CN101537914A - Macromolecular alloy packaging material - Google Patents
Macromolecular alloy packaging material Download PDFInfo
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- CN101537914A CN101537914A CN200910031402A CN200910031402A CN101537914A CN 101537914 A CN101537914 A CN 101537914A CN 200910031402 A CN200910031402 A CN 200910031402A CN 200910031402 A CN200910031402 A CN 200910031402A CN 101537914 A CN101537914 A CN 101537914A
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Abstract
The invention relates to a macromolecular alloy packaging material with the thickness ranging from 0.015 to 0.300mm, in particular to a high-performance multiplayer coextruded stretch compound packaging material that is compounded by 3 layers or more of resins by a coextrusion blowing or coextrusion stretch method and by changing orientation in a range of 30 to 1000 percent to change the molecular structure of polymer so as to control the permeability of gas and vapor, and physical and mechanical properties of materials. The vapor barrier is required to be controllable in a range of 0.05g/m<2>*24h*atm to 30g/m<2>*24h*atm; and the gas barrier is required to be controllable in a range of 0.05ml/m<2>*24h*atm to 2500ml/m<2>*24h*atm. The invention has more functions through secondary processing, such as printing, compounding, coating, thermal molding and sacking, and is suitable for the barrier applications, such as high humidity barrier, oxygen barrier, oil barrier and aroma conservation in various environments.
Description
Technical field
The present invention relates to a kind of thickness 〉=0.015 and≤0.300 millimeter scope in macromolecular alloy packaging material, be particularly related to a kind of compound by resin bed employing coextrusion blowing or coextrusion casting method more than three layers or three layers, by the change of the degree of orientation in the 30%-1000% scope, the molecular structure that changes poly-mer reaches the high-performance multilayer coextrusion stretching compound package material of the physical and mechanical properties of the durchgriff of the oxygen of control material, aqueous vapor and material.Its aqueous vapor intercepts and requires at 〉=0.05g/m
224hatm and≤30g/m
2Controlled in the 24hatm scope; Gas barrier requires at 〉=0.05ml/m
224hatm and≤2500ml/m
2Controlled in the 24hatm scope.This packing, can be widely used in food, manufactured meat series products, daily necessities, cosmetics, chemical products, agricultural chemicals, war products sealing flexible packaging, printing element, and satisfy inflation or vacuumize, various function packagings such as Heat forming, be particularly suitable for high resistant various environment under wet, hinder various barrier applications such as oxygen, oil resistance, guarantor's perfume (or spice).And can be by printing (intaglio plate, relief printing plate, gentle version, hectograph); Compound (dry type is compound, wet type is compound, solvent-free compound, heat compound, extrude compound); Coating (extrusion coated, K coating); Heat forming; Secondary processing methods such as bag are given new function.
Background technology
Along with on the continuous appearance of poly-mer new material and the market to the improving constantly of poly-mer extruded product performance requriements, the goods of one-component can't satisfy the specific (special) requirements of the aspects such as use, processing characteristics and outward appearance of goods because of its limitation.Multi-component composite product arises at the historic moment.Safety, function specialization, lightweight, ultra-thinization, exploitation new process, new material are the development main flows of following flexible packing material and technology.Functional high barrier plastic package material has extremely strong technical advantage and ease of use, and its demand was in rising trend always in recent years.Meanwhile, people have proposed higher quantized requirement to the barrier of plastic package material.
Though MULTILAYER COMPOSITE and cladding process can be given the multiple function of packing film and obtain the combination of difference in functionality according to demand by the combination of structure, but except can not significantly improving the mechanical property of material, the raising of the barrier of multi-layer co-extruded packing can only can obtain by the thickness that improves the correlation function layer material.Not only increased material cost greatly but also the lifting of performance has been very restricted.Want the excellent and professional more high barrier film of obtained performance, its job operation and material must have brand new to break through to new technical field development.
Film quality control index comprises modulus of elasticity, the tensile strength of vertical, horizontal, breaking elongation, percent thermal shrinkage, friction coefficient, turbidity, glossiness etc., these indexs mainly embody mechanical properties in films and optical property, and they have inseparable getting in touch with the state of aggregation of material macromolecular chain as orientation, crystallization etc.Polymer alloy material is in the course of processing, in power, under the effect of heat and electric field etc., the complicated orientation and the variation of crystallization have been experienced, orientation in the aggregated structure and crystallization will be to the optical properties of alloy material, mechanical property plays decisive influence, this project utilizes polymer molecule to have the constructional feature of long-chain, in the forming polymer course of processing, under the effect of external force field, macromolecular chain, segment or crystallite can be arranged in order along external force direction, produce orientation in various degree, form a kind of new aggregated structure-alignment state structure, cause material mechanics of machinery in different directions, the characteristic of optics and thermodynamic property generation marked change.Improve product quality by the control of molecule being carried out orientation positions and crystallization.
High molecular compatibility and low molecular intermiscibility have similarity, but incomplete same.For low molecular system, dissolving each other just is meant that each component can reach the mixing of molecular level, otherwise is exactly not dissolve each other.The Gibbs free of the requirement mixed process of dissolving each other is less than or equal to zero.But for macromolecule mixture, can not consider simply whether they are compatible, the more important thing is the quality of paying close attention to their compatibilities.Most of blended polymers can not reach the mixing of molecular level, belong to heterogeneous system.This system is a kind of unsure state on thermodynamic (al) viewpoint.But because the structure of poly-mer is with low molecular different, simultaneously again because the viscosity of system is very big, this system can not resemble and be easy to generation the low molecule Unstable Systems and further be separated.Thereby from dynam, polymer blend is in a kind of quasi-stationary state.Therefore this project will be found out the relevant rule of Polymer gradient function alloy material (heterogeneous system) orientation and can be used for suitability for industrialized production.
On the material microstructure form, alignment state and stratification have extremely important influence to the barrier of material.The two is general relevant with external factor such as processing conditions and methods.Many high molecule alloy materials have single-phase continuous microphase-separated type structure.Continuous phase generally plays a leading role to the permeability to air of alloy material.When having the high barrier discrete phase, this discrete phase is bigger along wall direction orientation positions and stratification degree, and the barrier of material is just stronger.After the crystal type material orientation, filtration coefficiont can reduce about 50%; Behind the non-crystalline type stretch orientation, can reduce 10%-15%.Therefore, in the alloy material preparation, the focus that orientation and stratification become high-barrier plastic package material preparation research also is the key problem in technology of this project research.
The strand of poly-mer is carefully grown, and the shape of its molecule has tangible geometric asymmetry.Usually being covalent bonds along the strand direction, then is the Van der Waals force combination perpendicular to the strand direction.Therefore, poly-mer under external force, strand will be arranged along outer field direction, this process is called orientation.For non-oriented poly-mer, wherein segment is a random orientation.Be segment towards any one party to equiprobability, thereby non-oriented poly-mer is isotropic.And the poly-mer of orientation, therefore segment preferred orientation on a certain direction presents anisotropy.
The stretch orientation of amorphous polymer is fairly simple.According to the difference of orientation unit, can be divided into the orientation of whole chain and the orientation of segment, be also referred to as large scale and undersized orientation.Chain segment orientation can be finished by the sub-chain motion that the inward turning of singly-bound is quoted.Just can carry out under the situation that this orientation is generally lower in temperature or pulling force is less; The orientation of whole strand then needs the cooperative motion of each segment of Polymer to realize.Therefore, only under the very big situation of temperature very high (as melt spinning) or pulling force, just can carry out.Because orientation process is the process of a sub-chain motion, must overcomes poly-mer in-to-in viscous resistance, thereby finish orientation process and need the regular hour.Two kinds of aligned suffered resistances are different.Under the effect of external force, will the orientation of segment at first takes place, be only the orientation of whole strand then.
The orientation process of crystallization poly-mer is much more complicated than amorphous polymer.The orientation of crystal grain also may take place in the stretch orientation process of crystallization poly-mer except the orientation of segment and strand may take place its amorphous area.Under external force, crystal grain will be along the external force direction preferred orientation.The destruction of crystalline region according to the viewpoint of folded-chain structure model, when the crystallization poly-mer stretches, after amorphous area is oriented to a certain degree, is just taken place and is rearranged in the concrete orientation process of crystallization poly-mer, forms new orientation crystal grain.
In sum, because the orientation process of amorphous polymer and crystallization poly-mer is diverse, prior art has only solved the orientation of single high polymers, for example: commercially available OPA, OPP, OPET etc.Along with science and technology development, the application of homogeneous material is restricted, MULTILAYER COMPOSITE and cladding process can give the multiple function of packing film and according to demand the combination by structure obtain difference in functionality application to reducing material cost, more effective raising barrier also is subjected to great limitation.
Summary of the invention
The invention provides a kind of macromolecular alloy packaging material in order to overcome above-mentioned defective, adopt the coextrusion complex technique, make the key element (composition, structure) of constituent material become continuously to change by a side direction opposite side, thereby the character of material and function are changed in gradient along thickness direction.Proposed the notion of internal stress gradient transition, promptly replaced abrupt interface, eliminated the sudden change of physical property, made internal stress reduce to minimum with the continually varying compositional gradient; Solved the employing heterogeneous composite material,, be easy to occur to peel off or the technical barrier of crack performance at the phase boundary place because the difference of the coefficient of thermal expansion of each phase and thermal stress is bigger.And by changing the degree of orientation of poly-mer, realized control and reduced the durchgriff of oxygen, carbon dioxide, aqueous vapor, and control and improve the physical and mechanical properties of material, have ultra-thin, lightweight, the quantifiable function of high-barrier and function.
The technical solution used in the present invention is:
1, the present invention proposes the technology theory that adopts coextrusion.Raw material is pressed design-calculated functional component coextrusion laminar texture, realized the quantitative control of the stratification degree of multi-layer compound package material, overcome in the stratification process, too much bulking agent is to the adverse effect of the barrier property generation of material.Under certain process conditions, the macromolecular alloy packaging material that fusion is prepared, but behavior of structure with function quantification effect.
2, with the supplementary means of blending method as coextrusion, satisfy and work as because of the function needs, between adjacent two layers, when homogenous material can not satisfy requiring of internal stress gradient mitigation, with the material blend of different performance, obtain the high molecule alloy material of internal stress gradient mitigation by the laminar texture of control and the auxiliary coextrusion of adjusting component ratio.
3, the present invention proposes the structure design theory that internal stress gradient is distributed bridge.The thermal stress of different materials is relaxed the technical barrier that has solved high molecule alloy material (heterogeneous system) orientation by transition.Distribute the viscosity of melt between bridge and control, regulating course and the homogeneity of moulding cooling shrinkage by internal stress gradient is set in structure, obtain the high molecule alloy material that internal stress gradient relaxes.
4, the present invention makes strand carry out orientations along some directions by orientation, utilize polymer molecule to have the constructional feature of long-chain, in the forming polymer course of processing, under the effect of external force field, macromolecular chain, segment or crystallite can be arranged in order along external force direction, produce orientation in various degree, form a kind of new aggregated structure-alignment state structure, cause the characteristic of material mechanics of machinery, optics and thermodynamic property generation marked change in different directions.The molecular structure that carries out the control break poly-mer of orientation positions in the 30%-1000% scope and crystallization by molecule reaches the high-performance multilayer coextrusion stretching compound package material of the physical and mechanical properties of the durchgriff of oxygen, aqueous vapor of control material and material.
5, on the material microstructure form, alignment state and stratification have extremely important influence to the barrier of material.The present invention utilizes multi-layer co-extruded technology to make High molecular material bigger along wall direction orientation positions and stratification degree, the barrier of the material strong principle that just heals.After making crystal type material orientation, filtration coefficiont can reduce about 50%; Behind the non-crystalline type stretch orientation, can reduce 10%-20%.
Related content and change interpretation in the technique scheme are as follows:
1, in the such scheme, it is the key that solves the technology of the present invention problem that internal stress gradient is distributed bridge construction.So-called internal stress gradient is distributed bridge Y
iAnd Y
jIt is a kind of stress set of the resin bed of pooling feature in gradient that has, it utilizes resin bed quantity, different materials different viscosity and the combination of thickness and material molecule degree of orientation four key elements under the same melt temperature, with between skin and the interlayer or/and the melt viscosity difference between internal layer and the interlayer transits to the technological requirement that satisfies coextrusion blowing or cast film stretch orientation gradually with gradient profile.Internal stress gradient distributes the concrete structure and the form of bridge to design according to actual needs, and wherein, it can be one deck resin bed that internal stress gradient is distributed bridge, a kind of melt viscosity material and thickness; Also can be two-layer tree fat layer, the combination of two kinds of melt viscosity materials and one or both thickness; Can also be two layers or more resin bed, the combination of different melt viscosity material and different-thickness.In a word, it is flexibly that internal stress gradient is distributed the design of bridge, its objective is the melt viscosity difference between layer and the layer is cushioned transition with gradient profile, thereby when the co-extrusion modling film stretching be orientated, can effectively finish the MULTILAYER COMPOSITE stretching of film next time at same processing conditions.
2, viscosity is one of most important basic conception of multi layer coex composite membranes processability, be the quantificational expression to flowing power, the coupling of viscosity change and interlayer viscosity directly influences the mechanical property of layer high molecule alloy packaging material, optical property, electric property and appearance of films quality.It is the key of avoiding the set up stresses concentration phenomenon.The factor that influences the viscosity variation has melt temperature, pressure, rate of shear and relative molecular mass etc.And viscosity of plastic melts is eager to excel to the sensivity of the sensivity comparison shear action of temperature.Along with the reduction of temperature, intermolecular, the motion between strand slows down, and the winding between the plastic molecules chain increases, and the distance between the molecule is dwindled, and the viscosity of plastic melt is the exponential function rising and causes viscosity to increase, flow difficulties, and insufficient formability, and elasticity is big.In the such scheme, being the function of rate of shear according to viscosity of plastic melts, also is the relation of the function of temperature simultaneously.Utilize difference in melt temperature and internal stress gradient between the resin bed to distribute the relation of bridge setting further to be: internal stress gradient to be set when melt temperature between A1 and the C differs in 〉=30 ℃ of scopes to distribute bridge Y
iInternal stress gradient is set when melt temperature between A2 and the C differs in 〉=30 ℃ of scopes distributes bridge Y
j
3, in the such scheme, when melt temperature between A2 and the C differ＜30 ℃ the time, j=0, its structure expression can further be reduced to: A1/Y
i/ C
In the formula: have only an internal stress gradient to distribute bridge Y
i
4, in the such scheme, when melt temperature between A1 and the C differ＜30 ℃ the time, i=0, its structure expression can further be reduced to: C/Y
j/ A2
In the formula: have only an internal stress gradient to distribute bridge Y
j
5, in the such scheme, described A1 can adopt identical resin material with A2, and forms symmetrical structure.
6, in the such scheme, described A1 can adopt different resin materials with A2, and forms unsymmetric structure.
7, in the such scheme, A1 and A2 can be homogenous material or different materials blend (comprise and add color masterbatch).
8, in the such scheme, about each layer resin material A1, A2, C, Y in the structure expression
i, and Y
jConcrete selection example:
(1), A1, A2, C comprise high temperature fusion, dystectic resin and their compounds such as HOPA, COPA, HOPP, COPP, MPP, PET, PBT, PS, HDPE, COC respectively; EVA, EMAA, EBA, EAA, ionic resin (sarin), LLDPE, MPE, LDPE, VLDPE, VLLDPE, CPE etc. have the synthetic resin of heat-sealing function and their compound; Heat sensitivity and watery fusion, low-melting resin and their compound such as EVA, EMAA, EAA, EVOH, PVA that comprise PVDC, PVC, high VA content.
(2), Y
i, Y
jComprise a kind of, two kinds, two or more and their compound in all resin materials that can be used for extrusion molding, comprise the copolymer of anhydride modified ethylene-vinyl acetate copolymer, anhydride modified low density polyethylene (LDPE), anhydride modified polyacrylic polymer, anhydride modified high density polyethylene (HDPE), ethene and methacrylate and their compound.Usually according between A1 and the C or the melt viscosity difference between A2 and the C carry out structure design and material design by gradient profile.
Principle of work of the present invention is: the notion of utilization internal stress gradient transition, adopt the coextrusion complex technique, make the key element (composition, structure) of constituent material become continuously to change by a side direction opposite side along thickness direction, promptly replace abrupt interface with the continually varying compositional gradient, eliminate the sudden change of physical property, make thermal stress reduce to minimum.By being set, internal stress gradient distributes bridge in structure, utilize when rate of shear is constant, viscosity of plastic melts is along with the rising of temperature, viscosity is the viscosity of melt between characteristic transition, adjusting and the key-course that the exponential function mode descends and the homogeneity of moulding cooling shrinkage, obtains the macromolecular alloy packaging material that internal stress gradient relaxes.
For the thermal stress that realizes different materials relaxes the problem that solves high molecule alloy material (heterogeneous system) orientation by transition.Different resins interlayer or difference in melt temperature reach the coex composite membranes product of 30 ℃ of-200 ℃ of scopes under identical forming temperature, the internal stress gradient that the set by the resin bed of continually varying compositional gradient constitutes is set between them distributes bridge Y
iAnd Y
jUtilize the combination of different melt viscosities of resin bed quantity, material and thickness, material molecule degree of orientation four key elements, will be under identical forming temperature the melt viscosity difference of different materials transit to the technological requirement that satisfies coextrusion blowing or the processing of cast film drawing and forming gradually with the form of gradient.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1, the present invention is according to the internal stress equilibrium principle, by internal stress gradient distribute bridge construction utilize resin bed quantity, material do not coexist the combination of different viscosity and thickness under the same melt temperature, material molecule degree of orientation four key elements reduce layer with layer between material poor because of the inter-laminar stress of the different generations of melt viscosity.From overall technical architecture, the present invention is skillfully constructed, internal stress gradient is distributed the design uniqueness of bridge, has very big alerting ability in practice, can adapt to the variation of melt differential stress between the various different materials, be a kind of new breakthrough of art technology, for functional multi layer coex composite membranes provides a kind of new approach.
2, reasonable in design of the present invention, and be rich in logicality can effectively realize the melt stress equilibrium, and the thermal stress of different materials is relaxed by transition, has fundamentally solved the technical barrier of high molecule alloy material (heterogeneous system) orientation.Distribute the viscosity of melt between bridge and control, regulating course and the homogeneity of moulding cooling shrinkage by internal stress gradient is set in structure, obtain the high molecule alloy material that the thermal stress gradient relaxes.Compared with prior art have outstanding substantive distinguishing features and significant technological advance.
3, between the synthetic resin that the present invention can satisfy between crystalline resin layer and the non-crystalline resin layer or thermal stress difference is big, difference in melt temperature is greater than 30 ℃ with less than the material of 200 ℃ of scopes, adopts the coextrusion processing mode to finish the stretching of the compound of multilayer film and 0.5 times-10 times.
4, the invention solves that dry type is compound, extrusion composite technology produces the environmental pollution that dissolvent residual causes and the wholesomeness problem of packaging material for food because of using solvent type adhesive.
The specific embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: structure expression is: C-Y-A
In the formula: C is specially PP; Y specifically represents the blending structure of two kinds of materials of one deck: MLDPE blend VLDPE; A is VLDPE.
Totally 3 layers of its concrete structures:
PP/MLDPE blend VLDPE/VLDPE;
Wherein, about about 250 ℃, about about 160 ℃, therefore, the melt-processed moulding temperature difference between C and A is 90 ℃ to the melt temperature of VLDPE (A) to the melt temperature of PP (C) greatly greatly; So being set, internal stress gradient distributes bridge Y between C and A, and by the viscosity of blend auxiliary adjustment interlayer melt and the homogeneity of moulding cooling shrinkage, through the high molecule alloy material of 10 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment two: structure expression is: A1-Y
1-C-Y
2-A2
In the formula, A1 is specially PP; Y
1Concrete single layer structure: the EVA that represents; C is specially PVDC; Y
2Concrete two-layer structure: the EVA/MLDPE that represents; A2 is specially ionic resin.
Totally 6 layers of its concrete structures:
The PP/EVA/PVDC/EVA/MLDPE/ ionic resin
Wherein, the melt temperature of PP (A1) is greatly about about 260 ℃, the melt temperature of PVDC (C) is greatly about about 140 ℃, the melt temperature of ionic resin (A2) is greatly about about 190 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 120 ℃, and the melt-processed moulding temperature difference between C and A2 is 50 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is set between C and A2 distributes bridge Y
2High molecule alloy material through 6 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment three: structure expression is: A1-Y
1-C-Y
2-A2
In the formula, A1 is specially PA; Y
1The concrete three-decker of representing: anhydride modified polyacrylic polymer/PP/EVA; C is specially PVDC; Y
2Concrete two-layer structure: the EVA/MPE that represents; A2 is specially LLDPE or LLDPE blend LDPE.
Totally 8 layers of its concrete structures:
Polyacrylic polymer/PP/EVA/PVDC/EVA/MPE/LLDPE that PA/ is anhydride modified or LLDPE blend LDPE
Wherein, the melt temperature of PA (A1) is greatly about about 270 ℃, the melt temperature of PVDC (C) is greatly about about 145 ℃, the melt temperature of LLDPE (A2) is greatly about about 210 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 125 ℃, and the melt-processed moulding temperature difference between A2 and the C is 65 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is set between C and A2 distributes bridge Y
2And by the viscosity of blend auxiliary adjustment interlayer melt and the homogeneity of moulding cooling shrinkage, through the high molecule alloy material of 4 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment four: structure expression is: A1-Y
1-C-Y
2-A2
In the formula, A1 is specially PET; Y
1The concrete three-decker of representing: anhydride modified low density polyethylene (LDPE)/LLDPE/EVA; C is specially PVDC; Y
2Concrete single layer structure: EVA/LDPE or the LLDPE blend EVA of representing; A2 is specially LLDPE.
Totally 7 layers of its concrete structures:
Low density polyethylene (LDPE)/LLDPE that PET/ is anhydride modified or LLDPE blend EVA/EVA/PVDC/EVA/LLDPE
Wherein, the melt temperature of PET (A1) is greatly about about 260 ℃, the melt temperature of PVDC (C) is greatly about about 145 ℃, the melt temperature of LLDPE (A2) is greatly about about 210 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 115 ℃, and the melt-processed moulding temperature difference between C and A2 is 55 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is set between C and A2 distributes bridge Y
2And by the viscosity of blend auxiliary adjustment interlayer melt and the homogeneity of moulding cooling shrinkage, through the high molecule alloy material of 7 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment five: structure expression is: A1-Y
1-C-Y
2-A2
In the formula, A1 is specially LDPE or LLDPE blend MPE; Y
1Same Y
2The concrete single layer structure of representing: anhydride modified low density polyethylene (LDPE) blend HDPE; C is specially PA; A2 specifically also is LDPE with A1.
Its concrete structure is 5 layers of symmetry:
The anhydride modified low density polyethylene (LDPE) blend HDPE/LDPE of low density polyethylene (LDPE) blend HDPE/PA/ that LDPE or LLDPE blend MPE/ are anhydride modified
Wherein, about about 180 ℃, about about 275 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 95 ℃ to the melt temperature of PA (C) to LDPE (A1) melt temperature (A2) greatly greatly, and the melt-processed moulding temperature difference between C and A2 also is 95 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is set between C and A2 distributes bridge Y
2And by the viscosity of blend auxiliary adjustment interlayer melt and the homogeneity of moulding cooling shrinkage, through the high molecule alloy material of 5 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment six: structure expression is: C-Y
2-A2
In the formula, C is specially PS; Y
2Concrete two-layer structure: the HDPE/LDPE that represents; A2 is specially EMAA.
Its concrete structure is 4 layers of symmetry:
PS/HDPE/LDPE/EMAA
Wherein, about about 230 ℃, about about 160 ℃, therefore, the melt-processed moulding temperature difference between C and A2 is 70 ℃ to the melt temperature of EMAA to the melt temperature of PS (A1) greatly greatly; So being set, internal stress gradient distributes bridge Y between C and A2
2High molecule alloy material through 9 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment seven: structure expression is: A1-Y
1-C-Y
2-A2
In the formula, A1 is specially PP; Y
1Same Y
2Concrete two-layer structure: the EMAA/EVA that represents; C is specially PVDC; A2 specifically also is PP with A1.
Its concrete structure is 7 layers of symmetries:
PP/EMAA/EVA/PVDC/EVA/EMAA/PP
Wherein, about about 260 ℃, about about 145 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 115 ℃ to the melt temperature of PVDC (C) to PP (A1) melt temperature (A2) greatly greatly, and the melt-processed moulding temperature difference between C and A2 also is 115 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is set between C and A2 distributes bridge Y
2High molecule alloy material through 3 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment eight: structure expression is: A1/Y
1/ C/A2
In the formula, A1 is specially PA66; Y
1The concrete four-layer structure of representing: anhydride modified high density polyethylene (HDPE) blend HDPE/HDPE/EMAA/EVA; C is specially PVDC; A2 is specially EVA.
Totally 7 layers of its concrete structures:
The high density polyethylene (HDPE) blend HDPE/HDPE/EMAA/EVA/PVDC/EVA that PA66/ is anhydride modified
Wherein, the melt temperature of PA66 (A1) is greatly about about 345 ℃, the melt temperature of PVDC (C) is greatly about about 145 ℃, the melt temperature of EMAA (A2) is greatly about about 170 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 200 ℃, and the melt-processed moulding temperature difference between C and A2 is 25 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is not set between C and A2 distributes bridge.High molecule alloy material through 1 times of acquisition thermal stress gradient mitigation that stretches.
Embodiment nine: structure expression is: A1/C/Y
2/ A2
In the formula, A1 is specially MODIFIED PP; C is specially COPP; Y
1The concrete two-layer structure of representing: anhydride modified low density polyethylene (LDPE) blend LLDPE/MPE; A2 is specially ionic resin (sarin).
Totally 5 layers of its concrete structures:
The low density polyethylene (LDPE) blend LLDPE/MPE/ ionic resin (sarin) that MODIFIED PP/COPP/ is anhydride modified
Wherein, the melt temperature of MODIFIED PP (A1) is greatly about about 240 ℃, the melt temperature of COPP (C) is greatly about about 245 ℃, the melt temperature of ionic resin sarin (A2) is greatly about about 170 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 5 ℃, and the melt-processed moulding temperature difference between C and A2 is 65 ℃; Do not distribute bridge so internal stress gradient is not set between A1 and C, internal stress gradient is set between C and A2 distributes bridge Y
2High molecule alloy material through 8 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment ten: structure expression is: A1/Y
1/ C/A2
In the formula: A1 is specially PS; Y
1Concrete five-layer structure: the HDPE/LDPE/MPE/EAA/EVA that represents; C is specially PVDC; A2 is specially EVA.
Totally 8 layers of its concrete structures:
PS/HDPE/LDPE/MPE/EAA/EVA/PVDC/EVA
Wherein, about about 250 ℃, the melt temperature of PVDC (C) is greatly about about 145 ℃ greatly for the melt temperature of PS (A1), the melt temperature of EVA (A2) is greatly about about 160 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 105 ℃, and the melt-processed moulding temperature difference between C and A2 is 15 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is not set between C and A2 distributes bridge.High molecule alloy material through 2 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment 11: structure expression is: A1/Y
1/ C/Y
2/ A2
In the formula, A1 is specially PS; Y
1Concrete five-layer structure: the HDPE/LDPE/MPE/EAA/EVA that represents; C is specially PVDC; Y
2Concrete five-layer structure: the EVA/EAA/MPE/LDPE/HDPE that represents; A2 is specially PP.
Totally 13 layers of its concrete structures:
PS/HDPE/LDPE/MPE/EAA/EVA/PVDC/EVA/EAA/MPE/LDPE/HDPE/PP
Wherein, about about 250 ℃, the melt temperature of PVDC (C) is greatly about about 145 ℃ greatly for the melt temperature of PS (A1), the melt temperature of PP (A2) is greatly about about 250 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 105 ℃, and the melt-processed moulding temperature difference between C and A2 is 105 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is set between C and A2 distributes bridge Y
2High molecule alloy material through 3 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment 12: structure expression is: A1/Y
1/ C/Y
2/ A2
In the formula, A1 is specially HDPE blend MPE; Y
1The concrete anhydride modified low density polyethylene (LDPE) of three single layer structures: LLDPE/LDPE/ of representing; C is specially PA; Y
2Concrete three single layer structures of representing: anhydride modified ethylene-vinyl acetate copolymer/EVA/EMAA; A2 is VLDPE (ultra-low density polyethylene).
Totally 9 layers of its concrete structures:
Anhydride modified ethylene-vinyl acetate copolymer/the EVA/EMAA/VLDPE of low density polyethylene (LDPE)/PA/ that HDPE blend MPE/LLDPE/LDPE/ is anhydride modified
Wherein, the melt temperature of HDPE blend MPE (A1) is greatly about about 190 ℃, the melt temperature of PA (C) is greatly about about 255 ℃, the melt temperature of VLDPE (A2) is greatly about about 160 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 65 ℃, and the melt-processed moulding temperature difference between C and A2 is 95 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is set between C and A2 distributes bridge Y
2High molecule alloy material through 0.5 times of acquisition thermal stress gradient mitigation that stretches.
Embodiment 13: structure expression is: A1/Y
1/ C/Y
2/ A2
In the formula, A1 is specially PA66; Y
1The concrete five-layer structure of representing: anhydride modified high density polyethylene (HDPE) blend HDPE/HDPE/LDPE/EAA/EVA; C is specially PVDC; Y
2Concrete three-decker: the EVA/MPE/HDPE that represents; A2 is specially COPP.
Totally 11 layers of its concrete structures:
The high density polyethylene (HDPE) blend HDPE/HDPE/LDPE/EAA/EVA/PVDC/EVA/MPE/HDPE/COPP that PA66/ is anhydride modified
Wherein, the melt temperature of PA66 (A1) is greatly about about 345 ℃, the melt temperature of PVDC (C) is greatly about about 145 ℃, the melt temperature of COPP (A2) is greatly about about 220 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 100 ℃, and the melt-processed moulding temperature difference between C and A2 is 75 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is set between C and A2 distributes bridge Y
2High molecule alloy material through 2.5 times of acquisition thermal stress gradients mitigations that stretch.
Embodiment 14: structure expression is: A1/Y
1/ C/Y
2/ A2
In the formula, A1 is specially PP; Y
1The concrete anhydride modified low density polyethylene (LDPE) of three-decker: HDPE/EVA/ of representing; C is specially EVOH; Y
2The concrete four-layer structure of representing: anhydride modified low density polyethylene (LDPE)/EVA/LDPE/MPE; A2 is specially Ionomer.
Totally 10 layers of its concrete structures:
Anhydride modified low density polyethylene (LDPE)/EVA/LDPE/MPE/ the Ionomer of low density polyethylene (LDPE)/EVOH/ that PP/HDPE/EVA/ is anhydride modified
Wherein, the melt temperature of PP (A1) is greatly about about 270 ℃, the melt temperature of EVOH (C) is greatly about about 210 ℃, the melt temperature of Ionomer (A2) is greatly about about 160 ℃, therefore, the melt-processed moulding temperature difference between A1 and C is 60 ℃, and the melt-processed moulding temperature difference between C and A2 is 50 ℃; So being set, internal stress gradient distributes bridge Y between A1 and C
1, internal stress gradient is set between C and A2 distributes bridge Y
2High molecule alloy material through 0.3 times of acquisition thermal stress gradient mitigation that stretches.
Claims (10)
1, a kind of macromolecular alloy packaging material thickness 〉=0.015 and≤0.300 millimeter scope in, by the auxiliary blending technology of resin more than three layers or three layers, adopt coextrusion blowing or coextrusion casting method compound, the durchgriff of the molecular structure that changes poly-mer by stretching and the gas of degree of orientation control material, aqueous vapor and the physical and mechanical properties of film form, and it is characterized in that:
Distribute bridge Y by including outer A, internal layer C and internal stress gradient in the resin bed more than three layers or three layers, the three-decker expression formula is: A-Y-C
In the formula: A represents skin; C represents internal layer; Y represents the internal stress gradient distribution bridge between A and the C;
When melt temperature between A and the C differs in 〉=30 ℃ and≤200 ℃ of scopes, internal stress gradient is set and distributes bridge Y; Described internal stress gradient distributes bridge Y to utilize the different characteristic of resin bed quantity, material, and the combination of thickness material molecular orientation degree four key elements, with the inconsistent internal stress difference that causes of homogeneity of different between the high molecule alloy material Structural layer and moulding cooling shrinkage because of the viscosity of melt with gradient profile gradually transition obtain the functional alloy material of internal stress gradient mitigation;
Structure expression is more than three layers:
A1-Y
i-C-Y
j-A2
In the formula: A1, A2 represent skin; C represents interlayer; Y
iInternal stress gradient between expression A1 and the C is distributed bridge, Y
jInternal stress gradient between expression A2 and the C is distributed bridge, and wherein, subscript i and j represent the resin bed quantity of internal stress gradient distribution bridge respectively, and i=0,1,2,3..., j=0,1,2,3..., i and j are not 0 simultaneously;
When melt temperature between A1 and the C differs in 〉=30 ℃ and≤200 ℃ of scopes, internal stress gradient is set and distributes bridge Y
iWhen melt temperature between A2 and the C differs in 〉=30 ℃ and≤200 ℃ of scopes, internal stress gradient is set and distributes bridge Y
jDescribed internal stress gradient is distributed bridge Y
iAnd Y
jUtilize the combination of different characteristic, thickness and material molecule degree of orientation four key elements of resin bed quantity, material, with the inconsistent internal stress difference that causes of homogeneity of different between the high molecule alloy material Structural layer and moulding cooling shrinkage because of the viscosity of melt with gradient profile gradually transition obtain the functional alloy material of internal stress gradient mitigation.
2, macromolecular alloy packaging material according to claim 1 is characterized in that:
When aqueous vapor intercept to require at 〉=0.05g/m
224hatm and≤30g/m
2Functional layer A1 is set or/and A2 in the time of in the 24hatm scope; Described functional layer A1 is or/and A2 utilizes the combination of different characteristic, thickness and material molecule degree of orientation four key elements of resin bed quantity, material;
When gas barrier requires at 〉=0.05ml/m
224hatm and≤2500ml/m
2Functional layer C is set in the time of in the 24hatm scope; Described functional layer C utilizes the combination of different characteristic, thickness and material molecule degree of orientation four key elements of resin bed quantity, material.
3, macromolecular alloy packaging material according to claim 1 is characterized in that: the molecular structure by stretch changing poly-mer and in gas, the durchgriff of aqueous vapor and the physical and mechanical properties of film of 〉=30% and≤1000% degree of orientation scope inner control material.
4, macromolecular alloy packaging material according to claim 1 is characterized in that: described internal stress gradient distributes bridge Yi and Yj inner structure form to select down one of array structure respectively:
(1), single-layer resin material and different-thickness, the same orientation degree;
(2), single-layer resin material and different-thickness, the different orientation degree;
(3), single-layer resin material and same thickness, the different orientation degree;
(4), two-layer or two-layer above resin material of the same race, same thickness, same orientation degree;
(5), two-layer or two-layer above resin material of the same race, same thickness, different orientation degree;
(6), two-layer or two-layer above resin material of the same race, different-thickness, same orientation degree;
(7), two-layer or two-layer above resin material of the same race, different-thickness, different orientation degree;
(8), two-layer or two-layer more than resin material not of the same race, same thickness, same orientation degree;
(9), two-layer or two-layer more than resin material not of the same race, same thickness, different orientation degree;
(10), two-layer or two-layer more than resin material not of the same race, different-thickness, same orientation degree;
(11), two-layer or two-layer more than resin material not of the same race, different-thickness, different orientation degree.
5, macromolecular alloy packaging material according to claim 1, it is characterized in that: when the homogenous configuration film thickness 〉=0.015 and≤0.300 millimeter scope in the time, the molecular structure that the physical and mechanical properties of the gas of film, the durchgriff of aqueous vapor and film changes poly-mer by stretching and 〉=30% and≤regulate and control in 1000% the degree of orientation scope.
6, macromolecular alloy packaging material according to claim 1, it is characterized in that: when different structure film thickness one regularly, the molecular structure that the physical and mechanical properties of the gas of film, the durchgriff of aqueous vapor and film changes poly-mer by stretching and 〉=30% and≤regulate and control in 1000% the degree of orientation scope.
7, macromolecular alloy packaging material according to claim 1 is characterized in that: described A adopts identical resin material and forms symmetrical structure with C.
8, macromolecular alloy packaging material according to claim 1 is characterized in that: described A adopts different resin materials and forms unsymmetric structure with C.
9, macromolecular alloy packaging material according to claim 1 is characterized in that: A and C are the blend of the different proportion of homogenous material or two kinds and two or more different materials.
10, macromolecular alloy packaging material according to claim 1 is characterized in that: can pass through intaglio plate, relief printing plate, gentle version, hectographic printing; Dry type is compound, wet type is compound, solvent-free compound, heat compound, extrude compound; Extrusion coated, K coating; Heat forming, bag secondary processing method are given new function.
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| CN102189732A (en) * | 2011-03-07 | 2011-09-21 | 苏州海顺包装材料有限公司 | Multilayer co-extrusion cell culture container bag packaging film |
| CN104647813A (en) * | 2014-08-09 | 2015-05-27 | 廖张洁 | Macromolecule gradient material |
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| WO2018166509A1 (en) * | 2017-03-15 | 2018-09-20 | 嘉浦薄膜新材料（昆山）有限公司 | High-performance composite film for packing |
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| CN102029754B (en) * | 2010-09-21 | 2013-08-28 | 昆山加浦包装材料有限公司 | High barrier coextruded stretch film |
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| CN110303740A (en) * | 2019-07-18 | 2019-10-08 | 江苏嘉浦特种薄膜有限公司 | A kind of heat sealable coextrusion biaxial tension laminated film of multilayer |
| CN114407461A (en) * | 2022-01-29 | 2022-04-29 | 江苏彩华包装集团整体包装科技有限公司 | Biaxially oriented polyethylene base film with high surface energy |
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