CN102452204B - FFS film for heavy packaging - Google Patents
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Abstract
The invention relates to an FFS (Form, Fill, Seal) film for heavy packaging. The FFS film has a three layer structure with a thickness ratio of an external layer to a middle layer to an inner layer between 1:1:1 to 1:3:1; the external layer contains two varieties of m-LLDPEs proportioned with LDPE according to a certain proportion or is added with a certain amount of processing auxiliary agent and antistatic agent, etc.; the middle layer contains one variety of m-LLDPE proportioned with HDPE, LDPE and titanium white; and the inner layer contains two varieties of m-LLDPEs proportioned with LDPE according to a certain proportion or is added with a certain amount of processing auxiliary agent and opening agent, etc. The m-LLDPEs in the invention are all hexane copolymerizing m-LLDPEs. As application of a plurality of m-LLDPEs to the invention, a product has increased heat-seal performance; and application of m-LLDPE and HDPE enhances mechanical properties of the products. The FFS film prepared from the above raw material layers has characteristics of high strength, low unseal temperature, wide heat-seal window (a window of 120-200 DEG C) and good low temperature resistance, etc.; and the preparation technology is simple, requires no equipment addition and good economic and social benefits.
Description
Technical field
The present invention relates to a kind of packaging film, especially one is heavily packed and is used FFS film.FFS is bag (Form), charging (Fill) and sealing (Seal) integrated abbreviation, and it is a kind of advanced person's automatic packaging system, and feature is quick packaging, one-shot forming, possesses good sealed damp-proof and printing performance.The aspects such as FFS technology can be used for heavily packing, packaging for foodstuff, washing product packaging.FFS multilayer packing membrane is the film that is applicable to heavy wrapping that utilizes FFS production technology to produce.
Background technology
At present, owing to being applied to the diversity of packaging facilities of automatic packaging line of Chinese large-sized synthetical resin products, cause the very different of packaging facilities performance, and in resin transportation, there is the repeatedly feature such as transhipment, rash-and-rough way of loading and unloading, thereby make the many film products that match with the automatic packaging line of massive synthetic resin product on the market, in packaging process, there are problems, as tight in sealing, can not adapt to high-speed packaging, be stained with ash, mechanical strength not, in handling and transportation, occur that low temperature used and occurred the problems such as bale broken bale broken, winter.Along with the continuous appearance of new raw material, for the production of FFS film provides more alternative raw materials, by the selection of raw material and the appropriate design of formula, can ensure that film has good combination property in addition.The baling line update that the successful Application of FFS film can be petro-chemical corporation's naval stores lays the foundation, and to improving packaging efficiency, promotes image and has positive role.
Because having crystallization homogeneous, low melting point peak value, little molecule, metallocene LLDPE separates out the features such as less, narrow molecular weight distribution, high, the initial heat-sealing temperature of mechanical strength are low, good toughness; LDPE has higher molecular weight and moderate molecular weight distribution, higher melt strength, good mechanical property, higher melt strength and maximum melt are broken the balance of speed, good film in length and breadth to mechanical balance performance; HDPE has higher molecular weight, wide, good deflection and the rigidity of molecular weight distribution; So for the requirement to FFS film on market, FFS film is all generally to adopt m-LLDPE, LLDPE, HDPE, LDPE etc. as raw material both at home and abroad.Publication number is to disclose a kind of polyethylene repackaging film material composition in the patent documentation of CN101255249A, said composition comprises a kind of linear low density polyethylene (LLDPE), account for 60 ~ 80% of raw material total amount, and metallocene linear low density polyethylene, account for 10 ~ 30% of raw material total amount, publication number is in the patent documentation of CN101255249A, what raw material use was maximum is C6 comonomer linear low density polyethylene (LLDPE), the data of embodiment in comprehensive this patent, can find out, the patented product mechanical strength has just met standard-required, may be in the existing resin transport of China, transhipment, in cargo handling process, there will be the phenomenons such as bale broken.Publication number is the production method that the patent documentation of CN1978184A discloses a kind of blowing-film for bags, and the nexine of this film and skin all contain linear low density polyethylene (LLDPE), and intermediate layer does not comprise metallocene linear low density polyethylene.Publication number is that the patent documentation of CN1951773A discloses a kind of multilayer packing membrane and manufacture method thereof, and this film has used a large amount of linear low density polyethylene (LLDPE)s, but does not use metallocene linear low density polyethylene; Because it does not use metallocene linear-low density polyethylene, so the heat-sealing window of this product can be very narrow and its mechanical strength be not very high, from the embodiment of this patent documentation, can find out, its mechanical strength just meets standard-required, and do not mention the problem of heat-sealing, in the existing resin transport of China, transhipment, cargo handling process, there will be bale broken phenomenon.
In order to overcome the problems referred to above, the invention provides one and heavily pack and use FFS film, it has three-decker, its ectomesoderm: middle level: the Thickness Ratio of internal layer is between between 1:1:1 to 1:3:1; Skin contains two kinds of m-LLDPE, and itself and LDPE proportioning by a certain percentage also can add a certain amount of processing aid, antistatic additive etc.; 1 kind of m-LLDPE is contained in middle level, itself and HDPE, LDPE, titanium white proportioning by a certain percentage; Internal layer contains 2 kinds of m-LLDPE, and itself and LDPE proportioning by a certain percentage also can add a certain amount of processing aid, opening agent etc.; In the present invention, related m-LLDPE is hervene copolymer m-LLDPE.Due to the application of multiple m-LLDPE in the present invention, the heat sealability of product is improved; And the application of m-LLDPE, HDPE is improved the mechanical property of product.The FFS film that adopts above-mentioned each layer of raw material to make, have mechanical strength high, play that envelope temperature is low, heat-sealing window wide (window is 120 DEG C ~ 200 DEG C), the low temperature resistant feature such as effective, its preparation technology is simple, without increasing equipment, there is good economic benefit and social benefit.
Summary of the invention
The present invention relates to one and heavily pack and use FFS film, it has three-decker, it is characterized in that: skin: middle level: the Thickness Ratio of internal layer is between between 1:1:1 to 1:3:1; Skin comprises two kinds of m-LLDPE and a kind of LDPE, and a kind of m-LLDPE is wherein hervene copolymer m-LLDPE, and melt mass flow rate is 0.5g/10min ~ 1.5g/10min, and density is 0.918 ± 0.002g/cm
3, in layer, mass fraction is 20 ~ 60 parts, and another kind of m-LLDPE is also hervene copolymer m-LLDPE, and melt mass flow rate is 1.5g/10min ~ 2.5g/10min, and density is 0.913 ± 0.002g/cm
3, in layer, mass fraction is 10 ~ 50 parts, and LDPE is homopolymerization LDPE, and melt mass flow rate is 0.2g/10min ~ 0.4g/10min, and density is 0.922 ± 0.003g/cm
3, in layer, mass fraction is 20 ~ 40 parts; Middle level comprises m-LLDPE, HDPE, LDPE and titanium white, and wherein m-LLDPE is hervene copolymer m-LLDPE, and melt mass flow rate is 0.5g/10min ~ 1.5g/10min, and density is 0.918 ± 0.002g/cm
3, in layer, mass fraction is 40 ~ 80 parts, and HDPE is 1-butylene copolymerization HDPE, and melt mass flow rate is 0.05g/10min ~ 0.15g/10min, and density is 0.952 ± 0.004g/cm
3, in layer, mass fraction is 10 ~ 30 parts, and the melt mass flow rate of LDPE is 0.2g/10min ~ 0.4g/10min, and density is 0.922 ± 0.003g/cm
3, in layer, mass fraction is 10 ~ 30 parts, titanium white content is 6000 ~ 18000PPM; Internal layer comprises two kinds of m-LLDPE and a kind of LDPE, and a kind of m-LLDPE is wherein hervene copolymer m-LLDPE, and melt mass flow rate is 0.5g/10min ~ 1.5g/10min, and density is 0.918 ± 0.002g/cm
3, in layer, mass fraction is 20 ~ 60 parts, and the melt mass flow rate of another kind of m-LLDPE is 1.5g/10min ~ 2.5g/10min, and density is 0.913 ± 0.002g/cm
3, in layer, mass fraction is 10 ~ 50 parts, and LDPE is homopolymerization LDPE, and melt mass flow rate is 0.2g/10min ~ 0.4g/10min, and density is 0.922 ± 0.003g/cm
3, in layer, mass fraction is 10 ~ 30 parts.The above various raw material is commercial.
By above-mentioned each layer component list, set every layer of resin by mass parts each 100 parts, technique scheme is as shown in table 1.
Table 1, the each layer component of FFS film and proportioning thereof
Above-mentioned skin also can add appropriate processing aid, antistatic additive; Internal layer also can add appropriate processing aid, opening agent.
Described a kind of m-LLDPE is a kind of hexene copolymer, and melt mass flow rate (190 DEG C, 2.16kg) is 0.5g/10min ~ 1.5g/10min, and density is 0.918 ± 0.002g/cm
3, there is comonomer unit and be uniformly distributed on strand, crystallization homogeneous, without the large molecule of low co-monomer content, low melting point peak value, without the little molecule of high comonomer content, the feature such as molecule is separated out less, narrow molecular weight distribution; For film metallocene linear-low density polyethylene.
Described another kind of m-LLDPE is a kind of hexene copolymer, and melt mass flow rate (190 DEG C, 2.16kg) is 1.5g/10min ~ 2.5g/10min, and density is 0.913 ± 0.002g/cm
3, there is the features such as intensity is good, heat-sealing temperature is low, good toughness, narrow molecular weight distribution, be film metallocene linear-low density polyethylene.
Described HDPE is butene-1 copolymer, and melt mass flow rate (190 DEG C, 2.16kg) is 0.05g/10min ~ 0.15g/10min, and density is 0.952 ± 0.004g/cm
3, there is HMW, molecular weight distribution is wide, the good feature such as toughness, rigidity, for extrude or film resin dedicated.
Described LDPE is homopolymers, and for melt mass flow rate (190 DEG C, 2.16kg) is 0.2g/10min ~ 0.4g/10min, density is 0.922 ± 0.003g/cm
3there is higher molecular weight and moderate molecular weight distribution, the reasonably feature such as degree of branching control and stronger crystallizing power, thus make it to there is good mechanical property, balance that higher melt strength and maximum melt are broken speed, good processing characteristics, for film resin dedicated.
Described antistatic additive is quaternary amine or alkylphosphonic.
Described opening agent is synthetic silica class or diatom great soil group or talcs opening agent.
Described processing aid is fluoropolymer additive.
Main performance index and the testing standard of heavy duty packaging film product are as shown in table 2.
The main performance index of table 2, heavy duty packaging film product and testing standard
Detailed description of the invention
Embodiment 1
Heavily packaging is as shown in table 3 with the each layer component of FFS film and proportioning thereof.
Table 3, the heavily each layer component of FFS film and proportioning thereof for packaging
Note: 1018CA is EXXON company of U.S. product; SP1520 is Mitsui company product; LD163 is Yanshan Petrochemical product; DFDA6098 is Qilu Petrochemical product; Titanium white adds with master batch form, and titanium white master batch is Capote company product; Fluoropolymer additive is 3M company product.
The FFS film properties of producing with this formula is as shown in table 4.
Table 4, FFS film properties
Note: freezing fall-down test, mainly investigate this formula use in winter situation, China's winter temperature is less lower than the region of-21 DEG C, by the result of-21 DEG C of freezing experiments of 48 hours of test, in China's territorial scope, the use of low temperature environment FFS, representative.
Heat-sealing temperature and the heat sealing strength of the FFS film of producing with this formula are as shown in table 5.
Table 5, heat-sealing temperature and heat sealing strength
* note: heat sealed time 1 second, pressure is 0.4MPa.
Because China is not now about the definition that plays envelope temperature and heat-sealing window, synthesis's standard, practical experience, with reference to QB/T2358-1998 heat sealing strength standard, definition heat sealed time 1 second, pressure is 0.4Mpa, and when hot strength >=30N/15mm, heat-sealing temperature has been defined as envelope temperature; Heat sealing strength≤30N/15mm, or while there is serious heat-sealing breakoff phenomenon in film seal place, is defined as the highest heat-sealing temperature; From envelope temperature be defined as heat-sealing window to the highest heat-sealing temperature.
Embodiment 2
Heavily packaging is as shown in table 6 with the each layer component of FFS film and proportioning thereof.
Table 6, the heavily each layer component of FFS film and proportioning thereof for packaging
Note: 1018CA is EXXON company of U.S. product; SP1520 is Mitsui company product; LD163 is Yanshan Petrochemical product; DFDA6098 is Qilu Petrochemical product; Titanium white adds with master batch form, and titanium white master batch is Capote company product; Fluoropolymer additive is 3M company product.
The FFS film properties of producing with this formula is as shown in table 7.
Table 7, FFS film properties
Heat-sealing temperature and the heat sealing strength of the FFS film of producing with this formula are as shown in table 8.
Table 8 heat-sealing temperature and heat sealing strength
* note: heat sealed time 1 second, pressure is 0.4MPa.This embodiment, heat-sealing window is 125 DEG C ~ 200 DEG C.
Embodiment 3
Heavily packaging is as shown in table 9 with the each layer component of FFS film and proportioning thereof.
Table 9, the heavily each layer component of FFS film and proportioning thereof for packaging
Note: 1018CA is EXXON company of U.S. product; SP1520 is Mitsui company product; LD163 is Yanshan Petrochemical product; DFDA6098 is Qilu Petrochemical product; Titanium white adds with master batch form, and titanium white master batch is Capote company product; Fluoropolymer additive is 3M company product; Antistatic additive is to add with master batch form, this antistatic agent functional master batches AS G2 AE3 be a kind of taking low density polyethylene (LDPE) as carrier, the fast long-acting combination antistatic master granule that contains 2% glyceryl monostearate and 3% ethoxylated amine, be Rui Tulan (Tianjin) Science and Technology Ltd. product.
The FFS film properties of producing with this formula is as shown in table 10.
Table 10, FFS film properties
Heat-sealing temperature and the heat sealing strength of the FFS film of producing with this formula are as shown in table 11.
Table 11 heat-sealing temperature and heat sealing strength
Product antistatic effect is good, and heat seal strength is high, and heat-sealing window is wide, and heat-sealing window is 120 DEG C ~ 190 DEG C.
Embodiment 4
Heavily packaging is as shown in table 12 with the each layer component of FFS film and proportioning thereof.
Table 12, the heavily each layer component of FFS film and proportioning thereof for packaging
Note: 1018CA is EXXON company of U.S. product; SP1520 is Mitsui company product; LD163 is Yanshan Petrochemical product; DFDA6098 is Qilu Petrochemical product; Titanium white adds with master batch form, and titanium white master batch is Capote company product.
The FFS film properties of producing with this formula is as shown in table 13.
Table 13, FFS film properties
Heat-sealing temperature and the heat sealing strength of the FFS film of producing with this formula are as shown in table 14.
Table 14 heat-sealing temperature and heat sealing strength
Product heat seal strength is high, and heat-sealing window is wide, and heat-sealing window is 130 DEG C ~ 200 DEG C.
Embodiment 5
Heavily packaging is as shown in Table 15 with the each layer component of FFS film and proportioning thereof.
Table 15, the heavily each layer component of FFS film and proportioning thereof for packaging
Note: 1018CA is EXXON company of U.S. product; SP1520 is Mitsui company product; LD163 is Yanshan Petrochemical product; 7000F is Yanshan Petrochemical product; Titanium white adds with master batch form, and titanium white master batch is Capote company product.
The FFS film properties of producing with this formula is shown in table 16.
Table 16, FFS film properties
Heat-sealing temperature and the heat sealing strength of the FFS film of producing with this formula are shown in table 17.
Table 17 heat-sealing temperature and heat sealing strength
Product heat seal strength is high, and heat-sealing window is wide, and heat-sealing window is 120 DEG C ~ 200 DEG C.
Embodiment 6
Heavily packaging is shown in table 18 with the each layer component of FFS film and proportioning thereof.
Table 18, the heavily each layer component of FFS film and proportioning thereof for packaging
Note: 1018CA is EXXON company of U.S. product; SP1520 is Mitsui company product; LD163 is Yanshan Petrochemical product; DFDA6098 is Qilu Petrochemical product; Titanium white adds with master batch form, and titanium white master batch is Capote company product; AB905 is INEOS Silicas company product.
The FFS film properties of producing with this formula is shown in table 19.
Table 19, FFS film properties
Heat-sealing temperature and the heat sealing strength of the FFS film of producing with this formula are shown in table 20.
Table 20, heat-sealing temperature and heat sealing strength
Product heat seal strength is high, and heat-sealing window is wide, and heat-sealing window is 120 DEG C ~ 200 DEG C.
Embodiment 7
Heavily packaging is shown in table 21 with the each layer component of FFS film and proportioning thereof.
Table 21, the heavily each layer component of FFS film and proportioning thereof for packaging
Note: 1018CA is EXXON company of U.S. product; SP1520 is Mitsui company product; LD163 is Yanshan Petrochemical product; DFDA6098 is Qilu Petrochemical product; Titanium white adds with master batch form, and titanium white master batch is Capote company product.
The FFS film properties of producing with this formula is shown in table 22.
Table 22, FFS film properties
Heat-sealing temperature and the heat sealing strength of the FFS film of producing with this formula are shown in table 23.
Table 23 heat-sealing temperature and heat sealing strength
Product heat seal strength is high, and heat-sealing window is wide, and heat-sealing window is 125 DEG C ~ 195 DEG C.
Comparative example 1:
Each layer component and proportioning thereof are shown in table 24.
Table 24, each layer component and proportioning thereof
The FFS film properties of producing with this formula is as shown in Table 25.
Table 25, FFS film properties
Heat-sealing temperature and the heat sealing strength of the FFS film of producing with this formula are shown in table 26.
Table 26 heat-sealing temperature and heat sealing strength
The heat-sealing window of this contrast sample is 130 DEG C ~ 160 DEG C.
Can find out from the detection data of comparative example, its heat-sealing window is narrower than embodiment, and low temperature fall-down test fails to reach requirement.
Adopt three-layer co-extruded technology to produce FFS film, three-layer extrusion film can decompose quality index, reaches total quality and meets the requirements thereby utilize different retes to meet different product quality indicator items.Three-layer extrusion film more easily carrys out combination raw materials formula neatly according to the confession commodity price in market and user's request, and to reach optimum economic benefit, adaptability to raw materials is wide, and properties of product are more excellent.
According to the character of different retes and requirement, as each layer of raw material of design and proportionings such as requirement of strength, heat-sealing requirement, stiffness requirement and processing characteristics requirements.Selected formula proves through three layers of composite testing repeatedly, and this formula film-blowing process is stable, and the film mechanical strength of blowing is high, and especially heat sealability is with the obvious advantage.
-21 DEG C have been carried out 2 meters of fall-down tests after freezing 48 hours, after 6 directions are fallen for 6 times respectively, any breakage does not occur, and the resistance to drop performance after freezing has reached the requirement of the resistance to property fallen in product standard, illustrates that this formula has good intensity at low temperatures too.
Claims (7)
1. heavily packaging is used a FFS film, and it has three-decker, it is characterized in that: skin: middle level: the Thickness Ratio of internal layer is between between 1:1:1 to 1:3:1; Skin comprises two kinds of m-LLDPE and a kind of LDPE, and the melt mass flow rate of a kind of m-LLDPE is wherein 0.5g/10min ~ 1.5g/10min, and density is 0.918 ± 0.002g/cm
3, in layer, mass fraction is 20 ~ 60 parts, and the melt mass flow rate of another kind of m-LLDPE is 1.5g/10min ~ 2.5g/10min, and density is 0.913 ± 0.002g/cm
3, in layer, mass fraction is 10 ~ 50 parts, and the melt mass flow rate of LDPE is 0.2g/10min ~ 0.4g/10min, and density is 0.922 ± 0.003g/cm
3, in layer, mass fraction is 20 ~ 40 parts; Middle level comprises m-LLDPE, HDPE, LDPE and titanium white, and wherein the melt mass flow rate of m-LLDPE is 0.5g/10min ~ 1.5g/10min, and density is 0.918 ± 0.002g/cm
3, in layer, mass fraction is 40 ~ 80 parts, and the melt mass flow rate of HDPE is 0.05g/10min ~ 0.15g/10min, and density is 0.952 ± 0.004g/cm
3, in layer, mass fraction is 10 ~ 30 parts, and the melt mass flow rate of LDPE is 0.2g/10min ~ 0.4g/10min, and density is 0.922 ± 0.003g/cm
3, in layer, mass fraction is 10 ~ 30 parts, titanium white content is 6000 ~ 18000PPM; Internal layer comprises two kinds of m-LLDPE and a kind of LDPE, and the melt mass flow rate of a kind of m-LLDPE is wherein 0.5g/10min ~ 1.5g/10min, and density is 0.918 ± 0.002g/cm
3, in layer, mass fraction is 20 ~ 60 parts, and the melt mass flow rate of another kind of m-LLDPE is 1.5g/10min ~ 2.5g/10min, and density is 0.913 ± 0.002g/cm
3, in layer, mass fraction is 10 ~ 50 parts, and LDPE is homopolymers, and melt mass flow rate is 0.2g/10min ~ 0.4g/10min, and density is 0.922 ± 0.003g/cm
3, in layer, mass fraction is 10 ~ 30 parts; The m-LLDPE of above-mentioned each layer is hervene copolymer m-LLDPE, and the HDPE in middle level is 1-butylene copolymerization HDPE.
2. heavy packaging FFS film as claimed in claim 1, its skin also comprises antistatic additive.
3. heavy packaging FFS film as claimed in claim 1, its internal layer also comprises opening agent.
4. heavy packaging FFS film as claimed in claim 1, its skin or internal layer also comprise the conventional processing aid in this area.
5. heavy packaging FFS film as claimed in claim 2, described antistatic additive is quaternary amine or alkylphosphonic.
6. heavy packaging FFS film as claimed in claim 3, described opening agent is synthetic silica class, diatom great soil group or talcs opening agent.
7. heavy packaging FFS film as claimed in claim 4, described processing aid is fluoropolymer additive.
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| CN111483196B (en) * | 2020-04-09 | 2022-11-04 | 广州新文塑料有限公司 | Three-layer co-extrusion heavy packaging film and preparation method thereof |
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| JP特许第3367348号B2 2003.01.14 |
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| Publication number | Publication date |
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| CN102452204A (en) | 2012-05-16 |
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