a copolymer thereof.
Further, the thickness of the modified polyester layer is 40-70 microns, and the thickness of the modified polyethylene layer is 20-80 microns.
Further, the thickness of the composite flame retardant layer is 30-50 microns and is not more than one half of the sum of the thicknesses of the modified polyester layer and the modified polyethylene layer.
Further, the mass ratio of the microcrystalline wax and the montan wax of the dispersing agent is 2-3.5: 1.
The antioxidant is phosphite antioxidant, one or more of 168 and Revonox 608 is adopted, and Revonox 608 is preferred.
Compared with the prior art, the invention has the following advantages and effects:
1. the flame retardant selected by the invention is a silicon-phosphorus composite flame retardant, when the flame retardant burns, phosphorus in the flame retardant can generate white combustion residues and carbide to form a composite inorganic layer, so that volatile matters generated by burning can be prevented from escaping outwards, oxygen is prevented from contacting with a substrate, and a melt is prevented from dripping, thereby achieving the purpose of flame retardance; silicon increases the thermal stability of these inorganic layers, thereby exerting a phosphorus/silicon synergistic flame retardant effect. In the flame retardant, two elements of phosphorus and silicon are positioned in the same molecule, so that the flame-retardant synergistic effect is better than that of an additive flame-retardant synergistic effect, and the performance is more durable.
2. The carbamate is a surfactant, has good affinity with both the modified polyester and the modified polyethylene, increases the bonding performance of the composite flame retardant layer with the modified polyester layer and the modified polyethylene layer, and has high transparency and wider application range of products.
3. Antioxidant phosphite ester and anti-scratching agent silicon dioxide are added into the modified polyester layer and the modified polyethylene layer, so that the material has better service life, strength performance and the like.
Detailed Description
Example 1
The utility model provides a fire-retardant complex film, includes by outer modified polyester layer, compound flame retardant layer and the modified polyethylene layer that sets gradually in to: the thickness of the modified polyester layer is 50 micrometers, and the modified polyester layer comprises, by weight, 120 parts of dipropyl polyterephthalate, 10 parts of phosphite ester and 1.5 parts of silicon dioxide; the thickness of the modified polyethylene layer is 40 microns, and the components of the modified polyethylene layer comprise 150 parts of polyethylene, 10 parts of phosphite ester and 1.5 parts of silicon dioxide; the composite flame retardant layer of the composite flame retardant layer is 40 microns in thickness and comprises the components of 45 parts of carbamate, 20 parts of polyethylene terephthalate, 25 parts of silicon-phosphorus composite flame retardant, 1 part of Revonox 608 antioxidant, 0.6 part of microcrystalline wax and 0.3 part of montan wax.
Example 2
The utility model provides a fire-retardant complex film, includes by outer modified polyester layer, compound flame retardant layer and the modified polyethylene layer that sets gradually in to: the thickness of the modified polyester layer is 60 micrometers, and the modified polyester layer comprises 130 parts by weight of dipropyl terephthalate, 10 parts by weight of phosphite ester and 1.5 parts by weight of silicon dioxide; the thickness of the modified polyethylene layer is 40 microns, and the components of the modified polyethylene layer comprise 120 parts of polyethylene, 10 parts of phosphite ester and 1.5 parts of silicon dioxide; the composite flame retardant layer of the composite flame retardant layer is 30-50 microns in thickness, and comprises 50 parts of carbamate, 30 parts of polyethylene terephthalate, 15 parts of silicon-phosphorus composite flame retardant, 1.5 parts of Revonox 608 antioxidant, 0.6 part of microcrystalline wax and 0.3 part of montan wax.
Comparative example 1
A composite film comprises a modified polyester layer, a composite flame retardant layer and a modified polyethylene layer which are sequentially arranged from outside to inside: the thickness of the modified polyester layer is 50 micrometers, and the modified polyester layer comprises, by weight, 120 parts of dipropyl polyterephthalate, 10 parts of phosphite ester and 1.5 parts of silicon dioxide; the thickness of the modified polyethylene layer is 40 microns, and the components of the modified polyethylene layer comprise 150 parts of polyethylene, 10 parts of phosphite ester and 1.5 parts of silicon dioxide; the composite flame retardant layer of the composite flame retardant layer has a thickness of 40 microns and comprises the components of 45 parts of carbamate, 20 parts of polyethylene terephthalate, 1 part of Revonox 608 antioxidant, 0.6 part of microcrystalline wax and 0.3 part of montan wax.
Comparative example 2
A composite film comprises a polyester layer, a composite flame retardant layer and a polyethylene layer which are sequentially arranged from outside to inside: the thickness of the modified polyester layer is 50 micrometers, and the thickness of the modified polyethylene layer is 40 micrometers; the composite flame retardant layer of the composite flame retardant layer is 40 microns in thickness and comprises the components of 45 parts of carbamate, 20 parts of polyethylene terephthalate, 25 parts of silicon-phosphorus composite flame retardant, 1 part of Revonox 608 antioxidant, 0.6 part of microcrystalline wax and 0.3 part of montan wax.
And (3) testing the flame retardant property: the composite membranes of examples 1 and 2 and comparative examples 1 and 2 were cut into 4 samples of 20X 20 cm size, and the limiting oxygen index of each of the 4 samples was measured in an oxygen index measuring apparatus under the same conditions, and the results are shown in Table 1 below
TABLE 1
Sample classification Example 1 Example 2 Comparative example 1 Comparative example 2
Limiting oxygen index 28.6% 27.7% 22.5% 26.3%
By adopting the schemes of the embodiments 1-2, the composite film with good flame retardant effect can be obtained, and the flame retardant effect is obviously improved compared with that of the comparative example. The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. The flame-retardant composite film is characterized by comprising a modified polyester layer, a composite flame retardant layer and a modified polyethylene layer which are sequentially arranged from outside to inside; the composite flame retardant layer comprises the following components in parts by weight: 35-50 parts of carbamate, 20-30 parts of polyethylene terephthalate, 15-25 parts of silicon-phosphorus composite flame retardant, 0.5-1.5 parts of antioxidant and 0.4-1 part of dispersant.
2. The flame retardant composite film of claim 1 wherein the modified polyester layer is prepared from the following components in parts by weight: 60-130 parts of polyester, 5-10 parts of phosphite ester and 1-1.5 parts of silicon dioxide.
3. The flame retardant composite film of claim 1 wherein the modified polyethylene layer is prepared from the following components in parts by weight: 50-150 parts of polyethylene, 5-10 parts of phosphite ester and 1-1.5 parts of silicon dioxide.
4. The flame retardant composite film of claim 1 wherein the polyester is a polyester comprised of at least one of poly (dipropyl terephthalate), poly (ethylene naphthalate), poly (butylene terephthalate), and copolymers thereof.
5. The flame retardant composite film of claim 1 wherein the modified polyester layer has a thickness of 40 to 70 microns and the modified polyethylene layer has a thickness of 20 to 80 microns.
6. The flame retardant composite film of claim 1 wherein the composite flame retardant layer has a thickness of 30 to 50 microns and is no more than one-half of the sum of the thicknesses of the modified polyester layer and the modified polyethylene layer.
7. The flame-retardant composite film according to claim 1, wherein the dispersing agent is a mixture of microcrystalline wax and montan wax, and the mass ratio of the microcrystalline wax to the montan wax is 2-3.5: 1.
8. The flame retardant composite film according to claim 1 wherein the antioxidant is a phosphite based antioxidant, and is one or more of 168 or Revonox 608.
CN201910316849.2A 2019-04-19 2019-04-19 Flame-retardant composite film Active CN110105723B (en)

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CN201910316849.2A CN110105723B (en) 2019-04-19 2019-04-19 Flame-retardant composite film

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CN110105723B true CN110105723B (en) 2021-11-23

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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115139610A (en) * 2022-06-28 2022-10-04 惠州市尚佳包装制品有限公司 PE film and processing technology thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10002154A1 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Structurized amorphous thermoplastic film, used for interior and exterior purposes, e.g. cladding, advertising, display and lighting, contains soluble flame retardant
EP2186860B1 (en) * 2008-11-17 2011-08-24 Alpha Technical Research Co., Ltd Resin composition and sheet using resin composition
CN103589035A (en) * 2013-09-23 2014-02-19 苏州市涵信塑业有限公司 Wear-resistant flame-retardant film and production method thereof
CN104260452B (en) * 2014-09-24 2016-04-20 罗瑞尔工业薄膜（昆山）有限公司 Flame-retardant and thermal-insulated film
CN106147140A (en) * 2016-06-28 2016-11-23 周开雄 A kind of inflaming retarding membrane and preparation method thereof

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