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    • 专利摘要:
    The present invention relates to a laminate comprising at least one polyolefin, and also comprising a first biaxially stretched first polymer layer and a second polymer layer extruded on or thermally bonded to the first polymer. The laminate is characterized by a laminate shrinkage deviation in the transverse direction of less than about 0.6% for lengths of 100 m or more in the machine direction.
    公开号:KR20030010703A
    申请号:KR1020027016990
    申请日:2001-05-17
    公开日:2003-02-05
    发明作者:프랑케카르스텐；헤르트라인토마스
    申请人:쓰리엠 이노베이티브 프로퍼티즈 캄파니；
    IPC主号:
    专利说明:

    Laminates and Their Uses {LAMINATE AND ITS USE}
    [2] Laminates comprising at least one polyolefin-containing first polymer layer and a second polymer layer extruded on the first polymer layer are widely used in the industry, in particular in the disposable soft product industry.
    [3] WO 92 / 01,401 discloses a sheet of loop material comprising a backing having, for example, a backing with a longitudinally oriented fiber having a bow-shaped structure. In a more specific example of this sheet of loop material shown in FIG. 4 of WO'401, the backing adds a thermoplastic backing layer with the loop and a polymeric backing layer attached to the first thermoplastic backing surface opposite the loop. Equipped with. The polymerized backing layer thus further preferably contains a polyolefin, and is preferably printed on either of the main backing surfaces so that printing can be seen through the fiber sheet.
    [4] Such polyolefin containing further polymeric backing layers are generally printed prior to applying the thermoplastic backing layer. This means that the thermoplastic backing layer will be laminated to an additional backing layer containing polyolefin, and that the additional polymeric backing layer containing polyolefin may also be present on other surfaces such as polyolefin layers, which may be present in disposable soft products such as diapers, without any significant thermal deviation. Requires the roof material sheet to be laminated.
    [5] The conditions required with regard to the thermal dimensional stability of laminate polymerized or laminate polymerized films containing printable polyolefins are especially true in disposable soft products, in which a roll of polymeric film, typically several thousand meters long, is printed first and then The second polymer layer is extruded to one of the main surfaces of the polymer layer containing polyolefin to provide a laminate roll. These laminate rolls are then usually slitted to provide a smaller sized laminate roll having a width suitable for use in the manufacture of disposable soft products such as diapers. Thermal deformation, more specifically, when measured along the length of the roll (ie in the machine direction), the thermal deformation deviation in the width of the laminate (ie in the cross-web direction) is sufficiently low that the printing orientation is significantly more accurate. It is important that a laminate roll of size can be obtained by slitting while generating only a small amount of waste.
    [6] The inventors of the present invention often exhibit significant thermal deformations, with commercially available laminates comprising a first polymer layer containing at least one polyolefin and a second polymer layer extruded or thermally bonded to the first polymer layer. In particular, it results in a significant deviation of the thermal strain in the laminate width, making the laminate less suitable for printing applications, in particular less suitable for highly precise printing applications.
    [7] Therefore, a first object of the present invention is a novel laminate comprising at least one polyolefin-containing first polymer layer and a second polymer layer extruded on or thermally bonded to the first polymer layer, It is to provide a laminate that is substantially free from heat deformation and, in particular, has low heat deformation variation in laminate width. It is a second object of the present invention to provide a novel laminate of this type suitable for printing applications, in particular for industrial use of disposable soft products. Other objects of the present invention are described in the detailed description that follows.
    [1] The present invention relates to a laminate comprising a first polymerized layer containing at least one polyolefin and a second polymerized layer extruded or thermally bonded to the first polymer, a method for producing the laminate and a disposable soft product. It relates to the use of the laminate used in industry.
    [8] 1 shows a first polymerization layer 1 containing at least one polyolefin and coaxially elongated a first polymerization layer 1 and a second polymerization extruded on or thermally bonded to the first polymerization layer 1. It is a schematic diagram of the laminate of the invention comprising layer (2).
    [9] FIG. 2 shows a first polymerization layer 1 containing at least one polyolefin and coaxially elongated and a second polymerization extruded on or heat bonded to the first polymerization layer 1. As a schematic view of the laminate of the invention comprising a layer 2, it is shown here that the exposed surface of the second polymeric layer comprises a looped arm fastening member 3 of a mechanical fastening system having a bow-like structure. .
    [10] 3 shows a first polymerization layer 1 containing at least one polyolefin and coaxially elongated a first polymerization layer 1 and a second polymerization extruded on or heat bonded to the first polymerization layer 1. As a schematic view of the laminate of the invention comprising layer 2, it is shown here that the exposed surface of the second polymeric layer comprises a mushroom male fastening member of a mechanical fastening system.
    [11] Summary of the Invention
    [12] The present invention relates to a laminate comprising at least one polyolefin and comprising a first biaxially stretched first polymer layer and a second polymer layer extruded on or thermally bonded to the first polymer layer. Denotes a laminate shrinkage deviation in the transverse direction less than about 0.6% for a length of 100 m or more in the machine direction.
    [13] The present invention also relates to a process for producing such laminates and to the use of such laminates in the disposable soft product industry.
    [14] Detailed description of the invention
    [15] Most of the terms used in the description and the claims are generally well known, but certain terms need explanation. The term "simultaneous biaxially elongated" is used in the description to describe the film, and the film is stretched in two different directions within the film plane, i.e., in both directions, in the first and second directions. In each case, a significant proportion of stretching occurs simultaneously. In general, though not always, these two directions are nearly perpendicular and exist in the machine direction ("MD") of the film and in the transverse direction ("CD") of the film. Unless specifically stated, the terms "orient", "draw", and "extend" shall mean "oriented", "drawn", "extended", and "oriented", "drawn", and " Interchangeable with the term "extension".
    [16] The term “new equipment” described in the present specification is used to describe an elongation method or elongated film, and refers to the ratio of the linear dimension at a given portion of the stretched film to the linear dimension at a given portion of the film before stretching. Indicates. For example, for a stretched film with an MD stretching ratio of 5: 1, a given portion of an unstretched film having a linear measurement of 1 cm in the machine direction may have a measurement of 5 cm in the machine direction after stretching. For films stretched with a CD stretching ratio of 5: 1, a given portion of an unstretched film having a linear measurement of 1 cm in the transverse direction may have a measurement of 5 cm in the transverse direction after stretching.
    [17] The term "extension parameter" refers to a value obtained by subtracting 1 from an extension ratio, that is, a value of extension ratio-1. For example, the "first direction stretching parameter" and "second direction stretching parameter" used in the present specification refer to the value of the first direction stretching ratio -1 and the value of the second direction stretching ratio -1. Similarly, "MD stretch parameter" and "CD stretch parameter" refer to values of MD stretch ratio-1 and CD stretch ratio-1, respectively, in this specification. For example, a film not stretched in the machine direction has an MD stretching ratio of 1 (that is, the dimension after stretching is the same as that before stretching). Such films have an MD stretching parameter of 1-1, or 0 (ie, the film is not stretched). Similarly, a film with an MD stretch ratio of 7 has an MD stretch parameter of 6.
    [18] The term "peak first direction stretching parameter or peak second direction stretching parameter" is used to indicate the maximum value of the stretching parameter in each of the first or second directions when stretching the first polymer layer. This first polymeric layer is then partially relaxed with a "final first direction stretch parameter or final second direction stretch parameter". The terms "peak first direction stretch ratio or peak second direction stretch ratio" and "final first direction stretch ratio or final second direction stretch ratio" are used corresponding to each other.
    [19] The "mechanical stretch ratio", also known as the "nominal stretch ratio", is determined by the unexpanded and stretched dimensions of the entire film, and is generally a film gripper located on the film edge used to stretch the film in a particular device. Measurable at The term "total elongation ratio" refers to the total elongation ratio of the first polymeric layer, which is located adjacent to the gripper and excludes the area affected by the gripper upon stretching. The total elongation ratio may be equal to the mechanical elongation ratio if the input unstretched first polymeric layer has a constant thickness over its entire width and if the effect adjacent to the gripper during stretching is small. However, more specifically, by adjusting the thickness of the first unstretched first polymeric layer, it can be made thicker or thinner near the gripper than at the center of the film. In this case, the total stretch ratio will be different from the mechanical stretch ratio or nominal stretch ratio. Both these total or mechanical stretch ratios are distinguished from local stretch ratios. The local stretch ratio is determined by measuring a specific portion (eg, 1 cm portion) of the first polymer layer before and after stretching. If the elongation is not substantially uniform for the entire film where the edges are trimmed, the local ratio may be different from the overall ratio. If the elongation is substantially uniform with respect to the entire first polymer layer (except for the gripper periphery along the edge and the area immediately adjacent to the edge), the local ratio will be substantially equal to the overall ratio. Unless otherwise specified, the terms first direction stretch ratio and second direction stretch ratio are used herein to describe the total stretch ratio.
    [20] The first polymeric layer can be biaxially stretched at the same time by applying a "proportional stretch profile", wherein the first directional stretch parameter versus the second directional stretch parameter remain substantially constant throughout the stretch process. A particular embodiment of this is the case where the ratio of MD stretching parameters to CD stretching parameters remains substantially constant during the stretching process. The term " MD overbias " refers to an elongation profile that is greater than for proportional elongation profiles with the same final MD elongation ratio and final CD elongation ratio during which much of the stretching process occurs.
    [21] When many films are coaxially elongated at temperatures below the polymer's melting point, especially when coaxially biaxially stretched at or below the film's line pull out temperature, the films are nonuniformly stretched to provide a distinct boundary between the stretched and unextended portions To form. This phenomenon is referred to as necking or line drawing. When the entire film is stretched to a sufficiently high degree, the entire film is substantially uniformly stretched. The stretch ratio when this happens is referred to as "natural stretch ratio" or "natural draw ratio". The effects of necking and natural stretch ratios are described, for example, in US Pat. US Pat. No. 3,995,007 and US Pat. No. 4,335,069 describe primarily sequential biaxial orientation processes. That is, it is disclosed that the first direction stretching and the second direction stretching are performed sequentially. When the same biaxial stretching (or square stretching) is performed at the same time, the necking phenomenon is less likely to produce stretched regions with different local stretch ratios than with distinctly stretched and unstretched portions. In this situation, and in any simultaneous biaxial stretching process, the "natural stretching ratio" in a given direction is defined as the total stretching ratio when the relative standard deviation of the local stretching ratio measured at multiple points in the film is about 15% or less. Elongations higher than the natural elongation ratio are widely understood to provide significantly more uniform properties or properties such as thickness, tensile strength and elastic modulus. For any given film and stretching conditions, the natural elongation ratio is determined by factors such as shape due to polymer composition, molding web cooling, and the like, as well as elongation temperature and elongation rate. In addition, for coaxially stretched films, the natural stretching ratio in one direction is affected by the stretching conditions, including the final stretching ratio in the other direction. Therefore, given a fixed stretch ratio in the other direction, one direction will be a natural stretch ratio, or a pair of stretch ratios (1 in MD and 1 in CD) representing local stretch uniformity levels by the natural stretch ratio defined above. Can be.
    [22] A schematic diagram of a laminate of the present invention containing a first polymerized layer 1 and a second polymerized layer 2 extruded onto the first polymerized layer 1 is shown in FIG.
    [23] The first polymerized layer comprises at least one polyolefin, which may be a homopolymer, a copolymer of two or more olefins, or a copolymer containing one or more olefins in a mass ratio of at least 50% by weight relative to the mass of the polyolefin. The first polymer layer preferably contains at least 50% by weight, more preferably at least 65% by weight, and most preferably at least 80% by weight of one or more polyolefins, based on the mass of the first polymer layer. The polyolefin preferably contains polyethylene and polypropylene. Isotropic polypropylene is most preferred.
    [24] For the purposes of the present invention, the term "polypropylene" is meant to include copolymers comprising at least about 90% by weight of propylene monomer units. "Polypropylene" is also meant to include polymer mixtures containing at least about 75 weight percent polypropylene. It is preferable that the polypropylene used for this invention has superior isotropy. Isotropic polypropylene has at least about 80% by weight of chain isoprotective water, less than about 15% by weight of n-heptane soluble content, and a density range of about 0.86 to 0.92 g / cm 3 as measured by ASTM D1505-96 (according to "density gradient technology Density of plastics "). Typical polypropylenes used in the present invention have a melt flow index of about 0.1 to 15 g / 10 minutes as measured by ASTM D1238-95 at a temperature of 230 ° C. and a force of 21.6 N. Flow rate), and also has a weight average molecular weight of about 100,000 to 400,000 and a polydispersity index of about 2-15. The general polypropylene used in the present invention is higher than about 130 ° C. as measured using a differential scanning calorimeter. , Preferably higher than 140 ° C. and most preferably higher than about 150 ° C. Polypropylenes useful in the present invention are copolymers, terpolymers, tetrapolymers, etc., which are 4-8 carbon alpha-olefins. Having a monomer unit and / or an ethylene monomer unit, the content of this comonomer is present at less than 10% by weight Examples of other suitable comonomers include, but are not limited to: , 1-decene, 1-dodecene, vinylcyclohexene, styrene, allylbenzene, cyclopentene, norbornene and 5-methylnorbornene One suitable polypropylene resin is an isotropic polypropylene homopolymer. The melt flow index is 2.5 g / 10 min, which is commercially available from FINA Oil & Chemical Co., Dallas, Texas, as product number 3376. Polypropylene, in the course of the process, may contain organic peroxides, such as up to 6 May be intentionally partially deteriorated by addition of dialkyl peroxides having a yl group with carbon number, ie 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and ditert-butyl peroxide A deterioration coefficient of about 2-15 is suitable, for example, recycled or reprocessed polypropylene in the form of a scrap film or in the form of edge trimmings may also be incorporated into the polypropylene in an amount of less than about 60% by weight.
    [25] Mixtures having at least about 75% isotropic polypropylene and containing up to about 25% of other polymer (s) can also be advantageously used in the process of the present invention. Suitable additional polymers present in such mixtures include, but are not limited to, copolymers of propylene with other olefins such as ethylene, olefins containing 4-8 carbon atoms, and other polypropylene resins.
    [26] The polypropylene used in the present invention may optionally contain 1-40% by weight of a resin, either synthetic or natural, having a molecular weight of about 300-8000 and a softening point of about 60 ° C to 180 ° C. In general, such resins are selected from one of four classes: petroleum resins, styrene resins, cyclopentadiene resins, and terpene resins. Optionally, the resins belonging to these classes may be partially or wholly hydrogenated. Petroleum resins generally include styrene, methylstyrene, vinyltoluene, indene, methylindene, butadiene, isoprene, piperylene, and / or pentylene as monomeric components. Styrene resins generally include styrene, methylstyrene, vinyltoluene and / or butadiene as monomeric components. In general, cyclopentadiene resins have cyclopentadiene and optionally other monomers as monomer components. Terpene resins generally have pinene, alpha-pinene, dipentene, limonene, myrcene, and camphor as monomeric components.
    [27] The polypropylene used in the present invention optionally includes additives and other components known in the art. For example, the films of the present invention can be used in fillers, pigments and other colorants, antiblocking agents, lubricants, plasticizers, processing aids, antistatic agents, nucleating agents, antioxidants and heat stabilizers, UV stabilizers, and other properties of modifiers. It includes. Fillers and other entry agents are preferably added in selected effective amounts so as not to deleteriously affect the properties obtained by the preferred embodiments described in this specification. Once these materials are applied into the polymer (eg, in the molten polymer prior to extrusion into the film) before being made into an oriented film. Organic fillers are organic dyes and resins, as well as organic fibers (e.g. nylon and polyimide fibers) and other optionally crosslinked polymers such as polyethylene, polyesters, polycarbonates, polystyrenes, polyamides, halogenated polymers, poly Methyl methacrylate and cycloolefin polymers. Inorganic fillers include pigments, fumed silica, and other forms of silicon dioxide, silicates such as aluminum silicate or magnesium silicate, kaolin, talc, sodium aluminate silicate, potassium aluminate silicate, calcium carbonate, magnesium carbonate, diatomaceous earth, gypsum And aluminum sulfate, barium sulfate, calcium phosphate, aluminum oxide, titanium dioxide, magnesium oxide, iron oxide, carbon fiber, carbon black, graphite, glass beads, glass bubbles, mineral fibers, clay particles, metal particles, and the like. In some cases, it may be advantageous to form cavities around the filler particles in the biaxially oriented process of the present invention. Many organic and inorganic fillers are effectively available as antiblocking agents. Alternatively or in addition, lubricants such as polydimethyl siloxane oil, metal soaps, waxes, higher aliphatic esters, and higher aliphatic acid amides (eg, erucamides, oleamides, stearamides, and behenamides) can be used.
    [28] Antistatic agents may also be used, which include aliphatic tertiary amines, glycerol monostearate, alkali metal alkanesulfonates, ethoxylated or propoxylated polydiorganosiloxanes, polyethylene glycol esters, polyethylene glycol ethers, fatty acid esters, ethanol amides, mono And diglycerides, ethoxylated fatty amides and the like. Organic nucleating agents or inorganic nucleating agents may also be incorporated, examples of which include dibenzylsorbitol or derivatives thereof, quinacridone and derivatives thereof, metal salts of benzoic acid (eg sodium benzoate), sodium bis (4-t -Butyl-phenyl) phosphate, silica, talc, bentonite and the like. Antioxidants and heat stabilizers include phenolic types (e.g. pentaerythryl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 1,3,5-trimethyl -2,4,6-tris (3,5, -di-t-butyl-4-hydroxybenzyl) benzene, and alkali and alkaline earth metal stearates, carbonates and the like are advantageously used. Other additives such as flame retardants, ultraviolet stabilizers, compatibilizers, bactericides (e.g. zinc oxide), electrical and thermal conductors (e.g. aluminum oxide, boron nitride, aluminum nitride, and nickel particles) are used to form the film. Can be incorporated into the polymer.
    [29] The first polymeric layer can be formed into a layer suitable for stretching into the desired film described in this specification by molding into sheet form as is known. When producing the polypropylene layer, a suitable method of shaping the sheet is a single screw, two screws, a feed hopper of cascade or other extrusion system with an extruder barrel temperature adjusted to produce a stable homogeneous melt. Feed into. The polypropylene melt can be passed through a sheet die and extruded on a rotating cold metal forming wheel. Optionally, the forming wheel may be partially immersed in a fluid filled cooling bath, or the forming sheet may be removed from the forming wheel and then passed through into the fluid filled cooling bath.
    [30] The sheet thus obtained is then biaxially stretched simultaneously in the first and second directions, where the first and second directions are at right angles to each other and in the machine direction MD and the web transverse direction CD, respectively. It is preferred that it is the corresponding direction. Of all the stretching methods, the most preferred method of commercially preparing the first polymerized layer of the laminate according to the invention involves carrying out biaxial stretching simultaneously using a flat film tenter apparatus. This stretching method is referred to herein as simultaneous biaxial tenter stretching. The apparatus used in this method is quite distinct from the conventional sequential biaxial stretching apparatus in which the film is stretched to MD by being propelled on a roller with a rising speed. Simultaneous biaxial tenter stretching is desirable because it prevents the rollers from contacting the film front during stretching. Simultaneous biaxial tenter stretching is carried out on a tenter device, which is a device that supports the sheet along the opposite edges of the sheet (using a number of clips-like means) and propels the support means at various speeds along the diverging rail. Here, the gripper and the clip are meant to include other film edge support means as well. Elongation at the MD occurs by increasing the clip speed to the MD. If such means as a divergent rail or the like is used, CD elongation also occurs. Such stretching may be performed by the methods and apparatus described in US Pat. Nos. 4,330,499, and 4,595,738, and more preferably US Pat. Nos. 4,675,582; 4,825,111; 4,853,602; 5,036,262; 5,501,225; And the method and tenter device disclosed in 5,072,493. The biaxial tenter device can perform both a sequential biaxial stretching process and a simultaneous biaxial stretching process, but the present invention includes only a simultaneous biaxial stretching process. As described above and below, the term simultaneous biaxial stretching refers to the simultaneous stretching of at least 10%, more preferably at least 25%, and most preferably at least 40% in each of the first and second directions. . Although coaxially stretched films can also be produced by tubular foamable film stretching processes, the first polymeric layer used in the laminates of the present invention is capable of reducing the thickness variation while avoiding the difficulties in performing processes typically found in tubular foamable film processes. In order to minimize it is desirable to prepare by the preferred flat film tenter stretching process just described above.
    [31] The final first and second directional stretching parameters are preferably 3: 1 to 15: 1 independently of each other, more preferably 4: 1 to 12: 1, and 5: 1 to 10: 1. Most preferred.
    [32] As described above, the first polymer layer is stretched using the overextension mode, and the stretching may be performed by applying various stretching profiles such as, for example, a proportional stretching profile or an MD or CD overbias stretching profile.
    [33] The first polymeric layer is each overextended with a peak first and / or second direction stretch ratio in one or more of the first and second directions, and then contracted with the final first and / or second direction stretch ratio. Overextension in at least one of the first and second directions has been found to be necessary to obtain sufficient thermal stability of the resulting laminate. In a preferred embodiment, the peak CD stretch parameter is preferably at least 1.15 times, more preferably at least 1.2 times, particularly preferably at least 1.3 times the final CD stretch parameter. The first polymer layer preferably has a peak CD stretching ratio of at least 1.1 times, more preferably at least 1.15 times of the final CD stretching ratio, and a peak MD stretching ratio of at least 1.05 times, more preferably of 1.1 times the final MD stretching parameter.
    [34] Sometimes it is desirable for the film to have high toughness and high elongation at break in a particular direction. This property can be achieved by a low final withdrawal ratio in that direction. Low final withdrawal ratios are conveniently obtained by applying an overbias profile as disclosed in WO 00 / 29,197 filed March 25, 1999. These profiles give the film uniform properties and thickness.
    [35] Simultaneous biaxial stretching of the first polymeric layer includes, but is not limited to, composition of the first polymeric layer, molding of the first polymeric layer, and soaking parameters, time-temperature relationship during film preheating prior to stretching, elongation temperature used. It is sensitive to many process conditions, including, and elongation rate. Prior to stretching to the peak first or second direction stretching parameters, the first polymeric layer is generally at a temperature of 80-180 ° C., more preferably 90-170 ° C., for a time of 1-500 seconds, preferably 5-300 seconds. Preheating is common. The stretching to the peak first and / or second directional stretching parameters is then usually carried out at a temperature of 100-200 ° C., more preferably 110-170 ° C., particularly preferably 140-160 ° C. The first polymeric layer is then shrunk to a final first and / or second directional stretching parameter so that generally at 80-200 ° C. for 0.1-100 seconds, more preferably 0.1-50 seconds in this contracted final state. Temperature, more preferably at a temperature of 90-180 ° C. After the stretching process is completed, the first polymeric layer is gradually cooled to room temperature but is preferably rapidly cooled at a cooling rate, such as 50 K / s or higher, which is then quickly removed from the stretcher. Next, the first polymer layer is rolled and stored in a roll form. The above mentioned parameters are just one example, and the use of a modified temperature-time profile is also possible. Details of suitable elongation parameters are described in US Application No. 09/192059, which is incorporated herein by reference. Thanks to the teachings in this specification and US application 09/192059, those skilled in the art can achieve various improvements in the degree of accuracy by adjusting all parameters or any parameters, or to determine the exact level of elongation profile overbias required to realize these improvements. Can be adjusted.
    [36] The first polymeric layer used in the present invention preferably has a final thickness of about 5-100 μm, more preferably about 10-55 μm. The first polymeric layer is based on the understanding that the film should be thick enough to avoid problems of excessive breakage or handling difficulties caused by being too thin, and not so thick that it becomes undesirably hard or stiff and difficult to handle or use. It may take the thickness of a film that is thicker or thinner than that presented above. The film thickness deviation is preferably less than 10% in the transverse direction of the inner width and the longitudinal direction of the web, excluding the edge area of the film, as measured by the standard deviation from the mean. This internal width varies with the relative area of the film edge relative to the film overall width. In general, film edges are not biaxially stretched, but rather exhibit stretch characteristics of a tendency towards a single axis even in the case of simultaneous biaxial stretching process use. Therefore, it may be necessary to cut and discard the edges before or after the first polymerized layer, for example, in the form of a roll.
    [37] Prior to applying the second polymerized layer, the first polymerized layer may be printed on one or both sides of the film main surface of the first polymerized layer by conventional printing methods such as screen printing, flexo printing or gravure. The printing can be of any type, including, for example, safety marks, cut marks or position marks or instructions, or graphics that rupture when peeling the second polymer layer from the first polymer layer.
    [38] Suitable polymers for the second polymerized layer are thermoplastic polymers, which may be chosen that are extruded or thermally bonded, ie those bonded by applying heat and optionally pressure to the first polymerized layer. As the second polymerized layer, it is preferred that the resulting laminate has a T-peeling force that exceeds the mechanically weaker cohesive force of the first polymerized layer and the second polymerized layer. The second polymeric layer can be screened by laminating the second polymeric layer on the first polymeric layer and separating the hand-generated laminate: if the laminate passes this test and cannot be separated by hand, the selected agent The second polymeric layer is compatible with the selected first polymeric layer.
    [39] The second polymer layer is polyester, polycarbonate, polyarylate, polyamide, polyimide, polyamide-imide, polyether-amide, polyetherimide, polyaryl ether, polyarylether ketone, aliphatic polyketone , Polyphenylene sulfides, polysulfones, polystyrenes and derivatives thereof, polyacrylates, polymethacrylates, cellulose derivatives, polyethylene, polyolefins, copolymers with predominantly olefin monomers, fluorinated polymers and copolymers, chlorinated polymers, Thermoplastic acrylonitrile, polyvinylacetate, polyvinyl alcohol, polyether, ionomer resin, elastomer, silicone resin, epoxy resin, and polyurethane. Miscible or immiscible polymer blends comprising any of the polymers set forth above and copolymers containing any of the constituent monomers of any of the above polymers may also be used, provided that the polymer layer produced from such blends or copolymers is Subject to extruded or thermally bonded onto the first polymeric layer. Particular preference is given to polymers containing at least one polyolefin, specifically polypropylene or polyethylene, preferably in an amount of at least 30% by weight, more preferably at least 40% by weight. The term "polyethylene" as used in connection with a second polymeric layer means a copolymer comprising at least about 90% by weight of ethylene monomer units. "Polyethylene" is also meant to include polymer mixtures containing polyethylene in an amount of at least about 75% by weight. The term "polypropylene" has the same meaning as defined above in the first polymeric layer.
    [40] Secondary polymers include fillers, pigments, and other complexing agents, antiblocking agents, lubricants, plasticizers, processing aids, antistatic agents, nucleating agents, antioxidants, and thermal stabilizers, UV stabilizers, and other properties of modifiers. Conventional additives may be included. The filler and other additives are preferably added in an effective amount selected so as not to deleteriously affect the bonding properties of the second polymer layer with respect to the first polymer layer. The amount of the additive added to the second polymer is preferably less than 35% by weight, more preferably less than 30% by weight relative to the mass of the second polymer. The additives set forth above for use in the first polymer are also advantageously usable for the second polymer.
    [41] The second polymeric layer is applied to the first polymeric layer using heat and optionally pressure. In the first method, the first polymerized layer and the second polymerized layer are bonded to each other by passing the first polymerized layer and the second polymerized layer into each other by applying sufficient heat and pressure to pass through the first polymerized layer and the second polymerized layer. In a second preferred method, the second polymer is preferably fed into a single screw, two screws, a casing feed hopper or into another extruder system having an extruder barrel temperature adjusted to produce a stable homogeneous melt. The second polymer melt is then extruded through a sheet die on the first polymeric layer, followed by air cooling, for example. The resulting laminate can then be wound up in the form of a roll.
    [42] The second polymeric layer may consist of two or a plurality of filler layers, which may be laminated to one another or co-extruded on the first polymeric layer, for example, before thermally bonding the second polymeric cake onto the first polymeric layer. It is. The polymers usefully used in the second polymer layer having a two layer structure or a multi layer structure are also preferably selected from the group consisting of the polymers presented for the second polymer layer.
    [43] It has surprisingly been found by the inventors that the laminates produced according to the invention have high dimensional stability, in particular small shrinkage variations to CD. They do not wish to be bound by this theory, but it is believed that this theory results from the high dimensional stability of the first polymer layer that can withstand exposure to heat and arbitrary pressures when applying the second polymer layer. . Laminate according to the present invention, when measured according to the measuring method described in the test items described below, the shrinkage of the laminate shrinkage to CD for a length of 100 m or more in the machine direction is about 0.6% or less, more preferably about 0.4% or less, most preferably Preferably about 0.2% or less. When measured according to the method described in the test item described below, the absolute value of the laminate shrinkage to CD for a length of 100 m or more in the machine direction is about ± 1.5% or less, more preferably less than about ± 1.0%.
    [44] The high dimensional stability of the laminate according to the invention is particularly advantageous in the case of the use where one major surface or both major surfaces of the first polymer layer are printed. Extrusion-bonding of the second polymer layer on the first polymer layer makes the printing substantially unaffected, not distorted when viewed with the naked eye, and also does not deform in the CD along the MD direction. If the laminate rolls need to be slit into two or more small rolls, this slitting generates only minimal waste and is easily performed to provide a roll with precisely positioned printing. In the case of state-of-the-art laminates in which the lamination shrinkage variation to CD is clearly high, slit rolls that provide precisely positioned printing allow for wider tolerances and can only be obtained if tolerating a larger amount of waste.
    [45] Laminates according to the invention may be modified and / or may comprise additional layers.
    [46] In a preferred embodiment, the exposed surface of the second polymeric layer represents the male fastening member of the mechanical containment system. A specific structure is shown in FIG. 2 with a mushroom-shaped water fastening member 4 at the exposed surface of the second polymeric layer 2, which can be prepared according to the method described in WO 94 / 23,610.
    [47] In a preferred embodiment according to the invention, the exposed surface of the second polymeric layer 2 comprises a female fastening member layer 3 of a mechanical containment system. A particular structure is shown in FIG. 3 that includes the longitudinally oriented fibers of the bow structure between anchor sites as such a fiber sheet layer is bonded to the exposed surface of the second polymeric layer. The fabrication of the structure of FIG. 3 is described in WO 92/01401.
    [48] The laminate of the present invention printed on at least one of the major surfaces of the first polymeric layer and exhibiting a mechanical fastening member present on or attached to the exposed surface of the second polymeric layer is a component of a disposable soft product, such as a diaper. Particularly suitable for use. It is particularly preferred that such a laminate is used to form the landing area of the containment fastening tape of the diaper including a mechanical fastening member which mutually fastens with a mechanical fastening member on the exposed surface of the laminate. .
    [49] The laminate according to the invention may also comprise at least one adhesive layer which is applicable to the exposed surface of each of the second or first polymeric layers. Particularly preferred laminates are laminates which show a mechanical bonding member attached to or resting on the exposed surface of the second polymeric layer and an adhesive layer on the exposed surface of the first polymeric layer. Preferred adhesives are those which are activatable by pressure, heat or a combination thereof. Suitable adhesives are adhesives by acrylates, rubber resins, epoxies, urethanes or combinations thereof. The adhesive layer can be applied by solution, waterborne coating or hot melt coating. Adhesives include hot melt coating formulations, transition coating formulations, solvent coating formulations, and latex formulations as well as laminating heat activated and water activated adhesives and binders. Useful adhesives according to the present invention include all pressure sensitive adhesives. Pressure-sensitive adhesives are known to have strong adhesion, permanent viscosity, be able to be attached only by acupressure, and possess properties including sufficient capacity to be supported on the attachment. Examples of adhesives useful in the present invention include polyacrylates; Polyvinyl ethers; Diene rubbers (eg, natural rubber, polyisoprene and polybutadiene); Polyisobutylene; Polychloroprene; Butyl rubber; Butadiene-acrylonitrile polymer; Thermoplastic elastomers; Block copolymers (eg, styrene-isoprene and styrene-isoprene-styrene (SIS) block copolymers, ethylene-propylene-diene polymers and styrene-butadiene polymers); Poly-alpha-olefins; Amorphous polyolefins; silicon; Ethylene-containing copolymers (eg, ethylene vinyl acetate, ethyl acrylate and ethyl methacrylate) and polyurethanes; Polyamides; Epoxy; Polyvinylpyrrolidone and vinylpyrrolidone copolymers; Polyester; Mixtures or blends thereof (continuous or discontinuous phase) and the like. The adhesive may also contain viscosifiers, plasticizers, fillers, antioxidants, stabilizers, pigments, diffusible materials, hardeners, fibers, filaments and additives such as solvents and the like. In addition, the adhesive may optionally be cured according to any known method.
    [50] A general description of useful pressure sensitive adhesives is given in "Polymer Science and Engineering Encyclopedia (Vol. 13)" published by Wiley-Interscience Press (NY, 1988). Additional descriptions of useful pressure sensitive adhesives can be found in Interscience Press (NY, 1964), "Encyclopedia of Polymer Sciences and Technology (Vol. 1)."
    [51] The invention is further embodied by the following examples. These examples are intended to further illustrate various specific and preferred embodiments and techniques. However, many modifications and variations are possible within the scope of the invention.
    [52] Before describing an embodiment, some test methods used in the embodiments are described.
    [53] Test method
    [54] Shrinkage of the First Polymerized Layer
    [55] A strip of the first polymeric layer having a width of 2.54 cm and a length of about 30 cm was cut from the first polymeric layer to be evaluated. The two marks were placed on the strip of the first polymeric layer so that they were 25.4 cm apart from each other. One end of the first polymeric layer strip was attached to a clamp and suspended in a forced air oven at 120 ° C. for 5 minutes. The first polymeric layer strip was removed from the oven and cooled to 23 ° C.
    [56] The distance between the marks was measured again and compared with the original distance. The difference was divided by the original distance and expressed in%. Each of the first polymeric layers tested was evaluated three times and the results averaged. The measurement was performed by CD and MD.
    [57] Laminate shrinkage (%) and deviation in the cross web direction
    [58] a) general method
    [59] A logo and a registration mark were printed on one major surface of the roll of the first polymeric layer with CD width and MD length.
    [60] The edge distance between each pair of neighboring precision marks was measured and recorded in the outermost wrap or outer wrap of the first polymeric layer roll. This procedure was repeated at MD further down the 80 mm of the web and averaged distances measured. In this case, 12 distances were measured.
    [61] The second polymer layer was then extruded onto the printed first polymer layer or thermally bonded to the polymer layer. After completing the extrusion bonding process, the laminate was cooled.
    [62] The edge distance of the precision mark was measured on the outermost wrap or outer wrap of the roll. This procedure can be carried out at a distance of 80 meters further away from the web to the MD, at least 100.8 meters away from the web at the inner wrap of the roll (ie, on the outermost wrap or outer wrap) as measured at least 100 meters away from the web to the MD. Distance), and at 80 mm further distance of the web to the MD (at a distance of 100.16 m or more down the MD as compared to that measured on the outermost lap or outer lap), and then averaged the measured distances The average distance between the marks on the laminate of the furnace was calculated.
    [63] Before applying the second polymerized layer, subtract the average distance between the marks on the first polymerized layer to the CD from the mark-to-mark average distance on the laminate to the CD, and then before applying the second polymerized layer to the average distance of the first polymerized layer to the CD. Dividing yielded laminate shrinkage to CD in%.
    [64] Laminate shrinkage deviation to CD is defined as the maximum value of laminate shrinkage (%) minus the minimum value of laminate shrinkage (%). If the measurement is high, the lamination shrinkage deviation corresponds to six times the standard deviation σ.
    [65] Laminate shrinkage to MD and laminate shrinkage to MD are similarly defined.
    [66] b) the specific method used in the following examples
    [67] In the examples described below, the following specific measurement procedure was used. The roll of the first polymer had a width of 1.60 m and a length of about 10,000 m. In this case, seven precision marks each having a size of 38 mm with CD and a size of 9 mm with MD were printed on the film. The center point of the precision marks is 240 mm away from each other.
    [68] The distance between each pair of adjacent precision mark edges was measured and recorded on the outermost wrap or outer wrap of the first polymeric layer roll. This measurement method was repeated at MD 80 mm further away from the web and averaged. All 12 distances were measured on the outermost wrap or outer wrap of the first polymeric layer. This measurement was repeated on the inner wrap of the roll of first laminate.
    [69] After applying the second polymer layer, the resulting laminate was slit into six rolls each 240 mm wide. Roughly cut through the center of each precision mark.
    [70] After observing each of the six slit laminate rolls, the distance between the edges of the precision marks on each roll was measured on the outermost wrap or outer wrap of this roll. This was repeated at 80 mm further distance of the web to the MD on each of the six rolls. Thus, twelve numbers were generated again and averaged.
    [71] This measurement was repeated at about 2,000 m further down the web with the MD of each of the six roll laminates and 80 mm further down the web with the MD.
    [72] The measured distance values were used to calculate the shrinkage to CD and shrinkage to CD deviations.
    [73] Laminate shrinkage in the machine direction (%)
    [74] a) general method
    [75] Lamination shrinkage to MD and laminate shrinkage deviation to MD are defined similarly to the corresponding extent to CD.
    [76] b) the specific method used in the examples described below
    [77] In the case of shrinkage to MD, the same procedure as for CD was used, except that the measurements were made at a point located 1.6m down the web from the beginning of the roll to the MD.
    [78] Tensile Strength and Elongation at Break
    [79] Specimens of each of the first polymeric layer and laminate having a width of 25.4 mm and a length of about 20 cm were evaluated using a tension tester (Zwick). The jaws were placed 100 mm apart. A cross head speed of 250 mm / min was used.
    [80] Bond Strength of Laminate
    [81] The laminate was separated by removing the loop-containing extruded second polymer layer from the first polymer layer. A qualitative assessment of the level of binding was made. Each laminate was scored as pass or fail if it could not be separated by hand or if it could be separated.
    [82] Coefficient of friction
    [83] The coefficient of motion friction in accordance with DIN 53375 was measured. 200 g weight was used. Three measurements were made each, with a new first layer sample or new laminate sample used for each test. The substrate or surface used in the test was a surface with a loop, which was commercially available as Extrusion Bonded Loop # EBL-1510 under 3M Deutsche GmbH, Neuss, Germany.
    [84] Toughness
    [85] The first polymeric layer or laminate strip, 25 mm wide and about 90 mm long, was cut so that the long side extended to the CD of each web. Two marks were placed 75 mm apart on the strip. The opposite ends of the strip were glued together so that the strip formed a loop so that the two marts overlap. The strip end was clamped in the bottom jaw of a conventional tensile tester. The upper jaw was then lowered to 210 mm / min. The loop was compressed into the upper jaw until the distance between the jaws was 12 mm. The force required to compress the loop to this point is reported as cN. The measurement was repeated three times to average the results.
    [86] Example 1
    [87] A coaxial biaxially oriented polypropylene (S-BOPP) first polymer layer was prepared using a LISIM® Tap 1241 tenter stretching device sold by Brueckner Maschinenbau GmbH, Ziegdorf, Germany. The polypropylene resin used was Fina 3376 with a density of 0.905 and a melt flow index of 2.5 (230 ° C. and 2.16 kg).
    [88] The first polymer layer was first stretched to have a peak CD stretch ratio of 7.3 and a peak MD stretch ratio of 6.0. Elongation was performed at 149 ° C.
    [89] Thereafter, in a controlled manner in which the first polymer layer was maintained at 165 ° C., the first polymer layer was then shrunk to a final CD elongation ratio of 6.7, a final MD elongation ratio of 5.4, and the final thickness of the film was 15 microns. The process parameters for the preparation of the coaxial biaxially oriented polypropylene (S-BOPP) first polymeric layer are summarized in Table 1.
    [90] The test treatment mentioned above was performed about the simultaneous biaxially oriented polypropylene (S-BOPP) 1st polymerization layer. The results of this test are summarized in Table 2 below.
    [91] The first polymer layer was then corona treated to have a surface tension of 48 dynes on one side and the logo design and precision marks were printed on the corona treated surface within 4 weeks to convert to a final laminate.
    [92] Longitudinally oriented fiber (50 mm length, 10 dtex diameter, polypropylene fiber, marketed by fiber vision a / s, Denmark, Bald, Hy-Comfort Phil), second polymeric layer (polypropylene / polyethylene blend, 45 Micron thickness) and an extrusion bonded laminate comprising a layer composed of the above-described simultaneous biaxially oriented polypropylene first polymer layer in the manner described in Example 3 of WO'401 using the apparatus according to FIG. 6 of WO'401. As prepared. The fibers were passed along a corrugated roll to provide a fibrous layer having a bow structure between anchor sites, where the fibrous layer was bonded to a second polymeric layer extruded onto the first polymeric layer. A schematic of the resulting extruded bond loop laminate is shown in FIG. 3. The first polymer layer was introduced into the extrusion bond laminate so that the printed surface was facing outward. The image was also visible on the opposite side through the roof layer.
    [93] Laminate shrinkage was observed using the test described above. Laminates were also evaluated qualitatively to determine the degree of bonding between the three layers. The properties of the extrusion bonded loop laminates are summarized in Table 3.
    [94] Example 2
    [95] Example 1 was repeated except that the process parameters for the preparation of the coaxially oriented polypropylene first polymer layer were varied. The film was stretched at 151 ° C. with a peak CD stretch ratio of 7.2 and a peak MD stretch ratio of 6.0. Next, the first polymer layer was shrunk to a final CD elongation ratio 6.5 and a final elongation ratio 5.4 to maintain a temperature of 165 ° C. The final thickness of the film was 15 microns. The process parameters used are summarized in Table 1.
    [96] The properties of the coaxial biaxially oriented polypropylene first polymer layer are summarized in Table 2. Test results for the laminates are reported in Table 3.
    [97] Comparative Example 1
    [98] The extrusion bonding process described in Example 1 was repeated except that the first polymer layer used was a foamed polyethylene film sold as EPF 023 from Bischof and Klein GmbH & Co. (Konzell, Germany). The properties of the first polymeric layer are summarized in Table 2 and the properties of the corresponding laminates are also described in Table 3.
    [99] Comparative Example 2
    [100] The extrusion bonding process described in Example 1 was repeated with the exception of using sequentially biaxially oriented polypropylene films using a sequential stretching device LEX commercially available from Brueckner Maschinenbau GmbH. The polypropylene resin used was Fina 3374. The final MD stretch ratio was 5.4 and the final CD stretch ratio was 9.0. The final thickness of the film was 19 microns.
    [101] Comparative Example 3
    [102] The extrusion bonding process of Example 1 was repeated except that the polyester (polyethylene terephthalate or PET) film was marketed under HOSTAPHAN® RHS12 and manufactured from Mitsubishi Polyester Film GmbH (Wisbaden, Germany) It was used as a polymerization layer.
    [103] Comparative Example 4
    [104] The extrusion bonding process described in Example 1 was repeated except that LXCPP-242.6-75, commercially available from Huntsman, Chippewa Falls, WI, was used as the molded polypropylene film. The film had a thickness of 30 microns.
    [105] Process Parameters for Preparation of S-BOPP First Polymerized LayerExample 1Example 2 Initial MD Elongation Ratio6.06.0 Final MD Elongation Ratio5.45.4 Relaxation MD, Final / Initial (%)90%90% Initial CD Elongation Ratio7.37.2 Final CD Elongation Ratio6.76.5 Relaxation CD; Final / Initial (%)92%90% Extension temperature [℃]149151 Tempering temperature [℃]165165
    [106] Properties of the First Polymerized Layer ExampleFirst polymeric layer typeFirst polymer layer thickness (micron)Average shrinkage CD,%Average shrinkage MD,%Friction Coefficient (MD, CD)Tensile Strength (MD), N / 25mmElongation at Break (MD)%Toughness, cN OneS-BOPP15-1.02.30.56, 0.9159.5133.70.3 2S-BOPP150.53.3-65.8140.20.3 C1Effervescent PE25MM0.41,0.3716.43300.3 C2BOPP191.32.1-75.21500.8 C3Polyester121.00.80.48,0.4862.51330.3 C4Molding PP301.20.80.56,0.5714.64500.3
    [107] M = melt under test conditions
    [108] Characteristics of Laminate ExampleFirst polymeric layer typeAverage laminate shrinkage, MD,%Laminate shrinkage, CD,%Bonding the First Polymerized Layer and the Second Polymerized Layer AverageDeviation OneS-BOPP<0.10.50.2Pass 2S-BOPP0.30.70.4Pass C1Effervescent PE1.322.4Pass C2BOPP-One1.0Pass C3Polyester---Pass C4Molded PP-One0.5Pass
    权利要求:
    Claims (21)
    [1" claim-type="Currently amended] A laminate comprising a first polymer layer comprising at least one polyolefin and coaxially elongated and a second polymer layer extruded on or thermally bonded to the first polymer layer, the laminate being in the machine direction Wherein the laminate shrinkage deviation in the transverse direction is less than about 0.6% for a length of at least 100 m.
    [2" claim-type="Currently amended] 2. The method of claim 1 wherein the first polymeric layer is simultaneously biaxially stretched with a peak first direction stretching parameter and a peak second direction stretching parameter separate from the peak first direction stretching parameter, in part with a final first direction stretching parameter. And relaxed with a final second direction stretching parameter separate from this final first direction stretching parameter.
    [3" claim-type="Currently amended] The laminate of claim 1, wherein the laminate shrinkage in the transverse direction for a length of at least 100 m in the machine direction is less than about −1.0% to + 1.0%.
    [4" claim-type="Currently amended] The laminate of claim 1 wherein the polymer of the first polymeric layer comprises at least 50% by weight of one or more polyolefins.
    [5" claim-type="Currently amended] The laminate of claim 1, wherein the polymer of the first polymeric layer comprises at least one copolymer and / or polypropylene comprising at least about 80% by weight of propylene monomer units.
    [6" claim-type="Currently amended] The laminate of claim 1 wherein the polymer of the second polymeric layer comprises at least one polyolefin.
    [7" claim-type="Currently amended] The laminate of claim 1, wherein the second polymeric layer is extruded to a thickness of 10-200 μm on the first polymeric layer.
    [8" claim-type="Currently amended] The laminate of claim 1, wherein the second polymeric layer is extruded at a temperature of 150-350 ° C. on the first polymeric layer.
    [9" claim-type="Currently amended] The laminate of claim 1 wherein the first direction and the second direction are located perpendicular to each other.
    [10" claim-type="Currently amended] 10. The laminate of claim 9, wherein the first and second directions are transverse (CD) and machine (MD) directions, respectively.
    [11" claim-type="Currently amended] The laminate of claim 1, wherein the final first direction stretching parameter is 4: 1 to 15: 1 and the final second direction stretching parameter is 4: 1 to 15: 1 apart from the final first direction stretching parameter. .
    [12" claim-type="Currently amended] The method of claim 1, wherein the first polymeric layer is stretched with a peak first direction stretching parameter that is at least 1.1 times the final first direction stretching parameter and / or is independent of the peak first final stretching parameter. And a stretch with a peak second direction stretching parameter that is at least 1.1 fold.
    [13" claim-type="Currently amended] The laminate according to claim 1, wherein the exposed surface of the second polymer layer is a microstructure.
    [14" claim-type="Currently amended] The laminate of claim 13, wherein the microstructured surface is a male member of a mechanical containment system.
    [15" claim-type="Currently amended] The laminate of claim 1 further comprising a third layer comprising members of a mechanical containment system attached to an exposed surface of the second polymeric layer.
    [16" claim-type="Currently amended] The laminate of claim 15 wherein the member comprises a loop of hook and loop system.
    [17" claim-type="Currently amended] The laminate of claim 1 wherein one major surface of the first polymeric layer is printed.
    [18" claim-type="Currently amended] The laminate of claim 1 wherein each of the exposed surfaces of the first or second polymeric layer has a pressure sensitive adhesive layer.
    [19" claim-type="Currently amended] The laminate of claim 1 wound up in a stable roll form.
    [20" claim-type="Currently amended] (a) providing a first polymer layer containing polyolefin,
    (b) applying a sufficiently high temperature to the film to provide a significant amount of biaxial stretching,
    (c) coaxial biaxial tenter stretching of the first polymeric layer with a peak first direction stretching parameter and a peak second direction stretching parameter separate from the peak first direction stretching parameter,
    (d) partially relaxing the first polymeric layer by shrinking the first polymeric layer to a final first directional stretching parameter and / or shrinking the first polymeric layer to a final second directional stretching parameter separate from the final first directional stretching parameter ,
    (e) tempering the first polymeric layer in this partially relaxed state to a temperature of 80-200 ° C.,
    (f) extruding the second polymer layer onto the first polymer layer at a temperature of 150-350 ° C.
    [21" claim-type="Currently amended] A personal incontinence product comprising the laminate according to claim 13.
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    同族专利:
    公开号 | 公开日
    CN1436125A|2003-08-13|
    PL359131A1|2004-08-23|
    EP1294563A1|2003-03-26|
    WO2001096113A1|2001-12-20|
    MXPA02011984A|2003-05-27|
    AR028702A1|2003-05-21|
    TW572828B|2004-01-21|
    RU2286882C2|2006-11-10|
    ES2239672T3|2005-10-01|
    JP2004503405A|2004-02-05|
    DE60109775T2|2006-02-02|
    DE60109775D1|2005-05-04|
    AU6175001A|2001-12-24|
    KR100826545B1|2008-05-02|
    AT292017T|2005-04-15|
    BR0111595A|2003-04-15|
    EP1164007A1|2001-12-19|
    EP1294563B1|2005-03-30|
    CN1217789C|2005-09-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-06-14|Priority to EP20000112621
    2000-06-14|Priority to EP00112621.8
    2001-05-17|Application filed by 쓰리엠 이노베이티브 프로퍼티즈 캄파니
    2001-05-17|Priority to PCT/US2001/016109
    2003-02-05|Publication of KR20030010703A
    2008-05-02|Application granted
    2008-05-02|Publication of KR100826545B1
    优先权:
    申请号 | 申请日 | 专利标题
    EP20000112621|EP1164007A1|2000-06-14|2000-06-14|Laminate and its use|
    EP00112621.8|2000-06-14|
    PCT/US2001/016109|WO2001096113A1|2000-06-14|2001-05-17|Laminate and its use|
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