CN103101273B - Laminated packaging material - Google Patents

Laminated packaging material Download PDF

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Publication number
CN103101273B
CN103101273B CN201210594654.2A CN201210594654A CN103101273B CN 103101273 B CN103101273 B CN 103101273B CN 201210594654 A CN201210594654 A CN 201210594654A CN 103101273 B CN103101273 B CN 103101273B
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ldpe
layer
10min
melt flow
flow index
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CN201210594654.2A
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CN103101273A (en
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吴壮
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TAIZHOU ZHUYE MACHINERY TECHNOLOGY Co Ltd
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TAIZHOU ZHUYE MACHINERY TECHNOLOGY Co Ltd
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Application filed by TAIZHOU ZHUYE MACHINERY TECHNOLOGY Co Ltd filed Critical TAIZHOU ZHUYE MACHINERY TECHNOLOGY Co Ltd
Priority to CN201510156846.9A priority Critical patent/CN104760379A/en
Priority to CN201210594654.2A priority patent/CN103101273B/en
Priority to CN201510156842.0A priority patent/CN104760354A/en
Priority to CN201510156835.0A priority patent/CN104760353A/en
Priority to CN201510156845.4A priority patent/CN104760355A/en
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Abstract

The invention provides a laminated packaging material. The laminated packaging material comprises an outermost thermoplastic material layer, a sandwich layer, an intermediate thermoplastic material layer, a barrier layer and an innermost thermoplastic material layer from outside to inside, wherein the intermediate thermoplastic material layer is made of metalloscene-catalyst-polymerized linear low-density polyethylene (mLLDPE) and LDPE; for the metalloscene catalyst polymerized mLLDPE, the mean density is 0.88-0.925g/cm<3>, the melt flow index (190 DEG C and 2.16kg) is 5-20g/10min, the peak melting point is 85-130 DEG C and the expansion ratio is 1.2-1.8; and for the LDPE, the mean density is 0.90-0.925g/cm<3>, the melt flow index (190 DEG C and 2.16kg) is 5-20g/10min, the peak melting point is 85-110 DEG C and the expansion ratio is 1.2-1.8. Packaging containers with good sealing strength can be obtained by using the laminated packaging material, the percent of pass of the prepared packaging containers is high, and liquid food in the prepared packaging containers is long in quality guarantee period.

Description

A kind of laminate wrapping material
Technical field
The present invention relates to a kind of laminate wrapping material, particularly relate to a kind of laminate wrapping material for packaging liquid food.
Background technology
At present, for the disposable ARTPackaging containers of liquid food, there is brick, square, triangle, cross section is hexagonal octahedral bodily form, the shapes such as pillow-like, the laminate wrapping material of usual these packing containers of manufacture comprises the thermoplastic outermost layer of lamination successively, sandwich layer, thermoplastic intermediate layer, barrier layer, adhesive phase and thermoplastic innermost layer, also low density polyethylene (LDPE) (LDPE)/printing layer of ink/paper (fiber) base layer/LDPE/ aluminium foil AL/LDPE/LDPE adopting high-pressure process to produce is had, LDPE/ prints layer of ink/paper matrix layer/LDPE/LDPE, printing layer of ink/LDPE/ paper matrix layer/LDPE/LDPE, the laminate wrapping material of the sandwich constructions such as layer of ink/paper matrix layer/LDPE/ aluminium/polyester (PET) is printed as LDPE/.The food liquid that these packing containers can be packed has fresh milk, yoghurt, fruit juice etc.
Conventional core material has paper, brown paper or hardboard etc., conventional barrier material has aluminium foil, metal/inorganic oxide film, ethylene-vinyl alcohol copolymer (EVOH), nylon etc., conventional thermoplastic outermost layer, intermediate layer, the low density polyethylene (LDPE) (LDPE) of the useful high-pressure process production of material of innermost layer, LLDPE (LLDPE), by the thermoplastic such as ethyleneα-olefincopolymer (mLLDPE) of metallocene catalyst catalyzed polymerization, conventional adhesive has polyurethane binder, Polyester Polyurethane Adhesive, polyether polyurethane adhesive, acrylic adhesive, polyester binder, polyamide binder, polyvinylacetate adhesive, epoxy adhesive, rubber adhesive etc.
The effect of each layer of packaging material is: thermoplastic outermost layer effectively can stop that extraneous moisture, pollution or other magazines enter in packaging material, and being formed in packing container process with thermoplastic innermost layer longitudinal sealing at laminate wrapping material is that laminate wrapping material forms tubulose; Sandwich layer can supporting package container; Thermoplastic intermediate layer and barrier layer can effectively prevent food liquid from entering into sandwich layer, and simultaneously starvation, sunlight make packing container not light leak, air tight, particularly do not leak oxygen, ensure that food liquid taste does not run off; Thermoplastic innermost layer directly contacts with food liquid, while guarantee food liquid quality, prevent food liquid to the infiltration of other each layers of packaging material; Adhesive phase adds the adhesion strength between high containment and thermoplastic innermost layer.
Fig. 1 shows a kind of common method manufacturing laminate wrapping material, machine guiding core layer coiled material 1 moves ahead by the pressure roller of stamping station 2, process the hole needed for packing container opening device and the impression needed for folded wrapping materials, continue to guide the sandwich layer coiled material 11 of perforate forward, arrive laminating bench 5, extruder 3 squeezes out thermoplastic intermediate layer coiled material and guides it to and reaches laminating bench 5 herein, barrier layer coiled material 4 is directed to laminating bench 5 simultaneously, laminating bench 5 pairs of three-layer coil materials carry out lamination, in its roll gap center core layer, thermoplastic intermediate layer and barrier layer are pressed together, and thermoplastic intermediate layer is between sandwich layer and barrier layer, become laminate 111. guide layer pressing plate 111 thus and arrive next stage laminating bench 6, herein by coextruding and coat the opposite side on thermoplastic innermost layer 7 paint laminate 111 barrier layer, in the roll gap of laminating bench 6, laminate 111 and thermoplastic innermost layer 7 are pressed together, form the laminated material 1111 that inner side is coated with thermoplastic innermost layer thus, afterwards by extrusion coated thermoplastic outermost layer on sandwich layer opposite side i.e. outside coating, so far the laminate wrapping material that packing container is used is obtained.Certainly, the outermost coating of thermoplastic might not be placed on final step and carry out, and also can according to circumstances apply in step suitable before.
The packing container of the laminate wrapping material Production and Packaging food liquid that available said method is made.Secondary pollution is suffered in order to prevent packaged food liquid, the production process of whole packing container is all aseptically carried out: be first shaped to by laminate wrapping material cylindric, and form tube in the longitudinal sealing-in of side, then the horizontal sealing-in in tube one end, form top or the bottom of packing container, fill required food liquid afterwards, finally the residue of tube is held horizontal sealing-in, make bottom or the top of packing container.By cutting transverse packed region, single independently packing container can be formed, and by these independently packing container deliver in final folding and shaped device and be converted into net shape, as brick or other shapes.Laminate wrapping material is in formation packing container process, and the bond strength between papery base layer and barrier layer affects the qualification rate of packing container and the shelf lives of food liquid.
Chinese invention patent application prospectus CN1337914A discloses a kind of paper container package material, the constituting layer at least comprised has thermoplastic outermost layer, papery base layer, thermoplastic intermediate layer, each constituting layer is also pressed said sequence lamination by barrier layer and thermoplastic innermost layer, be characterised in that: thermoplastic innermost layer at least comprises the LLDPE with narrow molecular weight distribution, there is following performance parameter: averag density 0.900-0.915, Peak melting point 88-103 DEG C, melt flow index 5-20, expansion ratio (SR) 1.4-1.6 and thickness 20-50 micron, thermoplastic intermediate layer also adopts the material identical with aforementioned innermost layer to make.These packaging material make to be easy to pouring package packing container and rapid heat-seal, obtain the more firm container sealed more by force, this material can be used for the excellent sealing that realizes independent of in-built food temperature and thus maintains the ability that in-built product never degenerates and guarantee the quality, but, this packaging material are in the extruding layer compression technology of manufacture process, serious necking phenomenon can be there is from during the die head film extrusion of extruder in thermoplastic intermediate layer in molten condition, namely extrusion die dual-side can to middle shrinkage, even there is the phenomenon of breach in edge thickness inequality, papery base layer both sides can be made like this to be capped or cladding thickness uneven, flaw is there is in order to prevent finished product packing material, usually three kinds of solutions are had, a kind of is do wider than the width on papery base layer and barrier layer by the die head of extruder, the defective part in extrusion die both sides is made not cover on papery base layer, in follow-up lamination operation, cooling forming excises again, another kind is done by the width on papery base layer and barrier layer wider, and after extruding lamination, the flaw part of excision packaging material both sides, obtains qualified packaging material, moreover reduce necking phenomenon infringement by increasing thermoplastic intermediate layer thickness.These three kinds of solutions all need many wider than the width on papery base layer and barrier layer of extruder die head, need more heat heating and melting thermoplastic, cause energy waste, and after lamination completes, also will excise the flaw part of packaging material both sides, cause waste of raw materials.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of laminate wrapping material, combine firmly between the barrier layer of this laminate wrapping material and sandwich layer, the qualification rate of the packing container made is high, the shelf lives of food liquid is long, and can not there is serious necking phenomenon when extruding lamination thermoplastic intermediate layer in the fabrication process in it, can not cause the serious energy and waste of raw materials.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is: a kind of laminate wrapping material, comprise thermoplastic outermost layer, sandwich layer, thermoplastic intermediate layer, barrier layer and thermoplastic innermost layer from outside to inside, wherein, described thermoplastic intermediate layer comprises LLDPE (MLLDPE) and the low density polyethylene (LDPE) (LDPE) of metalloscene catalyst polymerization; The LLDPE (mLLDPE) of described metalloscene catalyst polymerization has following parameter: averag density is 0.88g/cm3 ~ 0.925g/cm3, melt flow index (190 DEG C, 2.16kg) is 5g/10min ~ 20g/10min, Peak melting point is 85 DEG C ~ 130 DEG C, expansion ratio is 1.2 ~ 1.8; Described low density polyethylene (LDPE) (LDPE) has following parameter: averag density is 0.90g/cm 3~ 0.925g/cm 3, melt flow index (190 DEG C, 2.16kg) is 5g/10min ~ 20g/10min, Peak melting point is 85 DEG C ~ 110 DEG C, expansion ratio is 1.2 ~ 1.8.
In the present invention, melt flow index according in GB/T3682-2000 melt flow index assay method 190 DEG C, the condition determination of 2.16kg measures.Expansion ratio represents under the condition determination (namely 190 DEG C, 2.16kg) identical with GB/T3682-2000 melt flow index assay method, the cross sectional dimensions of the extrudate of measured depanning and the cross sectional dimensions ratio of die orifice.Peak melting point is obtained by differential scanning calorimetry, if two or more peak value, refers to first peak value.Low density polyethylene (LDPE) (LDPE) can be LLDPE (LLDPE), can be also non-linear low density polyethylene (LDPE), as long as have above-mentioned performance parameter just can meet requirement of the present invention.
One as technique scheme is improved, and wherein, the LLDPE (mLLDPE) of described metalloscene catalyst polymerization has following parameter: averag density is 0.90g/cm 3~ 0.915g/cm 3, melt flow index (190 DEG C, 2.16kg) is 5g/10min ~ 20g/10min, Peak melting point is 88 DEG C ~ 120 DEG C, expansion ratio is 1.4 ~ 1.6.
As the further improvement of technique scheme, wherein, the averag density of the LLDPE (mLLDPE) of described metalloscene catalyst polymerization is 0.905g/cm 3~ 0.910g/cm 3, melt flow index (190 DEG C, 2.16kg) is 5g/10min ~ 20g/10min, Peak melting point is 93 DEG C ~ 103 DEG C, expansion ratio is 1.4 ~ 1.6.
As the further improvement of technique scheme, wherein, described low density polyethylene (LDPE) (LDPE) has following parameter: averag density is 0.910g/cm 3~ 0.92g/cm 3, melt flow index (190 DEG C, 2.16kg) is 5g/10min ~ 20g/10min, Peak melting point is 85 DEG C ~ 110 DEG C, expansion ratio is 1.4 ~ 1.6.
As the further improvement of technique scheme, wherein, the averag density of described low density polyethylene (LDPE) (LDPE) is 0.915g/cm 3~ 0.920g/cm 3, melt flow index (190 DEG C, 2.16kg) is 5g/10min ~ 20g/10min, Peak melting point is 93 DEG C ~ 103 DEG C, expansion ratio is 1.4 ~ 1.6.
As the further improvement of technique scheme, wherein, the weight percentage (wt) of the LLDPE (mLLDPE) of described metalloscene catalyst polymerization is 50% ~ 80%, and the weight percentage (wt) of described low density polyethylene (LDPE) (LDPE) is 20% ~ 50%.
As the further improvement of technique scheme, wherein, the weight percentage (wt) of the LLDPE (mLLDPE) of described metalloscene catalyst polymerization is 60% ~ 75%, and the weight percentage (wt) of described low density polyethylene (LDPE) (LDPE) is 25% ~ 40%.
As the further improvement of technique scheme, wherein, the weight percentage (wt) of the LLDPE (mLLDPE) of described metalloscene catalyst polymerization is 70%, and the weight percentage (wt) of described low density polyethylene (LDPE) (LDPE) is 30%.
The present invention compared with prior art, thermoplastic intermediate layer due to laminate wrapping material have employed the LLDPE (MLLDPE) and low density polyethylene (LDPE) (LDPE) with the polymerization of particular characteristic parameter metalloscene catalyst, in the extruding layer compression technology of manufacture process, thermoplastic intermediate layer to obtain from the necking phenomenon during die head film extrusion of extruder in molten condition and largely reduces, the energy and waste of raw materials phenomenon have and largely suppress, and between barrier layer and sandwich layer in conjunction with firm, the qualification rate of the packing container made is high, the shelf lives of food liquid is long.
Figure of description
Fig. 1 is a kind of schematic diagram manufacturing laminate wrapping material method.
Fig. 2 is the cross sectional representation of a kind of laminate wrapping material of the present invention.
Detailed description of the invention
As shown in Figure 2, a kind of laminate wrapping material of the present invention comprises thermoplastic outermost layer 21, sandwich layer 22, thermoplastic intermediate layer 23, barrier layer 24, adhesive phase 25 and thermoplastic innermost layer 26 from outside to inside successively.
Thermoplastic intermediate layer 23 comprises LLDPE (MLLDPE) and the low density polyethylene (LDPE) (LDPE) of metalloscene catalyst polymerization, wherein, the LLDPE (mLLDPE) of metalloscene catalyst polymerization has following parameter: averag density is 0.88g/cm 3~ 0.925g/cm 3, melt flow index (190 DEG C, 2.16kg) is 5g/10min ~ 20g/10min, Peak melting point is 85 DEG C ~ 130 DEG C, expansion ratio is 1.2 ~ 1.8; Low density polyethylene (LDPE) (LDPE) has following parameter: averag density is 0.90g/cm 3~ 0.925g/cm 3, melt flow index (190 DEG C, 2.16kg) is 5g/10min ~ 20g/10min, Peak melting point is 85 DEG C ~ 110 DEG C, expansion ratio is 1.2 ~ 1.8, low density polyethylene (LDPE) (LDPE) can be LLDPE, also can be non-LLDPE.The weight percentage (wt) of the LLDPE (mLLDPE) of metalloscene catalyst polymerization is 50% ~ 80%, and the weight percentage (wt) of low density polyethylene (LDPE) (LDPE) is 20% ~ 50%.
Sandwich layer 22 is the coiled material of paper substrates, after lateral surface printed patterns, crease line is suppressed and after stamping out open hole through indentation roller, thermoplastic outermost layer 21 is formed in the outside of sandwich layer 22 by extruding layer compression technology with low-density polyethylene material, continue to guide the sandwich layer coiled material of impression perforate forward, arrive laminating bench, LLDPE (mLLDPE) and the low density polyethylene (LDPE) of the blended metalloscene catalyst polymerization of the weight percentage (wt) herein in extruder difference according to the form below 1 obtain blend, respectively with thickness for 10, 15, 20, the blend extruding layer of 25 microns is pressed onto on papery sandwich layer 21 medial surface and forms thermoplastic intermediate layer 23, aluminum foil coiled material simultaneously as barrier layer 24 is directed to laminating bench, laminating bench carries out lamination compound to trilaminate material, at its roll gap center core layer 22 medial surface, thermoplastic intermediate layer 23 and barrier layer 24 are pressed together, when this blend extrudes formation film from extruder die orifice, film both sides do not form breach, edge thickness is substantially even, dual-side can be very little to middle shrinkage, it is even that these multilayer material both sides are capped thickness, combine firmly between the sandwich layer 22 of the laminate wrapping material obtained and barrier layer 24, the qualification rate of the packing container made is high, the shelf lives of food liquid is long.
Then, form adhesive phase 25 being pressed onto on barrier layer 24 by polyvinylacetate adhesive extruding layer, the LLDPE (mLLDPE) of blended metalloscene catalyst polymerization and low density polyethylene (LDPE) obtain blend again, wherein, the LLDPE (mLLDPE) of metalloscene catalyst polymerization has following parameter: averag density is 0.910g/cm3, melt flow index (190 DEG C, 2.16kg) is 13g/10min, Peak melting point is 124 DEG C, expansion ratio is 1.5; Low density polyethylene (LDPE) (LDPE) has following parameter: averag density is 0.918g/cm 3, melt flow index (190 DEG C, 2.16kg) is 7g/10min, Peak melting point is 107 DEG C, expansion ratio is 1.6, and the adhesive phase 25 that the blend extruding layer being 22 microns with thickness is pressed onto this multilayer material forms thermoplastic innermost layer 26.
The LLDPE (mLLDPE) of blended metalloscene catalyst polymerization and low density polyethylene (LDPE) obtains blend time, can adopt and the particle Direct Uniform of both materials is mixed, also can adopt by bi-material mix after again melting stir, carry out granulation again and obtain blend particle, the mixture homogeneity of rear a kind of mode is better than front one.
Adhesive phase 25 and thermoplastic innermost layer 26 can adopt two-layer co-extrusion mode to be laminated on the aluminium foil on barrier layer 24, like this can Simplified flowsheet, and adhesive phase 25 and thermoplastic innermost layer 26 inter-layer bonding force good.
Table 1:

Claims (8)

1. a laminate wrapping material, comprise thermoplastic outermost layer (21), sandwich layer (22), thermoplastic intermediate layer (23), barrier layer (24) and thermoplastic innermost layer (26) from outside to inside, it is characterized in that: described thermoplastic intermediate layer (23) comprises LLDPE (mLLDPE) and the low density polyethylene (LDPE) (LDPE) of metalloscene catalyst polymerization;
The LLDPE (mLLDPE) of described metalloscene catalyst polymerization has following parameter: averag density is 0.88g/cm 3~ 0.925g/cm 3, melt flow index is 5 g/10min ~ 20 g/10min, Peak melting point is 85 DEG C ~ 130 DEG C, expansion ratio is 1.2 ~ 1.8;
Described low density polyethylene (LDPE) (LDPE) has following parameter: averag density is 0.90g/cm 3~ 0.925g/cm 3, melt flow index is 5g/10min ~ 20g/10min, Peak melting point is 85 DEG C ~ 110 DEG C, expansion ratio is 1.2 ~ 1.8;
Described melt flow index condition determination is 190 DEG C, 2.16kg.
2. a kind of laminate wrapping material according to claim 1, is characterized in that: the LLDPE (mLLDPE) of described metalloscene catalyst polymerization has following parameter: averag density is 0.90g/cm 3~ 0.915 g/cm 3, melt flow index is 5 g/10min ~ 20 g/10min, Peak melting point is 88 DEG C ~ 120 DEG C, expansion ratio is 1.4 ~ 1.6; Described melt flow index condition determination is 190 DEG C, 2.16kg.
3. a kind of laminate wrapping material according to claim 1, is characterized in that: the averag density of the LLDPE (mLLDPE) of described metalloscene catalyst polymerization is 0.905g/cm 3~ 0.910g/cm 3, melt flow index is 5g/10min ~ 20 g/10min, Peak melting point is 93 DEG C ~ 103 DEG C, expansion ratio is 1.4 ~ 1.6; Described melt flow index condition determination is 190 DEG C, 2.16kg.
4. a kind of laminate wrapping material according to claim 1, is characterized in that: described low density polyethylene (LDPE) (LDPE) has following parameter: averag density is 0.910 g/cm 3~ 0.92g/cm 3, melt flow index is 5 g/10min ~ 20 g/10min, Peak melting point is 85 DEG C ~ 110 DEG C, expansion ratio is 1.4 ~ 1.6; Described melt flow index condition determination is 190 DEG C, 2.16kg.
5. a kind of laminate wrapping material according to claim 4, is characterized in that: the averag density of described low density polyethylene (LDPE) (LDPE) is 0.915 g/cm 3~ 0.920g/cm 3, melt flow index is 5 g/10min ~ 20 g/10min, Peak melting point is 93 DEG C ~ 103 DEG C, expansion ratio is 1.4 ~ 1.6; Described melt flow index condition determination is 190 DEG C, 2.16kg.
6. a kind of laminate wrapping material according to any one of claim 1 to 5, it is characterized in that: in described thermoplastic intermediate layer (23), the weight percentage of the LLDPE (mLLDPE) of metalloscene catalyst polymerization is 50% ~ 80%, and the weight percentage of low density polyethylene (LDPE) (LDPE) is 20% ~ 50%.
7. a kind of laminate wrapping material according to any one of claim 1 to 5, it is characterized in that: in described thermoplastic intermediate layer (23), the weight percentage of the LLDPE (mLLDPE) of metalloscene catalyst polymerization is 60% ~ 75%, and the weight percentage of low density polyethylene (LDPE) (LDPE) is 25% ~ 40%.
8. a kind of laminate wrapping material according to any one of claim 1 to 5, it is characterized in that: in described thermoplastic intermediate layer (23), the weight percentage of the LLDPE (mLLDPE) of metalloscene catalyst polymerization is 70%, and the weight percentage of low density polyethylene (LDPE) (LDPE) is 30%.
CN201210594654.2A 2012-12-31 2012-12-31 Laminated packaging material Ceased CN103101273B (en)

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CN201510156846.9A CN104760379A (en) 2012-12-31 2012-12-31 Laminated packaging material
CN201210594654.2A CN103101273B (en) 2012-12-31 2012-12-31 Laminated packaging material
CN201510156842.0A CN104760354A (en) 2012-12-31 2012-12-31 Laminated packaging material
CN201510156835.0A CN104760353A (en) 2012-12-31 2012-12-31 Laminated packaging material
CN201510156845.4A CN104760355A (en) 2012-12-31 2012-12-31 Laminated packaging material

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CN201510156842.0A Division CN104760354A (en) 2012-12-31 2012-12-31 Laminated packaging material
CN201510156835.0A Division CN104760353A (en) 2012-12-31 2012-12-31 Laminated packaging material
CN201510156845.4A Division CN104760355A (en) 2012-12-31 2012-12-31 Laminated packaging material

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CN103786999B (en) * 2014-01-17 2015-08-26 冯英 Food liquid paper-plastic stick flexible packing material, box-packed white wine special box and production technology thereof

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CN104760354A (en) 2015-07-08

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