CN1974203B - Multiple laminates and method for reducing environment pollution - Google Patents
Multiple laminates and method for reducing environment pollution Download PDFInfo
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- CN1974203B CN1974203B CN2006101693243A CN200610169324A CN1974203B CN 1974203 B CN1974203 B CN 1974203B CN 2006101693243 A CN2006101693243 A CN 2006101693243A CN 200610169324 A CN200610169324 A CN 200610169324A CN 1974203 B CN1974203 B CN 1974203B
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Abstract
The present invention discloses a multilayer laminating film. Said multilayer laminating film comprises at least a layer including thermoplastic starch, and at least a layer of polyhydroxyalkanoate copolymer basically including at least two random repetitive monomeric units. The present invention also discloses a multilayer laminating film, said multilayer laminating film comprises at least a layer including thermoplastic starch, and at least two layers of polyhydroxyalkanoate copolymer basically includes at least two random repetitive monomeric units. The present invention also discloses a method of reducing environmental pollution with said multilayer laminating film.
Description
Patent application of the present invention is that international application no is PCT/US02/31545, international filing date is on October 2nd, 2002, the application number that enters the China national stage is 02820753.X, and denomination of invention is divided an application for the application for a patent for invention of " being used to make the polyhydroxy alkanoate copolymer/starch composites of laminated material and film ".
Technical field
The present invention relates to comprise the film of polyhydroxyalkanoatefrom (PHA) copolymer/converted starch blend.Also disclose the laminated material with ground floor and second layer, described ground floor is made up of pha copolymer basically, and the described second layer comprises pha copolymer/converted starch blend or thermoplastic starch.Film or laminated material are used to prepare the disposable product of degraded by environment, are particularly useful for the degraded under the oxygen free condition.
Background technology
The present invention relates to alleviate the needs of growing environmental problem, described environmental problem is meant that too much plastic refuse causes material volume mark cumulative in the garbage bury ground.Based on the requirement of the volume that reduces the annual solid waste that is produced by the consumer, biodegradable polymer and just become by the product that biodegradable polymer forms becomes more and more important.The invention still further relates to the demand of development of new plastic material, this material can be used for the application that biological degradability, compostability and biocompatibility are main expectation characteristics, especially under oxygen free condition.Carry out many trials and made degradable product.Yet, because how many business success are factors such as cost, difficulty of processing and final use energy almost do not obtain.Many compositions with splendid degradability only have limited machinability.On the contrary, be easy to composition processed and have relatively poor degradability.
Traditional disposable absorbent products has had compostability to a great extent.For example, typical disposable diaper contains 80% the compost material of having an appointment, for example, and wood pulp cellulose etc.Yet, the polyethylene egative film in the absorbent article need be replaced to the film of liquid-tight compost material especially, because one of maximum not compost component in the normally traditional disposable absorbent article of egative film.
In order to produce film, select acceptable biological degradation polyalcohol with challenging with the final use that is easier to accept.Degradable polymer should be thermoplastic, so that can adopt conventional processing film method, comprises the continuous production on the conversion machining production line.In addition, importantly film or big film fragments form much smaller particle in the starting stage of compost through initial disintegration.
In addition, people have produced interest to the gas permeability of disposal sanitary article gradually, and this gas permeability is used for farthest reducing and the relevant sense of discomfort of high humility accumulation.People are used to make this series products to the ventilative film that can receiving fluids allows moisture partly to see through simultaneously and nourish special interest.Before stretched operation,, filling agent particle controls the aperture in the film matrix by evenly and very being dispersed in meticulously.Material as polyolefin, has very low affinity to the filler surface, thereby is difficult to obtain good particle dispersion.Polyester has preferably to a lot of surfaces of solids that affinity makes that particle is easier to sprawl, yet if interact too by force, just can not produce the mechanical damage in required formed hole at the interface when stretching between filler and film matrix.Ventilative film needs to produce with filler the interactional material of proper level.And these materials must can fully extend basically, to prevent that macroscopical mechanical damage produces big tearing in the drawing process.For example, typical aromatic polyester such as PET are too fragile and can not tolerate local mechanical destruction around the single filling agent particle.
Normally hemicrystalline, the thermoplastic poly ester compounds of polyhydroxyalkanoatefrom (PHAs), as isotactic poly (3-butyric ester) or PHB, and isotaxy (3-hydroxyl fourth-acid esters-hydroxyl valerate) copolymer or PHBV.Two kinds of copolymers all have high crystalline and frangible/fragile shortcoming.Because crystallization rate is slow, even after cooling, also can adhere to each other by the film of PHBV preparation; Most of PHBV is still amorphous in long-time and is clamminess.In operation of injection moulding film and inflation film operation, residual adherence has limited processing.In the polyhydroxyalkanoatefrom of long-chain by the time, as isotactic poly Hydroxyoctanoic acid ester (PHOs), because amyl group that repeats and senior alkyl side chain, it comes down to unbodied.If exist, yet their crystalline portion has very low fusing point and extremely low crystallization rate.For example, people such as Gagnon " big molecule " (Macromolecules), 25, among the 3723-3728 (1992)-be incorporated herein by reference-show fusion temperature about 61 ℃, under its best crystallization temperature, reach maximum degree of crystallinity through about 3 weeks.
In addition, the composition of poly-(3-hydroxyalkyl acrylate) copolymer is by Kaneka (United States Patent (USP) 5,292,860) and Procter﹠amp; Gamble (United States Patent (USP) 5,498,692; 5,536,564; RE36,548; 5,685,756; 5,942,597; 5,990,271; 6,160,199) open.All these patents have all been described multiple degree of crystallinity and the fusing point method of adjusting to any required respective value that is lower than high-crystallinity PHB or PHBV with PHA, specifically are by introducing " defective " that part stops the controlled quentity controlled variable of crystallization process along main chain is random.The structure of merocrystalline copolymer can be adjusted to fusion in the typical scope of application between 80 ℃ to 150 ℃, and the influence of degradation is less in process.In addition, because these copolymers have lower degree of crystallinity and microorganism is had bigger sensitiveness, their biodegradation rate is higher.Although the mechanical performance of these copolymers and melt-processed condition improve to some extent than PHB or PHBV usually, their crystallization rate is low significantly, is usually less than PHB and PHBV.
Usually, the pha copolymer that these are newer and other biodegradable polymer, it is sizable challenge that the melting method by routine converts useful form to always.Polymer still has sizable viscosity after cooling down from its melt, like this always before obtaining enough degree of crystallinity, especially is higher than the pha copolymer of 10% percentage by weight for noncrystalline constituent content.Remaining adherence typically can cause material to be adhered together or to adhere on the process equipment, or simultaneously both of these case takes place, thus the speed of production of limit polymerization produce product, or hinder product and collect with the quality form that is fit to.
For the production environment degradable product, people use the existing technology of knowing in the plastics industry, attempt processing on standard device native starch.Because native starch generally has nutty structure, therefore need sex change before melt-processed.The fusion extensibility of having found the starch (one-component or as the main component of mixture) after the modification is relatively poor, therefore wants successful producd fibers, film, foam or analog that certain difficulty is arranged.
Be film or the laminated material that production has more acceptable processability and final serviceability, biodegradable polymer needs and starch combines.Acceptable be suitable for the selection of the mixed biodegradable polymers of starch challenging.Biodegradable polymer must have suitable fusion temperature.This fusion temperature must be enough high, with the stability that guarantees finally to use, thereby prevent fusion or malformation, but fusion temperature again can not be too high, so that starch can be processed and unlikely burning starch.These require to make that the selection of biodegradable polymers becomes very difficult when producing the film that contains starch.In addition, blend must be processed on the equipment for making film of routine.
United States Patent (USP) 5,874,486 disclose and have included starch ingredients and at least a polymer composition that has disperseed certain manually synthetic thermoplastic polymer components of filler therein and comprised the matrix of fluidizing reagent.United States Patent (USP) 6,117,925 disclose the mixture of starch and certain hydrophobic polymer product of transesterification reaction.United States Patent (USP) 6,096,809 disclose the composition that comprises thermoplastic starch and at least a certain polymer, and wherein the water content of composition is lower than 1% under molten state.United States Patent (USP) 5,844,023 discloses the polymeric dispersant of being made up of thermoplastic starch and at least a certain polymer and the mixture of the blender mutually that is used for molecule coupling two-phase basically.Can improve miscibility, machinability, structure, sense of touch and the adherence of composition in the prior art.
Making for ventilative film, need the material of exploitation degraded by environment, this material has suitable affinity for solid filler surface, thereby obtains good particle dispersiveness, and soft also being easy to extended, and destroys and produces aperture thereby only have local mechanical after stretching.
Summary of the invention
The invention discloses the blend film of the melt-processed of the degraded by environment that comprises polyhydroxy alkanoate copolymer (PHA) and converted starch.The invention also discloses the laminated material that comprises the ground floor and the second layer, described ground floor is basically by pha copolymer of the present invention, and the described second layer comprises pha copolymer of the present invention/converted starch blend or thermoplastic starch of the present invention.With independent pha copolymer or separately starch film relatively, this class blended composition or laminated material provide any one or multiple different and the performance of improving.For example, the difference of intermingling material or laminated material and the performance of improvement comprise for example hardness/softness, fragility/flexible, adherence, viscosity, toughness, ductility, machinability, opacity/transparency, or in the ventilative property any one.In addition, the invention discloses the breathable film that comprises the PHA/ starch blending.The invention also discloses the disposable product of the film that comprises degraded by environment.Mixture of the present invention is when keeping flexibility and flexible feature, and is all biodegradable under aerobic and oxygen free condition, not very sensitive to moisture, and good shelf life stability is arranged.
The most surprising aspect is not need the starch plasticizer can make the mixture fusion have machinability during with PHA and starch mixing.Starch can sex change in water.Water base then converted starch energy and PHA chemical combination, and then discharge water can not influence its molecular weight distribution conversely because of the PHA hydrolysis-stable simultaneously.
The specific embodiment
Copolymer compositions used herein is by mole percentage.Except as otherwise noted, all other percentages used herein, ratio and ratio all are the weight percent meters by composition.
This specification comprises following detailed description: (1) material of the present invention, the performance of (2) film or laminated material, the manufacture method of (3) film or laminated material and (4) disposable products.
The present invention relates to comprise the film or the laminated material composition of polyhydroxy alkanoate copolymer and converted starch.Polyhydroxy alkanoate copolymer causes film or laminated material environment degradable apace, especially under oxygen free condition.Starch is totally biodegradable.PHA/ starch blend of the present invention is to moisture stabilization, and the goods that prepare with this mixture still keep pliability.The invention still further relates to the breathable film that comprises pha copolymer/starch blend.Starch produces aperture during for stretch process nucleator is provided, thereby as particles filled dose.Yet, in the breathable films composition that particles filled dose can be added to pha copolymer/starch.
(1)
Material
Polyhydroxy alkanoate copolymer (PHAs)
Biodegradable film or laminated material are partly by the preparation of compositions that comprises biodegradable first polyhydroxy alkanoate copolymer at least, and described polyhydroxy alkanoate copolymer comprises at least two kinds of random repeated monomer unit (RRMU).The one RRMU has formula (I):
R wherein
1Be H or C1 or C2 alkyl, n is 1 or 2.In preferred embodiments, R1 is methyl (CH
3).In another preferred embodiment of a RRMU, R1 is a methyl, and n is 1, and polyhydroxy alkanoate copolymer comprises the 3-hydroxybutyrate units thus.
The 2nd RRMU that is included in the biodegradable polyhydroxy alkanoate copolymer comprises at least a monomeric unit, and this monomeric unit is selected from by structure (II) and the group (1II) formed:
R wherein
2For C3-C19 alkyl or C3-C19 alkenyl and
Wherein m is 2 to about 9.Usually, in the RRMU of formula (II), R
2Length will influence the whole crystalline reduction of copolymer to a certain extent.In preferred embodiments, R
2Be C3-C15 alkyl or alkenyl.In another preferred embodiment, R
2Be the C3-C9 alkyl; In going back another preferred embodiment, R
2Be C5 or C7 alkyl.In selective embodiment preferred, R
2Be C15-C19 alkyl or alkenyl.In the RRMU of formula (III), (CH
2)
mLength will influence the whole crystalline reduction of copolymer to a certain extent.In preferred embodiments, m is 2 to 9, more preferably 2 to 5.In a further preferred embodiment, m is 5.
Preferably, for when using the polyhydroxyalkanoatefrom composition, obtaining the favourable combination of the physical property that film has, comprise the have formula RRMU of the one RRMU structure of (I) at least about 50% copolymer by mole.What be fit to is that the mol ratio of a RRMU and the 2nd RRMU is about 50: 50 to about 98: 2 in the copolymer.More preferably, mol ratio is about 75: 20 to about 95: 5, in addition more preferably mol ratio at about 80: 20 to about 90: 10 scope.In addition, the suitable number-average molecular weight of polyhydroxy alkanoate copolymer is greater than about 150,000 gram/moles, and has the fusing point of being appointed as Tm1 in addition.
In another embodiment of first polyhydroxy alkanoate copolymer that is used for the laminated film composition, can comprise the RRMU that one or more are additional.What be fit to is that additional RRMU can have structure (IV):
R wherein
5Be H or C1-C19 alkyl or alkenyl, and s is 1 or 2, collateral condition is that the RRMU that adds is different from a RRMU or the 2nd RRMU.
In another preferred embodiment, the polyhydroxyalkanoatefrom composition comprises the biodegradable second polyhydroxyalkanoatefrom homopolymers or copolymer or its blend in addition.Preferred the 2nd PHA polymer or copolymer comprise at least a random repeated monomer unit with structure (V):
R wherein
3Be H or C1 or C2 alkyl, and p is 1 or 2.In preferred embodiments, R
3Be methyl (CH
3).In a further preferred embodiment, R
3Be methyl, and p is 1, second polyhydroxyalkanoatecopolymers copolymers comprises the 3-hydroxybutyrate units thus.In a further preferred embodiment, second polyhydroxyalkanoatecopolymers copolymers is the poly butyric ester homopolymer.Can be randomly, second polymer of degraded by environment comprises that two or more are selected from structure (V) and additional random repeated monomer unit (VII):
R wherein
4For C2-C19 alkyl or C2-C19 alkenyl and
Wherein q is 2 to about 16.For the 2nd RRMU that comprises structure (VII) monomeric unit, in preferred embodiments, q is 2 to about 10, more preferably about 4 to about 8.In another preferred embodiment, q is about 5.When existing, the content of additional random repeated monomer unit is no more than 25% by total monomer units, preferably is less than 15%, and wherein the second polyhydroxyalkanoatefrom homopolymers or copolymer suitably have greater than about 50, the number-average molecular weight of 000g/mol.In addition, biodegradable second polyhydroxyalkanoatefrom has fusing point Tm2, than the fusing point Tm1 height of biodegradable first polyhydroxyalkanoatefrom at least about 20 ℃, thereby satisfy formula Tm2＞Tm1+20 ℃.Melting point values is generally measured by DSC (differential scanning calorimetry), uses the method for describing among the ASTM D 3418 for example, adds in the heat scan temperature with the highest decalescence point that observes as this melting point values at DSC.Be not bound by theory, it is believed that if reach suitable blend composition, structure and high-caliber dispersion, biodegradable second polyhydroxyalkanoatefrom can be used as the nucleator of biodegradable first polyhydroxyalkanoatefrom, and improves the crystalline rate of described first copolymer thus.
If use second polyhydroxy alkanoate copolymer as stated above, most of PHA composition comprises the first biodegradable polyhydroxy alkanoate copolymer, the second biodegradable PHA is dispersed in the continuous phase or matrix of first copolymer subtly thus, and comprised, thereby improve the crystalline rate and/or the physical property of first copolymer with q.s.In one embodiment, composition comprises and counts about 0.01% to about 10% second pha copolymer by the gross weight of a PHA and second pha copolymer.In embodiment more specifically, composition comprises about by weight 0.1% to about 5% the 2nd PHA component.In addition more particular embodiment in, composition comprises about by weight 0.1% to about 3% second pha copolymer.
Biodegradable polyhydroxy alkanoate copolymer can be synthetic by disclosed chemistry or biological method, for example, is disclosed in United States Patent (USP) 5,618,855,5,942,597,5,990,271, RE36,548 or 6,160,199, each patent is incorporated herein by reference.
Copolymer can be used as continuous phase and is present in the composition.Composition can comprise the combination of polyhydroxy alkanoate copolymer, or the combination of itself and other polymers compositions, for example combination of Fu Jia polyester components etc.
Polyhydroxy alkanoate copolymer has fabulous affinity to solid particles surface such as starch, therefore allows this class particle directly to disperse when producing breathable films.Pha copolymer can be stretched and not produce macroscopic view and tear.
Typically, by the weight of the film of no plasticizer, polyhydroxy alkanoate copolymer amount in blend of the present invention is greater than 25% to 99%, is preferably 30% to 95%, more preferably is 40% to 90%, and is most preferably 50% to 80%.
Typically, by the weight of the film that plasticizer is arranged, the amount of polyhydroxy alkanoate copolymer in blend is 15% to 99%, is preferably 30% to 90%, more preferably is 40% to 80%, and is most preferably 50% to 70%.
Converted starch
The present invention relates to the i.e. use of naturally occurring polymer cheaply of starch.Because native starch generally has nutty structure, therefore need before melt-processed, carry out sex change.Usually, starch is by being dissolved in sex change in the water.Term " thermoplastic starch " is meant the starch with the plasticizer sex change.
Suitable naturally occurring starch can comprise, but be not limited to cornstarch, farina, sweet potato starch, wheaten starch, sago palm starch, cassava starch, rice starch, soybean starch, arrowroot starch, bracken starch, Rhizoma Nelumbinis starch, tapioca, waxy corn starch, amylomaize starch and commercial amylose.Also can use the mixture of starch.Although all starch can be used for the present invention, the native starch that the most normal employing of the present invention is obtained by agricultural raw material, it has supply and enriches, is easy to replenish and cheap advantage.Naturally occurring starch, especially cornstarch, wheaten starch and waxy corn starch are because their economy and practicality are preferred starch polymers.
The starch of modification is converted starch, also can use.The starch of modification is defined as non-replacement or the substituted starch (that is, molecular weight changes the change of still starch not being made other necessity) that original molecular weight characteristic changes.Use modified starch if desired, the chemical modification of starch typically comprises acidity or basic hydrolysis, or the oxidative cleavage effect reduces molecular weight or molecular weight distribution.Starch natural, that do not have modification generally has very high mean molecule quantity and wide molecular weight distribution (for example, the native corn starch mean molecule quantity is up to about 60,000,000 gram/mole).(for example degrade by acid reduction, redox, enzyme reduction, hydrolysis (acidity or base catalysis), physical/mechanical, hot mechanical energy input by process equipment), or they are used in combination, and the mean molecule quantity of starch can be reduced to the scope of wanting required for the present invention.When carried out at the scene on the spot, thermomechanical method and method for oxidation provided extra advantage.As long as mean molecule quantity is in an acceptable scope, chemical nature that starch is definite and molecular weight reduction method are not very important.The starch in the adding fused mass or the molecular weight ranges of starch mixture are that about 3,000 gram/moles are to about 10,000,000 gram/moles, be preferably about 10,000 gram/moles to about 2,000,000 gram/mole, more preferably be that about 20,000 gram/moles are to about 1,000,000 gram/mole.
About gelatification, starch can be in sex change in the presence of the solvent, solvent at this as plasticizer.Solvent and starch mixture typically heat under pressurized conditions, and shear the process of quickening gelling.Chemical reagent or enzyme agent also can be used to make starch denaturalization, for example by oxidation or derivatization.
Substituted starch also is a converted starch, although do not need, also can use.If expect substituted starch, the chemical modification of starch typically comprises etherification or esterification.Using substituted starch is for better compatibility or miscibility are arranged with pha copolymer.Yet this must balance each other with the reduction of their degradation rates.The replacement degree of the starch that replaces with chemical method is about 0.01 to 3.0, lower replacement degree, and 0.01 to 0.06, perhaps be preferred.
Typically, by the weight of the starch of no plasticizer, the amount of the converted starch part in the blend composition is about 1% to 75%, is preferably about 5% to 70%, more preferably is about 10% to about 60%, and is most preferably about 20% to about 50%.
Typically, by the film weight that plasticizer is arranged, the amount of converted starch part is 1% to 85% in the blend composition, is preferably 10% to 80%, more preferably is 20% to 70%, and is most preferably 30% to 60%.
The weight of starch comprises starch and naturally occurring bound water content in composition.Term " irreducible water " is meant starch and other component are mixed and made into the naturally occurring water of finding before the composition among the present invention in starch.Term " free water " is meant the water of composition that is used for making the present invention of adding.In case those of ordinary skill in the art can find that according to present disclosure component sneaks into composition, water just no longer can be distinguished out by its source again.By the weight of starch, the amount that starch typically contains irreducible water is about 5% to 16%.As everyone knows, extra free water can be used as polar solvent or plasticizer mixes, and is not counted in the weight of starch.
Can be used for example starch of the present invention has StarDri100, StaDex10, and StaDex15 or StaDex65 are all from Staley company.StaDex10 and StaDex15 come the dextrin of the white of dent corn starch from the beginning.These dextrin have lower dissolubility in cold water, in the full-bodied bonding application facet of needs as adhesive.StaDex65 also is the white dextrin from dent corn starch, and medium dissolubility is arranged in cold water, can be in the bonding application facet of the high viscosity of the medium solids content of needs as adhesive.The StarDri material is many dextrin of sex change in advance, typically is used for food applications.
Other composition
The thermoplastic polymer of the degraded by environment fully compatible with PHA and starch can be included in film of the present invention or the laminated material.So-called " compatible substantially " is meant when softening temperature that is heated to above composition and/or fusion temperature, and polymer is possible to mix the substantially uniform mixture of formation with PHA and starch under shearing or expansion.In addition, the field trash in the compatible polymeric should not reduce the performance of starch and PHA blend basically.Thermoplastic polymer must can flow when being heated to the machinable fused mass of formation, and can solidify again after generation crystallization or vitrifying.
Polymer must have fully low fusion temperature to prevent the obvious degradation in the process, and still enough again height make in film or the laminated material use has heat endurance.The suitable fusion temperature of biodegradable polymers is about 80 ℃ to about 230 ℃, and is preferably about 90 ℃ to about 200 ℃.Polymer must have and is suitable for film forming rheological properties.
Be applicable to that the non-limiting example at biodegradable thermoplastic polymer of the present invention comprises aliphatic poly esteramides, binary acid/dihydroxylic alcohols aliphatic polyester; The modified aromatic adoption ester of polybutylene terephthalate (PBT) that comprises PETG, the modification of modification; Aliphatic/aromatic copolyesters, PCL comprise poly-(3-butyric ester), poly-(3-hydroxy alkane acid ester), poly-(3-hydroxycaproic ester) and poly-(3-hydroxyl valerate); The polyester and the polyurethane that obtain by aliphatic polyol (for example, dialkyl group alkoxide polymer); Polyamide comprises the polyethylene/vinyl alcohol copolymer; Lactic acid polymer comprises lactic acid homopolymer and lactic acid copolymer; Lactide polymer comprises lactide homopolymers and lactide copolymer; Co-glycolide polymers comprises glycolide homopolymers and glycolide copolymer, and their mixture.
Be suitable for also have polyvinyl alcohol and its copolymer of the present invention.
Preferred fusion temperature is 160 ℃ of extremely about 175 ℃ PLA homopolymers or copolymers.The thermoplastic polymer of degraded by environment must be able at a good pace solidify, and preferably the flowing down of expansion, and then forms heat-staple membrane structure, as typically running in as injection molding or inflation film extrusion method in known processing method.
The specific embodiment that is applicable to preferred lactic acid polymer of the present invention or lactide polymer includes but not limited to those PLA-based polyalcohols or polylactide-based polyalcohol, and they are commonly referred to as " PLA " in industry.Therefore, term " PLA ", " polylactide " and " PLA " replaceable use, the homopolymers or the copolymer that comprise lactic acid or lactide, the polymer property of the polymer that this forms based on the polymer that is formed by certain monomers or minimum repeated monomer unit.But, should be appreciated that term " PLA ", " polylactide " and " PLA " are not represented the generation type of limit polymerization thing.The embodiment of commercially available polylactic acid polymer comprises various available from Chronopol Inc. (Golden, PLA CO), or with trade name
The polylactide of selling.Other embodiment of the commercially available PLA that is fit to comprises NATUREWORKS available from Cargill Dow, available from the LACEA of Mitsui Chemical, or available from BiomerPLA resin L5000.
Depend on used concrete polymer, processing method and film or the final use of laminated material, may be more than a kind of polymer.Preferably use two kinds of different polyester.For example, if use have fusion temperature for about 160 ℃ to about 175 ℃ crystallizable PLA, just can use than other PLA to have than low melting point with than low-crystallinity and/or than second PLA of high copolymer content.Alternatively, the aliphatic aromatic polyester can use with crystallizable PLA.Two kinds of polymer if desired, polymer only need distinguish by chemical stereospecificity or by molecular weight.
In one aspect of the invention, may need to use glass transition temperature to be lower than 0 ℃ biodegradable thermoplastic polymer.Polymer with so low glass transition temperature comprises EASTAR BIO and BIONELLE.
Plasticizer can be used for the present invention and takes converted starch and starch can be flowed, and promptly produces thermoplastic starch.Identical plasticizer or two kinds of independent plasticizer can be used for increasing melt processable.Plasticizer also can improve the pliability of final products, it is believed that it is because plasticizer can reduce the glass transition temperature of composition that pliability is improved.Plasticizer should be preferably fully compatible with polymeric component of the present invention, and plasticizer may change the character of composition effectively like this.Among the present invention, term " compatible substantially " is meant that when softening temperature that is heated to above composition and/or fusion temperature plasticizer energy and starch form full and uniform mixture.
The extra plasticizer or the diluent that are used for biodegradable thermoplastic polymer can exist, with the fusion temperature of reduction polymer and the compatibility of improvement and thermoplastic starch blend integral body.In addition, if there be plasticizer or the diluent that suppresses the polymer melted temperature, having more, the biodegradable thermoplastic polymer of high melting temperature can be used.Plasticizer typically has the molecular weight that is lower than about 100,000 gram/moles, may be preferably block or random copolymer or terpolymer, and so one or more chemical species and another plasticizer, starch, polymer or their mixture are compatible.
The non-restrictive example of useful hydroxyl plasticizer comprises sugar for example glucose, sucrose, fructose, gossypose, maltodextrose, galactolipin, wood sugar, maltose, lactose, mannose, erythrose, glycerine and pentaerythrite; Sugar alcohol is erythrite, xylitol, maltitol, mannitol and sorbierite for example; Polyalcohol is ethylene glycol, propane diols, dipropylene glycol, butanediol, hexanetriol or the like for example, and their condensate and their mixture.Also can be used for hydroxyl plasticizer of the present invention poloxomers and poloxamines are arranged.Also being applicable to of the present invention is the organic compound that does not have hydroxyl that forms hydrogen bond, comprises the derivative of urea and urea; The acid anhydrides of sugar alcohol such as the acid anhydrides of sorbitan; Animal protein is gelatin for example; The vegetable egg white matter is sunflower protein, soybean protein, cotton seed protein for example; And their mixture.Other suitable manufacturing methods has phthalic acid ester, dimethyl succinate and diethylester and relevant ester, glycerol triacetate, glycerine list and diacetate, glycerine list, two and tripropionate, butyrate, stearate, lactate, citrate, adipate ester, stearate, oleate and other biodegradable precursor (father) acid esters.Aliphatic acid such as ethylene acrylic, EMA, butadiene acrylic acid, butadiene maleic acid, acrylonitrile-acrylic acid, propylene maleic acid and other hydrocarbon are the acid on basis.All plasticizer can use separately or with its mixture.Low-molecular-weight plasticizer is preferred.The molecular weight that is fit to is less than about 20,000g/mol, preferably less than about 5,000g/mol, be more preferably less than about 1,000g/mol.The plasticizer that is more suitable for is at United States Patent (USP) 3,182, those that describe in 036 and 5,231,148.
Preferred plasticizer comprises glycerine, mannitol and sorbierite.The amount of plasticizer depends on the amount of molecular weight and starch and the plasticizer affinity to starch.Usually, the amount of plasticizer increases along with the increase of starch molecule amount.Typically, the plasticizer that exists in final film composite is about 2% to about 70%, more preferably is about 5% to about 55%, is most preferably about 10% to 50%.
Randomly, other composition can by composition weight count less than about 50%, preferred about 0.1% to about 20%, more preferably from about 0.1% mix in the composition to about 12% amount.Can use optional material to improve the physical property of processability and/or improvement final products, as elasticity, hot strength and modulus.Other benefit includes, but not limited to comprise the stability, brightness, color of oxidation stability, flexible, screen resilience, machinability, processing aid, viscosity modifier and smell control.
The non-limiting embodiment of other optional member comprises aromatics/aliphatic polyester copolymer; its easier hydrolytic cleavage; therefore be easier to biodegradation; as those at United States Patent (USP) 5; 053; 482; 5; 097; 004; 5; 097; 005 and 5; the copolymer of describing in 295,985; biodegradable aliphatic polyester amide polymer; polycaprolactone; be derived from the polyester or the polyurethane (being the dioxane polymeric diacyl) of aliphatic polyol; the polyamide that comprises the polyethylene/vinyl alcohol copolymer; the derivative of cellulose esters or its plasticising; salt; slip agent; crystallization accelerator such as nucleator; the crystallization delayed-action activator; odor mask; crosslinking agent; emulsifying agent; surfactant; cyclodextrin; lubricant; other processing aid; fluorescent whitening agent; antioxidant; fire retardant; dyestuff; pigment; filler; protein and their basic salt; wax; the clayization resin; filler; anticaking agent; antistatic additive; or their mixture.Can use slip agent to reduce the interior bonding or coefficient of friction of film.And, also can use slip agent to improve the stability of film, especially under high humility or high-temperature condition.The slip agent that is fit to has polyethylene.Also can in melt, add salt and make film, or salt is used as processing aid the easier response of water.The solubility that salt also helps to reduce adhesive is not dissolved it, but when they put into water or flushing, salt will dissolve, and impels the adhesive dissolving, thereby obtains the product to the easier response of water.
The making of breathable film comprises that the extension of pha copolymer/starch film stretches.Starch provides nucleator for the stretched operation that forms aperture, therefore as particles filled dose.Yet particles filled dose or grain pigment can be added in pha copolymer/starch breathable films composition.These fillers comprise polytype inorganic or organic solid, as talcum, calcium carbonate, mica, potter's clay, plasticising ball, latex etc.The other filler of inorganic filler such as magnesium, aluminium, silicon or titanyl compound; Hydrated magnesium silicate, titanium dioxide, clay, earth, chalk, boron nitride, lime stone, diatomite, glass, quartz or pottery.If exist, particles filled dose on the use basis of special composition and breathable films typically the amount with about 1% to about 50% exist.
According to disclosure of the present invention, other embodiment of other composition knows for the person of ordinary skill of the art.
Although starch is preferred natural polymer among the present invention, also can adopt polymer based on protein.The suitable polymer based on protein comprises soybean protein, zein, or their mixture.Based on the polymer of protein can about 0.1% to about 80%, 1% to about 60% the amount of being preferably about exists.
(2)
The performance of film or laminated material
The present invention adopts the form of film or laminated material, and these formal descriptions are in United States Patent (USP) 5,498, in 692, and uses blend of the present invention or lamination composition.Among the present invention, so-called " blend " is meant the composition (that is, PHA and converted starch) of two or more compositions.Among the present invention, so-called " film " is meant to have high length and thickness ratio and the high width and the continuous slice as thin as a wafer of thickness ratio.Though the accurate upper-bound to thickness does not require, preferred upper limit is about 0.254mm, more preferably from about 0.01mm even 0.005mm more preferably from about.The protection of any film is worth the continuity that depends on it, does not promptly have hole or crack.Breathable films has been stretched and has produced the continuous aperture that prevents the liquid infiltration but can see through moisture.Breathable films can be one deck of plural layers.Film can be plural layers, that is, and and laminated material or composite.Laminated material is meant the two-layer or plural layers that link together.Laminated material can have one or more layers pha copolymer/starch composites that comprises the blend that the present invention proposes.In another embodiment, laminated material can have the ground floor of the pha copolymer that comprises that the present invention describes and comprise pha copolymer/starch film that the present invention proposes or the second layer of thermoplastic starch.Laminated material can have the ground floor that comprises pha copolymer, and comprise the second layer of PHA/ starch blend or thermoplastic starch and comprise the 3rd layer of PHA, or the mixing of any conceivable layer.Terminology used here ground floor, the second layer or the 3rd layer only are used to describe different layers, and do not mean that the position of limiting layer.The preferred embodiment of the invention is that three layers laminated material is arranged, Wai Mian the two-layer pha copolymer that comprises wherein, and the intermediate layer comprises pha copolymer/starch blend or thermoplastic starch.
Film of the present invention can be used for multiple disposable product, including, but not limited to, disposable diaper, shrink wrapping (for example, packaging for foodstuff, consumer products packing, tray and/or crate packing, or the like) or sack (groceries bag, food preservation bag, sandwich bag, reclosable
Type bag, refuse bag, or the like).In one embodiment of the invention, film is a kind of egative film or porose top flat of liquid non-permeate, is suitable as absorbable disposable sanitary articles, for example disposable diaper, feminine hygiene products etc.Except improving biodegradable and/or compostability, film of the present invention also has United States Patent (USP) 5,990, the characteristic that proposes in 271.
Film or laminated material that the present invention produces are degraded by environment.So-called " degraded by environment " is meant biodegradable, disintegratable, " to water sensitive ", dispersible, flushable or compost or their combination.In the present invention, film, plural layers (laminated material) and goods are degraded by environment.Therefore, film and laminated material can be handled in existing compost facility easily and safely, or pour the gutter safely, and can not produce baleful consequences to existing sewer infrastructure system.The degraded by environment of film of the present invention or laminated material provides solution for these materials use the accumulation of back in environment in disposable product.The flushable property of film of the present invention when being used for disposable products such as cleaning piece and women sanitary articles provides extra convenient and dispersed for the consumer.Although biological degradability, disintegrative, " to water sensitivity ", dispersibility, stackable property and flushable property all have different standards, and by different experimental measurements, usually, film among the present invention or laminated material will satisfy more than more than one these standards.
" biodegradable " is meant, when material is exposed in aerobic and/or the oxygen-free environment, finally decays to monomer component owing to microorganism, hydrolysis and/or chemical action.Under aerobic conditions, biodegradation makes material be converted into end product such as carbon dioxide and water.Under oxygen free condition, biodegradation makes product be converted into carbon dioxide, water and methane.Biodegradation method is commonly called mineralising." biological degradability " is meant that all organic components of film finally all decompose by biologically active.
A plurality of tissues have been formulated multiple different standardized biological degradability method with country variant.Though the test under concrete test condition, method of testing and required testing standard is different, and rational uniformity is arranged between different testing schemes, makes them can obtain similar conclusion to most of materials.For the aerobic bioreactor degradability, U.S.'s test has been formulated ASTM D 5338-92 method of testing with materials association (ASTM): survey under in check composting conditions
14Decide the method for testing of the aerobic bioreactor degradability of plastic material.This tests the percentage of measuring the test material that is subjected to mineralising that has functional relation with the time by the burst size of monitoring carbon dioxide 58 ℃ of thermophilic temperature down, and the carbon dioxide that is discharged is that the assimilation absorption owing to microorganism produces in the presence of active compost.The CO 2 test can be carried out via the electrolysis respirometry.Also can use other standard scheme, as the 301B of the Organization of Economy and Cooperation Development (OECD) formulation.At the standard biological degradation test description under the anaerobic situation in various testing schemes, as ASTM D 5511-94.These testing schemes are used for simulating the biodegradation at anaerobic solid refuse treatment facility or sanitary landfill method material.
Film of the present invention or laminated material can fast degraded biologicallies.Quantitatively, described degraded is meant the percentage of the material that is converted into carbon dioxide after preset time.Also disintegration may take place.Disintegration is meant, when film or laminated material have the ability of quick fragmentation, and disintegration is fractionlet, and described fragment is enough little so that can not distinguish after compost sieves, and can not cause when flushing that perhaps drainpipe stops up.The material of disintegratable is also flushable.Most of disintegrative testing schemes have been measured measured material and have been exposed to the loss in weight of various matrix after a period of time.Aerobic and anaerobic disintegration test can be used.The loss in weight is after material is exposed to waste water and mud, by what no longer determined by the amount of the test material of 18 mesh sieves in 1mm hole collection.For disintegration, the difference between the dry weight of the sample of recovering on the weight of initial sample and the screen cloth will determine the speed and the degree of disintegration.Because these testing schemes use identical environment basically, so be similar to the test of disintegrative for biological degradability.For determining disintegrative, need to measure the weight of surplus material; And, then need to measure the gas of separating out in order to determine biological degradability.
Film of the present invention or laminated material also are composts.ASTM has developed about the method for testing of compost and standard.Three features of this thermometrically: biological degradability, disintegrative and do not have eco-toxicity.The method of testing of measuring biological degradability and disintegrative has been described above.For satisfying the biodegradation standard of compost, material must reach the carbon dioxide conversion at least about 60% in 40 days.For the disintegrative standard, must there be test material to remain on the 2mm screen cloth less than 10%, retained material has the true shape and the thickness of processed product.For determining the last item standard-no eco-toxicity, the accessory substance of biodegradation must not have adverse effect to germination and plant growth.A test of this standard is specified among the OECD 208.Reach ASTM 6400-99 specification in case product is verified, so international biodegradable product association (TheInternational Biodeg radable Products Institute) will issue the compostability sign.Testing scheme is followed the DIN 54900 of Germany, and it has measured the material of decomposition is finished in any permission in a compost circulation maximum ga(u)ge.
Film of the present invention can be heat bonding.Heat bondable film is that the bonding and ventilative heat bonding method of pressurized heat is necessary.Film also can be lamination or heat-sealing.The polymer that fusing point is lower is that heat seal process is required.Can preferred multiple material, to reach best heat seal condition.Comprise the film of PHA and starch blending or comprise that the pha copolymer/laminated material of starch blend layer can improve the bonding characteristic of film.
(3)
Make the method for film or laminated material
Have the degraded by environment of enhancing and/or the film and the laminated material of compost among the present invention, can on conventional equipment for making film, use the program processing of conventional production individual layer or plural layers.Converted starch mixes the heat treatable composition of generation with the hemicrystalline polyhydroxy alkanoate copolymer of ductility.The bead of PHA/ starch blend of the present invention can pass through at first dry mixed, and melting mixing is made in the film extruder then.Alternatively, if in the film extruder undercompounding, bead is dry mixed at first, melting mixing in the premixed extruder is then granulated again again, then carries out film and extrudes.
Need relative low processing temperature that the thermal decomposition of starch is minimized with the common processing of starch.PHA melts being lower than under 150 ℃ the temperature, so the thermal decomposition of starch is minimized.
PHA/ starch blend of the present invention can use injection moulding or inflation film extrusion method melt-processed to become film, and these two kinds of methods have description in " plastics extruding technology " second edition (Plastics Extrusion Technology-2nd Ed.) that Allan A.Griff (Van Nostrand Reinhold-1976) compiles.The injection moulding film is extruded from the linear slot mould.Usually plain net cools off on large-scale mobile polishing metal roll.Its very fast cooling is peeled off from first roll, through one or more auxiliary cooling roll, coats traction rollers or " retreatment " roll of rubber then by a cover, finally arrives the roll film wrapping head.
In inflation film was extruded, melt was upwards extruded by thin ring mould opening.The method is also referred to as tubular film and extrudes.Central authorities by mould introduce air, thereby also to make it to expand to the pipe inflation.Thereby the formation moving bubble, by the control internal air pressure size of moving bubble is remained unchanged.Film tube cools off with air, and air blows out from the one or more air rings around pipe.Then with the pair of traction rollers traction pipe formation flat structure that makes it to cave in, and with it around to wrapping head.When film is applied to egative film, can launch, and further be cut into the width that is applicable to product then with flat tubular film cutting opening.
Injection moulding film and blown film process may be used to produce individual layer or multi-layer film structure.For for single thermoplastic or thermoplastic component blend manufacture order layer film, only need to use single extruder and single manifold mould.
For the production of plural layers of the present invention or laminated material, preferably use the coextrusion method.These methods need be more than one extruder, and coextrusion feed sleeve pipe or branch manifold mold system or both combinations, to obtain multi-layer film structure.
United States Patent (USP): 4,152,387 and 4,197,069 discloses the feed principle of coextrusion.A plurality of extruders are connected with the feed sleeve pipe, and the relation that described feed sleeve pipe uses removable flow insulated wall to be directly proportional according to the volume with the polymer that passes through described fluid passage changes the geometric position of each fluid passage.The fluid passage is designed to: at the point of material, after eliminating interfacial stress and flow instability, material converges to together with identical speed and pressure.In case material converges in the feed sleeve pipe, they just flow in the single manifold mould as the fluid of composite construction.Importantly, melt viscosity between the material and melt temperature differ and are not big especially in these technologies; Otherwise flow instability can cause the layer thickness profile in the wayward plural layers of mould.
The coextrusion of alternative feed sleeve pipe be branch manifold mould or blade mold, as above-mentioned United States Patent (USP): 4,152,387,4,197,069 and United States Patent (USP) 4,533,308 in disclosed.Although melt-flow is externally converged before entering die body in the feed cannula system, in branch manifold mould or blade mold, each melt-flow has its manifold in mould, wherein polymer independent diffusion in its manifold separately.Each melt-flow near mould outlet with die width combination completely.Removable blade can provide the controllability of each fluid passage outlet, it is directly proportional with the volume of material that exports by the fluid road, thereby melt is flow to together with identical linear velocity, pressure and required width.
Because the melt flow property and the melt temperature of institute's processing materials may alter a great deal, therefore use blade mold just to have several advantages.Self has insulating characteristics mould, the material that differs greatly of fusing point wherein, and the material that for example differs up to 175 (80 ℃) can be processed together.
Each manifold can be designed and regulate to be used for specific polymer (or copolymer) in the blade mold.Thereby the influence of the manifold design that the flowing of every kind of polymer only is subjected to it, and be not subjected to the influence of the power that other polymer applies.This material that makes melt viscosity fall far short can coextrusion form plural layers.In addition, blade mold can also be regulated single manifold width, makes internal layer, and for example water-soluble biodegradable polymer such as Vinex2034 can be surrounded by the water-insoluble material fully, can not stay the exposed edge edge that is subject to the water influence.Above-mentioned patent also discloses being used in combination of feed cannula system and blade mold, thereby obtains more complex multilayered structures.
Plural layers of the present invention can comprise two-layer or more multi-layered.Usually, three layers and five layer films preferred balance or symmetry.Three layer multi-layer films of balance comprise intermediate core layer and two identical skins, and wherein said intermediate core layer is between described two skins.Five layer films of balance comprise intermediate core layer, two identical tack coats and two identical skins, and wherein said intermediate core layer is between described two tack coats, and each tack coat is between described sandwich layer and each skin.Though the balance film is optional for film of the present invention, they curl or distortion than non-equilibrium film is more difficult.
In three-layer thin-film, intermediate core layer can comprise 10% to 80% of overall film thickness, and each skin comprises 10% to 50% of overall film thickness.When using tack coat, each tack coat comprises about 5% to about 10% of overall film thickness.
Breathable films is made by the extension oriented film.Can run through film and carry out the homogeneous stretching, for example, by " plastic sheeting " (Plastics Films) second edition that J.H Briston publishes at New York Longman Inc. (1983), the stretching of in the tenter stentering, implementing of the 83rd to 85 page of description.Alternatively, can run through film and carry out the incremental stretching, for example in the operation of ring-roller, as United States Patent (USP) 4,116,892 and 5,296,184 is described such, wherein replaces parallel stretch zones and coexist with the zone that keeps reality not stretch.Oriented film causes that the local mechanical that adheres between starch and polymer substrate destroys.This destruction produces empty structure around the starch, causes passing the formation of the continuous aperture of film.The aperture is for enough little, thereby the feasible unbalanced big capillary force that causes owing to minimum radius of curvature can stop liquid to penetrate.Therefore, liquid is held safely by perforated membrane.Because the transportation of moisture is not subjected to the obstruction of capillary force, therefore aperture can transmit moisture continuously.Be the control that obtains aperture is formed, starch is dispersed in the film matrix before stretched operation equably and subtly.PHA or PHA/ starch blend can be stretched among the present invention, do not have macroscopical tear.
(4)
Disposable products
The invention still further relates to the disposable product that comprises PHA/ starch blend of the present invention or laminated material.For example, stackable absorbent article comprises liquid permeable topsheet, comprises the film of the present invention liquid-tight egative film of (for example, comprising the film of PHA/ starch blend among the present invention), and the absorbent cores between top flat and egative film.This class absorbent article comprises baby' diaper, adult-incontinence panties and protection pad and woman's sanitarg mapkin and liner.The disposable personal care product comprises ventilative product, but this product receiving fluids allows to see through some moisture simultaneously.
The additional product that comprises PHA/ starch blend of the present invention or laminated material comprises the personal cleansing wipe thing; Disposable hygienic health treatment such as bandage, wound dressing, wound is cleaned pad, operating coat, surgical mask, operation pad; The disposable product such as the clothes of other social public organizations and health care, cleaning piece, liner, bed clothes product such as coverlet and pillowcase, and foam pad mattress.
Film of the present invention or laminated material are when the egative film of the liquid non-permeate that is used as absorbent article of the present invention such as disposable diaper, and its thickness typically is 0.01mm to about 0.2mm, and preferred 0.012mm is to about 0.051mm.
Other embodiment of absorbent article of the present invention comprises the sanitary napkin that is used for receiving and holding vagina excreta such as menstruation.The effect that disposable sanitary napkin is designed to by clothing such as underwear or trousers or specially designed belt remains near the human body.The embodiment that is easy to be suitable for this type of sanitary napkin of the present invention is disclosed in the United States Patent (USP) 4,589,876 in United States Patent (USP) on May 20th, 4,687,478 and 1986 on August 18th, 1987.Obviously, comprise among the present invention that the film of PHA/ starch blend or laminated material of the present invention can be as the egative films of liquid non-permeate in this class sanitary napkin.On the other hand, should be appreciated that the present invention is not limited to any concrete sanitary napkin configuration or structure.
Importantly, absorbent article of the present invention is than using the conventional absorbent article such as polyolefine material (for example, polyethylene egative film) having biodegradable and/or compostability to a greater extent.
Embodiment 1
Present embodiment demonstration comprises the processing of binary blend of the converted starch of preferred polyhydroxy alkanoate copolymer and unplasticised mistake.Specifically, comprise the polyhydroxy alkanoate copolymer of 3-hydroxycaproic ester (hereinafter representing) of 3-butyric ester and about 12 molar percentages and the mixture of converted starch, utilize injection moulding film extrusion method melt-processed to become film with the PHBH copolymer.StarDri 1 and PHBH are in 150 ℃ of blend and thoroughly mixing.There is not the starch plasticizer to exist.On the basis of PHBH and starch equivalent dry weight, the content of PHBH is that 10 to 90 percentage by weights do not wait.It is found that for being formed with the film of usefulness, the content of PHBH need be on 25 percentage by weights.
Embodiment 2
Present embodiment demonstration comprises the processing of binary blend of sex change (thermoplasticity) starch of preferred polyhydroxy alkanoate copolymer and plasticising.Specifically, comprise the polyhydroxy alkanoate copolymer of 3-hydroxycaproic ester (hereinafter representing) of 3-butyric ester and about 12 molar percentages and the mixture of thermoplastic starch, utilize injection moulding film extrusion method melt-processed to become film with the PHBH copolymer.StarDr i 1/ sorbierite of 70/30 blend and PHBH are in 150 ℃ of blend and thoroughly mixing.On the basis of PHBH and starch equivalent dry weight, the content of PHBH is that 10 to 100 percentage by weights do not wait.It is found that for being formed with the within reason sticking film of usefulness, the content of PHBH need be on 15 percentage by weights.Film can present embodiment in whole ratio manufacturings.
Embodiment 3-32
The processing of present embodiment demonstration double-layer lamination film.The PHBH polymer of describing in embodiment 1 is as ground floor.The PHBH/ thermoplastic starch blend of describing in embodiment 2 is as the second layer.Laminated material utilizes the manufacturing of coextrusion method according to following form:
| Embodiment # | Ground floor | The second layer | The second layer | Form |
| ? | (％) | (％) | (％PHBH) | (% starch) |
| 3 | 10 | 90 | 0 | 100 |
| 4 | 10 | 90 | 10 | 90 |
| 5 | 10 | 90 | 25 | 75 |
| 6 | 10 | 90 | 50 | 50 |
| 7 | 10 | 90 | 75 | 25 |
| 8 | 10 | 90 | 90 | 10 |
| 9 | 25 | 75 | 0 | 100 |
| 10 | 25 | 75 | 10 | 90 |
| 11 | 25 | 75 | 25 | 75 |
| 12 | 25 | 75 | 50 | 50 |
| 13 | 25 | 75 | 75 | 25 |
| 14 | 25 | 75 | 90 | 10 |
| 15 | 50 | 50 | 0 | 100 |
| 16 | 50 | 50 | 10 | 90 |
| 17 | 50 | 50 | 25 | 75 |
| 18 | 50 | 50 | 50 | 50 |
| 19 | 50 | 50 | 75 | 25 |
| 20 | 50 | 50 | 90 | 10 |
| 21 | 75 | 25 | 0 | 100 |
| 22 | 75 | 25 | 10 | 90 |
| 23 | 75 | 25 | 25 | 75 |
| 24 | 75 | 25 | 50 | 50 |
| 25 | 75 | 25 | 75 | 25 |
| 26 | 75 | 25 | 90 | 10 |
| 27 | 90 | 10 | 0 | 100 |
| 28 | 90 | 10 | 10 | 90 |
| 29 | 90 | 10 | 25 | 75 |
| 30 | 90 | 10 | 50 | 50 |
| 31 | 90 | 10 | 75 | 25 |
| 32 | 90 | 10 | 90 | 10 |
Embodiment 33
Present embodiment three processing of ironed film layer by layer of having demonstrated, (the first and the 3rd) layer uses the PHBH copolymer among embodiment 1 outside, or alternatively uses at middle (second) layer.When the PHBH copolymer was skin, the PHA/ thermoplastic starch blend in embodiment 2 was used in the intermediate layer, in this embodiment, starch can account for blend up to about 90%.In this embodiment, in the mixture starch part up to 50%.Utilize coextrusion method manufacturing three press mold layer by layer, according to:
| Embodiment # | Ground floor | The second layer | The second layer | Form | The 3rd layer |
| ? | (％) | (％) | (％PHBH) | (% starch) | (％) |
| 34 | 10 | 80 | 0 | 100 | 10 |
| 35 | 10 | 80 | 10 | 90 | 10 |
| 36 | 10 | 80 | 25 | 75 | 10 |
| 37 | 10 | 80 | 50 | 50 | 10 |
| 38 | 10 | 80 | 75 | 25 | 10 |
| 39 | 10 | 80 | 90 | 10 | 10 |
| 40 | 25 | 50 | 0 | 100 | 25 |
| 41 | 25 | 50 | 10 | 90 | 25 |
| 42 | 25 | 50 | 25 | 75 | 25 |
| 43 | 25 | 50 | 50 | 50 | 25 |
| 44 | 25 | 50 | 75 | 25 | 25 |
| 45 | 25 | 50 | 90 | 10 | 25 |
| 46 | 50 | 50 | 0 | 100 | 10 |
| 47 | 50 | 40 | 10 | 90 | 10 |
| 48 | 50 | 40 | 25 | 75 | 10 |
| 49 | 50 | 40 | 50 | 50 | 10 |
| 50 | 50 | 40 | 75 | 25 | 10 |
| 51 | 50 | 40 | 90 | 10 | 10 |
| 52 | 50 | 25 | 0 | 100 | 25 |
| 53 | 50 | 25 | 10 | 90 | 25 |
| 54 | 50 | 25 | 25 | 75 | 25 |
| 55 | 50 | 25 | 50 | 50 | 25 |
| 56 | 50 | 25 | 75 | 25 | 25 |
| 57 | 50 | 25 | 90 | 10 | 25 |
| 58 | 45 | 10 | 0 | 100 | 45 |
| 59 | 45 | 10 | 10 | 90 | 45 |
| 60 | 45 | 10 | 25 | 75 | 45 |
| 61 | 45 | 10 | 50 | 50 | 45 |
| 62 | 45 | 10 | 75 | 25 | 45 |
| 63 | 45 | 10 | 90 | 10 | 45 |
Embodiment 64
Every square metre 100 gram, the PHBH resin/starch injection moulding film of the calcium carbonate filling of percent by volume 27.5% is biaxially oriented, and the assessment vapor transmission rate.Each sample stretches 400% and continue 5 seconds on machine direction.Processing stretching sample 0%, 50%, 100%, 150%, 250% and 400% on the vertical direction then.Each sample kept 5 seconds at stretch position.The vapor transmission rate of specimen then.Expectation only has relatively low vapor transmission rate at the film of machine direction stretch.Along with the increase of amount of tension on the processing vertical direction, the vapor transmission rate of oriented film will increase to the value of manyfold (promptly 4 to 30 times) than non-stretched film.
All patents of mentioning in this manual, patent application (with any patent at its announcement, and the foreign patent application of any corresponding publication) and the disclosure of publication all are incorporated herein by reference.Yet, clearly do not admit to introduce the present invention and lecture or disclose the present invention with any file for referencial use.
Though illustrated and described specific embodiments of the present invention, but it is evident that for those of ordinary skill in the art, according to disclosure of the present invention, under the situation that does not break away from the spirit and scope of the present invention, can carry out various other changes and modification to it.Therefore appending claims is intended to comprise that all these belong to change and modification within the scope of the present invention.
Claims (17)
1. multi-layer laminated films, described multi-layer laminated films has the one deck at least that comprises thermoplastic starch, and has one deck at least of being made up of the polyhydroxy alkanoate copolymer or the homopolymers of the monomeric unit that comprises at least two random repetitions basically
Wherein first monomeric unit has structure (I)
R wherein
1Be H or C1 or C2 alkyl, and n is 1 or 2; With
Wherein second monomeric unit has structure (II)
R wherein
2Be C3-C19 alkyl or C3-C19 alkenyl,
Or described second monomeric unit has structure (III)
Wherein m is 2 to 9.
2. multi-layer laminated films as claimed in claim 1, wherein said polyhydroxy alkanoate copolymer comprise the 3rd random repeated monomer unit, and described monomeric unit has structure (IV)
R wherein
5Be H or C1-C19 alkyl or alkenyl, and s is 1 or 2, collateral condition is that described the 3rd monomeric unit is different from described first or second monomeric unit.
3. sack, described sack comprises multi-layer laminated films as claimed in claim 1.
4. wrappage, described wrappage comprises multi-layer laminated films as claimed in claim 1.
5. absorbent article, described absorbent article comprises multi-layer laminated films as claimed in claim 1.
6. multi-layer laminated films as claimed in claim 1, described multi-layer laminated films are the oriented film form with continuous hole, and described continuous hole stops the infiltration of liquid and allows aqueous vapor to see through.
7. multi-layer laminated films as claimed in claim 1, described multi-layer laminated films have the one deck at least that comprises the dispersed microparticles filler.
8. the continuous hole that multi-layer laminated films as claimed in claim 7, described one deck at least are stretched and can stop the liquid infiltration and allow aqueous vapor to see through to produce.
9. multi-layer laminated films, described multi-layer laminated films has:
(a) comprise one deck at least of thermoplastic starch; With
(b) form by the polyhydroxy alkanoate copolymer of the monomeric unit that comprises at least two random repetitions or homopolymers basically at least two layers,
Wherein first monomeric unit has structure (I)
R wherein
1Be H or C1 or C2 alkyl, and n is 1 or 2; With
Wherein second monomeric unit has structure (II)
R wherein
2Be C3-C19 alkyl or C3-C19 alkenyl,
Or described second monomeric unit has structure (III)
Wherein m is 2 to 9.
10. multi-layer laminated films as claimed in claim 9, wherein said polyhydroxy alkanoate copolymer comprise the 3rd random repeated monomer unit, and described monomeric unit has structure (IV)
R wherein
5Be H or C1-C19 alkyl or alkenyl, and s is 1 or 2, collateral condition is that described the 3rd monomeric unit is different from described first or second monomeric unit.
11. multi-layer laminated films as claimed in claim 9, described multi-layer laminated films have two skins and an intermediate layer, wherein:
(a) described two skins are two layers of claim 9 described (b) part, and described two skins are made up of polyhydroxy alkanoate copolymer basically; With
(b) described intermediate layer is the layer of claim 9 described (a) part, and described intermediate layer comprises thermoplastic starch.
12. sack, described sack comprises multi-layer laminated films as claimed in claim 9.
13. wrappage, described wrappage comprises multi-layer laminated films as claimed in claim 9.
14. absorbent article, described absorbent article comprises multi-layer laminated films as claimed in claim 9.
15. multi-layer laminated films as claimed in claim 9, described multi-layer laminated films are the oriented film form with continuous hole, described continuous hole stops the infiltration of liquid and allows aqueous vapor to see through.
16. multi-layer laminated films as claimed in claim 9, described multi-layer laminated films have the one deck at least that comprises the dispersed microparticles filler.
17. the continuous hole that multi-layer laminated films as claimed in claim 16, described one deck at least are stretched and can stop the liquid infiltration and allow aqueous vapor to see through to produce.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34356901P | 2001-10-19 | 2001-10-19 | |
| US60/343,569 | 2001-10-19 | ||
| US10/080,042 | 2002-02-19 | ||
| US10/080,042 US7077994B2 (en) | 2001-10-19 | 2002-02-19 | Polyhydroxyalkanoate copolymer/starch compositions for laminates and films |
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| CNB02820753XA Division CN1326940C (en) | 2001-10-19 | 2002-10-02 | Hydroxyl radical alkanoate multipolymer/amylum composition for manufacturing laminated material and film |
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| CN1974203A CN1974203A (en) | 2007-06-06 |
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| CNB02820753XA Expired - Fee Related CN1326940C (en) | 2001-10-19 | 2002-10-02 | Hydroxyl radical alkanoate multipolymer/amylum composition for manufacturing laminated material and film |
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| CN (2) | CN1974203B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8466337B2 (en) * | 2009-12-22 | 2013-06-18 | Kimberly-Clark Worldwide, Inc. | Biodegradable and breathable film |
| US8586821B2 (en) * | 2009-12-23 | 2013-11-19 | Kimberly-Clark Worldwide, Inc. | Melt-processed films of thermoplastic cellulose and microbial aliphatic polyester |
| CN103588995B (en) * | 2013-09-22 | 2016-03-30 | 郑文彬 | Starch environment-friendlypaper paper and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5703160A (en) * | 1992-07-15 | 1997-12-30 | Solvay S.A. | Biodegradable moulding compositions comprising a starch, a biodegradable polyester, and a salt of a hydroxycarboxylic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR0111529A (en) * | 2000-06-09 | 2003-07-22 | Procter & Gamble | Biodegradable Coated Substrates |
-
2002
- 2002-10-02 CN CN2006101693243A patent/CN1974203B/en not_active Expired - Fee Related
- 2002-10-02 CN CNB02820753XA patent/CN1326940C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5703160A (en) * | 1992-07-15 | 1997-12-30 | Solvay S.A. | Biodegradable moulding compositions comprising a starch, a biodegradable polyester, and a salt of a hydroxycarboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1326940C (en) | 2007-07-18 |
| CN1974203A (en) | 2007-06-06 |
| CN1692140A (en) | 2005-11-02 |
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