CN1408756A - Heat seal film and tis use - Google Patents
Heat seal film and tis use Download PDFInfo
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- CN1408756A CN1408756A CN02142476A CN02142476A CN1408756A CN 1408756 A CN1408756 A CN 1408756A CN 02142476 A CN02142476 A CN 02142476A CN 02142476 A CN02142476 A CN 02142476A CN 1408756 A CN1408756 A CN 1408756A
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- propylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
- C08L2203/162—Applications used for films sealable films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The film is formed from a propylene polymer composition comprising a composition, which comprises a propylene polymer component (A) and a propylene/[alpha]-olefin random copolymer component (B) in a weight ratio of (A)/(B) of 80/20-95/5, and, further incorporated therewith, an ethylene/[alpha]- olefin random copolymer (C) in an amount of 10-30 wt.% of the whole composition. To provide a fusion bonding film suitable for packaging a retort food and the like which has low-temperature impact resistance and blocking resistance, retains heat sealing strength after a heat treatment and is prevented from or reduced in generation of unevenness on the surface of a package.
Description
Technical field
The present invention relates to a kind of heat-sealing film made from polypropene composition.This polypropene composition is suitable for as the wrapping material as sterilising food prods.More particularly, the present invention relates to a kind of wrapping material that are suitable for as sterilising food prods etc., this material has good antiblocking performance, rigidity and low-temperature impact resistance, even in thermal treatment when carrying out sterilising treatment, the heat seal strength of material is also unaffected, and just forms depression and projection on the packing material of being made by it.The present invention also relates to a kind ofly be applicable to the hot sealing layer press mold of making by described film that need are carried out that sterilising food prods that heat sterilization handles, medicine, pet food etc. pack, and a kind of need that utilize described laminated film sealing to make carry out the packing material that heat sterilization is handled to its content by described.
Background technology
The leave one's hometown increase of population of increase, two-earners family's age group of number of work of the occurent social change such as the national aging of population, the tendency of nuclear family, background is no exception, also have the increase of age for marriage etc., generally speaking above variation has all promoted the variation of cooking culture.Therefore people to save time and culinary art demand easily exceed add strong.So increasing people buys so-called sterilising food prods, this sterilising food prods by supplier in advance ready-made food pack in the sealing bag, render to market after the sterilization thermal treatment of pressurizeing then.The human consumer can in officely what is the need for and when wanting the sterilising food prods bag be put into boiling water, can have sterilising food prods wherein soon.This sterilising food prods not only obtains the acceptance of ordinary consumer, and has obtained Inst acceptance.Under above-mentioned trend, the increase of this wrapping material demand made a large amount of food are carried out batch package become possibility.
Because sterilising food prods needs at room temperature usually or deposit for some time in refrigeration and freezer storage, film as wrapping material just need have high heat seal strength and low temperature impact strength, so that the initial damage that packing material can not form owing to the heat seal lands at it ruptures.Consider the measure of effective control Food Quality, the pressurized heat that make the packing of putting into the pressurized heat jar have the sealing bag of food can bear about 100-140 ℃ is handled, and the heat seal lands of this packing must have enough thermotolerances and can keep heat seal strength.
Once the film that the film that was used for this purposes has the film that made by polypropylene and ethylene-, made by propylene-based block copolymer and film of making by described propylene-based block copolymer and ethylene-mixture or the like.Although the film of these kinds has good thermotolerance and low temperature impact strength, not talkative they between low-temperature impact resistance and resistance to blocking, have enough equilibriums, and their heat seal strength has been subjected to influence after sterilising treatment.
In order to prevent the reduction of sterilising treatment rear edge heat seal strength, the propylene-alpha-olefin segmented copolymer that has proposed to be made up of polypropylene block unit that accounts for the 95-70% weight ratio and the elastomer unit that accounts for the 5-30% weight ratio in Japanese kokai publication hei patent announcement 2000-255012 is as hot sealing layer.Yet, the film that the propylene-alpha-olefin segmented copolymer that the elastomeric blocks unit of clearly describing in above-mentioned disclosing by the propylene that contains 30-70 mole % is formed is made does not have enough low temperature impact strengths, and its sealing intensity reduces after sterilising treatment easily.This film also may slightly be made a list face (" tangerine peel ") and influence outward appearance in the formation of packing material surface.
For low-temperature impact resistance, the heat seal strength that improves bactericidal film, thermotolerance etc., proposed a kind of composition in Japanese kokai publication hei patent announcement 2000-119480, said composition is the ethylene-a-olefin block copolymer rubber of 1-10% weight ratio to be added in the propylene-ethylene block copolymer of 90-99% weight make.The limiting viscosity [η] of the p-Xylol solute of this propylene-ethylene block copolymer is 1.5-2.8 (dl/g).Although the film of being made by this composition has the low-temperature impact resistance of improvement, unsafty is its antiblocking performance, and the pressurization effect of sealing intensity has also reduced after the sterilising treatment.
Summary of the invention
From the above, one of purpose of the present invention provides a kind of heat-sealing film, and it is suitable for packing and need carries out article such as the sterilising food prods that heat sterilization is handled.
Another order of the present invention provides a kind of heat-sealing film, this heat-sealing film has rigidity and low-temperature impact resistance, demonstrate good resistance to blocking and heat seal strength, through its heat seal strength after the heat treated slight decline is only taking place, and it can prevent or alleviate depression and protruding generation on the packing material surface.
Another order of the present invention provides a kind of hot sealing layer press mold that contains the described heat-sealing film of one deck.
Another order of the present invention provides a kind of packing material, and the article of its packaging need carry out heat sterilization to be handled, and this packing material has used described hot sealing layer pressing mold.
Of the present invention other and further purpose and characteristics and advantage will be discussed in more detail below.
That is to say, the present invention relates to a kind of heat-sealing film of making by propylene polymers composition, it comprises propylene polymer component (A), propylene-alpha-olefin random copolymer component (B) and by ethene with have the random copolymer component (C) that the alpha-olefin of 4 or more carbon atom obtains, wherein, described composition is grouped into by following one-tenth:
(1) propylene polymer component (A) and propylene-alpha-olefin random copolymer component (B), its weight ratio scope is 80/20-95/5.
(2) propylene-alpha-olefin random copolymer component (B), its limiting viscosity [η] be more than or equal to 2, but be no more than 3.5 (dl/g), and contain the propylene units of 70-85% weight.
(3) ethene-alpha-olefin random copolymer component (C), its density is 0.865-0.910 (g/cm
3), account for the 10-30% of composition gross weight.
Described propylene polymerization composition preferably contains the p-Xylol solute of 15-30% weight in the time of 23 ℃, and contains the hexane solute smaller or equal to 2.6% weight in the time of 50 ℃.The melt flow that described propylene polymerization composition records in the time of 230 ℃ is preferably 2-10 (g/10min), and the ethylene unit weight content is 10-20%.The melt flow that described ethene-alpha-olefin random copolymers (C) records in the time of 190 ℃ is preferably 0.01-5 (g/10min).This film has good low-temperature impact resistance, even still keeps high heat seal strength and good surface appearance after sterilising treatment, therefore suitable article such as the sterilising food prods that needs sterilising treatment as packing.
In addition, the invention still further relates to a kind of hot sealing layer press mold, wherein, a substrate layer is pressed on the one side of described heat-sealing film, this laminated film is suitable for as the article of packing as sterilising food prods.
The invention still further relates to a kind of packaging sterilizing packaging for foodstuffs, can seal by the described heat-sealing film that packing is had article and make.
Embodiment
Below will be to heat-sealing film of the present invention, comprise the laminated film of the described film of one deck and describe in detail one by one with the packing material that need carry out sterilising treatment that contains that laminated film is made.
The propylene polymerization composition
Heat-sealing film among the present invention is obtained by the raw material propylene polymeric composition, and this propylene polymerization composition is mainly by propylene polymer component (A), and propylene-alpha-olefin random copolymer component (B) and ethene-alpha-olefin random copolymer component (C) are formed.
Represent the composition composition ratio with weight ratio, propylene polymer component (A)/propylene-alpha-olefin random copolymer component (B), promptly A/B is 80/20-95/5, is preferably 83/17-90/10.The content with respect to the composition gross weight of ethene-alpha-olefin random copolymer component (C) is 10-30%, is preferably 11-23%, more preferably 12-20%.The film that is obtained by this polymeric composition has good low temperature impact strength, rigidity, first heat seal strength and postheat treatment heat seal strength.The need that the film that is made by it is particularly suitable for packing as sterilising food prods carry out the article that heat sterilization is handled.
The melt flow of preferred compositions (MFR) scope is 2-10 (g/10min), more preferably 2.5-8 (g/10min).This test is to be 230 ℃ in temperature, and load is under the condition of 2.16kg, carries out according to the testing method of ASTM D-1238.When melt flow was in described scope, polymeric composition had good moldable film and makes film have good low-temperature impact resistance easily.The ethylene unit weight content of composition is preferably 10-20%, more preferably 12-18%.
For described propylene polymerization composition, the p-Xylol solute that under 23 ℃, contains 15-30% weight, and under 50 ℃, contain the use hygienic requirements etc. that hexane solute smaller or equal to 2.6% weight has satisfied the contact food etc. of FDA regulation, therefore be suitable for producing the packing film that the need that are used to pack as sterilising food prods carry out the article that heat sterilization handles.
Below, will introduce each moiety of forming the propylene polymerization composition respectively in detail.
Propylene polymer component
The main moiety propene polymer (A) of propylene polymerization composition can be an alfon, also can be preferably the multipolymer smaller or equal to the alpha-olefin of 5% weight by propylene with smaller or equal to 10% weight.Here said alpha-olefin is the alpha-olefin that contains 2-10 carbon atom except propylene, for example, and ethene, 1-butylene, 3-methyl-1-butene, 1-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene.In homopolymer and the multipolymer that makes by described comonomer, preferably use alfon, because it makes film have good thermotolerance.
The propylene-alpha-olefin random copolymer component
Propylene-alpha-olefin random copolymer component (B) is to be obtained by propylene and the aforesaid alpha-olefin copolymer that contains 2-10 carbon atom except propylene, and it has demonstrated the characteristic similar to the elastomerics inherent.This alpha-olefin is preferably ethene especially.
The content of propylene units is preferably and accounts for 70-85% weight in the described propylene-alpha-olefin random copolymers (B), more preferably accounts for 75-83% weight.The unitary content of alpha-olefin is preferably and accounts for 17-25% weight in the scope of 15-30% weight in the described multipolymer.When described propylene units content is in described scope, have good low-temperature impact resistance and low-temperature heat-sealing performance by containing the film that this composition of forming makes, and, even after sterilising treatment, still keep high heat seal strength, therefore suitable to packing article such as the sterilising food prods that needs sterilising treatment.Wherein, propylene units content can pass through infrared absorption spectrometry.
The ratio of the propylene-alpha-olefin random copolymers (B) that contains in the propylene polymerization composition can calculate by the following method: the composition of sample thief amount (a) (gram) is dissolved in the p-Xylol fully, solution was left standstill under 23 ℃ 24 hours, then, will precipitate (b) by centrifugation separates.At this moment, the p-Xylol solute of sample is propylene-alpha-olefin random copolymers (B), and its content can calculate by following formula:
Multipolymer (B) content=[(a-b)/a] * 100 (weight %)
The limiting viscosity [η] of propylene-alpha-olefin random copolymers (B) is more than or equal to 2, but is no more than 3.5 (dl/g), is preferably 2.5-3.3 (dl/g).When limiting viscosity [η] is in described scope, can make film with good antiblocking performance, can in the film course of processing, suppress the generation of shrinkage cavity simultaneously.
Obtain throw out based on the method for utilizing aforesaid adding excessive propanone separating dimethyl benzene solute, and the viscosity that the measurement recovery is deposited in the naphthane solvent under 135 ℃ calculates limiting viscosity [η].
The ethene-alpha-olefin random copolymer component
Ethene-alpha-olefin random copolymers (C) is formed by ethene and alpha-olefin random copolymerization, and wherein alpha-olefin contains 4 or more carbon atoms, and carbonatoms is preferably 4-10.These alpha-olefins for example, 1-butylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, tetradecene and 1-vaccenic acid.In these comonomers, 1-butylene, 1-hexene and 1-octene are particularly preferred.Alpha-olefin can contain a kind of comonomer, also can be made up of two or more comonomer.In addition, they can also exist with the mixed form of different ethene-alpha-olefin random copolymerss.
The special case of preferred ethene-alpha-olefin random copolymers (C) is ethene-1-butylene random copolymers, ethene-1-hexene random copolymers and ethene-1-octene random copolymers.
The density range of multipolymer (C) is 0.865-0.910 (g/cm
3), be preferably 0.875-0.900 (g/cm
3).
Acetate unit content in the ethene-alpha-olefin random copolymers (C) is preferably 70-95 mole %, 80-93 mole % more preferably, and alpha-olefin unit content preferable range is 5-30 mole %, more preferably 7-20 mole %.
This ethene-alpha-olefin random copolymers (C) is preferably has one or more following performances.The film that is made by the propylene polymerization composition that contains this ethene-alpha-olefin random copolymers (C) has excellent low temperature shock strength and shock of a fall intensity.
(1) its melt flow test is to be 230 ℃ in temperature, and load is under the condition of 2.16kg, carries out according to the testing method of ASTM D-1238.Its melt flow is preferably 0.01-5 (g/10min), more preferably 0.1-3 (g/10min).
(2) its degree of crystallinity records with the X-ray diffraction method, is preferably 5-40%, more preferably 7-30%.
(3) ratio of its weight-average molecular weight (Mw) and number-average molecular weight (Mn), i.e. Mw/Mn, (GPC) records with gel permeation chromatography, is preferably smaller or equal to 3, more preferably smaller or equal to 2.5.
(4) its fusing point is under the heating rate of 10 ℃ of per minutes, and the endothermic curve of drawing by dsc (DSC) determines that its fusing point is preferably 40-100 ℃, more preferably 60-90 ℃.
The preparation of compositions method
The propylene polymerization composition can be prepared as follows.
(1) the good propylene polymer component of prepared beforehand (A), propylene-alpha-olefin random copolymer component (B) and by ethene with contain the random copolymer component (C) of the alpha-olefin of 4 or more carbon atoms is mixed into these components in the homogeneous reaction still according to predetermined ratio then.
(2) mixture of good propylene polymer component of prepared beforehand (A) and propylene-alpha-olefin random copolymer component (B), then, the random copolymer component of ethene and alpha-olefin (C) is mixed with described mixture according to predetermined ratio.
The mixture of propylene polymer component (A) and propylene-alpha-olefin random copolymer component (B) can use respectively different polymerization processs prepare (A) and (B) after refabrication.These two kinds of polymerization processes can be carried out or carry out successively synchronously.In the previous case, any one process can be before another, and still preferred order is the polymerization process for preparing propylene polymer component (A) earlier, and this is because the polymkeric substance that obtains has high degree of crystallinity.But,,, be preferably continuous processing though batch process or continuous processing can be selected for first polymerization process.Continuously processing can be one and uses the single step polymerization process that polymerization reactor carries out, and also can be a process of using the multistep polymerization system that a plurality of polymerization reactors carry out.The propylene polymer component (A) that is obtained by described any one polymerization process and the mixture of propylene-alpha-olefin random copolymer component (B) are commonly called the propylene-alpha-olefin segmented copolymer.
The mixture of described propylene polymer component (A) and propylene-alpha-olefin random copolymers (B) can make by using stereoregular olefin polymerization catalysis such as ziegler-natta catalyzer and metallocene catalyst.In this polymerisation catalysts, the catalyst system that exemplifies can prepare as follows.A kind of solid titanium catalyst component of load on the organic or inorganic carrier contains requisite activated carbon compound, titanium compound, halogen compounds and interior electron donor(ED) component in this component; To wherein adding a kind of organometallic compound of deriving and obtaining by the metal in the periodic table of elements I-III family; And then to wherein adding external electronic donor.This catalyst system can be as the initial polyreaction of alpha-olefin before the polymerization of carrying out propylene etc.For described solid titanium catalyst component, when reaction product is in varsol, situation about obtaining in the reaction that contains between alcoholic acid magnesium compound and the titanium tetrachloride is preferred.For external electronic donor, diether compounds and/or silane compound are preferred.Aforesaid polymerisation catalysts also can be used for preparing ethene-alpha-olefin random copolymers (C).
For polymerization process, can be chosen in and carry out suspension polymerization in the varsol, in propylene solution, carry out any method in suspension polymerization, the vapour phase polymerization, and the combination of described polymerization process.For example, in the process of producing described two kinds of components, the first step can be carried out suspension polymerization in propylene solution, the second stepping promoting the circulation of qi phase-polymerization.
The mixture of propylene polymer component (A) and propylene-alpha-olefin random copolymers (B) can also prepare through being different from above-mentioned polymerization route, kneads and makes but two kinds of good components of prepared beforehand are carried out fusion.
Require to have under the situation of high impact-resistant film may using, described propylene polymerization composition can also contain elastomeric component.Common thermoplastic elastomer can be used as elastomeric component.For example, but the compound elastomeric component comprises, ethylene-propylene copolymer rubber, ethene-butene-1 copolymer rubber, ethene-1-hexene copolymer rubber, ethene-1-octene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene based block copolymer rubber, ethene-1-butylene-diene based block copolymer rubber, hydrogenated styrene-butadiene block copolymer and hydrogenated styrene-isoprene block copolymer.
Before the film forming step, can in the propylene polymerization composition, add oxidation inhibitor, thermo-stabilizer, lubricant, static inhibitor, spirit of salt absorption agent, antiblocking agent, release agent, pigment, dyestuff etc.
Oxidation inhibitor is phenolic antioxidant, organic phosphite oxidation inhibitor, thioether oxidation inhibitor, hindered amine oxidation inhibitor etc. for example.Antiblocking agent such as aluminum oxide, thin tripoli powder, poly-methyl iso-butylene ester powder, silicone resin etc.
Bisamide such as ethylenebis stearic amide, higher fatty acid amides such as amine hydroxybenzene, sinapinic acid acid amides etc. are arranged in the example of release agent.Lubricant is metal-salt such as nonacosane acid metal salt, polyolefin-wax such as the polyethylene wax and the Poly Propylene Wax etc. of calcium stearate, Zinic stearas, higher fatty acid for example.Nucleator is the part metals salt of benzylidene sorbitol, rosinyl nucleator such as sylvic acid for example, aluminium base nucleator, talcum etc.
Film
Heat-sealing film of the present invention is made by described propylene polymerization composition.Have no particular limits for the method for producing this film, any traditional method all can be used.For example, described propylene polymerization composition can be melt into bead or Powdered in single screw rod or twin screw extruder, then with the fused resin by being positioned at a concora crush punch die (T-mould) or a circular die film extrusion of forcing machine front end.Normally 200-300 ℃ of the temperature range of the molten resin in the forcing machine is preferably 200-280 ℃.
When molten resin by a concora crush punch die (T-mould) when extruding, the film of extruding is rolled in cooling when keeps the cylinder machine of certain temperature contact by water or other heat-eliminating mediums and curing and by a take-up device.When molten resin is extruded by a circular die, round towards the outside of film and/or inner by a heat-eliminating medium, as coolings such as freezing air, water.So film is after the cutting or rolled-up after making the film of predetermined shape.The thickness of the film that obtains like this is generally 20-1, and 000 μ m is preferably 30-200 μ m, more preferably 40-100 μ m.
The article such as the sterilising food prods that use the film of this primary individual layer shape to pack need to carry out heat sterilization to handle are fit closely.In addition, also this rete can be pressed onto on one deck stratum basale form layers press mold and have identical purposes.
The lamination mould
Lamination mould among the present invention is that one deck substrate layer is pressed onto the laminar structure that obtains on the one side of the film described in the present invention or the surface.As packing material, the type of stratum basale is also had no particular limits, its row shape can be plate, film, dish, container etc.
The dish that the available stratum basale comprises thermoplastic film and plate, made by the heating forming board and the container of hollow and utilize aluminium foil or similar articles that paper forms.In the example of film, if any the polyester resin film that makes by poly-(ethylidene terephthalate), poly-(ethylidene naphthoic acid ester) etc., polycarbonate membrane, by nylon-6, the polyamide membrane that nylon-66 etc. make, ethylene vinyl alcohol copolymer film, polyvinyl alcohol film, polychloroethylene film, polyvinylidene dichloride film and the polyolefin film that makes by polypropylene etc.
When stratum basale was a kind of form of film, this film can be the film of non-alignment films or single shaft or diaxial orientation.In addition, thermoplastic resin film is metalized film or deposited film, and this can obtain by metal such as aluminium, zinc etc., oxide compound such as silicon oxide, aluminum oxide or mineral compound etc. are deposited on the film.Substrate can also be composition or pressure layer that described film is combined.
For forming heat-sealing film among the present invention on side of stratum basale or surface, and the form layers press mold can adopt traditional laminating method to reach, and need not any improvement, can also be at the two-layer one deck of adding at the interface bonding coat.Laminating method for example, can on stratum basale, coat the first coating or the first layer material that are mainly carbamate or are mainly isocyanic ester, use the heat-sealing film dry lamination then, perhaps the propylene polymerization composition directly is expressed into finish in the substrate and extrudes lamination or extruding coating.When stratum basale is when being made by thermoplastic resin, the lamination mould can directly form in the coextrusion process.When the lamination mould of producing is to be used to pack need carry out article that heat sterilization handles such as food the time, substrate normally is laminated on the one side of heat-sealing film.When being used for different types of wrapping material, stratum basale can be laminated on the one or both sides of heat-sealing film.
In the lamination mould that obtains, the heat-sealing rete has high heat seal strength, and when it is used as wrapping material, has high stripping strength in heat seal lands, even through the sterilising treatment under the high pressure warming, still kept high heat seal strength.For example, it has kept being at least the stripping strength of 35 (N/15mm).
Laminated film of the present invention has the hot sealing layer that one deck forms on its surface, and this hot sealing layer has high thermotolerance, low temperature impact strength, high heat seal strength and rigidity.According to the different stratum basale that uses, additional high air screen performance of this lamination mould and physical strength have also been given.For these reasons, this lamination mould can be widely used in various fields, comprises the sterilising food prods packing.When being used for wrapping material, earlier it is become the shape of equatorial film or dish and container.
Packing material
Of the present invention being equipped with need be a kind of packing material that uses the lamination mould to make through the article of heat sterilization processing such as the packing material of food, medicine, medical instruments and pet food.The heat-sealing film with described performance in the lamination mould is laminated in the substrate as at least a wrapping material, thereby this layer heat-sealing film be in the internal surface of packing material, to be used for article such as packaging sterilizing food, at last again with the heat-sealing film heated sealant.
Although unitary film also can be used as wrapping material, adopt the lamination mould better, this is because the various proper properties of its stratum basale can obtain utilizing.When described lamination mould was used for the packing material of Production and Packaging sterilising food prods etc., the stratum basale in the following example was the preferred embodiment of lamination mould with combining of rete of heat-sealing.
Polyester layer/heat-sealing film
Aramid layer/heat-sealing film
Polyester layer/aluminium foil/heat-sealing film
Polyester layer/aramid layer/aluminium foil/heat-sealing film
Aramid layer/polyvinylidene dichloride layer/polyester layer/heat-sealing film
Owing to seal the innermost layer that the post heat-seal film is positioned over packing material, after handling as food sterilizing, heat sterilization still keeps high heat seal strength even therefore given the high heat seal strength of heat seal lands and experienced at packing material to having packed the article that need through heat sterilization is handled.
Therefore, as long as correct the processing, thisly be used for the situation that its packing material can appear leaking in transportation, storage, when family uses etc. in packaging sterilizing packaging for foodstuffs hardly, and the food of packing can go bad hardly under the condition of room temperature or refrigerating.Packing material of the present invention not only can be packed general food, and can pack all needs and carry out the thing handled as heat sterilization, as sterilising food prods, medicine, medical instruments, pet food etc.
Embodiment
By following example, can more easily understand the present invention, these examples be used to describe of the present invention, but the scope that can not be construed as limiting the invention.
The The performance test results of (being total to) polymkeric substance and polymeric composition and the evaluation result of film and laminated film are obtained according to following testing method respectively.
(1) testing method of polymer physics performance:
Ethylene content:
It is 720cm that ethylene content is based on the infrared absorption spectrum medium wavelength
-1The absorption measurement at place.
Limiting viscosity [η] is based on polymer samples is dissolved in the naphthane under 135 ℃, re-uses that viscosity number that Ubbelohde type viscometer records calculates.
Melt flow (MFR):
The test of melt flow is to be 230 ℃ in temperature, and load is under the condition of 2.16kg, carries out according to the testing method of ASTM D-1238.
The p-Xylol solute:
The p-Xylol solute is based on the aggregate combinations matter sample is dissolved in the p-Xylol fully, isolates precipitation by centrifugal from p-Xylol solution again, sample size is deducted value that precipitation capacity obtains calculates.Before described step with centrifugal separation, p-Xylol solution left standstill under 23 ℃ 24 hours earlier.
The hexane solute:
The aggregate combinations matter samples of 2 grams are put into 1 liter of hexane, under 50 ℃,, filter out solids solution stirring 2 hours.Then, with the complete evaporate to dryness of the hexane of liquid state, the residuum that obtains is the hexane solute.Weighing hexane solute, and report observed value.
(2) film properties testing method:
Low temperature impact strength:
Low temperature impact strength is to test according to the film impact test instrument that the testing method among the ASTM D-3420 has adopted YasudaPrecision Machinery Co. to produce.Except probe temperature is 10 ℃ that bear, the preceding diameter of hammer is 1 inch (2.54cm), and the energy of hammer is 3 joules.The sample thickness is 70 μ m.
Resistance to blocking:
Resistance to blocking is the testing method according to ASTM D-1893, and the thick film of 70 μ m under 60 ℃, is applied 40 kilograms load 7 days continuously, measures its adhesion degree then and obtains.
Anti-around the Qu Zhibai performance:
With the hands that one be cut into the A4 size (9 " * 12 " or the both sides of 210 * 297mm) sample film, sample is rubbed the wrinkle 30 albefaction parts of after this checking at film around bent portions.
Opacity:
Opacity is measured according to the method among the ASTM D-1003.
(3) testing method of the physicals of laminated film:
Heat seal strength:
A slice laminated film is placed on another sheet laminated film, makes the sack of the 3 ends heat-sealing of an envelope shape, its size just in time can be held the article of 105mm (vertically), 155mm (laterally).Heat-sealing is to be under 200 ℃ and 210 ℃ with a wide sealed strip of 5mm at seal temperature, pressure be 0.2Mpa down heat-sealing finished in 1 second.
From the vertical heat seal lands (heat-sealing is carried out along lateral edges) and the wide sample of horizontal heat seal lands (heat-sealing is carried out along feather edge) cutting 15mm of the sack of the envelope shape that makes, then sample pinblock speed with 500mm/min on peeling tester is peeled off test.The heat seal strength (N/15mm) of the stripping strength that records before as sterilising treatment.
Simultaneously, the heat seal strength after the sterilising treatment (" back-thermal treatment heat seal strength ") records with following method.Be about to the liquid that 9 parts of water and 1 portion of salad oil are mixed into 200mL, pour the sack of the 3 ends heat-sealing of described envelope shape then into, subject to the foregoing opening is sealed then.This sack of having filled article was placed 30 minutes in 121 ℃ in the high pressure-temperature Sterilizers of a shower type.Then,, exenterate again, and with residual oily matter in the sanitising agent flush away sack, at last, sack is at air drying sack cooling.Immediately, the sample that cuts from sack is carried out and through the identical test mode of the sample of sterilising treatment according to aforesaid step test heat seal strength (N/15mm).
Shock of a fall intensity:
A slice laminated film is placed on another sheet laminated film, makes the sack of the 3 ends heat-sealing of an envelope shape, its size just in time can be held the article of 105mm (vertically), 155mm (laterally).Heat-sealing is to be under 200 ℃ with a wide sealed strip of 10mm at seal temperature, pressure be 0.2Mpa down heat-sealing finished in 2 seconds.
9 parts of water and 1 portion of salad oil are mixed into the liquid of 200mL, pour the sack of the 3 ends heat-sealing of described envelope shape then into, subject to the foregoing opening is sealed then.Prepare 10 such sacks, and all pass through identical aforesaid sterilising treatment.Then, these sacks are stored in temperature maintenance in 5 ℃ refrigerator 7 days.
All sample sacks are fallen and carry out the shock of a fall test.The weight of each sample sack is 1 kilogram much at one.The sack that in 5 ℃ refrigerator, stores successively from 80cm (situation a) and the height of 60cm (situation b) freely fall to a Stainless Steel Disc that places on the concrete floor respectively.All 10 sacks are repeated drop shutter test, till breaking has all appearred in each sack.Record causes the number of times that falls of each bag breakage, obtains the number of times that on average falls.The number of times that on average falls that obtains is shock of a fall intensity.
Surface flatness:
A slice laminated film is placed on another sheet laminated film, makes the sack of the 3 ends heat-sealing of an envelope shape, its size just in time can be held the article of 105mm (vertically), 155mm (laterally).Heat-sealing is to be under 200 ℃ with a wide sealed strip of 5mm at seal temperature, pressure be 0.2Mpa down heat-sealing finished in 2 seconds.
140 grams " stirfried bean curd in hot sauce (Karakuchi) " [bean curd of Chinese local flavor (strong sharp flavor), Marumiya Co. makes] are put into bag.Prepare 5 such sacks, all in the high pressure-temperature Sterilizers, carry out sterilising treatment.Then, the surface flatness of the outside surface of sack (upper surface and following outside surface) is observed.Estimate surface flatness with following standard:
Fabulous: as to be difficult to find out inhomogeneous.
Good: as to find out inhomogeneous partly.
Relatively poor: as to find out large-area shallow depression and projection.
Difference: dark depression and the projection of finding out small area.
Embodiment 1
Prepared the polymeric composition that the propylene-ethylene block copolymer conduct with following character contains propene polymer and propylene-alpha-olefin random copolymer component.And, prepared have following character ethene-1-butylene random copolymers as the ethene-alpha-olefin random copolymers.
Propylene-ethylene block copolymer
Propylene homopolymer component: 85.9% (weight)
Propylene-ethylene random copolymer component: 14.1% (weight)
Ethylene content: 19.5% (weight)
Propylene content: 80.5% (weight)
Limiting viscosity [η]: 3.1 (dl/g)
The melt flow of segmented copolymer (230 ℃): 3.2 (g/10min)
Ethene-1-butylene random copolymers
Density: 0.885g/cm
3Ethylene content: 89mol%
Degree of crystallinity: 13% fusing point: 68 ℃
Mw/Mn:2.0 melt flow (190 ℃): 0.5 (g/10min)
(be total to) concentrated being shown in Table 1 of character of polymkeric substance accordingly.
After following additive joins described (being total to) polymkeric substance, material is extruded into propylene polymerization composition bead (" making the granulous composition ") with single screw extrusion machine.
(1) propylene-ethylene block copolymer: 85% (weight)
(2) ethene-1-butylene random copolymers: 15% (weight)
(3) phenols thermo-stabilizer
(manufacturers: Ciba Speciality Chemicals Co. trade(brand)name: Irganox 1010): 0.1% (weight)
(4) organophosphorus thermo-stabilizer
(manufacturers: Ciba Speciality Chemicals Co. trade(brand)name: Irgafos 168): 0.1% (weight)
(5) calcium stearate: 0.1% (weight)
These are made the granulous composition and have following character:
P-Xylol solute (23 ℃): 25.7% (weight)
Hexane solute (50 ℃): 1.7% (weight)
Melt flow (230 ℃): 2.8 (g/10min)
The character of the composition that obtains is concentrated and is shown in Table 1.
To make the granulous composition and put into a forcing machine,, then molten resin be passed through a concora crush punch die (T-mould) film extrusion in 230 ℃ of following fusions.Extrudate cooling and solidify and rolled by a take-up device when one 30 ℃ metal roller machine contacts obtains the thick film of 70 μ m.Test the performance of this film, test result is shown in table 1.
Comparative Examples 1
Method according to embodiment 1 makes the thick film of one 70 μ m, and different with it is has only used propylene-ethylene block copolymer in the table 1 as raw material.Test the performance of this film, test result is shown in Table 1 in the lump.
Comparative Examples 2
Propylene-ethylene block copolymer and ethylene-propylene random copolymer that preparation has following character respectively.
Propylene-ethylene block copolymer
Propylene homopolymer component: 84.0% (weight)
Propylene-ethylene random copolymer component: 16.0% (weight)
Ethylene content: 26.0% (weight)
Propylene content: 74.0% (weight)
Limiting viscosity [η]: 1.9 (dl/g)
The melt flow of segmented copolymer: 1.8 (g/10min)
Ethylene-propylene random copolymer
Density: 0.870g/cm
3Ethylene content: 82.6mol%
Mw/Mn:2.0 melt flow (190 ℃): 3.6 (g/10min)
The character of corresponding multipolymer is concentrated and is shown in Table 1.
Method according to embodiment 1 makes the thick film of one 70 μ m, and different with it being to use contains propylene polymerization composition that the ethylene-propylene random copolymer of the described propylene-ethylene block copolymer of 95% weight and 5% weight forms as the propylene polymerization composition that uses in embodiment 1.Test the performance of this film, test result is shown in Table 1 in the lump.
Comparative Examples 3
Propylene-ethylene block copolymer and ethene-1-butylene random copolymers that preparation has following character respectively.
Propylene-ethylene block copolymer
Propylene homopolymer component: 85.9% (weight)
Propylene-ethylene random copolymer component: 14.1% (weight)
Ethylene content: 19.5% (weight)
Propylene content: 80.5% (weight)
Limiting viscosity [η]: 3.8 (dl/g)
The melt flow of segmented copolymer (230 ℃): 3.2 (g/10min)
Ethene-1-butylene random copolymers
Density: 0.885g/cm
3Ethylene content: 89mol%
Degree of crystallinity: 13% fusing point: 68 ℃
The character of the corresponding multipolymer of Mw/Mn:2.0 melt flow (190 ℃): 0.5 (g/10min) is concentrated and is shown in Table 1.
Method according to embodiment 1 makes the thick film of one 70 μ m, and different with it being to use contains the propylene polymerization composition of the described propylene-ethylene block copolymer of 95% weight and the ethene of 5% weight-1-butylene random copolymers composition as the propylene polymerization composition that uses in embodiment 1.Test the performance of this film.Owing on film, observe many shrinkage cavities, can judge that therefore this film is unsuitable for as packing film.
Table 1
| Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| The polymeric composition component | ||||
| Propylene-ethylene block copolymer MFR, (230 ℃) g/10min weight acrylic polymer % propylene-ethylene random copolymers weight % limiting viscosities [η], (dl/g) propylene content weight % | ??3.2 ??85.9 ??14.1 ??3.1 ??80.5 | ??0.8 ??87.0 ??13.0 ??2.7 ??65.0 | ??1.8 ??84.0 ??16.0 ??1.9 ??74.0 | ??3.2 ??85.9 ??14.1 ??3.8 ??80.5 |
| The ethene-alpha-olefin random copolymers | ||||
| Alpha-olefin kind MFR (190 ℃) g/10min density g/cm 3Chemical combination ratio parts by weight in the ethylene content mole % degree of crystallinity % fusing point ℃ Mw/Mn composition | 1-butylene 0.5 0.885 89 13 68 2.0 15 | ??- ??- ??- ??- ??- ??- ??- ? ??0 | Propylene 3.6 0.870 82.6 does not have 2.0 5 | Butylene 0.5 0.885 89 13 68 2.0 15 |
| The polymeric composition characteristic | ||||
| MFR (230 ℃) g/10min ethylene content weight % p-Xylol solute (23 ℃) weight % hexane solute (50 ℃) weight % | ??2.8 ??15.3 ??25.7 ? ??1.7 | ??0.8 ??4.6 ??13.0 ? ??0.9 | ??2.5 ??8.0 ??20.4 ? ??1.1 | ??2.8 ??15.3 ??25.3 ? ??1.6 |
| Film properties | ||||
| Resistance to blocking N/m low temperature impact strength (10 ℃) kJ/m opacity % is anti-around the Qu Zhibai performance | 0.30 14 41 no changes | 0.30 9 49 bleach | 8.40 16 20 no changes | |
Embodiment 2
Polyethylene terephthalate (PET) film that with a layer thickness is the diaxial orientation of 12 μ m is with to be mainly the urethane adhesive dry-pressing be on the aluminium foil of 7 μ m at a layer thickness, then, the film that makes among the embodiment 1 with being mainly the urethane adhesive dry-pressing on aluminium foil surface, being made and presses layer.The pressure layer that obtains is carried out performance test, and the result is shown in Table 2 in the lump.
Comparative Examples 4 and 5
Make with the method identical with embodiment 2 and to press layer, different with it is, the film that makes in Comparative Examples 1 and 2 is respectively aluminium foil lip-deep in the pressure layer formed of the polyethylene terephthalate film and the aluminium foil by diaxial orientation of dry-pressing in embodiment 2.The film that obtains is carried out performance test, the results are shown in the table 2.
Table 2
| Embodiment 2 | Comparative Examples 4 | Comparative Examples 5 | ||
| The heat seal strength (N/15mm) of pressing layer is vertical and horizontal direction (vertical/horizontal stroke) | ||||
| Heat-sealing temperature | 200℃ 210℃ | 41.8/54.9 41.9/61.3 | 44.6/47.9 47.2/48.0 | 32.1/41.4 34.8/43.5 |
| The heat seal strength (N/15mm) of the pressure layer after the thermal treatment is at vertical and horizontal direction (vertical/horizontal stroke) (heating state: 121 ℃, 30 minutes) | ||||
| Heat-sealing temperature | 200℃ 210℃ | 36.6/57.8 41.2/59.8 | 37.2/40.1 39.1/41.7 | 28.4/36.5 30.4/38.1 |
| Shock of a fall intensity (cause disruptive fall number of times) | ||||
| Situation a | ????5.7 | ????1.9 | ????2.5 | |
| Situation b | ????6.4 | ????3.3 | ????4.0 | |
| Surface flatness is estimated | ||||
| The end face bottom surface | Fabulous | Good | Fabulous | |
| Relatively poor | Difference | Relatively poor | ||
Heat-sealing film among the present invention has high heat seal strength, and slight following general only appears in its heat seal strength after thermal treatment, demonstrates good resistance to blocking and anti-around the Qu Zhibai performance, has high rigidity and low temperature impact strength.Therefore, this film is not only applicable to pack general article, can also carry out the packing film of heat sterilization processing as article such as sterilising food prods as need.
Hot sealing layer press mold of the present invention is owing to form hot sealing layer on its surface with the heat-sealing film with aforementioned properties, but therefore suitable wrapping material as sterilising food prods and other connection with wrapping of piece.
Even packing of the present invention has and need carry out article that heat sterilization handles such as the packing material of sterilising food prods is still keeping high heat seal strength through after the sterilising treatment, prevent or alleviated the formation of packing material surface depression and projection, have good surface appearance and described character.Therefore, this packing material in fact makes the article of its packing transport or avoid damaging under ordinary temp or refrigerating condition.
Claims (8)
1. heat-sealing film that makes by the propylene polymerization composition, it comprises propylene polymer component (A), propylene-alpha-olefin random copolymer component (B) and by ethene with contain the random copolymer component (C) of the alpha-olefin of 4 or more carbon atoms, wherein said composition is constructed as follows
(1) propylene polymer component (A) is 80/20-95/5 with the weight ratio of propylene-alpha-olefin random copolymer component (B),
(2) limiting viscosity [η] of propylene-alpha-olefin random copolymer component (B) is more than or equal to 2, but is no more than 3.5 (dl/g), contains the propylene units of 70-85% weight,
(3) density of ethene-alpha-olefin random copolymer component (C) is 0.865-0.910 (g/cm
3), account for the 10-30% of composition total weight.
2. heat-sealing film according to claim 1, wherein said propylene polymerization composition contains the p-Xylol solute of 15-30% weight and at 50 ℃ of hexane solutes that contain smaller or equal to 2.5% at 23 ℃.
3. according to the heat-sealing film described in claim 1 or 2, the melt flow that wherein said propylene polymerization composition records in the time of 230 ℃ is 2-10 (g/10min), and contains the ethylene unit of 10-20% weight.
4. according to each described heat-sealing film in the claim 1 to 3, wherein said ethene-alpha-olefin random copolymers (C) 190 ℃ the time melt flow that records be 0.01-5 (g/10min).
5. according to each described heat-sealing film in the claim 1 to 4, it is intended to be used for need heat sterilization to handle the relevant purposes of article with packing.
6. hot sealing layer press mold, substrate layer wherein is pressed onto on the one side of each described heat-sealing film in the claim 1 to 4.
7. hot sealing layer press mold according to claim 6, it is intended to needing with packing to be used for the relevant purposes of article of heat sterilization processing.
8. one kind is equipped with the packing material that needs the article that heat sterilization handles, and it comes connection with wrapping of piece by the described hot sealing layer press mold of heat-sealing claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001287247 | 2001-09-20 | ||
| JP2001287247 | 2001-09-20 |
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| Publication Number | Publication Date |
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| CN1408756A true CN1408756A (en) | 2003-04-09 |
| CN1241982C CN1241982C (en) | 2006-02-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021424764A Expired - Lifetime CN1241982C (en) | 2001-09-20 | 2002-09-20 | Heat seal film and tis use |
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|---|---|
| KR (1) | KR100845504B1 (en) |
| CN (1) | CN1241982C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1906032B (en) * | 2003-11-04 | 2010-10-20 | 伯斯蒂克公司 | Cling film laminate structure |
| CN107383586A (en) * | 2017-06-02 | 2017-11-24 | 蚌埠天成包装科技股份有限公司 | A kind of preparation method of the wide sealing thermoplastic film in Hot Tack temperature region |
| CN111971341A (en) * | 2018-03-30 | 2020-11-20 | 普瑞曼聚合物株式会社 | Propylene resin composition, film using the same, and use thereof |
| CN116478477A (en) * | 2023-05-08 | 2023-07-25 | 佐藤技研(江门)股份有限公司 | Linear easy-to-tear polypropylene composition film and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105252860A (en) * | 2008-04-03 | 2016-01-20 | 东赛璐株式会社 | Heat sealable multilayer film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3570797B2 (en) * | 1995-05-24 | 2004-09-29 | 三井化学株式会社 | Propylene polymer composition |
| JP4297546B2 (en) * | 1999-03-09 | 2009-07-15 | オカモト株式会社 | Multilayer laminate |
-
2002
- 2002-09-19 KR KR1020020057254A patent/KR100845504B1/en active IP Right Grant
- 2002-09-20 CN CNB021424764A patent/CN1241982C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1906032B (en) * | 2003-11-04 | 2010-10-20 | 伯斯蒂克公司 | Cling film laminate structure |
| CN107383586A (en) * | 2017-06-02 | 2017-11-24 | 蚌埠天成包装科技股份有限公司 | A kind of preparation method of the wide sealing thermoplastic film in Hot Tack temperature region |
| CN111971341A (en) * | 2018-03-30 | 2020-11-20 | 普瑞曼聚合物株式会社 | Propylene resin composition, film using the same, and use thereof |
| CN111971341B (en) * | 2018-03-30 | 2023-04-28 | 普瑞曼聚合物株式会社 | Propylene resin composition, film using the same and use thereof |
| CN116478477A (en) * | 2023-05-08 | 2023-07-25 | 佐藤技研(江门)股份有限公司 | Linear easy-to-tear polypropylene composition film and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1241982C (en) | 2006-02-15 |
| KR20030025878A (en) | 2003-03-29 |
| KR100845504B1 (en) | 2008-07-10 |
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