CN103101273A - Laminated packaging material - Google Patents

Laminated packaging material Download PDF

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Publication number
CN103101273A
CN103101273A CN2012105946542A CN201210594654A CN103101273A CN 103101273 A CN103101273 A CN 103101273A CN 2012105946542 A CN2012105946542 A CN 2012105946542A CN 201210594654 A CN201210594654 A CN 201210594654A CN 103101273 A CN103101273 A CN 103101273A
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ldpe
layer
10min
lldpe
density polyethylene
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CN103101273B (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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Priority to CN201210594654.2A priority Critical patent/CN103101273B/en
Priority to CN201510156845.4A priority patent/CN104760355A/en
Priority to CN201510156835.0A priority patent/CN104760353A/en
Priority to CN201510156846.9A priority patent/CN104760379A/en
Priority to CN201510156842.0A priority patent/CN104760354A/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, relate in particular to a kind of laminate wrapping material for packaging liquid food.
Background technology
at present, the disposable disposal type packing container that is used for liquid food, brick is arranged, square, triangle, cross section is hexagonal octahedral bodily form, the shapes such as pillow-like, usually the laminate wrapping material of making these packing containers comprises the thermoplastic outermost layer of lamination successively, sandwich layer, the thermoplastic intermediate layer, the barrier layer, adhesive phase and thermoplastic innermost layer, the low density polyethylene (LDPE) (LDPE) that adopts high-pressure process to produce/printer's ink layer/paper (fiber) base layer/LDPE/ aluminium foil AL/LDPE/LDPE is also arranged, LDPE/ printer's ink layer/paper base layer/LDPE/LDPE, printer's ink layer/LDPE/ paper base layer/LDPE/LDPE, laminate wrapping material as LDPE/ printer's ink layer/paper base layer/sandwich constructions such as LDPE/ aluminium/polyester (PET).The food liquid that these packing containers can be packed has fresh milk, yoghurt, fruit juice etc.
core material commonly used has paper, brown paper or hardboard etc., barrier material commonly used has aluminium foil, metal/inorganic oxide film, ethylene-vinyl alcohol copolymer (EVOH), nylon etc., thermoplastic outermost layer commonly used, the intermediate layer, the low density polyethylene (LDPE) (LDPE) that the useful high-pressure process of the material of innermost layer is produced, LLDPE (LLDPE), the thermoplastics such as ethyleneα-olefincopolymer (mLLDPE) by the metalloscene catalyst catalytic polymerization, adhesive commonly used has polyurethane binder, Polyester Polyurethane Adhesive, the polyether-polyurethane adhesive, acrylic adhesive, polyester binder, polyamide binder, the polyvinyl acetate ester adhesive, epoxy adhesive, rubber adhesive etc.
The effect of each layer of packaging material is: the thermoplastic outermost layer can stop effectively that extraneous moisture, pollution or other magazines enter in packaging material, and forming in the packing container process at laminate wrapping material is that laminate wrapping material forms tubulose with thermoplastic innermost layer longitudinal sealing; Sandwich layer can the supporting package container; Thermoplastic intermediate layer and barrier layer can prevent effectively that food liquid from entering into sandwich layer, and starvation, sunlight make not light leak, air tight of packing container simultaneously, particularly do not leak oxygen, guarantee that the food liquid taste does not run off; The thermoplastic innermost layer directly contacts with food liquid, prevents that food liquid is to the infiltration of other each layers of packaging material when guaranteeing the food liquid quality; Adhesive phase adds the adhesion strength between high containment and thermoplastic innermost layer.
Fig. 1 shows a kind of common method of making laminate wrapping material, machine guiding core layer coiled material 1 moves ahead by the pressure roller of punching press platform 2, process hole and the required impression of FOLD AND PACK material of the required use of packing container opening device, 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, 5 pairs of three-layer coil materials of laminating bench carry out lamination, in its roll gap center core layer, thermoplastic intermediate layer and barrier layer are pressed together, and the thermoplastic intermediate layer is between sandwich layer and barrier layer, become thus laminate 111. guide layer pressing plates 111 and arrive next stage laminating bench 6, herein by coextruding and coat the opposite side with thermoplastic innermost layer 7 paint laminate 111 barrier layers, in the roll gap of laminating bench 6, laminate 111 and thermoplastic innermost layer 7 are pressed together, form thus the inboard laminated material 1111 that is coated with the thermoplastic innermost layer, afterwards by extrusion coated thermoplastic outermost layer in the i.e. outside coating of sandwich layer opposite side, so far obtain packing container laminate wrapping material used.Certainly, the outermost coating of thermoplastic might not be placed on final step to be carried out, and also can according to circumstances apply in suitable before step.
The packing container of the laminate wrapping material Production and Packaging food liquid that available said method is made.In order to prevent that packaged food liquid from suffering secondary pollution, the production process of whole packing container is all carried out under aseptic condition: first laminate wrapping material is shaped to cylindric, and form tube in the vertical sealing-in of side, then in the tube one horizontal sealing-in of end, form top or the bottom of packing container, fill afterwards required food liquid, at last with the horizontal sealing-in of residue end of tube, bottom or the top of making packing container.By cutting transverse packed zone, can form single independently packing container, and with these independently packing container deliver in final folding and shaped device and be converted into net shape, as brick type or other shapes.Laminate wrapping material is in forming the packing container process, and the bond strength between papery base layer and barrier layer affects the qualification rate of packing container and guaranteeing the quality the time of food liquid.
Chinese invention patent application prospectus CN1337914A discloses a kind of paper container package material, at least the constituting layer that comprises has the thermoplastic outermost layer, the papery base layer, the thermoplastic intermediate layer, barrier layer and thermoplastic innermost layer are also pressed the said sequence lamination with each constituting layer, be characterised in that: the thermoplastic innermost layer comprises the LLDPE with narrow molecular weight distribution at least, has following performance parameter: averag density 0.900-0.915, 88-103 ℃ of peak value fusing point, melt flow index 5-20, expansion ratio (SR) 1.4-1.6 and bed thickness 20-50 micron, the thermoplastic intermediate layer also adopts the material identical with aforementioned innermost layer to make.these packaging material make and are easy to pouring package packing container and rapid heat-seal, obtain the more firm container of sealing more by force, this material can be used for realizing being independent of in-built food temperature excellent sealing and thereby keep the ability that in-built product never degenerates and guarantees the quality, but, this packaging material are in the extruding layer compression technology of manufacture process, serious necking phenomenon can occur in molten condition during from the die head film extrusion of extruder in the thermoplastic intermediate layer, be that the extrusion die dual-side can shrink to the centre, the phenomenon of breach even appears in the edge thickness inequality, papery base layer both sides can not be capped or cladding thickness inhomogeneous, in order to prevent that flaw from appearring in the finished product packing material, three kinds of solutions are arranged usually, a kind of is to do the die head of extruder wider than the width on papery base layer and barrier layer, the defective part in extrusion die both sides is not covered on the papery base layer, cooling forming excises again in follow-up lamination operation, another kind be with the width on papery base layer and barrier layer do wider, after extruding lamination, the flaw part of excision packaging material both sides obtains qualified packaging material, moreover reduce the necking phenomenon infringement by increasing the thermoplastic intermediate layer thickness.These three kinds of solutions all need extruder die head than wide many of the width on papery base layer and barrier layer, need more heat heating and melting thermoplastic, cause energy waste, and also will excise the flaw part of packaging material both sides after lamination is completed, 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, between the barrier layer of this laminate wrapping material and sandwich layer, combination firmly, the qualification rate of the packing container of making is high, the time of guaranteeing the quality of food liquid is long, and serious necking phenomenon can not occur when it extrudes lamination thermoplastic intermediate layer in manufacture process, 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 from outside to inside thermoplastic outermost layer, sandwich layer, thermoplastic intermediate layer, barrier layer and thermoplastic innermost layer, wherein, described thermoplastic intermediate layer comprises LLDPE (MLLDPE) and the low density polyethylene (LDPE) (LDPE) of metalloscene catalyst polymerization; The LLDPE of described metalloscene catalyst polymerization (mLLDPE) has following parameter: averag density be 0.88g/cm3~0.925g/cm3, melt flow index (190 ℃, 2.16kg) for 5g/10min~20g/10min, peak value fusing point be that 85 ℃~130 ℃, expansion ratio are 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 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 85 ℃~110 ℃, expansion ratio are 1.2~1.8.
In the present invention, melt flow index is measured according to 190 ℃, the condition determination of 2.16kg in GB/T3682-2000 melt flow index assay method.Expansion ratio be illustrated in GB/T3682-2000 melt flow index assay method under identical condition determination (namely 190 ℃, 2.16kg), the cross sectional dimensions ratio of the cross sectional dimensions of the extrudate of measured depanning and die orifice.The peak value fusing 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), also can be non-linear low density polyethylene (LDPE), just can satisfy requirement of the present invention as long as have above-mentioned performance parameter.
As a kind of improvement of technique scheme, wherein, the LLDPE of described metalloscene catalyst polymerization (mLLDPE) has following parameter: averag density is 0.90g/cm 3~0.915g/cm 3, melt flow index (190 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 88 ℃~120 ℃, expansion ratio are 1.4~1.6.
As further improvement in the technical proposal, wherein, the averag density of the LLDPE of described metalloscene catalyst polymerization (mLLDPE) is 0.905g/cm 3~0.910g/cm 3, melt flow index (190 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 93 ℃~103 ℃, expansion ratio are 1.4~1.6.
As further improvement in the technical proposal, 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 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 85 ℃~110 ℃, expansion ratio are 1.4~1.6.
As further improvement in the technical proposal, wherein, the averag density of described low density polyethylene (LDPE) (LDPE) is 0.915g/cm 3~0.920g/cm 3, melt flow index (190 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 93 ℃~103 ℃, expansion ratio are 1.4~1.6.
As further improvement in the technical proposal, wherein, the weight percentage (wt) of the LLDPE of described metalloscene catalyst polymerization (mLLDPE) is 50%~80%, and the weight percentage (wt) of described low density polyethylene (LDPE) (LDPE) is 20%~50%.
As further improvement in the technical proposal, wherein, the weight percentage (wt) of the LLDPE of described metalloscene catalyst polymerization (mLLDPE) is 60%~75%, and the weight percentage (wt) of described low density polyethylene (LDPE) (LDPE) is 25%~40%.
As further improvement in the technical proposal, wherein, the weight percentage (wt) of the LLDPE of described metalloscene catalyst polymerization (mLLDPE) is 70%, and the weight percentage (wt) of described low density polyethylene (LDPE) (LDPE) is 30%.
the present invention compared with prior art, because LLDPE (MLLDPE) and the low density polyethylene (LDPE) (LDPE) with the polymerization of particular characteristic parameter metalloscene catalyst adopted in the thermoplastic intermediate layer of laminate wrapping material, in the extruding layer compression technology of manufacture process, necking phenomenon during from the die head film extrusion of extruder has obtained largely reducing in molten condition in the thermoplastic intermediate layer, the energy and waste of raw materials phenomenon have largely inhibition, and the combination between barrier layer and sandwich layer is firm, the qualification rate of the packing container of making is high, the time of guaranteeing the quality of food liquid is long.
Figure of description
Fig. 1 is a kind of schematic diagram of making the laminate wrapping material method.
Fig. 2 is the cross sectional representation of a kind of laminate wrapping material of the present invention.
The specific embodiment
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 of metalloscene catalyst polymerization (mLLDPE) has following parameter: averag density is 0.88g/cm 3~0.925g/cm 3, melt flow index (190 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 85 ℃~130 ℃, expansion ratio are 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 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 85 ℃~110 ℃, expansion ratio are 1.2~1.8, low density polyethylene (LDPE) (LDPE) can be LLDPE, can be also non-LLDPE.The weight percentage (wt) of the LLDPE of metalloscene catalyst polymerization (mLLDPE) 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 the lateral surface printed patterns, after indentation roller is suppressed crease line and is stamped out open hole, form thermoplastic outermost layer 21 in the outside of sandwich layer 22 by the 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 weight percentage (wt) the blend metalloscene catalyst polymerization in extruder difference according to the form below 1 obtain blend herein, respectively take bed thickness as 10, 15, 20, the blend extruding layer of 25 microns is pressed onto formation thermoplastic intermediate layer 23 on papery sandwich layer 21 medial surfaces, aluminum foil coiled material as barrier layer 24 is directed to laminating bench simultaneously, it is compound that laminating bench carries out lamination to trilaminate material, at its roll gap center core layer 22 medial surfaces, thermoplastic intermediate layer 23 and barrier layer 24 are pressed together, when this blend is extruded the formation film from the extruder die orifice, the film both sides do not form breach, edge thickness is substantially even, dual-side can shrink to the centre very little, this capped even thickness in multilayer material both sides, between the sandwich layer 22 of the laminate wrapping material that obtains and barrier layer 24, combination firmly, the qualification rate of the packing container of making is high, the time of guaranteeing the quality of food liquid is long.
Then, polyvinyl acetate ester adhesive extruding layer is being pressed onto formation adhesive phase 25 on barrier layer 24, the LLDPE of blend metalloscene catalyst polymerization (mLLDPE) and low density polyethylene (LDPE) obtain blend again, wherein, the LLDPE of metalloscene catalyst polymerization (mLLDPE) has following parameter: averag density be 0.910g/cm3, melt flow index (190 ℃, 2.16kg) for 13g/10min, peak value fusing point be that 124 ℃, expansion ratio are 1.5; Low density polyethylene (LDPE) (LDPE) has following parameter: averag density is 0.918g/cm 3, melt flow index (190 ℃, 2.16kg) is that 7g/10min, peak value fusing point are that 107 ℃, expansion ratio are 1.6, be pressed onto take bed thickness as the blend extruding layer of 22 microns on the adhesive phase 25 of this multilayer material and form thermoplastic innermost layer 26.
When the LLDPE (mLLDPE) of blend metalloscene catalyst polymerization and low density polyethylene (LDPE) obtain blend, can adopt the particle Direct Uniform with both materials to mix, also can adopt bi-material is mixed after again melting stir, carry out granulation again and obtain the blend particle, the mixture homogeneity of rear a kind of mode is a kind of better than front.
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, can simplify technique like this, and adhesive phase 25 and thermoplastic innermost layer 26 interlayer adhesions good.
Table 1:
Figure BDA00002696512800051

Claims (10)

1. laminate wrapping material, comprise from outside to inside thermoplastic outermost layer (21), sandwich layer (22), thermoplastic intermediate layer (23), barrier layer (24) and thermoplastic innermost layer (26), 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 of described metalloscene catalyst polymerization (mLLDPE) has following parameter: averag density is 0.88g/cm 3~0.925g/cm 3, melt flow index (190 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 85 ℃~130 ℃, expansion ratio are 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 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 85 ℃~110 ℃, expansion ratio are 1.2~1.8.
2. a kind of laminate wrapping material according to claim 1, it is characterized in that: the LLDPE of described metalloscene catalyst polymerization (mLLDPE) has following parameter: averag density is 0.90g/cm 3~0.915g/cm 3, melt flow index (190 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 88 ℃~120 ℃, expansion ratio are 1.4~1.6.
3. a kind of laminate wrapping material according to claim 1, it is characterized in that: the averag density of the LLDPE of described metalloscene catalyst polymerization (mLLDPE) is 0.905g/cm 3~0.910g/cm 3, melt flow index (190 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 93 ℃~103 ℃, expansion ratio are 1.4~1.6.
4. a kind of laminate wrapping material according to claim 1, it is characterized in that: described low density polyethylene (LDPE) (LDPE) has following parameter: averag density is 0.910g/cm 3~0.92g/cm 3, melt flow index (190 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 85 ℃~110 ℃, expansion ratio are 1.4~1.6.
5. a kind of laminate wrapping material according to claim 4, it is characterized in that: the averag density of described low density polyethylene (LDPE) (LDPE) is 0.915g/cm 3~0.920g/cm 3, melt flow index (190 ℃, 2.16kg) is that 5g/10min~20g/10min, peak value fusing point are that 93 ℃~103 ℃, expansion ratio are 1.4~1.6.
6. a kind of laminate wrapping material according to claim 1, it is characterized in that: described low density polyethylene (LDPE) (LDPE) is LLDPE (LLDPE).
7. a kind of laminate wrapping material according to claim 1, it is characterized in that: described low density polyethylene (LDPE) (LDPE) is non-linear low density polyethylene (LDPE).
8. the described a kind of laminate wrapping material of any one according to claim 1 to 7, it is characterized in that: the weight percentage (wt) of the LLDPE of described metalloscene catalyst polymerization (mLLDPE) is 50%~80%, and the weight percentage (wt) of described low density polyethylene (LDPE) (LDPE) is 20%~50%.
9. the described a kind of laminate wrapping material of any one according to claim 1 to 7, it is characterized in that: the weight percentage (wt) of the LLDPE of described metalloscene catalyst polymerization (mLLDPE) is 60%~75%, and the weight percentage (wt) of described low density polyethylene (LDPE) (LDPE) is 25%~40%.
10. the described a kind of laminate wrapping material of any one according to claim 1 to 7, it is characterized in that: the weight percentage (wt) of the LLDPE of described metalloscene catalyst polymerization (mLLDPE) is 70%, and the weight percentage (wt) of described low density polyethylene (LDPE) (LDPE) is 30%.
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CN201210594654.2A CN103101273B (en) 2012-12-31 2012-12-31 Laminated packaging material
CN201510156845.4A CN104760355A (en) 2012-12-31 2012-12-31 Laminated packaging material
CN201510156835.0A CN104760353A (en) 2012-12-31 2012-12-31 Laminated packaging material
CN201510156846.9A CN104760379A (en) 2012-12-31 2012-12-31 Laminated packaging material
CN201510156842.0A CN104760354A (en) 2012-12-31 2012-12-31 Laminated packaging material

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CN201510156845.4A Division CN104760355A (en) 2012-12-31 2012-12-31 Laminated packaging material
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JPH04234645A (en) * 1990-12-20 1992-08-24 Westvaco Corp Paperboard container and manufacture thereof
JPH07148895A (en) * 1993-11-30 1995-06-13 Dainippon Printing Co Ltd Paper container
JP2000167973A (en) * 1998-12-08 2000-06-20 Dainippon Printing Co Ltd Transparent barrier film, and lamination material and package container employing the film
US6974612B1 (en) * 1999-01-27 2005-12-13 Tetra Laval Holdings & Finance S.A. Laminated packaging material for paper container

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103786999A (en) * 2014-01-17 2014-05-14 冯英 Liquid food paper-plastic lamination soft packaging material, box special for box-packaged liquor and production technology thereof
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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