CN113637252A - Strong cross membrane, preparation method and application thereof - Google Patents

Strong cross membrane, preparation method and application thereof Download PDF

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CN113637252A
CN113637252A CN202110973696.6A CN202110973696A CN113637252A CN 113637252 A CN113637252 A CN 113637252A CN 202110973696 A CN202110973696 A CN 202110973696A CN 113637252 A CN113637252 A CN 113637252A
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film
sigma
epsilon
max
strain
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CN113637252B (en
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李良彬
施信波
赵浩远
孟令蒲
王道亮
张文文
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Institute of Advanced Technology University of Science and Technology of China
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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
    • 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
    • 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
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

The invention discloses a strong cross membrane, a preparation method and application thereof, wherein the preparation method comprises the following steps: blowing the raw materials to obtain a film; performing secondary stretching and heat setting on the film to obtain a base film, and performing stretching test on the obtained base film on a universal testing machine along the traction direction to obtain a stress sigma-strain epsilon curve, wherein the maximum stress is sigmamaxMaximum strain εmaxPerforming first-order derivation on the stress sigma-strain epsilon curve to obtain d sigma/d epsilon, wherein sigma is more than or equal to 45MPamax≤150MPa，150％≤εmaxLess than or equal to 800 percent, d sigma/d epsilon satisfies that d sigma/d epsilon is more than or equal to 0; and performing cross compounding on the base membrane after spiral cutting to obtain the strong cross membrane. By making the base film satisfyThe tensile property is as above, so that when the finally obtained strong crossed film is in service in a small deformation area, the yield failure of the common strong crossed film can not occur, and a new microcosmic force bearing unit is formed under a certain strain condition; meanwhile, the maximum stress and strain in a specific range also enable the strong crossed film to have excellent tensile strength and elongation at break.

Description

Strong cross membrane, preparation method and application thereof
Technical Field
The invention relates to the technical field of polymer film processing, in particular to a strong cross membrane, a preparation method and application thereof.
Background
The strong crossed film is formed by crossing and compounding two or more uniaxially oriented films, has higher strength, toughness, tearing resistance and dimensional stability compared with common blown film products and biaxially oriented films, and is widely applied to the fields of label films, packaging films, waterproof rolls and the like.
At present, when the mechanical properties of the strong cross film, particularly the tensile strength of the strong cross film, are concerned, the evaluation and improvement of the properties of the strong cross film are generally performed from the viewpoint of the maximum tensile force at the time of breakage of the strong cross film and the elongation at the time of the maximum tensile force. The maximum tensile force when the strong cross membrane is broken is one of important indexes for evaluating the mechanical performance of the strong cross membrane, however, even if the strong cross membrane has high tensile strength, service defects such as wrinkles, hollows, bubbles and the like still occur in the actual use process, the defects are not usually accompanied with the tensile and tearing breakage of the strong cross membrane, the defects are the breakage generated under the condition of small deformation of the strong cross membrane, and the service performance of the strong cross membrane is seriously influenced.
Disclosure of Invention
The invention mainly aims to provide a strong crossed membrane, a preparation method and application thereof, and aims to solve the problem that the service performance of the strong crossed membrane is influenced by damage of the strong crossed membrane under a small deformation condition.
In order to achieve the above object, the present invention provides a method for preparing a strong cross membrane, comprising the steps of:
processing a raw material by blowing a film to obtain a film, wherein the raw material comprises a polyethylene mixture, the polyethylene mixture comprises high-density polyethylene and linear low-density polyethylene, the melt flow rate of the high-density polyethylene is 0.015-0.45 g/10min, the melting point temperature of the high-density polyethylene is Tm, the melt flow rate of the linear low-density polyethylene is 0.5-0.8 g/10min, the temperature of air ring cooling air in the film blowing processing step is 0-28 ℃, the temperature of a mouth mold is Tm + 100-Tm +150 ℃, and the traction ratio is 2.8-15.0;
performing secondary stretching and heat setting on the film to obtain a base film, and performing stretching test on the obtained base film on a universal testing machine along the traction direction to obtain a stress sigma-strain epsilon curve, wherein the maximum stress is sigmamaxMaximum strain εmaxPerforming first-order derivation on the stress sigma-strain epsilon curve to obtain d sigma/d epsilon, wherein sigma is more than or equal to 45MPamax≤150MPa，150％≤εmaxLess than or equal to 800 percent, d sigma/d epsilon satisfies that d sigma/d epsilon is more than or equal to 0;
and performing cross compounding on the base membrane after spiral cutting to obtain the strong cross membrane.
Optionally, the film obtained by the film blowing processing is subjected to a tensile test in a traction direction on a universal tester to obtain a stress sigma ' -strain epsilon ' curve, and the maximum stress is sigma 'maxOf maximum strain is ε'maxAnd performing first-order derivation on the stress sigma ' -strain epsilon ' curve to obtain d sigma '/d epsilon ', wherein yield behavior exists at least twice in the stress sigma ' -strain epsilon ' curve, and 35MPa is less than or equal to sigma 'max≤120MPa，300％≤ε'maxIs less than or equal to 1400 percent, and d sigma '/d epsilon' meets the condition that d sigma '/d epsilon' is more than or equal to-0.1.
Optionally, the stretching ratio of the secondary stretching is 1.8-4.5, and the heat setting temperature is Tm-35 ℃ to Tm-5 ℃.
Optionally, the linear low density polyethylene comprises a metallocene linear low density polyethylene; and/or the presence of a gas in the gas,
in the polyethylene mixture, the mass percent of the high-density polyethylene is not less than 75%.
Optionally, the weight average molecular weight of the high-density polyethylene is 160000-360000 g/mol, and the molecular weight distribution is 3.2-9.0; and/or the presence of a gas in the gas,
the weight average molecular weight of the low-density polyethylene is 80000-250000 g/mol.
Optionally, the temperature of the air ring cooling air is 5-25 ℃, and the traction ratio is 3.0-12.0.
Optionally, the stretching ratio of the secondary stretching is 1.8-4.5, and the heat setting temperature is Tm-35 ℃ to Tm-5 ℃.
Optionally, the maximum stress is σmaxMaximum strain εmaxD sigma/d epsilon obtained by performing first-order derivation on the stress sigma-strain epsilon curve meets the following condition:
60MPa≤σmax＜150MPa，200％≤εmaxless than or equal to 700 percent, d sigma/d epsilon satisfies d sigma/d epsilon is more than 0.
Furthermore, the invention also provides a strong crossed membrane prepared by the preparation method of the strong crossed membrane.
In addition, the invention also provides a waterproof coiled material, which comprises the strong crossed membrane.
The invention also provides a label film which comprises the strong cross film.
In the technical scheme provided by the invention, through the design of the raw materials and the technological parameters of the film blowing processing step, the base film prepared by film blowing processing, secondary stretching and heat setting is subjected to stretching test along the traction direction on a universal testing machine to obtain a stress sigma-strain epsilon curve, wherein the maximum stress is sigmamaxMaximum strain εmaxPerforming first-order derivation on the stress sigma-strain epsilon curve to obtain d sigma/d epsilon, wherein sigma is more than or equal to 45MPamax≤150MPa，150％≤εmaxThe content of d sigma/d epsilon is not more than 800 percent, and d sigma/d epsilon is not less than 0, so that when the strong crossed membrane obtained by cross compounding the base membrane is in service in a small deformation area, yield failure which can occur in the common strong crossed membrane can not occur, and a new microscopic bearing unit is formed under a certain strain condition; simultaneously, the maximum stress and strain in a specific range also enable the strong crossed film to have excellent tensile strengthAnd elongation at break.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a stress-strain curve obtained by a tensile test of a film produced by blown film processing in example 1 of the present invention;
FIG. 2 is a first derivative curve corresponding to the stress-strain curve of FIG. 1;
FIG. 3 is a schematic view of the structure of a base film obtained in example 1 of the present invention;
FIG. 4 is a stress-strain curve obtained by subjecting the base film obtained in example 1 of the present invention to a tensile test;
FIG. 5 is a first derivative curve corresponding to the stress-strain curve of FIG. 4;
FIG. 6 is a schematic structural diagram of a strong crossover membrane prepared in example 1 of the present invention;
FIG. 7 is a stress-strain curve obtained by subjecting a film obtained by the blown film process of comparative example 1 of the present invention to a tensile test;
FIG. 8 is a first derivative curve corresponding to the stress-strain curve of FIG. 7;
FIG. 9 is a stress-strain curve obtained by subjecting the base film obtained in comparative example 1 of the present invention to a tensile test;
fig. 10 is a first derivative curve corresponding to the stress-strain curve of fig. 9.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The maximum tensile force when the strong cross membrane is broken is one of important indexes for evaluating the mechanical performance of the strong cross membrane, however, even if the strong cross membrane has high tensile strength, service defects such as wrinkles, hollows, bubbles and the like still occur in the actual use process, the defects generally do not accompany the tensile and tearing breakage of the strong cross membrane, are the breakage generated under the condition of small deformation of the strong cross membrane, and seriously affect the service performance of the strong cross membrane.
In view of this, the present invention provides a method for preparing a strong crossed membrane, comprising the steps of:
s10, performing blown film processing on a raw material to obtain a film, wherein the raw material comprises a polyethylene mixture, the polyethylene mixture comprises high-density polyethylene and linear low-density polyethylene, the melt flow rate of the high-density polyethylene is 0.015-0.45 g/10min, the melting point temperature of the high-density polyethylene is Tm, the melt flow rate of the linear low-density polyethylene is 0.5-0.8 g/10min, the temperature of air ring cooling air in the blown film processing step is 0-28 ℃, the temperature of a mouth mold is Tm + 100-Tm +150 ℃, and the traction ratio is 2.8-15.0;
step S20, carrying out secondary stretching and heat setting on the film to obtain a base film;
and step S30, performing cross compounding on the base membrane after spiral cutting to obtain the strong cross membrane.
According to the microstructure analysis of the strong crossed film and the research of the structure transformation process under the real service condition, the inventor finds that: service defects of the strong crossed membrane when the strong crossed membrane is not stretched or torn are mainly related to non-uniformity of a crystal structure and a microstructure of a small deformation area, and specifically, non-uniform wrinkles, hollows and the like generated in the use process are directly influenced by structural evolution near a yield point in the stretching process.
The invention makes the base film prepared in the step S20 be subjected to tensile test along the traction direction on a universal testing machine to obtain a stress sigma-strain epsilon curve through the design of the raw materials, the technological parameters of film blowing processing and the preparation steps, and the maximum stress is sigmamaxMaximum strain εmaxPerforming first-order derivation on the stress sigma-strain epsilon curve to obtain d sigma/d epsilon, wherein sigma is more than or equal to 45MPamax≤150MPa，150％≤εmaxThe content of d sigma/d epsilon is not more than 800 percent, and d sigma/d epsilon is not less than 0, so that when a strong crossed membrane prepared by compounding the base membrane through the crossed membrane is in service in a small deformation area, yield failure which can occur in a common strong crossed membrane can not occur, and a new microscopic bearing unit is formed under a certain strain condition; meanwhile, the maximum stress and strain in a specific range also enable the strong crossed film to have excellent tensile strength and elongation at break. In a preferred embodiment, 60MPa ≦ σmax＜150MPa，200％≤εmaxLess than or equal to 700 percent, d sigma/d epsilon satisfies d sigma/d epsilon is more than 0.
In order to obtain the above base film, the stretch property of the film obtained by the blown film process in step S10 is a key to obtaining the above base film. Further, in this embodiment, by adjusting and controlling the specific formula of the raw materials and the specific process parameters of the film blowing process, the film universal testing machine manufactured by the film blowing process is subjected to a tensile test along the traction direction to obtain a stress σ ' -strain epsilon ' curve, and the maximum stress is σ 'maxOf maximum strain is ε'maxAnd performing first-order derivation on the stress sigma '-strain epsilon' curve to obtain d sigma'/d ε ', wherein there is at least two yield behaviors in the stress σ ' -strain ε ' curve, 35MPa ≦ σ 'max≤120MPa，300％≤ε'max1400% or less, d sigma '/d epsilon' satisfies d sigma '/d epsilon' is more than or equal to-0.1, thus, the film obtained by film blowing processing is stretched and heat-set for the second time, and the base film can be obtained.
In the technical scheme provided by the invention, the proportion of raw materials, the temperature of a die in a film blowing process, the temperature of cooling air of an air ring and the traction ratio have a linkage effect, when one parameter is changed, the other three parameters also need to be correspondingly changed, and the four parameters are matched with each other to obtain the film with the tensile property. That is, by defining the stretch properties of the film produced by the blown film process, the relationship among the raw material, the die temperature during the blown film process, the air ring cooling air temperature, and the draw ratio can be determined.
To facilitate the production of films having the above-described tensile properties, in one embodiment, the linear low density polyethylene comprises a metallic linear low density polyethylene; and/or the mass percent of the high-density polyethylene in the polyethylene mixture is not less than 75%.
Further, the melt flow rate of the polyethylene is influenced by a plurality of parameters such as the weight average molecular weight, the molecular weight distribution and the branched chain of the polyethylene, and in this embodiment, the weight average molecular weight of the high-density polyethylene is 160000-360000 g/mol (i.e. 1.6 × 10)5～3.6×105g/mol) and the molecular weight distribution is 3.2-9.0; and/or the weight average molecular weight of the low-density polyethylene is 80000-250000 g/mol (namely 0.8 multiplied by 10)5～2.5×105g/mol). In another embodiment, the comonomer of the metallocene linear low density polyethylene is hexene, and the branched chain content is 1.2-1.5 mol%. Thus, the film can be obtained by using high-density polyethylene and metallocene linear low-density polyethylene containing specific molecular parameters as raw materials and controlling key process parameters of the neck ring temperature, the air ring cooling air temperature and the traction ratio in the film blowing process.
Specifically, the temperature of the die set by the invention is higher than the film blowing temperature of the conventional polyethylene, the temperature of the cooling air of the air ring is lower than the set temperature of the conventional film blowing, and the film with the tensile property can be obtained by the polyethylene with a specific structure under the condition of high supercooling degree. Therefore, when the blown film temperature is set low, the temperature of the air ring cooling air is also set low so that the temperature difference is large. In a preferred embodiment, the temperature of the air ring cooling air is 5-25 ℃, and the traction ratio is 3.0-12.0.
In specific implementation, the polyethylene mixture is added into a film blowing machine to be processed by film blowing to obtain a film. Wherein, the inflation film manufacturing machine can be a monolayer inflation film manufacturing machine, also can be multilayer coextrusion inflation film manufacturing machine. In addition, the melting point temperature Tm of the high density polyethylene refers to the peak temperature of the melting curve of the high density polyethylene.
In order to make the performance of the strong cross-linked film better and facilitate the use according to different requirements, in this embodiment, the raw materials further include a processing aid and a color master batch. The color master batch is a plastic colorant which is prepared by well dispersing pigment or additive with high proportion and thermoplastic resin, and the powerful cross film can be made into different colors according to actual needs by adding the color master batch. The invention does not limit the specific kind of the processing aid, and can be a conventional aid in the field of strong crossed membranes. In a specific embodiment, the processing aid comprises an antioxidant and an ultraviolet absorber. Further, the total mass of the ultraviolet absorber, the antioxidant and the color master batch is 1-3%, preferably 1.5% of the total mass of the polyethylene mixture (i.e. the high-density polyethylene and the metallocene linear low-density polyethylene).
The invention does not limit how the film containing the tensile property obtained by the film blowing processing is processed by the secondary stretching and heat setting processing technology to obtain the base film with the tensile property, in the embodiment, the stretching ratio of the secondary stretching is 1.8-4.5, and the heat setting temperature is Tm-35-Tm-5 ℃.
Wherein, the secondary stretching and heat setting process can be carried out by adopting a tubular film mode, a flat film method and a multi-roller longitudinal stretching method.
In an embodiment, step S30 specifically includes: carrying out spiral cutting on the base film to obtain a plurality of membranes; and then, performing cross compounding on at least 2 membrane sheets to obtain the strong cross membrane. In another embodiment, the base film is subjected to post-treatment such as coating, modification and the like, and then is subjected to spiral cutting to obtain a plurality of membrane sheets; and then performing cross compounding on at least 2 membrane sheets to obtain the strong cross membrane.
The tensile curve of the film and the base film provided by the invention is obtained by testing with reference to GB/T1040.3-2006, wherein the tensile rate is 50-200 mm/min, and preferably 50 mm/min.
In the technical scheme provided by the invention, the film meeting the following tensile properties can be prepared by designing the raw materials and the technological parameters of blown film processing: the film is subjected to tensile test in the traction direction on a universal testing machine to obtain a stress sigma ' -strain epsilon ' curve, and the maximum stress is sigma 'maxOf maximum strain is ε'maxThe stress sigma ' -strain epsilon ' curve is subjected to first order derivation to obtain d sigma '/d epsilon ', wherein 35MPa is less than or equal to sigma 'max≤120MPa，300％≤ε'max1400 percent or less, d sigma '/d epsilon' satisfies d sigma '/d epsilon' is more than or equal to-0.1, and the stress sigma '-strain epsilon' curve has at least two yield behaviors; then through the design of secondary stretching and heat setting parameters, the base film meeting the following stretching performance can be prepared: the base film is subjected to tensile test along the traction direction on a universal testing machine to obtain a stress sigma-strain epsilon curve, and the maximum stress is sigmamaxMaximum strain εmaxPerforming first-order derivation on the stress sigma-strain epsilon curve to obtain d sigma/d epsilon, wherein sigma is more than or equal to 45MPamax≤150MPa，150％≤εmaxLess than or equal to 800 percent, d sigma/d epsilon satisfies that d sigma/d epsilon is more than or equal to 0. Therefore, when the strong crossed membrane obtained by cross compounding the base membrane is in service in a small deformation area, the yield failure of the common strong crossed membrane can not occur, and a new microcosmic force-bearing unit is formed under a certain strain condition; meanwhile, the maximum stress and strain in a specific range also enable the strong crossed film to have excellent tensile strength and elongation at break.
Further, the invention also provides a strong cross membrane, and the strong cross membrane is prepared by the preparation method of the strong cross membrane. The specific preparation method of the strong cross membrane refers to the above embodiments, and the waterproof roll adopts all technical solutions of all the above embodiments, so that the waterproof roll at least has all beneficial effects brought by the technical solutions of the above embodiments, and further description is omitted.
In addition, the invention also provides a waterproof roll, which comprises the strong crossed film, wherein the strong crossed film is prepared by the preparation method of the strong crossed film. Specifically, the polyethylene strong cross membrane is used as one layer of the waterproof roll, and is compounded with other functional layers such as an asphalt layer to obtain the waterproof roll. The specific preparation method of the strong cross membrane refers to the above embodiments, and the waterproof roll adopts all technical solutions of all the above embodiments, so that the waterproof roll at least has all beneficial effects brought by the technical solutions of the above embodiments, and further description is omitted.
The invention also provides a label film or a packaging film, which comprises the strong cross film. The strong cross film can be directly used as a label film or a packaging film, and can also be compounded with other functional substances according to actual needs to obtain the label film or the packaging film with the required functions. Specifically, the surface of the polyethylene strong cross membrane can be coated with special coatings, such as thermosensitive coatings, writing ink coatings and the like, and can also be compounded with some special materials, so that the polyethylene strong cross membrane is high-temperature resistant, easy to print and corrosion resistant. The specific components and the ratio of the components of the strong cross film refer to the above embodiments, and the label film or the packaging film adopts all technical solutions of all the above embodiments, so that the label film or the packaging film at least has all the beneficial effects brought by the technical solutions of the above embodiments, and details are not repeated herein.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Mixing 90 wt% of the mixturePolyethylene (wherein the high density polyethylene has a melt flow rate of 0.055g/10min and a weight average molecular weight of 1.85 × 10)5g/mol, molecular weight distribution 4.2, melting point 129.4 ℃) and 10 wt% of metallocene linear low density polyethylene (wherein, the melt flow rate of the metallocene linear low density polyethylene is 0.6g/10min, the comonomer is hexene, the branched chain content is 1.5 mol%, and the weight average molecular weight is 1.1 multiplied by 105g/mol), adding 0.3 wt% of antioxidant (specifically, antioxidant 1010), 0.7 wt% of ultraviolet absorbent (specifically, obtained by compounding UV-0 and UV-944 in equal proportion) and 0.5 wt% of color master batch, uniformly mixing to obtain a raw material, and performing film blowing on the raw material to obtain a film, wherein the temperature of a neck ring is set to be 250 ℃ (Tm +120.6 ℃) in the film blowing process, and the temperature of cooling air of an air ring is 15 ℃ and the traction ratio is 10 by installing a refrigerant between the air ring and a fan. The film was subjected to a tensile test to obtain a tensile curve as shown in FIG. 1, as can be seen from FIG. 1, there were two yield behaviors in the tensile curve, the maximum stress was 50.8MPa, and the maximum strain was 994.8%, and the first derivative of the tensile curve was carried out to obtain the curve as shown in FIG. 2, as can be seen from FIG. 2, d σ/d ε > -0.1.
(2) And (2) performing secondary stretching and heat setting on the film to obtain a base film, wherein the stretching ratio of the secondary stretching is 3.5, the heat setting temperature is 100 ℃ (namely Tm-29.4 ℃), the structure of the base film is shown in figure 3, the horizontal transverse line in figure 3 represents the orientation direction of a molecular chain and is consistent with the traction direction in the film blowing process, and the sample is prepared along the direction when the stretching performance is tested. The base film was subjected to a tensile test to obtain a tensile curve as shown in FIG. 4, as can be seen from FIG. 4, the maximum stress was 100.4MPa, the maximum strain was 427.0%, and the tensile curve was subjected to a first order derivation to obtain a curve as shown in FIG. 5, as can be seen from FIG. 5, d σ/d ε was 0 or more.
(3) And (3) performing spiral cutting on the base membrane to obtain a plurality of membrane sheets, and performing cross compounding on 2 membrane sheets to obtain a strong cross membrane, wherein the structure of the strong cross membrane is shown in fig. 6.
Example 2
(1) 80% by weight of a high-density polyethylene (which isThe melt flow rate of the high-density polyethylene is 0.055g/10min, and the weight-average molecular weight is 1.85 multiplied by 105g/mol, molecular weight distribution 4.2, melting point 129.4 ℃) and 20 wt% of metallocene linear low density polyethylene (wherein, the melt flow rate of the metallocene linear low density polyethylene is 0.6g/10min, the comonomer is hexene, the branched chain content is 1.5 mol%, and the weight average molecular weight is 1.1 multiplied by 105g/mol), adding 0.4 wt% of antioxidant (specifically, antioxidant 1010), 0.6 wt% of ultraviolet absorbent (specifically, UV-0) and 0.6 wt% of color master batch, then mixing uniformly to obtain a raw material, and carrying out film blowing processing on the raw material to obtain a film, wherein the temperature of a neck ring is set to 245 ℃ (namely Tm +115.6 ℃) in the film blowing process, and the temperature of cooling air of an air ring is 13 ℃ and the traction ratio is 12 by installing a refrigerant between the air ring and a fan. And (3) carrying out a tensile curve obtained by carrying out a tensile test on the film, wherein the tensile curve has two yield behaviors, the maximum stress is 50.8MPa, the maximum strain is 994.8%, and the tensile curve is subjected to first-order derivation to obtain a first-order derivation curve, wherein d sigma/d epsilon is not less than-0.1.
(2) And (2) carrying out secondary stretching and heat setting on the film to obtain a base film, wherein the stretching ratio of the secondary stretching is 3.5, the heat setting temperature is 98 ℃ (namely Tm-31.4 ℃), the base film is subjected to a stretching test to obtain a stretching curve, the maximum stress in the stretching curve is 98.7MPa, the maximum strain is 444.1%, and the stretching curve is subjected to first-order derivation, wherein in the first-order derivation curve, the d sigma/d epsilon is more than or equal to 0.
(3) And (3) carrying out spiral cutting on the base membrane to obtain a plurality of membrane sheets, and carrying out cross compounding on 2 membrane sheets to obtain the strong cross membrane.
Example 3
(1) 75 wt% of high density polyethylene (wherein, the melt flow rate of the high density polyethylene is 0.015g/10min, and the weight average molecular weight is 1.6 multiplied by 105g/mol, molecular weight distribution of 3.2, melting point of 129.9 ℃) and 25 wt% of metallocene linear low density polyethylene (wherein, the melt flow rate of the metallocene linear low density polyethylene is 0.8g/10min, the comonomer is hexene, the branched chain content is 1.5 mol%, and the weight average molecular weight is 1.1 multiplied by 105g/mol) are mixed uniformlyAfter the mixing, 0.5 wt% of antioxidant (the antioxidant 1010 and the antioxidant 168 are compounded in equal proportion), 0.4 wt% of ultraviolet absorbent (the ultraviolet absorbent UV-531 and the ultraviolet absorbent UV-622 are compounded in equal proportion) and 0.6 wt% of color master batch are added, then the mixture is uniformly mixed to obtain a raw material, the raw material is subjected to film blowing to obtain a film, wherein the temperature of a neck ring is set to 230 ℃ (namely Tm +100.1 ℃) in the film blowing process, and a refrigerant is arranged between a wind ring and a fan to ensure that the temperature of cooling wind of the wind ring is 0 ℃ and the traction ratio is 15. And (3) carrying out a tensile curve obtained by carrying out a tensile test on the film, wherein the tensile curve has two yield behaviors, the maximum stress is 36.7MPa, the maximum strain is 1200.5%, and the tensile curve is subjected to first-order derivation to obtain a first-order derivation curve, wherein d sigma/d epsilon is not less than-0.1.
(2) And (2) carrying out secondary stretching and heat setting on the film to obtain a base film, wherein the stretching ratio of the secondary stretching is 4.5, the heat setting temperature is 95 ℃ (namely Tm-34.9 ℃), the base film is subjected to a stretching test to obtain a stretching curve, the maximum stress in the stretching curve is 85.5MPa, the maximum strain is 554.3%, and the stretching curve is subjected to first-order derivation, wherein the d sigma/d epsilon is more than or equal to 0 in the first-order derivation curve.
(3) And (3) carrying out spiral cutting on the base membrane to obtain a plurality of membrane sheets, and carrying out cross compounding on 2 membrane sheets to obtain the strong cross membrane.
Example 4
(1) 85 wt% of high density polyethylene (wherein, the melt flow rate of the high density polyethylene is 0.45g/10min, and the weight average molecular weight is 3.6 multiplied by 10)5g/mol, molecular weight distribution 9, melting point 130.2 ℃) and 15 wt% of metallocene linear low density polyethylene (wherein, the melt flow rate of the metallocene linear low density polyethylene is 0.5g/10min, the comonomer is hexene, the branched chain content is 1.2 mol%, and the weight average molecular weight is 2.5 multiplied by 105g/mol) to obtain a raw material, and performing film blowing processing on the raw material to obtain a film, wherein the temperature of a neck ring is set to be 280 ℃ (namely Tm +149.8 ℃) in the film blowing process, the temperature of cooling air of an air ring is 28 ℃ by installing a refrigerant between the air ring and a fan, and the traction ratio is 2.8. The tensile curve obtained by performing tensile test on the film has two yielding behaviors, and mostThe large stress is 81.4MPa, the maximum strain is 606.5%, and the first-order derivation is carried out on the tensile curve to obtain a first-order derivation curve, wherein d sigma/d epsilon is more than or equal to-0.1.
(2) And (2) carrying out secondary stretching and heat setting on the film to obtain a base film, wherein the stretching ratio of the secondary stretching is 1.8, the heat setting temperature is 115 ℃ (namely Tm-15.2 ℃), the base film is subjected to a stretching test to obtain a stretching curve, the maximum stress in the stretching curve is 101.6MPa, the maximum strain is 321.5%, and the stretching curve is subjected to first-order derivation, wherein in the first-order derivation curve, the d sigma/d epsilon is more than or equal to 0.
(3) And (3) carrying out spiral cutting on the base membrane to obtain a plurality of membrane sheets, and carrying out cross compounding on 2 membrane sheets to obtain the strong cross membrane.
Comparative example 1
(1) The raw material is a strong cross membrane with high-density polyethylene accounting for 88 percent, the rest 12 percent is an auxiliary agent, wherein the melting point of the high-density polyethylene is 130.2 ℃, the raw material is processed into a film by film blowing, the temperature of a mouth mold in the film blowing process is set to be 210 ℃ (namely Tm +79.8 ℃), the temperature of cooling air of an air ring is 30 ℃ by installing a refrigerant between the air ring and a fan, and the traction ratio is 15. The film was subjected to a tensile test to obtain a tensile curve as shown in FIG. 7, as can be seen from FIG. 7, the yield behavior was present 1 time in the tensile curve, the maximum stress was 30.9MPa, and the maximum strain was 951.6%, and the tensile curve was subjected to a first derivative to obtain a curve as shown in FIG. 8, as can be seen from FIG. 8, there was a case where d σ/d ε was less than-0.1.
(2) The film was subjected to secondary stretching and heat-setting to obtain a base film, wherein the stretch ratio of the secondary stretching was 3.5, the heat-setting temperature was 100 ℃ (i.e., Tm-30.2 ℃), and the base film was subjected to a stretching test to obtain a stretching curve as shown in fig. 9, as can be seen from fig. 9, the maximum stress was 71.0MPa, and the maximum strain was 348.2%, and the stretching curve was subjected to a first derivation to obtain a curve as shown in fig. 5, and as can be seen from fig. 5, d σ/d ∈ was less than 0.
(3) And (3) carrying out spiral cutting on the base membrane to obtain a plurality of membrane sheets, and carrying out cross compounding on 2 membrane sheets to obtain the strong cross membrane.
Comparative example 2
(1) Mixing 90 wt% of high density polyethylene (wherein the high density polyethylene has a melt flow rate of 0.055g/10min and a weight average molecular weight of 1.85 × 105g/mol, molecular weight distribution 4.2, melting point 129.4 ℃) and 10 wt% of metallocene linear low density polyethylene (wherein, the melt flow rate of the metallocene linear low density polyethylene is 0.6g/10min, the comonomer is hexene, the branched chain content is 1.5 mol%, and the weight average molecular weight is 1.1 multiplied by 105g/mol), adding 0.3 wt% of antioxidant (specifically, antioxidant 1010), 0.7 wt% of ultraviolet absorbent (specifically, obtained by compounding UV-0 and UV-944 in equal proportion) and 0.5 wt% of color master batch, uniformly mixing to obtain a raw material, and performing film blowing on the raw material to obtain a film, wherein the temperature of a neck ring is set to 220 ℃ (Tm +109.4 ℃) in the film blowing process, and the temperature of cooling air of an air ring is 30 ℃ and the traction ratio is 10 by installing a refrigerant between the air ring and a fan.
(2) And (2) performing secondary stretching and heat setting on the film to obtain a base film, wherein the stretching magnification of the secondary stretching is 3.5, the heat setting temperature is 100 ℃ (namely Tm-29.4 ℃), the base film is subjected to a stretching test to obtain a stretching curve, the maximum stress in the stretching curve is 80.6MPa, the maximum strain is 336.4%, and the stretching curve is subjected to first-order derivation, wherein the d sigma/d epsilon is less than 0 in the first-order derivation curve.
(3) And (3) carrying out spiral cutting on the base membrane to obtain a plurality of membrane sheets, and carrying out cross compounding on 2 membrane sheets to obtain the strong cross membrane.
Comparative example 3
(1) Mixing high density polyethylene (wherein the high density polyethylene has melt flow rate of 0.01g/10min, and weight average molecular weight of 1.93 × 105g/mol, the molecular weight distribution is 3.1, the melting point is 130.1 ℃), then 0.3 wt% of antioxidant (specifically, antioxidant 1010), 0.7 wt% of ultraviolet absorbent (specifically, UV-0 and UV-944 are compounded in equal proportion) and 0.5 wt% of color master batch are added, then the mixture is uniformly mixed to obtain raw material, the raw material is processed by film blowing to obtain the film, wherein the temperature of a neck ring in the film blowing process is set to be 220 ℃ (Tm +89.9 ℃),the temperature of the cooling air of the air ring is 30 ℃ by installing a refrigerant between the air ring and the fan, and the traction ratio is 12.
(2) And (2) performing secondary stretching and heat setting on the film to obtain a base film, wherein the stretching magnification of the secondary stretching is 3.5, the heat setting temperature is 100 ℃ (namely Tm-30.1 ℃), the base film is subjected to a stretching test to obtain a stretching curve, the maximum stress in the stretching curve is 78.4MPa, the maximum strain in the stretching curve is 294.1%, and the stretching curve is subjected to first-order derivation, wherein d sigma/d epsilon is less than 0 in the first-order derivation curve.
(3) And (3) carrying out spiral cutting on the base membrane to obtain a plurality of membrane sheets, and carrying out cross compounding on 2 membrane sheets to obtain the strong cross membrane.
After the base films prepared in the examples and the comparative examples are subjected to rotary cutting, film coating and cross compounding, a strong cross film (i.e., one more film coating step than the preparation of the strong cross film of the examples and the comparative examples) is prepared and compounded with self-adhesive rubber asphalt (i.e., a waterproof roll) and is subjected to actual construction tests, so as to obtain the test results shown in table 1, it should be noted that, for convenience of comparison, relevant parameters of the tensile curve of the base film are also set in table 1, wherein:
o: during the construction process, the strong cross membrane has no wrinkle and bubble defects;
and (delta): in the construction process, the strong cross membrane has a small amount of wrinkle and bubble defects;
x: in the construction process, the strong cross membrane has a large number of defects of folds and bubbles.
TABLE 1 tensile Curve and Performance test results
Figure BDA0003224377200000131
As can be seen from FIGS. 1 to 10 and Table 1, the base films prepared in examples 1 to 4 have the characteristics of high strength and high toughness, and the stress does not decrease (d σ/d ε is more than or equal to 0) in a small deformation area (less than or equal to 100%), which indicates that the base film does not generate serious microstructure damage under the action of external force, thereby preventing the service defects of the strong crossed film under the condition of small deformation. In contrast, as can be seen from comparative example 1, a typical polyethylene stretching yield phenomenon occurs in a film obtained in a film blowing stage on a common strong crossed film production line in a stretching process, namely, stress is remarkably reduced, and a finally obtained base film also has a stress reduction phenomenon in a small deformation region, which indicates that the base film has structural damage in the stretching process, and a stress plateau region appears after yielding, which represents that a material has neck expansion caused by non-uniform deformation, and the phenomena macroscopically cause service defects such as wrinkles, hollows and the like of the strong crossed film. As can be seen from comparative examples 2 and 3, when one of the parameters of the raw material formulation, the die temperature of the blown film process, the air ring cooling air temperature, etc. is not within the range provided by the present invention, a film within the tensile property range defined by the present invention is not obtained, and a base film within the tensile property range defined by the present invention is also not obtained. Meanwhile, as can be seen from comparative examples 1 to 3, when the tensile property of the base film is not within the range provided by the present invention, the strong crossed film finally prepared is easy to generate defects such as bubbling during the use process, that is, the parameters of the tensile curve of the base film have direct correlation with the generation of defects such as bubbling.
In conclusion, the invention can obtain the film meeting the tensile property by designing the parameters such as the raw material formula, the temperature of a neck ring, the cooling air temperature of an air ring, the traction ratio and the like in the film blowing processing process, and then obtain the base film with a specific tensile curve by secondary stretching and heat setting, so that the yield failure of the finally prepared strong crossed film in a small deformation area can be reduced compared with the common strong crossed film, the occurrence of service defects such as wrinkles, hollows and the like is avoided, and the finally prepared strong crossed film has excellent tensile strength and elongation at break.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.

Claims (10)

1. A preparation method of a strong cross membrane is characterized by comprising the following steps:
processing a raw material by blowing a film to obtain a film, wherein the raw material comprises a polyethylene mixture, the polyethylene mixture comprises high-density polyethylene and linear low-density polyethylene, the melt flow rate of the high-density polyethylene is 0.015-0.45 g/10min, the melting point temperature of the high-density polyethylene is Tm, the melt flow rate of the linear low-density polyethylene is 0.5-0.8 g/10min, the temperature of air ring cooling air in the film blowing processing step is 0-28 ℃, the temperature of a mouth mold is Tm + 100-Tm +150 ℃, and the traction ratio is 2.8-15.0;
performing secondary stretching and heat setting on the film to obtain a base film, and performing stretching test on the obtained base film on a universal testing machine along the traction direction to obtain a stress sigma-strain epsilon curve, wherein the maximum stress is sigmamaxMaximum strain εmaxPerforming first-order derivation on the stress sigma-strain epsilon curve to obtain d sigma/d epsilon, wherein sigma is more than or equal to 45MPamax≤150MPa，150％≤εmaxLess than or equal to 800 percent, d sigma/d epsilon satisfies that d sigma/d epsilon is more than or equal to 0;
and performing cross compounding on the base membrane after spiral cutting to obtain the strong cross membrane.
2. The method of claim 1, wherein the film obtained by the blown film process is subjected to a tensile test in a drawing direction on a universal tester to obtain a stress σ ' -strain ε ' curve, wherein the maximum stress is σ 'maxOf maximum strain is ε'maxAnd performing first-order derivation on the stress sigma ' -strain epsilon ' curve to obtain d sigma '/d epsilon ', wherein yield behavior exists at least twice in the stress sigma ' -strain epsilon ' curve, and 35MPa is less than or equal to sigma 'max≤120MPa，300％≤ε'maxIs less than or equal to 1400 percent, and d sigma '/d epsilon' meets the condition that d sigma '/d epsilon' is more than or equal to-0.1.
3. The method for producing a strong crossover film according to claim 2, wherein the secondary stretching has a stretch ratio of 1.8 to 4.5, and the heat-setting temperature is Tm-35 ℃ to Tm-5 ℃.
4. The method of making a strong crossover film of claim 1, wherein the linear low density polyethylene comprises a metallocene linear low density polyethylene; and/or the presence of a gas in the gas,
in the polyethylene mixture, the mass percent of the high-density polyethylene is not less than 75%.
5. The method for preparing a strong cross membrane according to claim 1, wherein the high density polyethylene has a weight average molecular weight of 160000-360000 g/mol and a molecular weight distribution of 3.2-9.0; and/or the presence of a gas in the gas,
the weight average molecular weight of the low-density polyethylene is 80000-250000 g/mol.
6. The method for preparing a strong crossed membrane according to claim 1, wherein the temperature of the air ring cooling air is 5-25 ℃, and the traction ratio is 3.0-12.0.
7. The method of making a strong crossover film of claim 1, wherein the maximum stress is σmaxMaximum strain εmaxD sigma/d epsilon obtained by performing first-order derivation on the stress sigma-strain epsilon curve meets the following condition:
60MPa≤σmax＜150MPa，200％≤εmaxless than or equal to 700 percent, d sigma/d epsilon satisfies d sigma/d epsilon is more than 0.
8. A strong crossover film prepared by the method of any one of claims 1 to 7.
9. A waterproofing roll characterized in that it comprises the strong crossover film of claim 8.
10. A label film comprising the strong cross-over film of claim 8.
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