CN109572118A - A kind of ultralow thickness PE/PA laminated film and preparation method thereof - Google Patents

Abstract

The present invention relates to plastic film fields, and in particular to arrives a kind of ultralow thickness PE/PA laminated film and preparation method thereof.The raw material for preparing of the laminated film includes TIE resin；The TIE resin is the concentration polyolefin resin of modified by maleic acid anhydride graft；0.5~10wt% of maleic anhydride grafting ratio in the concentration TIE resin of the modified by maleic acid anhydride graft.

Description

A kind of ultralow thickness PE/PA laminated film and preparation method thereof

Technical field

The present invention relates to plastic film fields, and in particular to arrives a kind of ultralow thickness PE/PA laminated film and its preparation side Method.

Background technique

In recent decades, plastic package material replaces the ratio of conventional packaging material constantly to increase, and Devoting Major Efforts To Developing height is additional The functional plastic packaging material of value, it has also become the development trend of countries in the world plastic package material.

The developing history of composite membrane is not long, but its development speed is quickly, at present mainly using multi-layer co-extruded technology come Prepare laminated film.Multi-layer co-extruded technology directlys adopt three kinds or more of plastic pellet as raw material, passes through screw extruder point After not making every kind of plastic molten melt plasticizing, feed in a secondary mouth mold (or passing through distributor, the plastics that each extruder is supplied converge Mouth mold is fed after closing), it is then handled by further processing, multi-layer compound film is made.The product of domestic and international composite membrane at present Kind is more than 500 kinds, favor of the composite membrane increasingly by packaging industry and food industry.

Wherein polyethylene and the compound film being prepared of polyamide are due to its excellent barrier properties for gases and higher property Valence ratio is widely used in packaging, delivery industry.Existing related compound film thickness is generally 0.06~0.08 millimeter, master With on the product costly such as air valve air column, not only production cost it is expensive, using it is cumbersome and also there are performance it is superfluous Problem.Wherein, the thickness for reducing laminated film can not only reduce the manufacturing cost of product, improve the utilization rate of raw material, reduce Energy consumption and waste, while being also avoided that the use bring environmental pollution of a large amount of plastic film.

However, being asked during preparation low thickness polyethylene/polyamide laminated film (LDPA laminated film) there are some Topic, such as since film is too thin, causes occur phenomena such as film bubble shake, corrugation, rupture in blow-molding process, cause frequently disconnected Film substantially reduces production efficiency；Further, since film thickness decline leads to the bondline thickness between composite layer for bonding It can decline, cause the cohesive force of interlayer inadequate, the problems such as slip layer delamination occur, and due to the reduction of film thickness, certain Also the performances such as tensile strength, puncture force, the barrier properties for gases of film be will affect in degree；Secondly, the laminated film of low thickness is wanted Ask board die head that there is very high accuracy, precision not enough will cause film became uneven, and the problems such as defect occur in monolayer strengths.

Summary of the invention

In view of the above technical problems, the first aspect of the present invention provides a kind of low thickness PE/PA laminated film, preparation Raw material includes TIE resin；The TIE resin is the concentration polyolefin resin of modified by maleic acid anhydride graft；The maleic anhydride connects 0.5~10wt% of maleic anhydride grafting ratio in the modified concentration TIE resin of branch.

As a kind of perferred technical scheme, the low thickness PE/PA laminated film includes adhesive layer；The adhesive layer Raw material is prepared to be made of the concentration TIE resin of linear low density polyethylene and the modified by maleic acid anhydride graft；The maleic acid The concentration TIE resin of acid anhydride graft modification and the weight ratio of the linear low density polyethylene are 1:(3~6).

As a kind of perferred technical scheme, the total weight of the adhesive layer accounts for the low thickness PE/PA laminated film weight 40~50wt% of amount.

As a kind of perferred technical scheme, the low thickness PE/PA laminated film includes internal layer；The preparation of the internal layer Raw material is made of metallocene PE, linear low density polyethylene, high temperature open agent and PPA rheological agent；The linea low density It is identical that polyethylene with adhesive layer prepares the linear low density polyethylene in raw material.

As a kind of perferred technical scheme, the density of the linear low density polyethylene is 0.910~0.925g/cm³； Melt index of the linear low density polyethylene under 190 DEG C, 2.16kg load-up condition is 1.0~3.5g/10min.

As a kind of perferred technical scheme, the low thickness PE/PA laminated film includes outer layer, middle layer and internal layer, and And it is bonded and is connected by adhesive layer between adjacent two layers；

The outer layer prepares raw material, in parts by weight, comprising:

The adhesive layer prepares raw material, in parts by weight, comprising:

Linear low density polyethylene 75~85；

TIE resin 15~25；

The TIE resin is the concentration polyolefin resin of modified by maleic acid anhydride graft；The modified by maleic acid anhydride graft 0.5~10wt% of maleic anhydride grafting ratio in polyolefin resin is concentrated；

The internal layer prepares raw material, in parts by weight, comprising:

The raw material for preparing in the middle layer is copolymer nylon.

As a kind of perferred technical scheme, the density of the TIE resin is 0.910~0.925g/cm³；The TIE tree Melt index of the rouge under 190 DEG C, 2.16kg load-up condition is 1.0~1.9g/10min.

As a kind of perferred technical scheme, the glutinous number of the copolymer nylon is 210~226cm³/g。

The second aspect of the invention provides the preparation method of low thickness PE/PA laminated film as described above, including such as Lower step:

S01: pre-treatment is carried out to the TIE resin and the copolymer nylon and passes through mixing according to formula rate later Machine is stirred mixing；

S02: by resulting mixture according to each layer of weight ratio, by screw extruder melting and high pressing die head is squeezed out It is blow molded into a film；

S03: resulting cylinder film is post-processed to obtain the low thickness PE/PA laminated film.

The third aspect of the invention provides the application of low thickness PE/PA laminated film as described above, is applied to buffering Air cushion field.

The utility model has the advantages that ultralow thickness PE/PA laminated film provided by the invention is compared with existing film with excellent Comprehensive performance.Five layers of unsymmetric structure laminated film are used in the present invention, by regulating and controlling the weight ratio between each layer, every Thickness is prepared in 25 microns in one layer of the parameters such as raw material components, proportion that prepare, and has excellent tensile strength, fracture The mechanical performances such as elongation, puncture resistance, impact strength, while also there is excellent heat seal strength, mixed gas to obstruct Property and excellent processing performance.Caking property between each layer for not influencing laminated film does not cause delamination etc. unfavorable existing As, while avoiding occurring during the preparation process shake, corrugation, in uneven thickness and stress concentration point etc. is formed inside film again Under the premise of causing the unfavorable factors such as the performances such as barrier property decline due to film thining, ultralow thickness is successfully prepared in defect Five layers of unsymmetric structure laminated film of degree.And the Good All-around Property of the laminated film can be able to smoothly industry system Except making, moreover it is possible to play efficient effect in fields such as buffering pneumatic cushion films.

Specific embodiment

It is further clear, complete that the technical characteristic work in technical solution is provided to the present invention With reference to embodiment Description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this Embodiment in invention, every other reality obtained by those of ordinary skill in the art without making creative efforts Example is applied, shall fall within the protection scope of the present invention.

Word " preferred ", " preferably ", " preferred " in the present invention etc. refer to, can provide certain in some cases The embodiment of the present invention of a little beneficial effects.However, other embodiments may also under identical circumstances or in the case of other It is preferred.In addition, not implying that other embodiments are unavailable to the statement of one or more preferred embodiments, it is not yet It is intended to exclude other embodiments except the scope of the present invention.

It should be appreciated that expression for example illustrates in the case where in addition in any operational instances or otherwise pointing out All numbers of the amount of ingredient used in book and claim should be understood to be modified by term " about " in all cases.Cause This, unless indicated to the contrary, the numerical parameter otherwise illustrated in the following description and appended dependent claims is institute according to the present invention The expected performance to be obtained and the approximation changed.It is at least not intended to the applicable claim that is limited in of doctrine of equivalents In range, each numerical parameter should at least be solved according to the number of the effective digital of report and by the common rounding-off technology of application It releases.

The raw materials such as LLDPE, mLLDPE of the invention can be obtained from purchase on the market, corresponding LLDPE on the market, The opening agent (erucyl amide) of 0.01~0.5wt% or so content is added in the meeting that the products such as mLLDPE are defaulted during the preparation process, Therefore unless otherwise specified, the erucyl amide containing above-mentioned content is open in LLDPE, mLLDPE in the present invention Agent.

In view of the above technical problems, the first aspect of the present invention provides a kind of low thickness PE/PA laminated film, preparation Raw material includes TIE resin；The TIE resin is the concentration polyolefin resin of modified by maleic acid anhydride graft；The maleic anhydride connects 0.5~10wt% of maleic anhydride grafting ratio in the modified concentration TIE resin of branch；Preferably, the modified by maleic acid anhydride graft 4~7wt% of maleic anhydride grafting ratio in TIE resin is concentrated.

TIE resin in the present invention be there is amphiphatic binder resin, thus help to realize PE (polyethylene) layer and The bonding of PA (polyamide) layer.Maleic anhydride in the present invention is also known as maleic anhydride (MAH), and abbreviation cis-butenedioic anhydride is maleic The acid anhydrides of diacid.Such as alkene, ethylene, propylene, 1- butylene, 1- amylene, 1- hexene, 1- are pungent for the polyolefin in the present invention The alpha-olefins such as alkene, 4-methyl-1-pentene and certain cycloolefins be polymerized alone or combined polymerization obtained from one kind thermoplastic resin General name, heretofore described polyolefin can be for polyethylene, polypropylene etc., preferred polyethylene.The maleic anhydride grafting changes Property concentration the preferred modified by maleic acid anhydride graft of polyolefin concentration polyethylene.The concentration polyethylene of modified by maleic acid anhydride graft can To be prepared by melt grafting.Such as by maleic anhydride (MAH) and initiator (if oxidation isopropylbenzene) according to (0.5 ~10): the mixing of 0.3 weight ratio, and be completely dissolved with acetone, then solution is poured into 100 weight account polyethylenes (preferably linearly Low density polyethylene (LDPE)) in, with high-speed mixer heating stirring 5 minutes, then open place made acetone all volatilize for 12 hours, most Feed the mixture into cocurrent and parallel screw pelletizer group again afterwards, melting extrusion is concentrated to get the concentration of modified by maleic acid anhydride graft Polyethylene.

Applicant especially prepares the ultralow thickness THIN COMPOSITE with a thickness of 25 microns in preparation low thickness laminated film When film, find to will cause the bonding force of laminated film interlayer since adhesive layer dosage therein can be fewer than conventional laminated film Deficiency, influences the comprehensive performance of film at phenomena such as being easy to happen delamination between outer layer, middle layer and internal layer.When the high grafting rate of use Modified by maleic acid anhydride graft concentration polyethylene as part adhesive layer raw material when the bonding effect of interlayer can be improved.Due to this Maleic anhydride polar group in graft is easy to have stronger active force with polyamide (nylon copolymer) raw material in middle layer, It is readily susceptible to the bonding of diffusion two interlayers of enhancing therebetween.Simultaneously because the related group such as amino, amido bond in polyamide can be in height Temperature is lower to react with maleic anhydride, and middle layer is bonded together with ectonexine by way of chemical bonding, plays bonding Effect.So the grafting rate of regulation maleic anhydride can be effectively improved the bonding effect of adhesive layer.Applicant have discovered that Malaysia The grafting rate of acid anhydrides is too high also to make the bonding effect of adhesive layer be remarkably decreased, applicant speculate itself the possible reason is, bonding It is anti-that bonding between layer and middle layer relies primarily on the chemistry between the groups such as amino, amide groups in maleic anhydride and polyamide It answers, and by power the effects of hydrogen bond between molecule to play adhesive effect, the raising of maleic anhydride grafting ratio can be improved Chemical reaction degree between maleic anhydride and copolymer nylon improves bonding effect between adhesive layer and middle layer.However maleic acid The too high polarity that can make TIE binder resin of acid anhydride grafting rate is got higher, with the non-polar polymers such as Conventional linear low density polyethylene it Between cohesion energy density difference become larger, interaction of molecules and diffusion hindered therebetween, in addition occur adhesive layer raw material with it is inside and outside The case where mutually being separated between layer raw material, and compatibility poor between material leads to bonding effect between adhesive layer and outer layer, internal layer The problems such as difference, gained laminated film still remains delamination.

Certainly the concentration polyethylene of the modified by maleic acid anhydride graft in the present invention can also be by buying acquisition on the market, can The high grafting rate raw material being commercially available to be blended with linear low density polyethylene, the operations such as melting extrusion is granulated, to regulate and control State the maleic anhydride grafting ratio of the concentration polyethylene of maleic anhydride grafted modification.

Maleic anhydride grafting ratio in the present invention is can be measured by titration, the specific steps are as follows:

Precise determinand 0.5g is placed in addition 80ml dimethylbenzene in the three-necked flask of 500ml, is heated to reflux 10min Dissolution, is then added a drop distilled water and a drop pyridine, and 1.5ml potassium hydroxide-ethanol standard solution is added using pipette, then Flow back 30min, and 6ml aqueous isopropanol is then added, and two places phenolphthalein indicator is added, and hydrochloric acid-is then added under agitation The titration of isopropanol standard solution, volume V2 carry out blank test with above-mentioned similar method.Horse is calculated by following formula Carry out the grafting rate C of acid anhydrides_MAH%=9.806* [C₁(V₁-ΔV)-V₂C₂]/2m, wherein C_MAHFor grafting rate %；M is maleic anhydride The quality of Grafted Polyethylene；V₁Potassium hydroxide-ethanol standard solution volume；C₁It is dense for potassium hydroxide-ethanol standard solution Degree；V₂For hydrochloric acid-isopropanol standard solution volume；C₂For hydrochloric acid-isopropanol concentration of standard solution；98.06 being maleic anhydride molecule Amount.

In some preferred embodiments, the density of the TIE resin is 0.910~0.925g/cm³；The TIE tree Melt index of the rouge under 190 DEG C, 2.16kg load-up condition is 1.0~1.9g/10min；It is further preferred that the TIE tree The density of rouge is 0.918g/cm³；Melt index of the TIE resin under 190 DEG C, 2.16kg load-up condition is 1.3g/ 10min.

In some preferred embodiments, the low thickness PE/PA laminated film includes adhesive layer；The adhesive layer Raw material is prepared to be made of the concentration TIE resin of linear low density polyethylene and the modified by maleic acid anhydride graft；The maleic acid The concentration TIE resin of acid anhydride graft modification and the weight ratio of the linear low density polyethylene are 1:(3~6)；Preferably, described The concentration TIE resin of modified by maleic acid anhydride graft and the weight ratio of the linear low density polyethylene are 1:(4.5~6).

Adhesive layer prepares and is added without opening agent in raw material in the present invention, and linear low density polyethylene therein is also free from out The Special polyethylene product of mouth agent.Opening agent is a kind of slipping agent, can hinder amino, acyl in copolymer nylon to a certain extent Contact between amido isopolarity group and maleic anhydride influences reaction rate and the extent of reaction therebetween, to influence to bond Adhesive strength between layer and middle layer etc..By facilitating effective guarantee layer using the LLDPE without opening agent in adhesive layer Between adhesive strength, the problems such as avoiding the occurrence of delamination.

It is found by the applicant that the weight ratio of concentration TIE resin and linear low density polyethylene, and in concentration TIE resin The grafting rate of maleic anhydride has significant impact to the comprehensive performance of preparation gained laminated film.Due to linear low density polyethylene The difference of the parameters such as the cohesion energy density between alkene and copolymer nylon, cause the raw material of outer layer, middle layer and internal layer melting extrusion, The poor compatibility of storeroom during die head convergence, and blow molding etc. needs in by the way that reaction makes between the material in adhesive layer It bonds and is film-made between layer and other layers.Pass through maleic acid in the concentration TIE resin of regulation modified by maleic acid anhydride graft in the present invention The grafting rate of acid anhydride can make the linear low density polyethylene content in adhesive layer higher, make its weight ratio up to 1:(4.5~6) Shi Yiran has good adhesive property, avoids occurring phenomena such as film breakage in preparing thin-film process, improves the preparation work of film Skill.Simultaneously the unexpected discovery of applicant, by grafting rate, the regulation of adhesive layer raw material weight ratio, then with each layer raw material Between synergistic effect under can help improve the compactness extent of laminated film, significantly improve the barrier property of film and anti- Puncture resistance.

Linear low density polyethylene (LLDPE) in the present invention is ethylene as primary raw material, with a small amount of alpha-olefin (such as fourth Alkene -1, octene-1 etc.), the polymer that gas fluidised bed polymerisation obtains is carried out through high pressure or low pressure under the action of catalyst, wherein The catalyst does not include metallocene catalyst.Linear low density polyethylene has few compared with conventional polyvinyl on strand The short-chain branch of amount, linear degree is higher, also therefore has more regular molecules align, biggish crystallinity and heat resistance.

In some preferred embodiments, the total weight of the adhesive layer accounts for the low thickness PE/PA laminated film weight 40~50wt% of amount.

The adhesive layer in the present invention is made of the first adhesive layer and the second adhesive layer, wherein the setting of the first adhesive layer exists Between outer layer and middle layer, the setting of the second adhesive layer is in middle level between internal layer.Heretofore described first adhesive layer and second glues The weight ratio closed between layer may be the same or different.

The thickness of adhesive layer typically constitutes from the 7~15 of total laminated film weight, the too high meeting of amount in traditional laminated film In the case where guaranteeing that overall film thickness is certain, other layers of content will necessarily be made to decline, influence tensile property, the barrier of film Etc. comprehensive performances, or even significantly affect the preparation process of film.Overall thickness to reduce laminated film will necessarily make adhesive layer Content decline, and this necessarily will affect the bonding between outer layer and middle layer and middle layer and internal layer, and interlayer is caused to slide The rough sledding such as de-, delamination.It has been found that in the present invention adhesive layer total content can make within the scope of 40~50wt% it is compound Situations such as film has good adhesive strength, is not in interlayer slippage or delamination, while not influencing the comprehensive of laminated film again Close performance.

In some embodiments, the low thickness PE/PA laminated film includes internal layer；The internal layer prepare raw material by Metallocene PE, linear low density polyethylene, high temperature open agent and PPA rheological agent composition；The linear low density polyethylene It is identical that the linear low density polyethylene in raw material is prepared with adhesive layer；It is further preferred that the weight of the internal layer account for it is described low 25~35wt% of thickness PE/PA laminated film weight.

In some preferred embodiments, the low thickness PE/PA laminated film includes five-layer structure, from outside to inside according to Secondary is outer layer, the first adhesive layer, middle layer, the second adhesive layer and internal layer；The adhesive layer is by the first adhesive layer and the second adhesive layer Composition；Preferably, the weight ratio of the outer layer, the first adhesive layer, middle layer, the second adhesive layer and internal layer be 12~18:15~ 22:15~20:15~22:25~35；It is furthermore preferred that its weight ratio is 15:20:18:20:27.

In some embodiments, the thickness of the low thickness PE/PA laminated film is not higher than 40 microns；Preferably, no Higher than 30 microns；It is further preferred that being not higher than 25 microns.

Heretofore described metallocene PE is the poly- second produced using metallocene (MAO) for polymerization catalyst Alkene.Preferably, the density of the metallocene PE is 0.910~0.927g/cm³；The metallocene PE at 190 DEG C, Melt index under 2.16kg load-up condition is 0.6~1.5g/10min；It is furthermore preferred that the density of the metallocene PE is 0.918g/cm³；Melt index of the metallocene PE under 190 DEG C, 2.16kg load-up condition is 1g/10min.

The density of the materials such as linear low density polyethylene, metallocene low density polyethylene (LDPE) is all according to ASTM D- in the present invention 792 standards are tested to obtain, and melt index is to be tested to obtain according to the standard of ASTM D-1238.It is melted in the present invention Index is a kind of parameter for measuring material melt mobile performance, refers to plastifying material after melting, in certain temperature and load Lotus flows through the quality grams that diameter is 2.095mm round tube in lower 10 minutes, specific steps are carried out according to routine operation.

It is found by the applicant that adhesive layer can be improved using linear low density polyethylene identical with adhesive layer in ectonexine Interaction force and diffusion velocity between raw material and ectonexine raw material, improve the bonding effect of interlayer, the meeting when preparing film Make to help to improve the mechanical strength of film without apparent boundary between the ectonexine of film and the second adhesive layer.In addition, Shen Ask someone unexpected discovery in adhesive layer using linear low density polyethylene as internal layer under the premise of, by pair The regulation of each layer weight part accounting, moreover it is possible to make laminated film that there is excellent heat sealability, allow in lower temperature It is lower to melt, and can quick cooled and solidified, the gas in block film, and its leakproofness and pressure holding effect are significant It is promoted.

High temperature open agent in the present invention is a kind of processing aid, in material processing, can be formed in surface of material One layer of flexible film, reduces the coefficient of friction of material surface, and melt-processed is made to be more easier to carry out, and helps to reduce film Resistance when die head out avoids film from mucous membrane, film breakage phenomenon occur when drawing and stretch from die head.However due to the formation of elastic membrane The contact between the other layers of material such as adhesive layer material and middle layer can be prevented, maleic anhydride and amido bond isopolarity group can be reduced Between reaction, phenomena such as causing cohesive force between layers inadequate, be easy to appear delamination.

PPA rheological agent one kind plastic additive in the present invention, the apparent density that can effectively reduce material and melt are in screw rod The pressure of melting extrusion in extruder helps avoid phenomena such as melt fracture, sharkskin occur, while helping to reduce energy Consumption.To the type of PPA rheological agent, there is no special restrictions in the present invention, and the conventional PPA of plastic film processing can be used Rheological agent can be obtained from purchase on the market, such as Hong Kong Hua friendship auxiliary agent Related product etc..

In some embodiments, the density of the linear low density polyethylene is 0.910~0.925g/cm³；The line Property low density polyethylene (LDPE) at 190 DEG C, melt index under 2.16kg load-up condition is 1.0~3.5g/10min；Preferably, described The density of linear low density polyethylene is 0.918g/cm³；The linear low density polyethylene is at 190 DEG C, 2.16kg load-up condition Under melt index be 2g/10min.

In some preferred embodiments, the low thickness PE/PA laminated film includes outer layer, middle layer and internal layer, and And it is bonded and is connected by adhesive layer between adjacent two layers；

The outer layer prepares raw material, in parts by weight, comprising:

The adhesive layer prepares raw material, in parts by weight, comprising:

Linear low density polyethylene 75~85；

TIE resin 15~25；

The TIE resin is the concentration polyolefin resin of modified by maleic acid anhydride graft；The modified by maleic acid anhydride graft 0.5~10wt% of maleic anhydride grafting ratio in TIE resin is concentrated；

The internal layer prepares raw material, in parts by weight, comprising:

The raw material for preparing in the middle layer is copolymer nylon.

In some embodiments, the glutinous number of the copolymer nylon is 210~226cm³/g；Further preferred；It is described total The density of poly- nylon is 1.10~1.20g/cm³(preferably 1.14g/cm³).In the present invention it is preferable to use PA6 and PA66 monomer according to The copolymer nylon that certain molar ratio is copolymerized, generally PA66 ingredient highest accounts for 15wt% or so in the copolymer nylon.By It is arranged in PA66 molecular symmetry, is easy to be formed hydrogen bond in the molecule into ordered structure, therefore the addition of PA66 ingredient can change altogether The microstructure of poly- nylon.The wherein too high processing temperature that can improve raw material of PA66 ingredient, while also will affect film interlayer Adhesiveness, the mechanical performance etc. of film.The copolymer nylon for meeting above-mentioned condition can be by being commercially available on the market, such as can adopt With the nylon product of the BASF copolymer nylon B36SLN trade mark.

Copolymer nylon tool in the present invention is in melting extrusion and be blow molded cooling and shaping when is easy to orderly be arranged in densification Structure, help to improve tensile strength, barrier property of laminated film etc., regulate and control viscosity number, density of the copolymer nylon etc. ginseng Number helps to improve above-mentioned performance.It can effectively improve the entanglement between polymer molecular chain using the copolymer nylon of high viscosity number Degree, helps to improve the parameters such as the heat resistance, intensity, barrier property of laminated film.However discovery uses in actual production The copolymer nylon of high viscosity number screw back pressure easy to increase squeezes out material and is easy to appear film bubble shake, corrugation in blow-molding process, Phenomena such as even rupturing, not can effectively improve the above-mentioned performance of film, instead because of film corrugation, the uneven thickness of interlayer part Even, the problems such as there are stress concentration points, the performances such as barrier property, the intensity of laminated film is caused to be remarkably decreased.Pass through in the present invention The viscosity number for regulating and controlling copolymer nylon reduces screw back pressure using the copolymer nylon of proper flow, improves processing technology.And Shen Ask someone to find, to viscosity number, the regulation of the parameters such as density also contribute to improving between middle layer and ectonexine material it is mutual flow and Diffusion, helps that the higher laminated film such as plunger bond strength, consistency is prepared, helps to improve the comprehensive of laminated film Close performance.

Further, since the difference of nylon 6 and nylon66 fiber monomer structure, can change copolymer nylon aggregated structure, weaken poly- The effects of intramolecular hydrogen bond inside amide molecule power, it is too strong to avoid the occurrence of nylon polymer intramolecular action power, therein Amido bond isopolarity group is embedded after portion is tightly packed in the molecule by nonpolar fatty segment, weakens (outstanding with adhesive layer raw material It is maleic groups) between active force.Relative viscosity is used to prepare in the present invention no more than 3.6 copolymer nylon compound When film, discovery is conducive to improve the bonding force between adhesive layer and middle layer, is guaranteeing that ply adhesion effect is not affected Under the premise of, it can have higher inflation ratio, the wide cut of film made to reach 1400mm (die orifice width is about 450mm).Simultaneously The uniformity in middle layer can also be improved, middle layer is not easy the problems such as defect, became uneven occur when blown film.It is the possible reason is altogether Poly- nylon, which is compared, has relatively higher degree of randomness with homopolymerization nylon, and polymer molecular chain changes needed for conformation, deformation, stretching etc. Energy it is lower, therefore its melt is easy flowing under the same conditions, and film product also has better tensile property.And it is adopting Higher with relative viscosity, (such as trade mark is BASF C40, specific ratio between usually C40 and B36LN to for example 4.0 copolymer nylon The mixture of example) when preparation gained laminated film ply adhesion effect will receive certain influence, and cost is also costly, And when homopolymerization nylon (such as BASF B36LN) is used alone, film wide cut is shorter during the preparation process, it can only accomplish 900~ 980mm, influences the overall thickness of gained film, and will affect the bonding effect of film interlayer.

It is a parameter for measuring nylon mobility and processing performance quality that the nylon in the present invention, which sticks number, value Height will affect laminated film processing technology, while also will affect and preparing products obtained therefrom comprehensive performance.Heretofore described glutinous number It is to be measured according to standard GB/T/T 12006.1-2009 " 1 polyamide first part of plastics: sticking the measurement of number ".

In addition, it is found by the applicant that being used in compounding metallocene PE and linear low density polyethylene in ectonexine can change The processing technology of kind film, so that laminated film has the mechanicalnesses such as excellent tensile strength, heat seal strength, punctured resistance Energy.Although metallocene PE is conducive to make compared to having higher regularity for common linear low density polyethylene Standby to obtain the better laminated film of mechanical performance, but since metallocene PE is at high cost, when exclusive use, will increase film Preparation cost, and viscosity is too high during melt extrusion for metallocene PE, when screw back pressure and film go out die head Resistance is higher, its processing performance is caused to receive large effect, can also to be easy to produce defect in resulting film, influence thin The comprehensive performance of film.

The second aspect of the invention provides the preparation method of low thickness PE/PA laminated film as described above, including such as Lower step:

S01: will be mixed by high speed according to formula rate after carrying out pre-treatment to the TIE resin and the copolymer nylon It closes blender and is stirred mixing；

S02: by resulting mixture according to each layer of weight ratio, by screw extruder melting and high pressing die head is squeezed out It is blow molded into a film；

S03: resulting cylinder film is post-processed to obtain the low thickness PE/PA laminated film.

In the present invention, it is found by the applicant that if the accuracy of die head not enough to will cause laminated film local thickness uneven, can Thus stress can be led to problems such as not concentrate and to occur bubble break, barrier properties for gases bad, in order to be accurately controlled die head Accuracy, the present invention in can use pinpoint accuracy die head, such as Ma Qi company, Italy, Lai Fenhaoshe company, Germany etc. The corresponding die head of company's production.

In some preferred embodiments, the screw extruder heating temperature in the middle layer is 240~250 DEG C；It is described The heating temperature of adhesive layer screw extruder is identical, is 210~240 DEG C；The heating temperature of the outer layer and internal layer screw extruder Spend it is identical, be 200~220 DEG C.

It is specific:

1. adhesive layer raw material and copolymer nylon can be placed on in 80 DEG C of baking ovens dry baking 12H, it is ensured that do not have in material There is moisture；

2. each component raw material is mixed by mixed at high speed stirred tank according to formula rate；

3. uniformly mixed material is added into each screw rod electrometer batch box, each layer ratio is controlled by electrometer batch box And screw rod revolution, precision can be controlled in 0.2%；

4. by high pressing die head extrusion-blown modling at wide cut be 800~1400mm among to the cylinder film cutd open.Three layers of board extrusion Screw temperature set is as follows:

Outer layer: 1-200-210 DEG C of area ,-210-220 DEG C of 2nd area ,-210-220 DEG C of 3rd area ,-210-220 DEG C of 4th area, 5 area-210- 220 DEG C, -210-220 DEG C of 6th area, -210-220 DEG C of head area；

First adhesive layer: 1-210-220 DEG C of area ,-230-240 DEG C of 2nd area ,-230-240 DEG C of 3rd area ,-230-240 DEG C of 4th area, 5 - 230-240 DEG C of area, -230-240 DEG C of 6th area, -230-240 DEG C of head area；

Middle layer: 1-240-250 DEG C of area ,-240-250 DEG C of 2nd area ,-240-250 DEG C of 3rd area ,-240-250 DEG C of 4th area, 5 area-240- 250 DEG C, -240-250 DEG C of 6th area, -240-250 DEG C of head area；

Second adhesive layer: 1-210-220 DEG C of area ,-230-240 DEG C of 2nd area ,-230-240 DEG C of 3rd area ,-230-240 DEG C of 4th area, 5 - 230-240 DEG C of area, -230-240 DEG C of 6th area, -230-240 DEG C of head area；

Internal layer: 1-200-210 DEG C of area ,-210-220 DEG C of 2nd area ,-210-220 DEG C of 3rd area ,-210-220 DEG C of 4th area, 5 area-210- 220 DEG C, -210-220 DEG C of 6th area, -210-220 DEG C of head area；

5. control board speed is 20-25m/min, drawing tension is set as 100-120N, because the very thin tension of film can not It is too big, it is easy film breakage；

6. automatically controlling film thickness and wide cut precision by itself precision of import extrusion die and electrometer batch box；

7. carrying out a bag making heat seal to be made into for example big small gourd structure of various patterns buffering pneumatic cushion, size double the unilateral tin film splitted Arrange structure etc..

Applicant is preparing thickness in five layers of asymmetric compound film of 25 microns (or lower), since film is total Phenomena such as thickness is low and guarantees certain thickness adhesive layer again, guarantees the bonding effect between every layer, avoids the occurrence of delamination, The inside and outside intima-media thickness that will cause film is too low, raw material by screw extruder melting extrusion and in blow-molding process the rigidity of film and Hardness is inadequate, causes the problems such as film bubble is easy to appear shake, corrugation in blow-molding process.And due to the thickness mistake of laminated film Low, the material of melting accuracy in die head convergence assigning process not enough will cause the in uneven thickness of film, and monolayer strengths go out Existing defect, occurs stress concentration point inside laminated film, the comprehensive performances such as film strength, barrier property, processability is caused to receive Serious influence.Applicant passes through to laminated film each layer of raw material components, content, the ginseng such as the accounting of each layer in the film Number, has been prepared high comprehensive performance with the use of high-precision pertinent instruments, has been easily worked operation, ultralow thickness at low cost Spend laminated film.

The third aspect of the invention provides the application of low thickness PE/PA laminated film as described above, is applied to buffering Air cushion field.

Low thickness PE/PA laminated film in the present invention is used mainly as air-cushion film, according to known in the art normal Low thickness PE/PA laminated film can be prepared into air-cushion film use by rule method, mainly be inflated to film air cushioning machine, heat-sealing Air-cushion film is prepared.Existing air-cushion film is mainly prepared by polyolefine materials such as polyethylene, polypropylene, for different need The product for needing processability different is sought, comprehensive performance is general.In the present invention, ingredient, the ratio of raw material are prepared to laminated film Etc. being regulated and controled and selected, keeps film and air cushion machine matching good, do not have to prepare special air cushioning machine or heat-sealing component etc. The air-cushion film with Good All-around Property is prepared.

Embodiment

Embodiment 1

Embodiment 1 provides a kind of low thickness PE/PA laminated film, the low thickness PE/PA laminated film include outer layer, Middle layer and internal layer, and bonded and connected by adhesive layer between adjacent two layers；The adhesive layer is bonded by the first adhesive layer and second Layer composition；

The outer layer prepares raw material, in parts by weight, comprising:

The adhesive layer prepares raw material, in parts by weight, comprising:

Linear low density polyethylene 45；

TIE resin 15；

The TIE resin is the concentration polyvinyl resin of modified by maleic acid anhydride graft；The modified by maleic acid anhydride graft Maleic anhydride grafting ratio 0.6% in TIE resin is concentrated, melt index is that 1.9g/10min is purchased from Mitsui Chemicals；Described first is viscous It is identical that conjunction layer and the second adhesive layer prepare raw material；

The internal layer prepares raw material, in parts by weight, comprising:

The raw material for preparing in the middle layer is copolymer nylon.

Wherein, the metallocene PE be the Brazilian Quattor trade mark be MF-28006 mLLDPE (density is 0.926g/cm³, melt index 0.6g/10min)；The linear low density polyethylene is that the Exxon Mobil trade mark is LLDPE (the density 0.918g/cm of LL1001XV³, melt index 1.0g/10min)；The high temperature open agent and PPA stream Become agent and is purchased from Hong Kong Hua friendship auxiliary agent；The copolymer nylon is BASF copolymer nylon B36SLN；The outer layer, the first adhesive layer, The weight ratio in middle layer, the second adhesive layer and internal layer is 12:15:15:15:25；The laminated film overall thickness is 25 ± 1 μm.

This example additionally provides the preparation method of above-mentioned laminated film, includes the following steps:

1. adhesive layer raw material and copolymer nylon can be placed on in 80 DEG C of baking ovens dry baking 12H, it is ensured that do not have in material There is moisture；

2. each component raw material is mixed by mixed at high speed stirred tank according to formula rate；

3. uniformly mixed material is added into each screw rod electrometer batch box, each layer ratio is controlled by electrometer batch box And screw rod revolution, precision can be controlled in 0.2%；

4. by high pressing die head extrusion-blown modling at wide cut be 800mm among to the cylinder film cutd open.Three layers of extrusion screw rod temperature of board Degree setting is as follows:

Outer layer: 1-205 DEG C of area ,-215 DEG C of 2nd area ,-215 DEG C of 3rd area ,-215 DEG C of 4th area ,-215 DEG C of 5th area ,-215 DEG C of 6th area, head - 215 DEG C of area；

First adhesive layer: 1-215 DEG C of area ,-235 DEG C of 2nd area ,-235 DEG C of 3rd area ,-235 DEG C of 4th area ,-235 DEG C of 5th area, 6 areas-235 DEG C, -235 DEG C of head area；

Middle layer: 1-245 DEG C of area ,-245 DEG C of 2nd area ,-245 DEG C of 3rd area ,-245 DEG C of 4th area ,-245 DEG C of 5th area ,-245 DEG C of 6th area, head - 245 DEG C of area；

Second adhesive layer: 1-215 DEG C of area ,-235 DEG C of 2nd area ,-235 DEG C of 3rd area ,-235 DEG C of 4th area ,-235 DEG C of 5th area, 6 areas-235 DEG C, -235 DEG C of head area；

Internal layer: 1-205 DEG C of area ,-215 DEG C of 2nd area ,-215 DEG C of 3rd area ,-215 DEG C of 4th area ,-215 DEG C of 5th area ,-215 DEG C of 6th area, head - 215 DEG C of area；

5. control board speed is 22m/min, drawing tension is set as 110N, because the very thin tension of film can not be too big, holds Easy film breakage；

6. automatically controlling film thickness and wide cut precision by itself precision of import extrusion die and electrometer batch box；

7. by it is unilateral split a tin film and carry out a bag making heat seal be made into various patterns buffering pneumatic cushion.Above-mentioned temperature therein, speed Etc. parameters have the fluctuation up and down in zone of reasonableness.

Embodiment 2

Embodiment 2 provides a kind of low thickness PE/PA laminated film, the low thickness PE/PA laminated film include outer layer, Middle layer and internal layer, and bonded and connected by adhesive layer between adjacent two layers；The adhesive layer is bonded by the first adhesive layer and second Layer composition；

The outer layer prepares raw material, in parts by weight, comprising:

The adhesive layer prepares raw material, in parts by weight, comprising:

Linear low density polyethylene 90；

TIE resin 25；

The TIE resin is the concentration polyvinyl resin of modified by maleic acid anhydride graft；The modified by maleic acid anhydride graft Maleic anhydride grafting ratio 10% in TIE resin is concentrated, melt index is that 1.9g/10min is purchased from Mitsui Chemicals；First bonding It is identical that layer with the second adhesive layer prepares raw material；

The internal layer prepares raw material, in parts by weight, comprising:

The raw material for preparing in the middle layer is copolymer nylon.

Wherein, the metallocene PE is mLLDPE (the density 0.918g/ that the Exxon Mobil trade mark is E1518HA cm³, melt index 1.5g/10min)；The linear low density polyethylene is that the Exxon Mobil trade mark is LL-1002's LLDPE (density 0.925g/cm³, melt index 3.5g/10min)；The high temperature open agent and PPA rheological agent are purchased from perfume Port China friendship auxiliary agent；The copolymer nylon is BASF copolymer nylon B36SLN；The outer layer, the first adhesive layer, middle layer, second are glued The weight ratio for closing layer and internal layer is 12:15:15:15:25；The laminated film overall thickness is 25 ± 1 μm.

This example additionally provides the preparation method of above-mentioned laminated film, includes the following steps:

1. adhesive layer raw material and copolymer nylon can be placed on in 80 DEG C of baking ovens dry baking 12H, it is ensured that do not have in material There is moisture；

2. each component raw material is mixed by mixed at high speed stirred tank according to formula rate；

3. uniformly mixed material is added into each screw rod electrometer batch box, each layer ratio is controlled by electrometer batch box And screw rod revolution, precision can be controlled in 0.2%；

4. by high pressing die head extrusion-blown modling at wide cut be 800mm among to the cylinder film cutd open.Three layers of extrusion screw rod temperature of board Degree setting is as follows:

Outer layer: 1-205 DEG C of area ,-215 DEG C of 2nd area ,-215 DEG C of 3rd area ,-215 DEG C of 4th area ,-215 DEG C of 5th area ,-215 DEG C of 6th area, head - 215 DEG C of area；

First adhesive layer: 1-215 DEG C of area ,-235 DEG C of 2nd area ,-235 DEG C of 3rd area ,-235 DEG C of 4th area ,-235 DEG C of 5th area, 6 areas-235 DEG C, -235 DEG C of head area；

Middle layer: 1-245 DEG C of area ,-245 DEG C of 2nd area ,-245 DEG C of 3rd area ,-245 DEG C of 4th area ,-245 DEG C of 5th area ,-245 DEG C of 6th area, head - 245 DEG C of area；

Second adhesive layer: 1-215 DEG C of area ,-235 DEG C of 2nd area ,-235 DEG C of 3rd area ,-235 DEG C of 4th area ,-235 DEG C of 5th area, 6 areas-235 DEG C, -235 DEG C of head area；

Internal layer: 1-205 DEG C of area ,-215 DEG C of 2nd area ,-215 DEG C of 3rd area ,-215 DEG C of 4th area ,-215 DEG C of 5th area ,-215 DEG C of 6th area, head - 215 DEG C of area；

5. control board speed is 22m/min, drawing tension is set as 110N, because the very thin tension of film can not be too big, holds Easy film breakage；

6. automatically controlling film thickness and wide cut precision by itself precision of import extrusion die and electrometer batch box；

7. by it is unilateral split a tin film and carry out a bag making heat seal be made into various patterns buffering pneumatic cushion.Above-mentioned temperature therein, speed Etc. parameters have the fluctuation up and down in zone of reasonableness.

Embodiment 3

Embodiment 3 provides a kind of low thickness PE/PA laminated film, the low thickness PE/PA laminated film include outer layer, Middle layer and internal layer, and bonded and connected by adhesive layer between adjacent two layers；The adhesive layer is bonded by the first adhesive layer and second Layer composition；

The outer layer prepares raw material, in parts by weight, comprising:

The adhesive layer prepares raw material, in parts by weight, comprising:

Linear low density polyethylene 75；

TIE resin 15；

The TIE resin is the concentration polyvinyl resin of modified by maleic acid anhydride graft；The modified by maleic acid anhydride graft Maleic anhydride grafting ratio 4% in TIE resin is concentrated, melt index is that 1.3g/10min is purchased from Mitsui Chemicals；First bonding It is identical that layer with the second adhesive layer prepares raw material；

The internal layer prepares raw material, in parts by weight, comprising:

The raw material for preparing in the middle layer is copolymer nylon.

Wherein, the metallocene PE is mLLDPE (the density 0.918g/ that the Exxon Mobil trade mark is E1018KB cm³, melt index 1.0g/10min)；The linear low density polyethylene is that the Exxon Mobil trade mark is LL-1002's LLDPE (density 0.918g/cm³, melt index 2.0g/10min)；The high temperature open agent and PPA rheological agent are purchased from perfume Port China friendship auxiliary agent；The copolymer nylon is BASF copolymer nylon B36SLN；The outer layer, the first adhesive layer, middle layer, second are glued The weight ratio for closing layer and internal layer is 12:15:15:15:25；The laminated film overall thickness is 25 ± 1 μm.

This example additionally provides the preparation method of above-mentioned laminated film, includes the following steps:

1. adhesive layer raw material and copolymer nylon can be placed on in 80 DEG C of baking ovens dry baking 12H, it is ensured that do not have in material There is moisture；

2. each component raw material is mixed by mixed at high speed stirred tank according to formula rate；

3. uniformly mixed material is added into each screw rod electrometer batch box, each layer ratio is controlled by electrometer batch box And screw rod revolution, precision can be controlled in 0.2%；

4. by high pressing die head extrusion-blown modling at wide cut be 800mm among to the cylinder film cutd open.Three layers of extrusion screw rod temperature of board Degree setting is as follows:

Outer layer: 1-205 DEG C of area ,-215 DEG C of 2nd area ,-215 DEG C of 3rd area ,-215 DEG C of 4th area ,-215 DEG C of 5th area ,-215 DEG C of 6th area, head - 215 DEG C of area；

First adhesive layer: 1-215 DEG C of area ,-235 DEG C of 2nd area ,-235 DEG C of 3rd area ,-235 DEG C of 4th area ,-235 DEG C of 5th area, 6 areas-235 DEG C, -235 DEG C of head area；

Middle layer: 1-245 DEG C of area ,-245 DEG C of 2nd area ,-245 DEG C of 3rd area ,-245 DEG C of 4th area ,-245 DEG C of 5th area ,-245 DEG C of 6th area, head - 245 DEG C of area；

Second adhesive layer: 1-215 DEG C of area ,-235 DEG C of 2nd area ,-235 DEG C of 3rd area ,-235 DEG C of 4th area ,-235 DEG C of 5th area, 6 areas-235 DEG C, -235 DEG C of head area；

Internal layer: 1-205 DEG C of area ,-215 DEG C of 2nd area ,-215 DEG C of 3rd area ,-215 DEG C of 4th area ,-215 DEG C of 5th area ,-215 DEG C of 6th area, head - 215 DEG C of area；

5. control board speed is 22m/min, drawing tension is set as 110N, because the very thin tension of film can not be too big, holds Easy film breakage；

6. automatically controlling film thickness and wide cut precision by itself precision of import extrusion die and electrometer batch box；

7. by it is unilateral split a tin film and carry out a bag making heat seal be made into various patterns buffering pneumatic cushion.Above-mentioned temperature therein, speed Etc. parameters have the fluctuation up and down in zone of reasonableness.

Embodiment 4

Embodiment 4 provides a kind of low thickness PE/PA laminated film, the low thickness PE/PA laminated film include outer layer, Middle layer and internal layer, and bonded and connected by adhesive layer between adjacent two layers；The adhesive layer is bonded by the first adhesive layer and second Layer composition；

The outer layer prepares raw material, in parts by weight, comprising:

The adhesive layer prepares raw material, in parts by weight, comprising:

Linear low density polyethylene 85；

TIE resin 25；

The TIE resin is the concentration polyvinyl resin of modified by maleic acid anhydride graft；The modified by maleic acid anhydride graft Maleic anhydride grafting ratio 6% in TIE resin is concentrated, melt index is that 1.3g/10min is purchased from Mitsui Chemicals；First bonding It is identical that layer with the second adhesive layer prepares raw material；

The internal layer prepares raw material, in parts by weight, comprising:

The raw material for preparing in the middle layer is copolymer nylon.

Wherein, the metallocene PE is mLLDPE (the density 0.918g/ that the Exxon Mobil trade mark is E1018KB cm³, melt index 1.0g/10min)；The linear low density polyethylene is that the Exxon Mobil trade mark is LL-1002's LLDPE (density 0.918g/cm³, melt index 2.0g/10min)；The high temperature open agent and PPA rheological agent are purchased from perfume Port China friendship auxiliary agent corresponding product；The copolymer nylon is BASF copolymer nylon B36SLN；The outer layer, the first adhesive layer, in The weight ratio of layer, the second adhesive layer and internal layer is 12:15:15:15:25；The laminated film overall thickness is 25 ± 1 μm.

This example additionally provides the preparation method of above-mentioned laminated film, includes the following steps:

1. adhesive layer raw material and copolymer nylon can be placed on in 80 DEG C of baking ovens dry baking 12H, it is ensured that do not have in material There is moisture；

2. each component raw material is mixed by mixed at high speed stirred tank according to formula rate；

3. uniformly mixed material is added into each screw rod electrometer batch box, each layer ratio is controlled by electrometer batch box And screw rod revolution, precision can be controlled in 0.2%；

4. by high pressing die head extrusion-blown modling at wide cut be 800mm among to the cylinder film cutd open.Three layers of extrusion screw rod temperature of board Degree setting is as follows:

Outer layer: 1-205 DEG C of area ,-215 DEG C of 2nd area ,-215 DEG C of 3rd area ,-215 DEG C of 4th area ,-215 DEG C of 5th area ,-215 DEG C of 6th area, head - 215 DEG C of area；

First adhesive layer: 1-215 DEG C of area ,-235 DEG C of 2nd area ,-235 DEG C of 3rd area ,-235 DEG C of 4th area ,-235 DEG C of 5th area, 6 areas-235 DEG C, -235 DEG C of head area；

Middle layer: 1-245 DEG C of area ,-245 DEG C of 2nd area ,-245 DEG C of 3rd area ,-245 DEG C of 4th area ,-245 DEG C of 5th area ,-245 DEG C of 6th area, head - 245 DEG C of area；

Second adhesive layer: 1-215 DEG C of area ,-235 DEG C of 2nd area ,-235 DEG C of 3rd area ,-235 DEG C of 4th area ,-235 DEG C of 5th area, 6 areas-235 DEG C, -235 DEG C of head area；

Internal layer: 1-205 DEG C of area ,-215 DEG C of 2nd area ,-215 DEG C of 3rd area ,-215 DEG C of 4th area ,-215 DEG C of 5th area ,-215 DEG C of 6th area, head - 215 DEG C of area；

5. control board speed is 22m/min, drawing tension is set as 110N, because the very thin tension of film can not be too big, holds Easy film breakage；

6. automatically controlling film thickness and wide cut precision by itself precision of import extrusion die and electrometer batch box；

7. by it is unilateral split a tin film and carry out a bag making heat seal be made into various patterns buffering pneumatic cushion.Above-mentioned temperature therein, speed Etc. parameters have the fluctuation up and down in zone of reasonableness.

Embodiment 5

Embodiment 5 provides a kind of low thickness PE/PA laminated film, the low thickness PE/PA laminated film include outer layer, Middle layer and internal layer, and bonded and connected by adhesive layer between adjacent two layers；The adhesive layer is bonded by the first adhesive layer and second Layer composition；

The outer layer prepares raw material, in parts by weight, comprising:

The adhesive layer prepares raw material, in parts by weight, comprising:

Linear low density polyethylene 80；

TIE resin 16；

The TIE resin is the concentration polyvinyl resin of modified by maleic acid anhydride graft；The modified by maleic acid anhydride graft Maleic anhydride grafting ratio 4% in TIE resin is concentrated, melt index is that 1.3g/10min is purchased from Mitsui Chemicals；First bonding It is identical that layer with the second adhesive layer prepares raw material；

The internal layer prepares raw material, in parts by weight, comprising:

The raw material for preparing in the middle layer is copolymer nylon.

Wherein, the metallocene PE is mLLDPE (the density 0.918g/ that the Exxon Mobil trade mark is E1018KB cm³, melt index 1.0g/10min)；The linear low density polyethylene is that the Exxon Mobil trade mark is LL-1002's LLDPE (density 0.918g/cm³, melt index 2.0g/10min)；The high temperature open agent and PPA rheological agent are purchased from perfume Port China friendship auxiliary agent corresponding product；The copolymer nylon is BASF copolymer nylon B36SLN (glutinous number is 210~226)；It is described outer Layer, the first adhesive layer, middle layer, the second adhesive layer and internal layer weight ratio be 18:22:20:22:35；The laminated film is total With a thickness of 25 ± 1 μm.

This example additionally provides the preparation method of above-mentioned laminated film, includes the following steps:

1. adhesive layer raw material and copolymer nylon can be placed on in 80 DEG C of baking ovens dry baking 12H, it is ensured that do not have in material There is moisture；

2. each component raw material is mixed by mixed at high speed stirred tank according to formula rate；

3. uniformly mixed material is added into each screw rod electrometer batch box, each layer ratio is controlled by electrometer batch box And screw rod revolution, precision can be controlled in 0.2%；

4. by high pressing die head extrusion-blown modling at wide cut be 800mm among to the cylinder film cutd open.Three layers of extrusion screw rod temperature of board Degree setting is as follows:

Outer layer: 1-205 DEG C of area ,-215 DEG C of 2nd area ,-215 DEG C of 3rd area ,-215 DEG C of 4th area ,-215 DEG C of 5th area ,-215 DEG C of 6th area, head - 215 DEG C of area；

First adhesive layer: 1-215 DEG C of area ,-235 DEG C of 2nd area ,-235 DEG C of 3rd area ,-235 DEG C of 4th area ,-235 DEG C of 5th area, 6 areas-235 DEG C, -235 DEG C of head area；

Middle layer: 1-245 DEG C of area ,-245 DEG C of 2nd area ,-245 DEG C of 3rd area ,-245 DEG C of 4th area ,-245 DEG C of 5th area ,-245 DEG C of 6th area, head - 245 DEG C of area；

Second adhesive layer: 1-215 DEG C of area ,-235 DEG C of 2nd area ,-235 DEG C of 3rd area ,-235 DEG C of 4th area ,-235 DEG C of 5th area, 6 areas-235 DEG C, -235 DEG C of head area；

Internal layer: 1-205 DEG C of area ,-215 DEG C of 2nd area ,-215 DEG C of 3rd area ,-215 DEG C of 4th area ,-215 DEG C of 5th area ,-215 DEG C of 6th area, head - 215 DEG C of area；

5. control board speed is 22m/min, drawing tension is set as 110N, because the very thin tension of film can not be too big, holds Easy film breakage；

6. automatically controlling film thickness and wide cut precision by itself precision of import extrusion die and electrometer batch box；

7. by it is unilateral split a tin film and carry out a bag making heat seal be made into various patterns buffering pneumatic cushion.Above-mentioned temperature therein, speed Etc. parameters have the fluctuation up and down in zone of reasonableness.

Embodiment 6

Embodiment 6 provides a kind of low thickness PE/PA laminated film, and difference from Example 5 is, the outer layer, First adhesive layer, middle layer, the second adhesive layer and internal layer weight ratio be 15:20:18:20:27.

This example additionally provides the preparation method of above-mentioned laminated film, same as Example 6.

Comparative example 1

Comparative example 1 provides a kind of low thickness PE/PA laminated film, and difference from Example 6 is, described outer Layer, the first adhesive layer, middle layer, the second adhesive layer and internal layer weight ratio be 15:4:18:4:27.

This example additionally provides the preparation method of above-mentioned laminated film, same as Example 6.

Comparative example 2

Comparative example 2 provides a kind of low thickness PE/PA laminated film, and difference from Example 6 is, the bonding Layer to prepare linear low density polyethylene described in raw material identical with the weight of the TIE resin (i.e. weight ratio be 1:1).

This example additionally provides the preparation method of above-mentioned laminated film, same as Example 6.

Comparative example 3

Comparative example 3 provides a kind of low thickness PE/PA laminated film, and difference from Example 6 is, the outer layer Prepare raw material, in parts by weight, comprising:

This example additionally provides the preparation method of above-mentioned laminated film, same as Example 6.

Comparative example 4

Comparative example 4 provides a kind of low thickness PE/PA laminated film, and difference from Example 6 is, the bonding Layer prepares raw material, in parts by weight, comprising:

Linear low density polyethylene 80；

TIE resin 16；

High temperature open agent 1.5；

The high temperature open agent is same as Example 6.

This example additionally provides the preparation method of above-mentioned laminated film, same as Example 6.

Comparative example 5

Comparative example 5 provides a kind of low thickness PE/PA laminated film, and difference from Example 6 is, adhesive phase Prepare linear low density polyethylene described in raw material be the Exxon Mobil trade mark be LL-1002 LLDPE (density is 0.925g/cm³, melt index 3.5g/10min) and (linear low density polyethylene and internal layer i.e. in adhesive layer are prepared in raw material Linear low density polyethylene it is different).

Comparative example 6

Comparative example 6 provides a kind of low thickness PE/PA laminated film, and difference from Example 6 is, middle layer preparation Copolymer nylon described in raw material is that the copolymer nylon that the BASF trade mark is B3S is (glutinous to count as 145cm³/g)。

Comparative example 7

Comparative example 7 provides a kind of low thickness PE/PA laminated film, and difference from Example 6 is, the outer layer Preparing does not include linear low density polyethylene in raw material.

Comparative example 8

Comparative example 8 provides a kind of low thickness PE/PA laminated film, and difference from Example 6 is, the internal layer Preparing does not include linear low density polyethylene in raw material.

Comparative example 9

Comparative example 9 provides a kind of low thickness PE/PA laminated film, and difference from Example 6 is, described outer Layer, the first adhesive layer, middle layer, the second adhesive layer and internal layer weight ratio be 15:20:18:20:18.

Performance evaluation

The film provided the embodiment of the present invention and comparative example is tested for the property according to corresponding standard, and result is as follows Shown in table.

1, tensile strength (MPa) and elongation at break (%) are tested according to GB/T1040.3-2006, and result is such as Shown in table 1.

1 tensile property of table tests table

2, the film that the method according to QB/T2358-1998 company standard provides the embodiment of the present application and comparative example Carry out heat seal strength (N/15mm) test；Respectively according to GB/T9639.1-2008 national standard and GB/T10004-2008 country The film that method described in standard provides the embodiment of the present application and comparative example carries out the test of membrane puncture power and dart impact is surveyed Examination, the results are shown in Table 2.

The impact of table 2 and heat seal strength test table

3. the film provided according to method described in GB/T1038-2000 national standard the embodiment of the present application and comparative example Carry out the test (unit are as follows: 10 μm of (g/m of average mixed gas transmitance (mixed gas main component is oxygen and nitrogen)²· 24h)).And situations such as whether swing, film bubble is unstable occur in blow molding during the preparation process to film, is observed and is examined Core, according to film breakage number every month number evaluated, it is 10 that every monthly average film breakage number, which is not higher than primary scoring,；Monthly It is 8 that average film breakage number, which is 2~5 scorings,；Every monthly average film breakage number is that 6~15 scorings are 5；Every monthly average film breakage number It is 3 for 15~30 scorings；Every monthly average film breakage number is more than that 30 scorings are 1, as a result as shown in table 3 below.

3 barrier property of table and processability test table

	Mix 10 μm of (g/m of vapor permeability2·24h)	Processing performance
			Embodiment 1	358.4±2.6	5
Embodiment 2	354.6±2.9	5
			Embodiment 3	356.7±2.5	8
Embodiment 4	340.2±2.3	8
			Embodiment 5	345.7±2.5	8
Embodiment 6	321.5±2.0	10
			Comparative example 1	421.4±2.4	1
Comparative example 2	428.5±2.6	1
			Comparative example 3	398.1±2.1	8
Comparative example 4	412.9±2.3	8
			Comparative example 5	419.0±3.1	3
Comparative example 6	445.7±3.0	8
			Comparative example 7	417.5±2.7	3
Comparative example 8	425.9±2.0	1
			Comparative example 9	394.5±2.4	5

Furthermore the laminated film provided the embodiment of the present application and comparative example carries out vacuum leakproofness test, passes through vacuum- Not burst experiments in the case of 45KPa, the laminated film that wherein embodiment 3~6 provides still will not be quick-fried after more than the 1min time Split that vacuum leakproofness is significantly good, with laminated film have the different degrees of explosion time, than answering in embodiment 3~6 It closes film and wants short more, vacuum leakproofness is poor.

Pressure maintaining test is carried out to above-mentioned laminated film, is 320mm*400mm in area, is laminated to 10kg, testing time 7 It, test result discovery, the laminated film leak rate that embodiment 6 provides is minimum, and leak rate less than 6%, answer by embodiment 3~5 Film leak rate is closed less than 10%, is above 10% with the leak rate of laminated film, wherein Examples 1 to 2 and comparative example 5 Obviously poorer than remaining film with the laminated film leak rate in 9, leak rate is more than 30%.

Low temperature is carried out using test to above-mentioned laminated film, buffering gas is made by conventional technique in above-mentioned laminated film Pad is stored 72 hours under -20 DEG C of environment, during which observes situations such as adhesive layer is with the presence or absence of shrinking or cracking.Wherein embodiment 6 Obviously there is not situations such as adhesive layer cracking in 72 hours in the laminated film of offer, and the laminated film in embodiment 3~5 exists Have in 48 hours and obviously the case where adhesive layer cracking occur, there is a degree of cracking in 72 hours；Remaining laminated film exists Situations such as thering is different degrees of adhesive layer to shrink and crack in 48 hours appearance.

Laminated film provided by the invention has excellent tensile property, anti-impact it can be seen from above-mentioned test result The mechanical performances such as performance, punctured resistance, heat seal strength are hit, while also there is excellent processing performance, weatherability, wearability And barrier property, oxygen, the nitrogen etc. in environment can effectively be obstructed, can be protected when air-cushion film field uses It holds at the product of encapsulation in a dry environment, protects product preferably, and can be in environment such as low temperature, high vacuum Under can still play its effect.

The above described is only a preferred embodiment of the present invention, be not the limitation for making other forms to invention, it is any Those skilled in the art are changed or are changed to the equivalent of equivalent variations possibly also with the technology contents of the disclosure above Embodiment, but without departing from the technical solutions of the present invention, above embodiments are made according to the technical essence of the invention Any simple modification, equivalent variations and remodeling, still fall within the protection scope of technical solution of the present invention.

Claims (10)

1. a kind of low thickness PE/PA laminated film, which is characterized in that it includes TIE resin that it, which prepares raw material,；The TIE resin is The concentration polyolefin resin of modified by maleic acid anhydride graft；Maleic anhydride in the concentration TIE resin of the modified by maleic acid anhydride graft 0.5~10wt% of grafting rate.

2. low thickness PE/PA laminated film as described in claim 1, which is characterized in that the low thickness PE/PA laminated film Including adhesive layer；The adhesive layer prepares raw material by the concentration of linear low density polyethylene and the modified by maleic acid anhydride graft TIE resin composition；The weight ratio of concentration the TIE resin and the linear low density polyethylene of the modified by maleic acid anhydride graft For 1:(3~6).

3. low thickness PE/PA laminated film as claimed in claim 2, which is characterized in that the total weight of the adhesive layer accounts for institute State 40~50wt% of low thickness PE/PA laminated film weight.

4. low thickness PE/PA laminated film as claimed in claim 3, which is characterized in that the low thickness PE/PA laminated film Including internal layer；The raw material for preparing of the internal layer is flowed by metallocene PE, linear low density polyethylene, high temperature open agent and PPA Become agent composition；It is identical that the linear low density polyethylene with adhesive layer prepares the linear low density polyethylene in raw material.

5. low thickness PE/PA laminated film as claimed in claim 4, which is characterized in that the linear low density polyethylene Density is 0.910~0.925g/cm³；Melting of the linear low density polyethylene under 190 DEG C, 2.16kg load-up condition refers to Number is 1.0~3.5g/10min.

6. low thickness PE/PA laminated film as described in claim 1, which is characterized in that the low thickness PE/PA laminated film Including outer layer, middle layer and internal layer, and is bonded and connected by adhesive layer between adjacent two layers；

The outer layer prepares raw material, in parts by weight, comprising:

The adhesive layer prepares raw material, in parts by weight, comprising:

Linear low density polyethylene 75~85；

TIE resin 15~25；

The TIE resin is the concentration polyolefin resin of modified by maleic acid anhydride graft；The concentration of the modified by maleic acid anhydride graft 0.5~10wt% of maleic anhydride grafting ratio in polyolefin resin；

The internal layer prepares raw material, in parts by weight, comprising:

The raw material for preparing in the middle layer is copolymer nylon.

7. low thickness PE/PA laminated film as claimed in claim 6, which is characterized in that the density of the TIE resin is 0.910~0.925g/cm³；Melt index of the TIE resin under 190 DEG C, 2.16kg load-up condition is 1.0~1.9g/ 10min。

8. low thickness PE/PA laminated film as claimed in claim 6, which is characterized in that the glutinous number of the copolymer nylon for 210~ 226cm³/g。

9. the preparation method of the low thickness PE/PA laminated film as described in claim 1~8 any one, which is characterized in that packet Include following steps:

S01: to the TIE resin and the copolymer nylon carry out after pre-treatment according to formula rate by mixing and blending machine into Row is stirred；

S02: by resulting mixture according to each layer of weight ratio, by screw extruder melting and high pressing die head extrusion-blown modling At cylinder film；

S03: resulting cylinder film is post-processed to obtain the low thickness PE/PA laminated film.

10. the application of low thickness PE/PA laminated film as claimed in any one of claims 1 to 9 wherein, which is characterized in that application In buffering pneumatic cushion field.