CN1384852A - Polymer products comprising soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and methods of preparing such polymer products - Google Patents
Polymer products comprising soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and methods of preparing such polymer products Download PDFInfo
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
Soft and elastic polymer products are obtained by stretching a composition comprising a biodegradable polyhydroxyalkanoate copolymer comprising at least two randomly repeating monomer units. The first randomly repeating monomer unit has the structure (I), wherein R<1> is H, or C1 or C2 alkyl, and n is 1 or 2. The second randomly repeating monomer unit has the structure (II), wherein R<2> is a C3-C19 alkyl or C3-C19 alkenyl. At least about 70 mole % of the copolymer comprises randomly repeating monomer units having the structure of the first randomly repeating monomer unit (I). The products exhibit advantageous combinations of softness and elasticity while maintaining strength.
Description
FIELD OF THE INVENTION
The present invention relates to polymeric articles, it include, but are not limited to will comprise the composition drawn of biodegradable the polyhydroxy alkanoate copolymer film, fiber, supatex fabric and the sheet that obtain.This product has the over-all properties that desirable flexibility and elasticity keep intensity simultaneously concurrently.These products can be used for various biodegradable goods, comprise diaper topsheets, diaper tergite, refuse bag, food product pack, disposable external-cover etc.
The background of invention
Reduce the volume of the annual solid waste that produces by the human consumer from hope, biodegradable polymkeric substance and more and more seem important by the product that biodegradable polymers is made.
In the past, once studied the biological degradability and the physicals of various polyhydroxyalkanoatefroms.Polyhydroxyalkanoatefrom is the petchem by various microorganisms such as bacterium and algae generation.Although polyhydroxyalkanoatefrom is owing to its biodegradable obtains common attention, its as the practical application of plastics owing to its thermolability is hindered.For example, poly--3-butyric ester (PHB) is the product of the natural storage energy of a kind of bacterium and algae, it is present in the cytoplasmic individual particle.PHB is thermoplastic, and its degree of crystallinity is high and have a melt temperature of about 180 ℃ fine qualification.Unfortunately, it is unstable that PHB seems, it is degraded under the elevated temperature near its melt temperature.Because this thermolability, the commercial applications of PHB is very limited.
The polyhydroxyalkanoatefrom of also once studying other is as gathering (3-butyric ester-3-hydroxyl valerate) (PHBV).The example of PHB homopolymer and PHBV multipolymer is described in the United States Patent (USP) 4,393,167 and 4,880 of Holmes etc., and in 59, and the PHBV multipolymer is purchased from Monsanto with trade(brand)name BIOPOL.Unfortunately, polyhydroxyalkanoatefrom such as PHB and PHBV are difficult to be processed into the used film of various uses.As mentioned above, to make this processing almost be impossible to the thermolability of PHB.And, the slow crystallization velocity of PHB and PHBV and the mobile processing difficulties that makes film.The valerate content of the PHBV multipolymer that makes generally is about 5-24mol%.The raising of valerate content can reduce the melt temperature of polymkeric substance.Yet, because crystallinity change is smaller, so that the PHBV film remains concerning many application usually is hard and crisp.
Improved biodegradable multipolymer for example is disclosed in the United States Patent (USP) 5,498,692,5,536,564,5,602,227 and 5,685,756 of Noda.The biodegradable multipolymer of Noda comprises at least two kinds of random repeated monomer unit (RRMU), and wherein the structural formula of first kind of RRMU is [O-CH (R
1)-(CH
2)
n-C (O)-], R wherein
1Be the alkyl of H or C1 or C2, n be 1 or the structural formula of 2, the second kind of RRMU be [O-CH (R
2)-CH
2-C (O)-], R wherein
2Be alkyl or the alkenyl of C4-C19, at least 50% RRMU has the structure of first kind of RRMU.The advantage of these multipolymers is that they are biodegradable and have the good comprehensive physicals that they can be processed film forming, sheet, fiber, foam materials, moulded parts, supatex fabric etc., thereby various useful goods are provided.Yet these multipolymers are not soft and resilient intensity when keeping their initial unstretched states simultaneously.
Known polyhydroxyalkanoatefrom (PHA) multipolymer of mainly being made up of the repeating unit of the longer side chain alkyl that contains three to nine carbon atoms has soft and elastomeric elasticity as poly-Hydroxyoctanoic acid ester, has to a certain degree intensity simultaneously (for example referring to K.D.Gagnon, R.W.Lenz, the macromole of R.J.Farris and R.C.Fuller (Macromolecules), the 25th volume, pp.3723-3728,1992).Yet the softness of being made by this pha copolymer and the application of elastic product seriously are subjected to the restriction of about 60 ℃ disappointed low melting glass.Even can reach be higher than 80 ℃ summer the warehouse temperature under, the also dimensional stability of entail dangers to product.Like this, wish a kind of biodegradable softness and elastic product of making by the higher polymkeric substance of melt temperature.
Usually wish thermoplastic polymer is stretched, so that change its physicals.Unfortunately, PHB and PHBV can form the fragility product, even only it is carried out the stretching of not half, described product generally also can rupture.Once attempted the whole bag of tricks and improve the drawing process and the gained performance of stretching PHB and PHBV product, described method for example is disclosed in the United States Patent (USP) 4,427,614 of the United States Patent (USP) 4,537,738 of Holmes and Barham etc.Other method then is disclosed in Safta Europe reference EP 736,563 A1, physics and the Europe reference EP of chemical research institute 849, the pure applied chemistry of the WO reference 97/22459 of 311 A2, Waldock, Kusaka etc. (Pure Appl.Chem.) 834 (2): international polymer processing (Intern.Polymer Processing) XII of 319-335 (1998) and Yamamoto etc., among (1997) 1:29-37.Yet these methods are not successful especially on the method for the drawn products of some over-all properties that provides easy manufacturing to have desired physical properties.Especially, prior art does not provide and has the polymeric articles that flexibility and elasticity keep intensity simultaneously.
Therefore, advantageously will obtain such polymeric articles, it is biodegradable and has and can make the flexibility and the elastic required over-all properties of this product application in various uses.
The general introduction of invention
Therefore, an object of the present invention is to provide the product and the method for the novelty that overcomes the prior art shortcoming.A relevant purpose of the present invention provides the polymeric articles of being made by the composition that comprises biodegradable polymers.A further object of the present invention provides the polymeric articles with good comprehensive physicals.Of the present invention one more specifically purpose provide and have the biodegradable polymeric articles that flexibility and elasticity keep intensity simultaneously.Another object of the present invention provides the method for this product of easy manufacturing.Of the present invention also have a purpose to provide the goods that comprise this polymeric articles.
These are provided by product of the present invention and method with additional purpose and advantage.In one embodiment, the present invention relates to will comprise the composition of the biodegradable polyhydroxy alkanoate copolymer polymeric articles that stretches and obtain.Biodegradable polyhydroxy alkanoate copolymer comprises at least two kinds of random repeated monomer unit (RRMU).First kind of RRMU has structural formula (I):
R wherein
1Be H or C1 or C2 alkyl, n is 1 or 2.Second kind of RRMU has structural formula (II):
R wherein
2Be C3-C19 alkyl or C3-C19 alkenyl.
Multipolymer randomly also comprises the third the random repeating unit with structural formula (III):
Wherein m is 2 to about 9.The RRMU that comprises (I) the first kind of RRMU structure that have formula at least about the multipolymer of 70mol%.The product that the suitable polymers product includes, but are not limited to film, sheet, fiber, supatex fabric and bondings such as many fibers such as non-woven sheets are got up to obtain.The advantage of polymeric articles of the present invention is that they have the over-all properties that flexibility and elasticity keep intensity simultaneously.
In another embodiment, the present invention relates to make the method for improved biodegradable polymers product.This method is included in the second-order transition temperature T that is higher than composition
gBut be lower than the melt temperature T of composition
mTemperature under will comprise biodegradable polyhydroxy alkanoate copolymer composition stretch.Biodegradable polyhydroxy alkanoate copolymer comprises at least two kinds of RRMU, and wherein first kind of RRMU has the structure of above-mentioned formula (I), and second kind of RRMU has the structure of above-mentioned formula (II).This multipolymer randomly also comprises the third RRMU, and wherein the third RRMU is different from first kind of RRMU, and it has the structure of above-mentioned formula (III).The RRMU that comprises (I) the first kind of RRMU structure that have formula at least about the multipolymer of 70mol%.
Can adopt conventional solid state drawing easily.Like this, method of the present invention comprises the easy step of comparing with the cumbersome methods that many prior arts are made the strained polymer products, and method of the present invention can provide the product of the strained polymer with good comprehensive physicals.
From following detailed description, can understand these and additional purpose and advantage more completely.
Describe in detail
Although do not think bound by theoryly, think that the drawing process that reaches to a certain degree can make the copolymer chain of product of the present invention be orientated.Strained polymer product of the present invention unexpectedly has good comprehensive physicals, especially has flexibility and elasticity and keeps intensity simultaneously.Specifically, compare with the not drawn products of same composition, strained polymer product of the present invention has higher intensity (for example being recorded by higher tensile stress at break) and higher flexibility (for example being recorded by lower tensile modulus).This over-all properties is the very beyond thought result of drawing process.In general, drawing process can make product strength bigger and harder (not too soft), rather than intensity is bigger and more soft.For example, for fiber, M.S.M.Mark is at the polymer science dictionary, Elsevier Applied Science, New York (1989), point out on the 295th page " stretch or the fiber of spinning intentionally along its length orientation; like this owing to uniaxial orientation improves in intensity and the rigidity that this side up ", with L.E.Nielson and R.F.Landel mechanical property at polymkeric substance and matrix material, the 2nd edition, Marcel Dekker, Inc., New York (1994) points out " many height-oriented Young's moduluss that fiber had are than an about big order of magnitude of non-oriented polymkeric substance " on the 116th page.For film, Nielson points out also that with Landel (the 116th page) " compare with non-oriented material, the film of the diaxial orientation that stretching makes on two orthogonal directions has the creep and the stress relaxation of decline.This result partly is because due to the modulus raising ".
This product has good elasticity, and promptly they can be replied fast when removing deformation force or pressure.In embodiment preferably, the elasticity that product of the present invention shows is springy, and promptly product is easy to respond the stress that is applied and it can return to its original shape apace after discharging deformation stress.Behavior this springy that the better product of the present invention shows and vulcanized rubber and the elastomeric elasticity of some synthetic thermoplastic are similar.Yet product of the present invention also has high intensity and creep resistance, and this product is with regard to the early deformation under the anti-low-stress of energy and anti-lax (sagging) so in use.Product of the present invention also has good flexibility, and promptly they can be bent, twist or be folding, and can not rupture.In embodiment preferably, have flexible quality in the time of flexibility, this quality makes material be easy to bending, distortion or folding, and does not have the vestige of any damage.Like this, product of the present invention can have usually by high oriented material could be transcendental high strength when the gross distortion, have softness and resilient feature when small deformation simultaneously, this feature can provide the snappiness or the drape of raising, and promptly product is more easily fitted and more cosily coincide around object.In addition, this product does not have and the relevant viscosity of many conventional elastomericss, does not use powder or other anti that may influence performance or required application be produced negative effect.Importantly, product of the present invention is biodegradable.
Make the strained polymer product by the composition that comprises the biodegradable polyhydroxy alkanoate copolymer that contains at least two kinds of RRMU.First kind of RRMU has structural formula (I):
R wherein
1Be H or C1 or C2 alkyl, n is 1 or 2.At one preferably in the embodiment, R
1Be methyl (CH
3), such first kind of RRMU has following structure:
Wherein n is 1 or 2.In another of first kind of RRMU preferably in the embodiment, R
1Be methyl, n is 1, and polyhydroxy alkanoate copolymer just comprises the 3-hydroxybutyrate units like this.
The second kind of RRMU that is included in the biodegradable polyhydroxy alkanoate copolymer has structural formula (II)
R wherein
2Be C3-C19 alkyl or C3-C19 alkenyl.In general, in the RRMU of formula (II), R
2Length can influence the decline of multipolymer overall crystallinity to a certain extent.At one preferably in the embodiment, R
2Be C3-C15 alkyl or alkenyl.At another preferably in the embodiment, R
2Be the C3-C9 alkyl, in the better implement scheme, R
2It is the C5 alkyl.At another preferably in the embodiment, R
2Be C15-C19 alkyl or alkenyl.
Biodegradable polyhydroxy alkanoate copolymer randomly can also comprise the third RRMU with structural formula (III):
Wherein m is 2 to about 9, and wherein the third RRMU is different from first kind of RRMU.M better is about 2-5, and m better is about 3.
In order to reach the biological degradability that good comprehensive physicals that strained polymer product of the present invention shows keeps polyhydroxy alkanoate copolymer simultaneously, comprise the RRMU of (I) the first kind of RRMU structure that have formula at least about the multipolymer of 70mol%.The mol ratio of first kind of RRMU and second kind of RRMU should be about 70 in the multipolymer: 30-98: 2.This mol ratio better is about 75: 25-95: 5, and this mol ratio is about 80 well again: 20-90: 10.As a result, the number-average molecular weight of polyhydroxy alkanoate copolymer should be greater than about 150,000g/mol.Although do not think bound by theoryly, think the side chain R of second kind of RRMU
2Can reduce by the degree of crystallinity of first kind of RRMU fully with the combination of specified molar weight, thereby make multipolymer with desired physical properties.
In the other embodiment of the used polyhydroxy alkanoate copolymer of composition, can comprise one or more additional RRMU.Additional RRMU should have following structural formula:
R wherein
3Be H or C1-C19 alkyl or alkenyl, p is 1 or 2, stipulates that additional RRMU and first kind, second kind or the third RRMU are inequality.
Biodegradable polyhydroxy alkanoate copolymer can be synthetic by chemistry or bio-based method, and described method for example is disclosed in the United States Patent (USP) 5,618 of Noda, 855 and the United States Patent (USP) 5 of Noda etc., in 942,597, the content of these two patents is quoted in this reference.
Composition better comprises the biodegradable polyhydroxy alkanoate copolymer greater than about 50 weight %, and described multipolymer better is present in the composition with the form of external phase.In one embodiment, composition can comprise polyhydroxy alkanoate copolymer as unique polymeric constituent, in other embodiment, can comprise one or more additional polymkeric substance or multipolymer and mix mutually with polyhydroxy alkanoate copolymer.For example, composition can comprise the combination of two or more this biodegradable polyhydroxy alkanoate copolymers, the combination of biodegradable polyhydroxy alkanoate copolymer described herein and other polyhydroxy alkanoate copolymer and/or additional polymeric constituent such as additional polyester components etc.In these embodiments, in composition, the content of biodegradable polyhydroxy alkanoate copolymer preferably at least about is 50 weight %, better is at least about 60 weight %, is at least about 75 weight % better.
Composition can also comprise various non-polymeric ingredients, comprises nucleator, anti, static inhibitor, surface slip agent, helps and add thermo-stabilizer (pro-heat stabilizers), antioxidant, help oxidation additive (pro-oxidant additives), pigment, filler etc.Although in general do not need these additives in composition, these additives can be measured routinely and use, to reach the excellent comprehensive performance of flexibility, elasticity and intensity.In addition, although similarly in general do not need softening agent, in composition, can use the softening agent of one or more convention amounts, to reach above-mentioned excellent comprehensive performance.
Have flexibility and elasticity and keep the upper limit of use temperature of biodegradable polymeric articles of the required over-all properties of intensity can be higher than room temperature significantly simultaneously, because it is higher to be used to make the melt temperature of polymkeric substance of this product.The upper limit of the use temperature of product better can surpass and is higher than 80 ℃, and can fusion or become undue soft, better is higher than 100 ℃, is higher than 120 ℃ well again.
Polymeric articles can be any physical form, the product that it generally comprises tensile film, sheet, fiber or supatex fabric or is made by stretched film, sheet, fiber or supatex fabric.For example, the tensile nonwoven products can make like this, be about to spunbond through comprising, melt and spray, non-woven structure that the ordinary method of the methods such as combination of air-laid, combing, Hydroentangled (hydroentangling) or aforesaid method makes stretches, wherein can adopt including, but not limited to the known any method bonded nonwoven fabric of prior art of heat, machinery, chemistry or adhesives.Perhaps, many oriented fibre can bond, and make the supatex fabric that has with similar flexibility, elasticity and the strength property of previous method.In addition, the tensile polymeric articles need not to be confined to single component structure, for example unitary film or monfil.The tensile polymeric articles also can comprise various polycomponent products, they comprise, but be not limited to fiber or supatex fabric that (1) has face-face, skin-core, many parts, fabric of island-in-sea type and matrix-fibrillar form, (2) by co-extruded films or sheet two-layer or that multilayer is formed, (3) matrix material of film/fiber, sheet/fiber, film/non-woven or sheet/supatex fabric, or the combination of (4) 1-3, as long as in composition, the content of pha copolymer is at least 50 weight %, better be at least about 60 weight %, be at least about 75 weight % better.And, the technology skilful person of this area will understand is that, the level of elasticity, intensity and flexibility that tensile multicomponent polymeric product shows is subjected to the specific form and the influence of structure, this case part is described in as the blend of polymkeric substance and alloy, M.J.Folkes and P.S.Hope (editor), Chapman ﹠amp; Hall, New York (1993) and plastics film, the 2nd edition, J.H.Briston, Longman Inc. is among the New York (1983).
The tensile polymeric articles can adopt conventional solid state drawing method to make easily, wherein is being higher than the second-order transition temperature T of composition
gBut be lower than the melt temperature T of composition
mTemperature under composition is stretched.Better be to obtain product like this, promptly at the high at least 20 ℃ of (T of second-order transition temperature than composition
g+ 20 ℃) but hang down 20 ℃ of (T at least than the melt temperature of composition
m-20 ℃) temperature under composition is carried out solid state drawing.The second-order transition temperature of the polyhydroxy alkanoate copolymer that the present composition is used is usually less than room temperature, promptly is lower than about 25 ℃.The melt temperature of multipolymer is usually above about 100 ℃.
The technology skilful person of this area will understand is that, the level of the elasticity that drawn products shows (comprising feature springy), intensity and the flexibility Temperature Influence that not only stretched, and be subjected to the influence of following factor, be tensile speed and degree, stretching is with constant or with variable velocity of displacement, strain or stress carry out, the tensile type, and concerning film, sheet or supatex fabric, stretching is to carry out with single shaft or with twin shaft, if carry out with twin shaft, then stretching step is according to the order of sequence, carries out simultaneously or in the mode of their certain combinations.Stretching can be carried out with constant or variable velocity of displacement, strain or stress by known method in the prior art, described method for example, for film, sheet and supatex fabric is tentering frame (tenter framing) method, for example J.H.Briston is at plastics film, the 2nd edition, LongmanInc., New York (1983), the 83-85 page or leaf the above, be spinning operation or the winding filament of using the Godet roller perhaps for fiber product, for example J.E.McIntyre and M.J.Denton be at the concise encyclopedia of polymer science and engineering, John Wiley ﹠amp; Sons, New York (1990), 390,391 and 395 pages the above.In addition, for film, sheet and supatex fabric, be stretching on the shaping thing and can carry out equably, for example in the tentering frame method, reached, perhaps on the shaping thing, can incrementally carry out, for example as United States Patent (USP) 4,116,892 and 5,296, annular roll operation (ring-rolling operation) described in 184, wherein tensile replaces parallel zone and in fact keeps not tensile zone coexistence.In addition, for the film and the sheet of blowing, stretching can be undertaken by two or tubular film bubble method, and for example J.H.Briston is at plastics film, the 2nd edition, Longman Inc., New York (1983), 85 pages the above.And, look final purposes, the stretching of film, sheet and supatex fabric can be carried out in the mode of single shaft or twin shaft, as if the words of carrying out in the mode of twin shaft, by known method in the prior art, stretching step can be according to the order of sequence, carry out simultaneously or in the mode of their any combinations.The method of above-mentioned all stretched film, sheet and supatex fabric comprises that all even stretching method that increases progressively can use, and they are all at this
In the scope of invention.
The tensile degree must surpass yield-point or the necking point (neckpoint) at least one direction of tensile, keeps below the breaking point on all draw directions simultaneously.Product better is to obtain by about 50% strained degree that stretching composition at least one direction reaches greater than its initial unstretched state, and being more preferably stretches to reach greater than about 100% strained degree of its initial unstretched state at least one direction obtains.In the better implement scheme, product is to obtain by about 200%-1500% strained degree that stretching composition at least one direction reaches its initial unstretched state, and being more preferably stretches at least one direction reaches about 300%-1000% strained degree of its initial unstretched state and obtain.In addition, what the technology skilful person of this area will further understand is that the process and the geometrical shape of distortion depended in the Effective strain on each draw direction.For example, in the even stretching method of like fibrous spinning, effectively strain by preliminary draft than determining, described preliminary draft than be the speed of fiber when leaving Godet or draw roll when entering Godet or draw roll divided by fiber speed and must ratio, it and sample length always be varied to direct ratio.By contrast, increasing progressively in the stretching method for example at similar annular roll, effectively strain by as at the United States Patent (USP) 4 of above-mentioned reference, 116, the stretch ratio in each stretching or metering zone (gauge section) that discloses in 892 is determined, length localized variation in described stretch ratio and each drawing zone is in direct ratio, it usually not with sample length always be varied to direct ratio.
In general, finish in case stretch, the tensile polymeric articles can be cooled to and be lower than its second-order transition temperature, perhaps can carry out the thermal-setting step it, wherein at the second-order transition temperature that is higher than composition but be lower than under the temperature of melt temperature of composition, generally at about T
g+ 20 ℃ to T
mUnder strain, tensile shaping thing is annealed under-20 ℃ the temperature.
Can use in the prior art known any suitable device to carry out solid state drawing, for example as mentioned above.Following example has illustrated that use Instron uses trier more, is that miscellaneous equipment also can use but those of ordinary skill should understand.Used Instron or other stretcher better are equipped with environmental chamber, so that the drawing process of thermal control to be provided.The technology skilful person of this area will understand is that, for said given composition, can look required end-use and determine stretching condition and annealing conditions (if employing).
Drawn products of the present invention has the good comprehensive performances that good flexibility and elasticity keep intensity simultaneously.More particularly, strained polymer product of the present invention has (1) higher intensity, for example record by higher tensile stress at break, (2) higher flexibility, for example record by lower Young's modulus, (3) higher elasticity is for example compared with the not drawn products of same composition, is recorded by higher answer percentage ratio after discharging deformation stress.In embodiment preferably, press the examples measure of ASTM D882-97 to film, the tensile strength of strained polymer product is greater than about 15MPa, better greater than about 20Mpa.In addition, in embodiment preferably, press the examples measure of ASTM D882-97 to film, the Young's modulus of strained polymer product is less than about 400MPa, and is better less than about 300MPa, good again less than about 200MPa.
The elasticity of the elasticity of drawn products, especially product can be replied product basically when this drawn products extends in as use.Like this, in embodiment preferably, the tensile polymeric articles demonstrates following elastic behavior, promptly as the measurement of film being carried out by ASTM D5459-95, when product elongation reaches approximately 50% the time, product has the answer greater than about 65% in the time that is less than about 15 seconds.Being more preferably the answer greater than about 75%, is well the answer that has greater than about 85% again.
The tensile product can be used for various biodegradable goods, and they comprise disposable, the packing good to environment, housing material, absorbent article (comprises diaper/catemenial/ sanitary napkin top flat, nonwoven core and tergite), stretched film (comprising food and tray packing), plastic film for agricultural use, mulch film, balloon, the lagging packing, stretch package, bag (comprising food and refuse bag), contraceptive (comprising condom and barrier film), shrink package, synthetic paper, carpet, the fishing line, hospital's long gown, gloves, sticking plaster, wound dressings (wound dressings), disposable external-cover (comprising shirt and socks), disposable surgery cord, suture, mail package and agricultural purposes (comprise the capable coverture of seedling, the seedbed coverture, turf coverture and weeds barrier).
Further illustrate product of the present invention and method in the following embodiments.In embodiment and specification sheets of the present invention in the whole text, except as otherwise noted outside, umber and percentage number average are by weight.
Embodiment 1
The present embodiment explanation is carried out uniaxial extension by the present invention to the casting films that melt extrudes.Specifically, the multipolymer of 3-butyric ester and 8.4mol%3-Hydroxyoctanoic acid ester (below be called the PHBO multipolymer) is melt extruded to become to have from about 0.003 casting films to about 0.004 inch variable thickness.Cut about 1 * 4 inch rectangular strip from this film, the parallel longitudinal of length dimension and manufacturing.With each be placed on Instron use more trier (model 1122, Canton, MA) in, make length dimension on the tensile direction, the gauge length of test is 1 inch.This trier is equipped with Sintech ReNew
TMThe 1122/R upgrade components, be used for the TestWorks of control test and analysis
TMV3.02 software and 200lb
fHigh/low wet moves chuck (model S512.01), derives from MTS Systems Corp. all, Research Triangle Park, NC, and environmental chamber is housed, and Series 3710, and it derives from MTS Direct, Eden Prairie, MN, thus the uniaxial extension of thermal control is provided.For the draft temperature test different with envrionment temperature, allow the about 2-3 of test bar balance minute, begin drawing process afterwards.The film bar of PHBO casting films can be elongated before fracture and surpass 1500% elongation.In addition, the tensile bar demonstrates elastic behavior, and when being about to draw back then between its thumb that is clipped in each hand of technician and the forefinger, film is easy to elongate and quickly recover to its original length after release.This behavior shows that the PHBO film composition is the height ductile, and tensile PHBO film composition is resilient.
Embodiment 2
The present embodiment explanation is carried out uniaxial extension by the present invention to PHBO multipolymer melt spun fibre.The PHBO multipolymer that derives from embodiment 1 is melt-spun into the fiber that diameter is about 4mm.Be about 3 inches test tow (strands) from PHBO fiber Cutting Length.According to embodiment 1 described stretching step, adopt the initial strain rate of about 60 ℃ draft temperature He about 2in/in-min, the wire harness of PHBO fiber is extending before fracture to surpass 1000%.In addition, the tensile fibre bundle demonstrates elastic behavior, and when being about to draw back then between its thumb that is clipped in each hand of technician and the forefinger, fiber is easy to elongate and quickly recover to its original length after release.This behavior shows that the PHBO fiber composition is the height ductile, and tensile PHBO fiber is resilient.
Embodiment 3
The present embodiment explanation is carried out uniaxial extension to the casting films that contrast melt extrudes.(New Castle, 3-butyric ester DE) and the multipolymer of 12mol%3-hydroxyl valerate (below be called the PHBV multipolymer) melt extrude into thickness and are about 0.003 inch casting films will to derive from ZenecaBioproducts Inc..According to embodiment 1 described preparation sample and the various draft temperature and the stretching step of initial strain rate, PHBV film bar can not stretch under situation about not rupturing and surpass 10% elongation.This behavior shows that the PHBV composition is hard and crisp, and it can not make the tensile polymeric articles usually.
Embodiment 4
The present embodiment explanation is carried out uniaxial extension by the present invention to the casting films that melt extrudes.The multipolymer of 3-butyric ester and 6.9mol%3-hydroxycaproic ester (below be called the PHBH multipolymer) is melt extruded into thickness be about 0.002 inch casting films.According to embodiment 1 described preparation sample and stretching step, adopt the initial strain rate of about 60 ℃ draft temperature He about 4in/in-min, the film bar of PHBH casting films can be elongated before fracture and surpass 400% elongation.In addition, the tensile bar demonstrates elastic behavior, and when being about to draw back then between its thumb that is clipped in each hand of technician and the forefinger, this film is easy to elongate to 1.5 times of its original length and quickly recovers to its original length after release.This behavior shows that the PHBH composition is a ductile, and tensile PHBH film composition is resilient.
Embodiment 5
The present embodiment explanation is carried out uniaxial extension by the present invention to the casting films that another kind melt extrudes.The multipolymer of 3-butyric ester and 9.7mol%3-hydroxyl octadecane acid esters (below be called the PHBOd multipolymer) melt extruded become to have about 0.002 casting films to about 0.005 inch variable thickness.According to embodiment 1 described preparation sample and stretching step, adopt the initial strain rate of about 60 ℃ draft temperature He about 60in/in-min, the film bar of PHBOd casting films can be elongated before fracture and surpass 1000% elongation.In addition, the tensile bar demonstrates elastic behavior, and when being about to draw back then between its thumb that is clipped in each hand of technician and the forefinger, this film is easy to elongate to 1.5 times of its original length and quickly recovers to its original length after release.This behavior shows that the PHBOd composition is the height ductile, and tensile PHBOd film composition is resilient.
Embodiment 6
The present embodiment explanation is carried out biaxial stretch-formed by the present invention to the casting films that PHBO melt extrudes.At first the initial strain rate with about 60 ℃ temperature and about 4in/in-min stretches about 300% by the film bar that embodiment 1 described step will derive from the PHBO multipolymer casting films of embodiment 1.In trier, such tensile sample revolved then and turn 90 degrees, make primary draw direction vertical with draw direction.Under the initial strain rate of about 60 ℃ temperature and about 4in/in-min, stretch the second time of carrying out about 300% elongation.The elastic property of gained Biaxially oriented film can easily be found out by following method, promptly only uses the hand stretched film, and this film quickly recovers to its original length after discharging deformation strain.
Embodiment 7
Present embodiment relatively stretches and the tensile property of tensile PHBO fusion extrusion casting film not.Specifically, adopt the method in ASTM D882-97, summarize, use and use trier more, determine to derive from the stretching of embodiment 1 and the tensile property of tensile PHBO fusion extrusion casting film bar not as embodiment 1 described Instron.Under the initial strain rate of about 60 ℃ draft temperature and about 100in/in-min, preparation stretching sample.Compare with tensile object of reference not, confirm that by higher rupture stress stretched film intensity is bigger, confirm that by lower Young's modulus stretched film is than softish, but confirm that by lower breaking strain stretched film is not too tensile.
Embodiment 8
The elastic recovery of present embodiment explanation tensile PHBO fusion extrusion casting film of the present invention.When stretching in how with trier as embodiment 1 described Instron, determine that the shown size of film replys, just can measure the elastic performance of the stretching PHBO casting films that derives from embodiment 1.Under the initial strain rate of about 60 ℃ draft temperature and about 100in/in-min, the preparation stretched film.With the initial strain rate of 1.0in/in-min, at ambient temperature stretched film is elongated to predetermined elongation, remove the stress that is applied, measure strained after the time of relaxation of second at about 10-15 and descend.From reaching about 100% elongation, tensile PHBO film bar demonstrates greater than about 85% short-term and replys.This behavior shows the secular mechanical elasticity of product of the present invention.
Embodiment 9
Elasticity, flexible sticking plaster that the present embodiment explanation makes from tensile PHBO casting films of the present invention.Prepare stretched film from the PHBO casting films of embodiment 1, wherein drawing process is to carry out under the initial strain rate of about 60 ℃ temperature and about 20in/in-min.Film bar from 0.75 * 3 inch of tensile PHBO film cutting.0.75 * 1.0 inch absorption pad longitudinally is glued to the central authorities of bar, the Velcro sheet of autoadhesion is bonded to each end, make sticking plaster.On forefinger, use sticking plaster to show that this film is easy to bending, and can make forefinger bending motion back and forth, and can not relax.
Embodiment 10
The present embodiment explanation has elastic force, softish non-woven sheets from tensile PHBO fiber of the present invention manufacturing.Make non-woven sheets from tensile PHBO fiber.Under the initial strain rate of about 60 ℃ temperature and about 3.0in/in-min, press embodiment 2 described stretching melt-spun PHBO fibers.Some tensile tow are cut into 3 inches long, they are placed on randomly that two 10mm are thick, between 6 * 6 inches tetrafluoroethylene (Teflon ) sheet, whole object are placed between the pressing plate of Carver hydraulic test constant pressure machine.Top board is preheating to the high about 15 ℃ temperature of the fusing point of measuring than the calorimetry of PHBO, and making it that 25 bonding diameters be arranged on per square inch is the spot gluing pattern of the equidistant arrangement of 1.0mm.Apply enough pressure, make the softening and fusing of bonding point.Relief pressure allows non-woven sheets be cooled to room temperature, removes the teflon plate of outside afterwards.The elastic performance of non-woven sheets can easily be found out by following method, promptly only uses the hand drawing sheet, and this sheet quickly recovers to its original size after discharging the strain that is applied.
Embodiment 11
The casting films that the present embodiment explanation melt extrudes routine is carried out uniaxial extension and its tensile property.Make the casting films that melt extrudes from some biodegradable polymkeric substance, described biodegradable polymkeric substance comprises polycaprolactone (Tone P787, Union Carbide,), Bionolle 1001 and 3001 (ShowaHighpolymer Co., LTD., Tokyo, JP), Eastar 14766 (Eastman Chemical Company, Kingsport, TN) and BAK 1095 (Bayer Corporation, Pittsburgh, PA), and make the casting films that melt extrudes from some nondegradable polymkeric substance, described nondegradable polymkeric substance comprises that (kind is 7300KF to polypropylene, Millennium Petrochemicals, Cincinnati, OH), (kind is LTPR059 to high density polyethylene(HDPE) (HDPE), Millennium Petrochemicals, Cincinnati, OH) and 50: 50 (weight) new LDPE (film grade)s (LDPE): (kind is respectively NA940000 and GA5010110 to the blend of LLDPE (LLDPE), MillenniumPetrochemicals, Cincinnati, OH).According to embodiment 1 described preparation sample and stretching step, adopt the initial strain rate of about 25 ℃ draft temperature He about 1.0in/in-min, the film bar of various casting films can elongate before fracture and surpass 300% elongation.This behavior is consistent with the ductile film composition.
Use and use trier more,, determine the tensile property of tensile fusion extrusion casting film bar by the method for summarizing among the ASTM 882-97 as embodiment 1 described Instron.Compare with tensile object of reference not, for typical case's representative of drawing process, promptly various stretched film confirm that by higher rupture stress it is that intensity is bigger, but confirm that by higher Young's modulus it is harder, confirm that by lower rupture stress it is not too tensile.
The tensile property that derives from the stretching PHBO film of embodiment 7 is made comparisons as can be seen with the tensile property that derives from the stretched film of present embodiment, compare with the stretched film of making from conventional composition, the PHBO film is than softish.In fact, drawing process can improve the flexibility of PHBO film, and this can be descended by Young's modulus and be confirmed, and the rigidity of conventional composition all improves, and this can be confirmed by the Young's modulus raising.In all cases, stretched film all demonstrates the answer of some degree to the distortion of little elongation; Yet, compare with stretched film of the present invention, elongating the stretched film made by conventional composition, to surpass less elongation much more difficult.For example, the drawing force of 10lb or the stress that is equivalent to 35MPA for 1 inch wide, 0.002 inch thick film bar can cause 50% elongation immediately concerning tensile PHBO film, and, demonstrate 8% elongation immediately at most for the stretched film of making by conventional composition.
Embodiment 12
The present embodiment explanation adopts meltblown to make non-woven sheets.The PHBO multipolymer that derives from embodiment 1 is sent in the forcing machine, and described forcing machine makes its fusion gradually when polymkeric substance is sent into meltblown beam.Die head is metered into polymkeric substance in the weighing road, described material road linear orientation on transverse and longitudinal, and the spinning nozzle direction in the some holes on every linear inch narrows down.In the exit, the polymkeric substance tow is under the effect of heat, high-speed air attenuate (attentuate).The fiber that forms is continuous and very thin, and it is online that it is sprayed onto mobile collector, forms the structure of supatex fabric.Allow fabric pile up roller by 2-roller stainless steel, fabric is carried out thermal caking, on a described roller, the diameter that bonds of having an appointment on per square inch 25 is the spot gluing pattern of 1.0mm.To pile up roller and be preheating to the high about 15 ℃ temperature of the fusing point of measuring than the calorimetry of PHBO composition, it be applied enough pressure when piling up roller, make the softening and fusing of spot gluing at fabric.Lack flexibility and can easily find out by following method, promptly only stretch supatex fabric with pulling, this fabric is difficult for elongation and it can not return to its original size after discharging the strain that is applied.
Embodiment 13
The present embodiment explanation is made resilient non-woven sheets from the melt-blown non-woven fabric.Cut about 1 * 4 inch rectangular strip, the parallel longitudinal of length dimension and manufacturing from embodiment 12 described agglutinating PHBO fabrics.According to embodiment 1 described stretching step, adopt the initial strain rate of about 60 ℃ draft temperature He about 1in/in-min, can make the tensile bars of PHBO supatex fabric.The elastic performance of draw nonwoven sheet can easily find out by following method, promptly only uses hand drawing sheet, this sheet to be easy to extend and it can quickly recover to its original size after discharging the strain that is applied.With making comparisons as can be seen of this behavior and embodiment 10, the non-woven sheets that is made by ordinary method by stretching or make non-woven sheets from the tensile fiber can make the similar nonwoven products of elasticity.
Embodiment 14
United States Patent (USP) 4,116 is pressed in the present embodiment explanation, and 892 modes with annular roll operation increase progressively stretching PHBO film and make resilient film product.Make vertically on, introduce the PHBO casting films that melt extrudes that derives from embodiment 1 by a pair of fluted roller that is preheating to about 60 ℃ of temperature.Groove is vertical vertical with film, and described groove has dark for 3mm, at a distance of the roughly sinusoidal shape of 3mm, and stretch ratio reaches about 2.When stretched film during with the shape of applying groove, the top film of inserting simultaneously of 8 grooves.Film is added in the roll gap of the intermeshing fluted roller that rotates with the speed of about 2RPM, feed rate reaches about 2 feet per minute clocks, reels with the speed of about 4 feet per minute clocks.Film contain with the corresponding 3mm of point of contact more transparent line at interval, or tensile zone is tensile opaque section not between them.With the direction of parallel longitudinal on the elastic performance through the PHBO film of annular roll operation can easily find out by following method, promptly only use hand drawing sheet, this sheet to be easy to extend and after discharging the strain that is applied, can quickly recover to its original size.By contrast, with vertical vertical direction on the stretched film product do not demonstrate elastic force or elasticity significantly arranged, this sheet is difficult for elongation also can not return to its original size after discharging the strain that is applied.Present embodiment illustrates that annular roll operation can make preferred film product have single shaft or directive elastic behavior.This method also is applicable to preferred sheet and nonwoven products.
Embodiment 15
(Tokyo JP) increases progressively stretching and makes the stretched film product mode that the present embodiment explanation is operated with annular roll for ShowaHighpolymer Co., LTD. to Bionolle 3001 films.Specifically, adopt temperature to be about 25 ℃ fluted roller, the fusion extrusion casting film that thickness is about 0.002 inch Bionolle 3001 is carried out annular roll operation by embodiment 14 described steps.Lack flexibility and easily to find out by following method, promptly with parallel longitudinal of making and vertical direction on only with pulling the film product of stretching through annular roll operation, this film is difficult for elongation and it can not return to its original size after discharging the strain that is applied.In fact, annular roll operation makes the distortion for good and all in the vertical of Bionolle 3001 films.
Embodiment 16
The mode that the present embodiment explanation is operated with annular roll increases progressively stretch multi-layer and makes shrinkability film product.Specifically, the PHBO multipolymer that derives from embodiment 1 is coextruded into two-layer casting films product with Bionolle 3001 resins that derive from embodiment 15, wherein the thickness of PHBO layer is about 0.002 inch, and the thickness of Bionolle3001 layer is about 0.001 inch.Adopt temperature to be about 60 ℃ fluted roller then, this PHBO/Bionolle film is carried out annular roll operation by embodiment 14 described steps.The result of annular roll operation has made shrinkability film product; wherein the PHBO layer is described resilient as embodiment 14; and 3001 layers of Bionolle do not have elasticity and a tension set as embodiment 15 is described; and when the PHBO layer shrank when discharging the strain that is applied, the Bionolle layer formed and draws in or pleat.In addition, the Bionolle layer limits the degree that makes the product elastic stretching at least and reaches the incipient extension point at most.
Embodiment 17
Present embodiment has illustrated manufacturing disposable infant diaper, and wherein listed size is the children that are used for 6-10 kilogram magnitude range.For the children of different sizes, or for the incontinence briefs of being grown up, these sizes can be by standard practices correct pro rata.
1. tergite: the film of the 0.020-0.038mm that forms by the PHBO multipolymer that derives from embodiment 1; The width of top and bottom is 33cm; The center width of otch is 28.5cm in both sides are oriented; Length is 50.2cm.
2. top flat: the polypropylene fibre of the staple length of combing and thermal caking (Hercules type 151 polypropylene); The width of top and bottom is 33cm; The center width of otch is 28.5cm in both sides are oriented; Length is 50.2cm.
3. absorbent core: 28.6g Mierocrystalline cellulose wood pulp and 4.9g absorption agent gel-like material particle (available from the commodity polyacrylic ester of NipponShokubai); Thickness is 8.4mm, calendering; The width of top and bottom is 28.6cm; The center width of otch is 10.2cm in both sides are oriented; Length is 44.5cm.
4. the elastic bottom bands of trouser legs: four independent string rubbers (every side has 2); Width is 4.77cm; Length is 37cm; Thickness is 0.178mm (top all sizes all are the sizes under relaxation state).
To be placed on the core material that top flat covers on the tergite and then glue together, prepare diaper with standard manner.
Flexible tie (be designated as " interior band " and " in addition ", they are respectively with the most close and the most corresponding away from being with of core) is stretched to about 50.2cm, its each vertical side along core (2 bands of every side) is placed between top flat/tergite.Be placed on the most about 55mm place (counting) of narrow width along the interior band of each side from the preglabellar field of flexible tie apart from core.So just can between the core edge of interior flexible tie and bending, provide the parts of spacing along each side that comprises the diaper of pliable and tough top flat/backsheet material.Along its length, under stretched state, band in the gummed.Be placed in addition apart from the about 13mm of interior band place, and, under stretched state, glue together it along its length.Top flat/tergite subassembly is flexible, and the band of gummed shrinks, and makes each side high resilience of diaper.
Embodiment 18
Replace the elasticity bottom bands of trouser legs with embodiment 1 described resilient PHBO film product, improve the diaper of embodiment 17.
Embodiment 19
Replace the elasticity bottom bands of trouser legs with embodiment 16 described shrinkability film products, improve the diaper of embodiment 17.
The described specific embodiment and the embodiment that provide above are only presented for purposes of illustration, and they are not limited to the scope of following claims.Other embodiments of the present invention and therefrom advantage be conspicuous to those skilled in the art, and they all scope in.
Claims (10)
1. polymeric articles, it obtains by a kind of composition that stretches, described composition is characterised in that and comprises at least two kinds of unitary biodegradable polyhydroxy alkanoate copolymers of random repeated monomer that wherein first kind of random repeated monomer unit has structural formula (I):
R wherein
1Be H or C1 or C2 alkyl, R
1Better be the C1 alkyl, n is 1 or 2, and n better is 1; Second kind of random repeated monomer unit has structural formula (II):
R wherein
2Be C3-C19 alkyl or C3-C19 alkenyl, R
2Better be the C3-C19 alkyl, R
2Be more preferably the C5 alkyl and
Wherein the multipolymer of 70mol% comprises the random repeated monomer unit with first kind of random repeated monomer unit (I) structure at least, first kind of random repeated monomer unit and second kind of unitary mol ratio of random repeated monomer are preferably 70 in the multipolymer: 30-98: 2, more preferably 75: 25-95: 5.
2. polymeric articles as claimed in claim 1, wherein product is to be higher than the second-order transition temperature T of composition
gBut be lower than the melt temperature T of composition
mTemperature under the stretching composition obtain.
3. polymeric articles as claimed in claim 1 or 2, wherein product is to obtain by the 50% strained degree that the stretching composition reaches greater than its initial unstretched state, better reach the 200%-1500% strained degree of its initial unstretched state and obtain, better reach the 300%-1000% strained degree of its initial unstretched state and obtain.
4. as each described polymeric articles among the claim 1-3, wherein composition comprises the biodegradable polyhydroxy alkanoate copolymer of at least 50 weight %, the number-average molecular weight of biodegradable polyhydroxy alkanoate copolymer is greater than 150,000g/mol.
5. as each described polymeric articles among the claim 1-4, wherein multipolymer also comprises the third the random repeated monomer unit with structural formula (III):
Wherein m is 2-9, and m better is 3, and wherein the third random repeating unit and first kind of random repeated monomer unit are inequality.
6. as each described polymeric articles among the claim 1-5, wherein product is the form of film.
7. polymeric articles as claimed in claim 6 wherein carries out single shaft or biaxial stretch-formed to film.
8. polymeric articles as claimed in claim 6 wherein comes stretched film by annular roll.
9. as each described polymeric articles among the claim 1-5, wherein product is the form of fiber or non-woven sheets.
10. as each described polymeric articles among the claim 1-9, wherein product demonstrates following elastic behavior, promptly when the product elongation reaches 50%, product has at least 65% answer, product better demonstrates following elastic behavior, promptly when the product elongation reached 50%, product had at least 85% answer.
Applications Claiming Priority (2)
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|---|---|---|---|
| US16196999P | 1999-10-28 | 1999-10-28 | |
| US60/161,969 | 1999-10-28 |
Publications (2)
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| CN1384852A true CN1384852A (en) | 2002-12-11 |
| CN1235951C CN1235951C (en) | 2006-01-11 |
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|---|---|---|---|
| CNB008151245A Expired - Fee Related CN1235951C (en) | 1999-10-28 | 2000-10-27 | Polymer products comprising soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and methods of preparing such polymer products |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1237992A1 (en) |
| JP (1) | JP2003513130A (en) |
| KR (1) | KR20020040916A (en) |
| CN (1) | CN1235951C (en) |
| AU (1) | AU1444701A (en) |
| BR (1) | BR0015092A (en) |
| CA (1) | CA2387073C (en) |
| WO (1) | WO2001030892A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6821612B1 (en) | 1999-10-28 | 2004-11-23 | The Procter & Gamble Company | Methods for preparing soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and polymer products comprising such compositions |
| KR20030025930A (en) * | 2000-06-09 | 2003-03-29 | 더 프록터 앤드 갬블 캄파니 | Biodegradable coated substrates |
| US6903053B2 (en) | 2000-06-09 | 2005-06-07 | The Procter & Gamble Company | Agricultural items and agricultural methods comprising biodegradable copolymers |
| JP2003534819A (en) * | 2000-06-09 | 2003-11-25 | ザ プロクター アンド ギャンブル カンパニー | Agricultural item and agricultural method containing biodegradable copolymer |
| WO2003070450A1 (en) * | 2002-02-21 | 2003-08-28 | Riken | High-strength film of polyhydroxyalkanoic acid and process for producing the same |
| JP4553733B2 (en) | 2002-11-08 | 2010-09-29 | 株式会社カネカ | Biodegradable polyester aqueous dispersion and method for producing the same |
| JP2005162884A (en) * | 2003-12-03 | 2005-06-23 | Kaneka Corp | Film using poly(3-hydroxyalkanoate) composition |
| WO2019142920A1 (en) * | 2018-01-22 | 2019-07-25 | 株式会社カネカ | Method for producing nonwoven fabric |
| US20230398257A1 (en) | 2020-10-26 | 2023-12-14 | Mitsubishi Gas Chemical Company, Inc. | Bioabsorbable fibrous medical material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0548225B1 (en) * | 1990-09-11 | 1995-10-25 | E.I. Du Pont De Nemours And Company | Heat shrinkable films containing polyhydroxy acids |
| ID23491A (en) * | 1994-01-28 | 1995-09-07 | Procter & Gamble | COOPOLYMERS WHICH CAN BE DIODODEGRADED AND PLASTIC MATERIALS CONTAINED FROM CO-COLLIMERS WHICH CAN BE DIBIODEGRADED |
| SK96996A3 (en) * | 1994-01-28 | 1997-06-04 | Procter & Gamble | Biodegradable copolymers and plastic articles comprising biodegradable copolymers of 3-hydroxyhexanoate |
| EP0736563A1 (en) * | 1995-04-07 | 1996-10-09 | SAFTA S.p.A. | Process for the manufacture of totally bio-decomposable films with high mechanical characteristics and relevant products and applications |
| GB9526165D0 (en) * | 1995-12-21 | 1996-02-21 | Zeneca Ltd | Oriented polyester |
| JPH10147653A (en) * | 1996-11-20 | 1998-06-02 | Gunze Ltd | Biodegradable oriented film |
| US6174990B1 (en) * | 1998-12-21 | 2001-01-16 | The Procter & Gamble Company | Films comprising biodegradable PHA copolymers |
-
2000
- 2000-10-27 WO PCT/US2000/029884 patent/WO2001030892A1/en not_active Application Discontinuation
- 2000-10-27 EP EP00976712A patent/EP1237992A1/en not_active Withdrawn
- 2000-10-27 AU AU14447/01A patent/AU1444701A/en not_active Abandoned
- 2000-10-27 CA CA002387073A patent/CA2387073C/en not_active Expired - Fee Related
- 2000-10-27 KR KR1020027005284A patent/KR20020040916A/en not_active Application Discontinuation
- 2000-10-27 BR BR0015092-4A patent/BR0015092A/en not_active Application Discontinuation
- 2000-10-27 CN CNB008151245A patent/CN1235951C/en not_active Expired - Fee Related
- 2000-10-27 JP JP2001533884A patent/JP2003513130A/en active Pending
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| CA2387073A1 (en) | 2001-05-03 |
| KR20020040916A (en) | 2002-05-30 |
| CN1235951C (en) | 2006-01-11 |
| CA2387073C (en) | 2007-03-27 |
| JP2003513130A (en) | 2003-04-08 |
| AU1444701A (en) | 2001-05-08 |
| WO2001030892A1 (en) | 2001-05-03 |
| EP1237992A1 (en) | 2002-09-11 |
| BR0015092A (en) | 2002-07-16 |
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