CN111909504B - Polyurethane flame-retardant film for invisible car clothes and preparation method and application thereof - Google Patents

Polyurethane flame-retardant film for invisible car clothes and preparation method and application thereof Download PDF

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CN111909504B
CN111909504B CN202010689270.3A CN202010689270A CN111909504B CN 111909504 B CN111909504 B CN 111909504B CN 202010689270 A CN202010689270 A CN 202010689270A CN 111909504 B CN111909504 B CN 111909504B
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film
kneading
polyurethane
flame
retardant
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CN111909504A (en
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王晨怡
姜媛
庄田雨
陈建君
王亦可
张均
王亦加
庄润禾
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Beijing Pujiang Brothers Technology Co ltd
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    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0026—Flame proofing or flame retarding agents
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2427/08—Homopolymers or copolymers of vinylidene chloride

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Abstract

The invention provides a polyurethane flame-retardant film for invisible car clothes, a method and application thereof, wherein the polyurethane flame-retardant film comprises the following raw materials in parts by weight: 55-70 parts of Thermoplastic Polyurethane (TPU), 10-15 parts of polyvinylidene chloride (PVDC) and 20-30 parts of Chlorinated Polyethylene (CPE), wherein the combustion speed of the polyurethane flame-retardant film for the invisible car clothing is not more than 100mm/min, the tensile strength is 23-32MPa, and the elongation at break is 580-750%. The polyurethane flame retardant provided by the invention can overcome the technical defect that the existing invisible car clothing film base material layer is flammable or has general flame retardant property, and has excellent mechanical property while ensuring the flame retardant effect.

Description

Polyurethane flame-retardant film for invisible car clothes and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyurethane flame-retardant film for an invisible car clothing film, and a preparation method and application thereof.
Background
The car clothes film is a high-performance novel environment-friendly film, is widely applied to the automobile beauty maintenance industry, is pasted on the surface of the car body paint surface, and is a car paint surface protective film. The car clothes film has super strong toughness, strength, tear resistance and other performances, and can isolate the car paint surface from air after being attached, thereby protecting the paint surface for a long time.
The car clothing film has four layers from outside to inside, namely an anti-scratch layer, a base material layer, a pressure sensitive adhesive layer and a PET temporary bottom layer, wherein the base material layer is the main component (the thickness of the base material layer accounts for more than 70 percent of the thickness of the car clothing film) of the car clothing film, and the service performance is directly influenced. The material of the substrate layer specially designed for the automobile body film on the market at present mainly comprises a polyvinyl chloride (PVC) film and a Thermoplastic Polyurethane (TPU) film. Among them, the PVC film has many characteristics such as flexibility, scratch resistance, high gloss, weather resistance, and convenience for construction, and thus is widely used for attaching to the surface of home and high-end equipment substrates. However, a large amount of PVC plasticizer is usually added to PVC film, and the problems of plasticizer migration in summer and hardening in winter easily occur during the use process, which affects the service life. The TPU film is a thermoplastic film, does not have the problem of a plasticizer, is rich and diverse in variety, can meet most performance requirements, such as UV resistance and yellowing resistance, has super toughness and wear resistance, is easy to adhere, resists collision and scratch, prevents acid rain and oxidation, resists scratch, and permanently protects the automobile paint surface.
The TPU substrate layer of the existing car clothing film mainly has the following problems: the traditional TPU base material layer has no flame retardance, and fire accidents are easily caused in the processes of production, storage, transportation, vehicle film pasting construction and vehicle use of vehicle films. Secondly, the traditional TPU substrate layer does not have fire resistance and is not suitable for special fireproof vehicle requirements.
The invention patent of CN110183985A discloses a manufacturing process of a recessive car cover protective film of a TPU substrate, wherein the raw material components of the TPU substrate comprise polyester-polyether copolymer with the hardness of 85-95A or TPU with the hardness of 85-95A of 80-90 parts, slipping agent of 1-7 parts, anti-UV agent of 6-12 parts and transparent master batch of 1 part, all the raw materials are melted and processed into a film with the thickness of 0.15mm by adopting a calendering molding mode, and the TPU substrate layer is prepared. The TPU substrate used in this patent is a conventional thermoplastic polyurethane, which is improved primarily in terms of high adhesion and aging resistance, and does not involve an improvement in flame retardant properties.
The invention patent of CN109796862A discloses a TPU invisible car coating film for repairing the surface protection of an automobile in seconds, wherein the TPU car coating film comprises the following components in parts by weight: 80-130 parts of aliphatic diisocyanate, 20-40 parts of aromatic diisocyanate, 650 parts of hydroxyl polyether polyol 550-containing material, 20-30 parts of catalyst, 30-50 parts of chain extender, 5-10 parts of antioxidant, 5-10 parts of anti-ultraviolet assistant, 50-100 parts of polyurethane resin, 300 parts of solvent 200-containing material, 5-10 parts of dispersant and 10-20 parts of defoaming agent. By reducing the weight part of aromatic diisocyanate, improving the weight part of aliphatic diisocyanate, and adding a certain amount of aliphatic anionic polyurethane resin and a certain amount of antioxidant and ultraviolet-resistant auxiliary agent into the raw materials, the car clothes film can realize the rapid healing and repairing of a scratched part during scratching, realize the second repairing function, and meanwhile, the second repairing TPU invisible car clothes film also has excellent yellowing resistance and ultraviolet radiation resistance. Also, the TPU substrate used in this patent is a conventional thermoplastic polyurethane, and does not provide any improvement in flame retardancy.
The invention patent of CN108587113A discloses a preparation method of a self-cleaning polyurethane elastomer film for automobile clothes, which is to mix fluoropolymer and TPU resin evenly and then cast the mixture into a film by an extruder. The blended TPU film prepared by the method has low surface energy, is not easy to fall ash, and pollutants are easy to wash, so that the blended TPU film has antifouling and self-cleaning functions. The TPU substrate used in the patent has no flame retardant property, has potential safety hazard in the construction and use processes of the vehicle coating film, and particularly cannot meet the requirements of special vehicles (fire trucks, oil tank trucks, police cars, military vehicles and the like).
Generally, a widely used flame retardant technology for polyurethane TPU materials is the additional addition of liquid or solid flame retardants. In order to achieve a certain level of flame retardant effect, the additive flame retardant is often added in a large amount, and the weight ratio of the additive flame retardant needs to be more than 15%. However, while the flame retardant property is ensured, the mechanical property of the material is greatly influenced and reduced, and the surface of the material is easy to have the migration of the flame retardant at high temperature, so that the flame retardant effect is reduced, and the environment is polluted, therefore, the existing additive type flame retardant technology of the polyurethane material is not suitable for the field of car clothes films, and the large-scale production and application of the polyurethane material are limited.
In summary, a flame retardant polyurethane (TPU) base material layer for a hidden car cover film is sought, which can meet the requirements of flame retardancy and environmental friendliness in the construction and use processes of the car cover film, and also has excellent mechanical properties, and is a problem to be solved in the field.
Disclosure of Invention
In order to solve the problems, the invention provides the polyurethane flame-retardant film for the invisible car clothing, which can overcome the technical defect that the conventional substrate layer of the invisible car clothing film is flammable or has general flame retardant property, and has excellent mechanical property while ensuring the flame retardant effect.
The technical scheme of the invention is as follows:
the polyurethane flame-retardant film for the invisible car clothing comprises the following raw materials in parts by weight:
55-70 parts by weight of Thermoplastic Polyurethane (TPU);
10-15 parts of polyvinylidene chloride (PVDC);
20-30 parts by weight of chlorinated polyethylene CPE;
wherein the combustion speed of the polyurethane flame-retardant film for the invisible car clothing is not more than 100mm/min, the tensile strength is 23-32MPa, and the elongation at break is 580-750%.
Preferably, the light transmittance of the polyurethane flame-retardant film for the invisible car clothing is more than or equal to 85%.
Preferably, the tensile strength of the polyurethane flame-retardant film for the invisible car clothing is 25-30MPa, and the elongation at break is 600-700%.
Particularly preferably, the polyurethane flame-retardant film for the invisible car clothes has the tensile strength of 28-30MPa and the elongation at break of 650-700%.
Further, in the polyurethane flame-retardant film for invisible car clothes, the weight part of the thermoplastic polyurethane TPU is preferably 60-70%.
Further, the hardness of the thermoplastic polyurethane TPU is 64D-80D Shore, preferably 70D-80D Shore, and particularly preferably 75D-80D Shore.
Further, the chlorinated polyethylene CPE has a chlorine content of 35 to 40 wt%, preferably 36 to 40%, particularly preferably 39 to 40%, based on the weight of the chlorinated polyethylene CPE; the polyvinylidene chloride PVDC has a chlorine content of 15 to 20 wt.%, preferably 15 to 19 wt.%, particularly preferably 15 to 18 wt.%, based on the weight of the polyvinylidene chloride PVDC.
Further, in the polyurethane flame-retardant film for the invisible car clothing, the weight ratio of the chlorinated polyethylene CPE to the polyvinylidene chloride PVDC is 2: 1.
The invention also provides a preparation method of the polyurethane flame-retardant film for the invisible car clothing, which comprises the following steps:
(1) kneading: weighing the raw materials according to the weight ratio, firstly adding chlorinated polyethylene CPE and polyvinylidene chloride PVDC into a vacuum kneading machine for primary kneading, controlling the kneading temperature to be 70-150 ℃, the vacuum degree to be-0.08-0.1 MPa and the kneading time to be 0.2-2h, adding thermoplastic polyurethane TPU into the materials for secondary kneading after the primary kneading is finished, controlling the kneading temperature to be 70-150 ℃, the kneading time to be 0.2-2h and the vacuum degree to be-0.08-0.1 MPa;
(2) plasticizing and extruding: putting the materials kneaded twice into a screw extruder, and blending, plasticizing and extruding the materials to obtain molten materials;
(3) and carrying out tape casting and cooling setting on the molten material to obtain the polyurethane flame-retardant film for the invisible car clothing.
Further, the plasticizing temperature of the screw extruder body is 30-80 ℃, 80-145 ℃, 145-200 ℃, 180-245 ℃, 180-220 ℃ and 170-210 ℃ in sequence from the feeding end to the head, and the screw rotating speed is 15-45 rpm.
Further, in the step (3), the molten material is cast onto the surface of a cooling roller through a casting mold to be cooled and formed into a film, wherein the casting mold temperature sequentially ranges from left to right from 180-; the temperature of the cooling roller is-10-30 ℃, the rotating speed is 20-40rpm, and the drafting ratio is 1:2-1: 5.
Further, the slit gaps of the casting die were 35 μm, 34 μm, 33 μm, 32 μm, 31 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, respectively.
Further, after the step (3), the polyurethane flame-retardant film for the invisible car clothes is subjected to edge cutting by an edge cutting machine to obtain a product with a regular size, wherein the edge cutting speed is 0.5-45m/min, and then the film subjected to edge cutting is wound by a winding machine, wherein the winding tension is 10-450N.
The invention also provides application of the polyurethane flame-retardant film for the invisible car clothing as a base material layer of the invisible car clothing film.
The technical scheme provided by the invention can have the following beneficial effects:
1) the invention adopts three high molecular materials, namely Thermoplastic Polyurethane (TPU), polyvinylidene chloride (PVDC) and Chlorinated Polyethylene (CPE), to form a blended alloy structure, thereby overcoming the defects that the strength of a polyurethane TPU film is easy to degrade due to a small molecular additive flame retardant, and the flame retardant property of the polyurethane TPU film is reduced due to the surface migration and volatilization of the small molecular additive flame retardant at high temperature, and the like, not only ensuring that the mechanical properties such as tensile strength and elongation at break meet the industrial use standard of the car clothing film base material layer, but also meeting the flame retardant property with the combustion speed of not more than 100mm/min, and particularly under the outdoor high-temperature environment, the stable structure of the high molecular composite base material layer can prolong the service life of the car clothing film base material layer.
2) The main chain of the PVDC contains chlorine, a carbonized layer can be formed on the surface of the automobile coating film base material layer when the PVDC is burnt by naked flame, and the carbonized layer has excellent heat insulation effect and can block heat transfer between a fire source and the automobile coating film base material layer; however, the compatibility between the PVDC and the TPU is poor, so in order to improve the compatibility between the TPU and the PVDC, the mechanical property and the flame retardancy of the base material layer of the car coat film can be simultaneously realized by adding the polymer compatilizer CPE into the TPU and the PVDC.
3) The optimal balance of the flame retardance and the mechanical property of the base material layer of the car coat film is realized by adjusting the hardness of the TPU and the ratio of the TPU to the PVDC to the CPE. On one hand, the lower the hardness of the TPU is, the poorer the tensile strength of the base material layer of the car clothes film is, and meanwhile, the lower the softening point is due to the lower content of carbamate in the TPU, so that the TPU is easy to drop and decompose during combustion to generate combustible gas; on the other hand, when the adding proportion of the PVDC and the CPE is higher, the flame retardant property of the car clothes film base material layer is higher, but the mechanical property of the car clothes film base material layer is influenced, and when the adding proportion of the PVDC and the CPE is lower, the mechanical property is higher, but the flame retardant property of the car clothes film base material layer is poorer.
4) The chlorine content of the PVDC also influences the performance of the base material layer of the car clothes film, if the chlorine content is too high, although the flame retardance is improved, the compatibility of the PVDC and the TPU is not good, and the mechanical property and the light transmittance of the final base material layer of the car clothes film are influenced; if the chlorine content is low, although the compatibility of PVDC and TPU is improved, the flame retardancy of the film substrate layer of the automobile cover is deteriorated. Therefore, it is necessary to appropriately control the chlorine content of PVDC within a certain range to achieve the optimal arrangement of the cover film base material layer.
5) The preparation method of the polyurethane flame-retardant film for the invisible car clothing is simple, the reaction conditions are mild, the technological parameters are easy to control, and the polyurethane flame-retardant film can be produced in a large scale.
6) The flame-retardant car clothing film base material layer disclosed by the invention not only reduces the construction difficulty, but also has higher flatness, transparency and glossiness than the existing car clothing film base material layer in the market, and the service life of the flame-retardant car clothing film base material layer can reach more than decades.
Drawings
FIG. 1 is a schematic structural view of a PVDC/CPE/TPU blended alloy of example 2 of the present invention, wherein 1-thermoplastic polyurethane TPU; 2-polyvinylidene chloride PVDC; 3-chlorinated polyethylene CPE.
FIG. 2 is a scanning electron micrograph of PVDC/CPE/TPU according to example 2 of the present invention wherein 1-thermoplastic polyurethane TPU; 2-polyvinylidene chloride PVDC; 3-chlorinated polyethylene CPE.
Detailed Description
The invention is further illustrated by the following specific examples:
the sources of the raw materials used in the inventive examples and comparative examples are shown in table 1.
Figure GDA0003462131680000051
Example 1
The preparation method comprises the following steps:
(1) kneading: weighing the raw materials according to the composition and the proportion shown in Table 2, firstly adding chlorinated polyethylene CPE and polyvinylidene chloride PVDC into a vacuum kneader for primary kneading, controlling the kneading temperature to be 70 ℃, the vacuum degree to be-0.08 MPa and the kneading time to be 2h, adding thermoplastic polyurethane TPU into the materials for secondary kneading after the primary kneading is finished, controlling the kneading temperature to be 115 ℃, the kneading time to be 0.2h and the vacuum degree to be-0.08 MPa;
(2) plasticizing and extruding: the materials kneaded twice are put into a screw extruder, and are subjected to blending, plasticizing and extruding at the rotating speed of 20rpm to obtain molten materials,
wherein the plasticizing temperature of the screw extruder body is 60 ℃, 145 ℃, 180 ℃, 210 ℃, 220 ℃ and 210 ℃ from the feeding end to the extruder head in sequence;
(3) casting the molten material onto the surface of a cooling roller through a casting die to form a film by cooling,
wherein the temperature of the casting die is 220 ℃, 215 ℃, 210 ℃ and 220 ℃ from left to right in sequence; the temperature of the cooling roller is 30 ℃, the rotating speed is 20rpm, and the drafting ratio is 1: 2;
(4) and (4) passing the film obtained in the step (3) through an edge trimmer at the edge trimming speed of 2.7m/min, and then rolling the edge-trimmed film through a rolling machine at the rolling tension of 75N.
Example 2
The preparation method comprises the following steps:
(1) kneading: weighing the raw materials according to the composition and proportion shown in Table 2, firstly adding chlorinated polyethylene CPE and polyvinylidene chloride PVDC into a vacuum kneader to be kneaded for the first time, controlling the kneading temperature to be 100 ℃, the vacuum degree to be-0.095 MPa and the kneading time to be 0.5h, adding thermoplastic polyurethane TPU into the materials to be kneaded for the second time after the first kneading is finished, controlling the kneading temperature to be 100 ℃, the kneading time to be 0.5h and the vacuum degree to be-0.095 MPa;
(2) plasticizing and extruding: the materials kneaded twice are put into a screw extruder, and are subjected to blending, plasticizing and extruding at the rotating speed of 27rpm to obtain molten materials,
wherein the plasticizing temperature of the screw extruder body is 30 ℃, 80 ℃, 170 ℃, 200 ℃, 220 ℃ and 210 ℃ from the feeding end to the extruder head in sequence;
(3) casting the molten material onto the surface of a cooling roller through a casting die to form a film by cooling,
wherein the temperature of the casting die is 200 ℃, 190 ℃, 180 ℃, 190 ℃ and 200 ℃ from left to right in sequence; the temperature of the cooling roller is 0 ℃, the rotating speed is 30rpm, and the drafting ratio is 1: 3;
(4) and (4) passing the film obtained in the step (3) through an edge trimmer at the edge trimming speed of 5.8m/min, and then rolling the edge-trimmed film through a rolling machine at the rolling tension of 75N.
Example 3
The preparation method comprises the following steps:
(1) kneading: weighing the raw materials according to the composition and the proportion shown in Table 2, firstly adding chlorinated polyethylene CPE and polyvinylidene chloride PVDC into a vacuum kneader for primary kneading, controlling the kneading temperature to be 70 ℃, the vacuum degree to be-0.1 Pa and the kneading time to be 1.2h, adding thermoplastic polyurethane TPU into the materials for secondary kneading after the primary kneading is finished, controlling the kneading temperature to be 70 ℃, the kneading time to be 2h and the vacuum degree to be-0.10 MPa;
(2) plasticizing and extruding: the materials kneaded twice are put into a screw extruder, and are subjected to blending, plasticizing and extruding at the rotating speed of 30rpm to obtain molten materials,
wherein the plasticizing temperature of the screw extruder body is 70 ℃, 145 ℃, 200 ℃, 210 ℃, 200 ℃ and 180 ℃ from the feeding end to the extruder head in sequence;
(3) casting the molten material onto the surface of a cooling roller through a casting die to form a film by cooling,
wherein the temperature of the casting die is (180 ℃, 175 ℃, 170 ℃, 175 ℃ and 180 ℃) from left to right, the temperature of the cooling roller is-10 ℃, the rotating speed is 40rpm, and the drafting ratio is 1: 5;
(4) and (4) passing the film obtained in the step (3) through an edge trimmer at the edge trimming speed of 8.3m/min, and then rolling the edge-trimmed film through a rolling machine at the rolling tension of 75N.
Comparative example 1
The preparation method comprises the following steps:
(1) kneading: weighing the raw materials according to the composition and proportion shown in Table 2, firstly adding chlorinated polyethylene CPE and polyvinylidene chloride PVDC into a vacuum kneader to be kneaded for the first time, controlling the kneading temperature to be 150 ℃, the vacuum degree to be-0.10 MPa and the kneading time to be 0.2h, adding thermoplastic polyurethane TPU into the materials to be kneaded for the second time after the first kneading is finished, controlling the kneading temperature to be 150 ℃, the kneading time to be 0.2h and the vacuum degree to be-0.1 MPa;
(2) plasticizing and extruding: the materials kneaded twice are put into a screw extruder, and are subjected to blending, plasticizing and extruding at the rotating speed of 40rpm to obtain molten materials,
wherein the plasticizing temperature of the screw extruder body is 195 ℃, 185 ℃, 180 ℃, 185 ℃ and 195 ℃ from the feeding end to the extruder head;
(3) casting the molten material onto the surface of a cooling roller through a casting die to form a film by cooling,
wherein the temperature of the casting die is 220 ℃, 210 ℃, 200 ℃, 210 ℃ and 220 ℃ from left to right in sequence; the temperature of the cooling roller is 10 ℃, the rotating speed is 30rpm, and the drafting ratio is 1: 3;
(4) and (4) passing the film obtained in the step (3) through an edge trimmer at the edge trimming speed of 5.8m/min, and then rolling the edge-trimmed film through a rolling machine at the rolling tension of 75N.
Comparative example 2
The preparation method comprises the following steps:
(1) kneading: weighing the raw materials according to the composition and the proportion shown in Table 2, firstly adding chlorinated polyethylene CPE and polyvinylidene chloride PVDC into a vacuum kneader for primary kneading, controlling the kneading temperature to be 100 ℃, the vacuum degree to be-0.097 MPa and the kneading time to be 1h, adding thermoplastic polyurethane TPU into the materials for secondary kneading after the primary kneading is finished, controlling the kneading temperature to be 120 ℃, the kneading time to be 1h and the vacuum degree to be-0.097 MPa;
(2) plasticizing and extruding: the materials kneaded twice are put into a screw extruder, and are subjected to blending, plasticizing and extruding at the rotating speed of 35rpm to obtain molten materials,
wherein the plasticizing temperature of the screw extruder body is 80 ℃, 145 ℃, 190 ℃, 220 ℃ and 210 ℃ from the feeding end to the extruder head in sequence;
(3) casting the molten material onto the surface of a cooling roller through a casting die to form a film by cooling,
wherein the temperature of the casting die is 200 ℃, 190 ℃, 185 ℃, 190 ℃ and 200 ℃ from left to right in sequence; the temperature of the cooling roller is 10 ℃, the rotating speed is 30rpm, and the drafting ratio is 1: 3;
(4) and (4) passing the film obtained in the step (3) through an edge trimmer at the edge trimming speed of 5.8m/min, and then rolling the edge-trimmed film through a rolling machine at the rolling tension of 75N.
Comparative example 3
The preparation method comprises the following steps:
(1) kneading: weighing the raw materials according to the composition and the proportion shown in Table 2, firstly adding chlorinated polyethylene CPE and polyvinylidene chloride PVDC into a vacuum kneader for primary kneading, controlling the kneading temperature to be 100 ℃, the vacuum degree to be-0.097 MPa and the kneading time to be 1h, adding thermoplastic polyurethane TPU into the materials for secondary kneading after the primary kneading is finished, controlling the kneading temperature to be 120 ℃, the kneading time to be 1h and the vacuum degree to be-0.097 MPa;
(2) plasticizing and extruding: the materials kneaded twice are put into a screw extruder, and are subjected to blending, plasticizing and extruding at the rotating speed of 20rpm to obtain molten materials,
wherein the plasticizing temperature of the screw extruder body is 80 ℃, 145 ℃, 180 ℃, 210 ℃, 220 ℃ and 170 ℃ from the feeding end to the extruder head in sequence;
(3) casting the molten material onto the surface of a cooling roller through a casting die to form a film by cooling,
wherein the temperature of the casting die is 200 ℃, 190 ℃, 185 ℃, 190 ℃ and 200 ℃ from left to right in sequence; the temperature of the cooling roller is 10 ℃, the rotating speed is 30rpm, and the drafting ratio is 1: 3;
(4) and (4) passing the film obtained in the step (3) through an edge trimmer at the edge trimming speed of 5.8m/min, and then rolling the edge-trimmed film through a rolling machine at the rolling tension of 75N.
Comparative example 4
The preparation method comprises the following steps:
(1) kneading: weighing the raw materials according to the composition and the proportion shown in Table 2, firstly adding chlorinated polyethylene CPE and polyvinylidene chloride PVDC into a vacuum kneader for primary kneading, controlling the kneading temperature to be 100 ℃, the vacuum degree to be-0.097 MPa and the kneading time to be 1h, adding thermoplastic polyurethane TPU into the materials for secondary kneading after the primary kneading is finished, controlling the kneading temperature to be 120 ℃, the kneading time to be 1h and the vacuum degree to be-0.097 MPa;
(2) plasticizing and extruding: the materials kneaded twice are put into a screw extruder, and are subjected to blending, plasticizing and extruding at the rotating speed of 30rpm to obtain molten materials,
wherein the plasticizing temperature of the screw extruder body is 65 ℃, 145 ℃, 180 ℃, 210 ℃, 180 ℃ and 180 ℃ from the feeding end to the extruder head in sequence;
(3) casting the molten material onto the surface of a cooling roller through a casting die to form a film by cooling,
wherein the temperature of the casting die is 200 ℃, 190 ℃, 185 ℃, 190 ℃ and 200 ℃ from left to right in sequence; the temperature of the cooling roller is 10 ℃, the rotating speed is 30rpm, and the drafting ratio is 1: 3;
(4) and (4) passing the film obtained in the step (3) through an edge trimmer at the edge trimming speed of 5.8m/min, and then rolling the edge-trimmed film through a rolling machine at the rolling tension of 75N.
Comparative example 5
The preparation method comprises the following steps:
(1) kneading: weighing the raw materials according to the composition and the proportion shown in Table 2, firstly adding chlorinated polyethylene CPE and polyvinylidene chloride PVDC into a vacuum kneader for primary kneading, controlling the kneading temperature to be 100 ℃, the vacuum degree to be-0.097 MPa and the kneading time to be 1h, adding thermoplastic polyurethane TPU into the materials for secondary kneading after the primary kneading is finished, controlling the kneading temperature to be 120 ℃, the kneading time to be 1h and the vacuum degree to be-0.097 MPa;
(2) plasticizing and extruding: the materials kneaded twice are put into a screw extruder, and are subjected to blending, plasticizing and extruding at the rotating speed of 32rpm to obtain molten materials,
wherein the plasticizing temperature of the screw extruder body is 30 ℃, 90 ℃, 145 ℃, 185 ℃, 210 ℃ and 210 ℃ from the feeding end to the extruder head in sequence;
(3) casting the molten material onto the surface of a cooling roller through a casting die to form a film by cooling,
wherein the temperature of the casting die is 200 ℃, 190 ℃, 185 ℃, 190 ℃ and 200 ℃ from left to right in sequence; the temperature of the cooling roller is 10 ℃, the rotating speed is 30rpm, and the drafting ratio is 1: 3;
(4) and (4) passing the film obtained in the step (3) through an edge trimmer at the edge trimming speed of 5.8m/min, and then rolling the edge-trimmed film through a rolling machine at the rolling tension of 75N.
TABLE 2 raw material compositions and compounding ratios of examples 1-3 and comparative examples 1-5
Figure GDA0003462131680000091
Figure GDA0003462131680000101
The following performance tests were performed on each of the polyurethane flame-retardant film samples for invisible car clothes obtained by the preparation of the above examples 1 to 3 and comparative examples 1 to 5, and the results of the performance tests are shown in Table 3.
1) The tensile strength and elongation at break of the samples were tested according to the test method for tensile Properties of Plastic films GB/T13022-1991. The tensile strength is more than or equal to 20MPa, meets the industrial standard of the car clothes film and is evaluated to be good; the tensile strength is less than 20MPa, does not meet the industrial standard of the car clothes and films, and is evaluated as poor. The elongation is more than or equal to 500 percent, and the performance is good; elongation < 500% and poor properties.
2) The burning rate of the sample was tested according to GB 8410-2006 burning characteristics of automotive interior materials. The burning speed is less than or equal to 100mm/min, and the performance is good; the burning speed is more than 100mm/min, and the performance is poor.
3) The light transmittance of the sample was measured according to GB/T2410-2008 determination of light transmittance and haze of transparent plastics. The light transmittance is more than or equal to 85 percent, and the performance is good; the light transmittance is less than 85 percent, and the performance is poor.
TABLE 3 results of testing samples of examples 1-3 and comparative examples 1-5
Figure GDA0003462131680000102
As can be seen from Table 3, examples 1-3 performed better than the samples of comparative examples 1-5. Therefore, the polyurethane flame-retardant film for the invisible car clothing prepared by the method has stable mechanical property, meets the requirement of GB 8410-2006 burning characteristic of automotive interior materials, has the burning speed of not more than 100mm/min, and can be used as a substrate layer of the invisible car clothing of ordinary vehicles and even special vehicles.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, but any modifications or equivalent variations made according to the technical spirit of the present invention are within the scope of the present invention as claimed.

Claims (7)

1. The flame-retardant polyurethane film for the invisible car clothing is characterized by comprising the following raw materials in parts by weight:
55-70 parts of Thermoplastic Polyurethane (TPU);
10-15 parts of polyvinylidene chloride (PVDC);
20-30 parts of chlorinated polyethylene CPE;
the hardness of the thermoplastic polyurethane TPU is 64D-80D on Shore; and
the polyvinylidene chloride (PVDC) has a chlorine content of 15-20 wt%, based on the weight of the PVDC; the chlorinated polyethylene CPE has a chlorine content of 35 to 40 wt%, based on the weight of the chlorinated polyethylene CPE;
wherein the combustion speed of the polyurethane flame-retardant film for the invisible car clothing is not more than 100mm/min, the tensile strength is 23-32MPa, and the elongation at break is 580-750%.
2. The flame retardant polyurethane film for invisible car clothes according to claim 1, wherein the weight ratio of the chlorinated polyethylene CPE to the polyvinylidene chloride PVDC is 2: 1.
3. The preparation method of the polyurethane flame-retardant film for the invisible car clothes, which is characterized by comprising the following steps of:
(1) kneading: weighing the raw materials according to the weight ratio, firstly adding chlorinated polyethylene CPE and polyvinylidene chloride PVDC into a vacuum kneading machine for primary kneading, controlling the kneading temperature to be 70-150 ℃, the vacuum degree to be-0.08-0.1 MPa and the kneading time to be 0.2-2h, adding thermoplastic polyurethane TPU into the materials for secondary kneading after the primary kneading is finished, controlling the kneading temperature to be 70-150 ℃, the kneading time to be 0.2-2h and the vacuum degree to be-0.08-0.1 MPa;
(2) plasticizing and extruding: putting the materials kneaded twice into a screw extruder, and blending, plasticizing and extruding the materials to obtain molten materials;
(3) and carrying out tape casting and cooling setting on the molten material to obtain the polyurethane flame-retardant film for the invisible car clothing.
4. The preparation method as claimed in claim 3, wherein in the step (2), the screw extruder has a body plasticizing temperature of 30-80 ℃, 80-145 ℃, 145-200 ℃, 180-245 ℃, 180-220 ℃ and 170-210 ℃ in sequence from the feeding end to the head, and a screw rotation speed of 15-45 rpm.
5. The preparation method according to claim 3, wherein in the step (3), the molten material is cast onto the surface of a cooling roller through a casting mold for cooling film formation, wherein the casting mold temperature is, from left to right, 180-; the temperature of the cooling roller is-10-30 ℃, the rotating speed is 20-40rpm, and the drafting ratio is 1:2-1: 5.
6. The preparation method according to claim 3, wherein after the step (3), the polyurethane flame-retardant film for the invisible car clothes is subjected to edge cutting by an edge cutting machine to obtain a product with a regular size, the edge cutting speed is 0.5-45m/min, and then the film after edge cutting is wound by a winding machine, wherein the winding tension is 10-450N.
7. Use of the polyurethane flame-retardant film for invisible car clothes according to any one of claims 1 to 2 as a substrate layer of an invisible car clothes film.
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