microporous material

专利摘要:
microporous material microporous materials are described which include organic thermoplastic polyolefinic polymers (eg, ultra-high molecular weight polyolefin), particulate charge (eg, precipitated silica), and an interconnected pore network. the microporous materials of the present invention have controlled volatile material transfer properties. microporous materials can have a density of at least 0.8 g / cm3; and a rate of transfer of volatile material, from the contact surface of volatile material to the vapor release surface of the microporous material, from 0.04 to 0.6 mg / (hour * cm2). furthermore, when the volatile material is transferred from the volatile material contact surface to the vapor release surface, the vapor release surface is substantially free of volatile material in liquid form.
公开号:BR112012026337B1
申请号:R112012026337
申请日:2011-03-08
公开日:2020-01-21
发明作者:L Knox Carol；Gardner Christine；L Boyer James；M Parrinello Luciano；Swisher Robert
申请人:Ppg Ind Ohio Inc；
IPC主号:

专利说明:

“MICROPOROUS MATERIAL
Field of the invention [0001] The present invention relates to microporous materials that include thermoplastic organic polymer, particulate filler, and an interconnected pore network. The microporous materials of the present invention have controlled volatile material transfer properties. Background of the invention [0002] The release of volatile materials, such as fragrances (such as, for example, air flavorings) can be achieved by means of a release apparatus that includes a reservoir containing volatile material. The delivery apparatus typically includes a vapor permeable membrane that covers or closes the reservoir. The volatile material inside the reservoir passes through the vapor permeable membrane and is released into the atmosphere (eg air) on the outside of the membrane facing the atmosphere. Vapor-permeable membranes are typically made from organic polymers and are porous.
[0003] The speed at which volatile material passes through the vapor-permeable membrane is generally an important factor. For example, if the speed at which the volatile material passes through the vapor-permeable membrane is too slow, the properties associated with the volatile material, such as fragrance, will typically be undesirably low or imperceptible. If, for example, the speed at which the volatile material passes through the vapor permeable membrane is too high, the reservoir of volatile material can be emptied very quickly, and the properties associated with the volatile material, such as fragrance, can be
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2/63 undesirably high or, in some cases, excessively strong.
[0004] It is generally desirable to minimize or prevent the formation of volatile liquid material in the atmosphere or external part of the permeable membrane, from which the volatile material is released into the atmosphere (eg into the air). Volatile liquid material that forms on the outside of the vapor-permeable membrane can be collected (eg, accumulated) inside and leak from the release device, resulting, for example, in stains on clothing or furniture that come into contact with it. In addition, the formation of volatile liquid material on the outside of the vapor permeable membrane can result in irregular release of volatile material from the release device.
[0005] When exposed to an increase in the temperature of the environment, the speed at which the volatile material passes through the vapor permeable membrane can increase until it reaches an undesirably high level. For example, a release device used inside the passenger compartment of an automobile can be exposed to increases in ambient temperature. Therefore, it is typically desirable to minimize the increase in the speed at which the material passes through the vapor-permeable membrane, as a function of increasing the temperature of the environment.
[0006] It would be desirable to develop new microporous materials that have controlled transfer properties of volatile material. It would also be desirable for these newly developed microporous materials to minimize the formation of volatile liquid material on the outside or surface thereof. In addition, speed in
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3/63 which volatile material passes through such newly developed microporous materials undergoes a minimal elevation when the ambient temperature rises.
summary of invention [0007] According with the present invention one is provided material microporous comprising: The. an matrix in polymer organic thermoplastic
substantially insoluble in water comprising polyolefin;
B. finely divided particulate charge and substantially insoluble in water, said particulate charge being distributed throughout the matrix and constituting 40 to 90 weight percent, based on the total weight of said microporous material; and
ç. a network of interconnected pores that communicate substantially across all microporous material;
said microporous material having a density of at least 0.8 g / cm ³ ;
a contact surface of volatile material, a surface of vapor release, said contact surface of volatile material and said vapor release surface are substantially opposed to each other, and a transfer speed of volatile material, of said surface of contact of volatile material for said vapor release surface, from 0.04 to 0.6 mg / (hour * cm ² ), and
being that when the material volatile is transferred from said surface in contact in material volatile for said surface in release in steam (at a speed in transfer of material volatile 0 , 04 to 0.6 mg / (hour * cm ² )), said surface in steam release stay
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4/63 substantially free of volatile material in liquid form. [0008] In addition, the present invention provides a microporous material comprising:
The. a substantially water-insoluble thermoplastic organic polymer matrix comprising polyolefin;
B. finely divided particulate charge and substantially insoluble in water, said particulate charge being distributed throughout said matrix and constituting 40 to 90 weight percent, based on the total weight of said microporous material; and
ç. a network of interconnected pores that communicates substantially through all said microporous material;
said microporous material having a density of less than 0.8 g / cm ³ ;
a contact surface of volatile material, a vapor release surface, said contact surface of volatile material and said vapor release surface are substantially opposed to each other, with (i) at least a portion of said surface of vapor contact of volatile material has a first coating on it, and / or (ii) at least a portion of said vapor release surface has a second coating on it, a transfer rate of volatile material, of said
surface in contact in volatile material for said surface in release of steam from 0.04 to 0.6 mg / (hour * cm ² ), andbeing that when the material volatile is transferred from said surface in contact in volatile material for said surface in release in steam (at a speed transfer volatile material from 0.04 to 0.6 mg / (hour * cm ² )), said surface in release of steam gets
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5/63 substantially free of volatile material in liquid form. [0009] Likewise, the present invention provides a microporous material comprising:
The. a substantially water-insoluble thermoplastic organic polymer matrix comprising polyolefin;
B. finely divided particulate charge and substantially insoluble in water, said particulate charge being distributed throughout said matrix and constituting 40 to 90 weight percent, based on the total weight of said microporous material; and
ç. a network of interconnected pores that communicates substantially through all said microporous material;
said microporous material having a contact surface of volatile material, a vapor release surface, said contact surface of volatile material and said vapor release surface being substantially opposed to each other, with (i) at least a portion of said contact surface of volatile material has a first coating on it, and / or (ii) at least a portion of said vapor release surface has a second coating on it, said first coating and said second coating each, independently selected from a coating composition comprising polyvinyl alcohol, and
a speed transfer of volatile material, said surface in contact of material volatile for said surface in release of steam of hair any less 0.04 mg / (hour * cm ² ), and being that said material microporous (that is, the material microporous coated with polyvinyl alcohol) is exposed to a
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6/63 temperature increase from 25 ° C to 60 ° C, said transfer speed of volatile material at a percentage equal to or less than 150 percent.
Detailed description of the invention [0010] As used in this report and in the claims, the contact surface of volatile material is that surface of the microporous material that confronts and is typically in contact with the volatile material that is, for example, contained in a test reservoir, as described in more detail below.
[0011] As used in this report and the claims, the vapor release surface is that surface of the microporous material that does not confront and / or is not in direct contact with the volatile material, and from which the volatile material is released to the outside atmosphere in gaseous or vapor form.
[0012] As used in this report and in the claims, the term (meth) acrylate and similar terms, such as esters of (meth) acrylic acid mean acrylates and / or methacrylates.
[0013] As used in this report and in the claims, the transfer rate of volatile material from microporous materials was determined according to the following description. A test reservoir was manufactured with a transparent thermoplastic polymer, with an internal volume sufficient to contain 2 milliliters of volatile material such as benzyl acetate. The internal dimensions of the reservoir were defined by a circular diameter at the edge of the open face of approximately 4 centimeters and a depth of no more than 1 centimeter. THE
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7/63 open face was used to determine the transfer speed of volatile material. With the test reservoir in a horizontal position (with the open side facing up), about 2 milliliters of benzyl acetate were introduced into the test reservoir. With the benzyl acetate introduced into the test reservoir, a sheet of microporous material 6 to 8 mils thick was placed on the open face / side of the test reservoir, so that 12.5 cm ² of the material contact surface of the microporous sheet were exposed to the interior of the reservoir. The test vessel was weighed to obtain an initial weight for the entire loaded set. The test reservoir containing benzyl acetate and closed with the sheet of microporous material, was then placed in an upright position in a chemical laboratory hood (dimensions) approximately 5 feet (height) x 5 feet (width) x 2 feet (depth). With the test reservoir in an upright position, benzyl acetate was in direct contact with at least a portion of the volatile material contact surface of the microporous sheet. The chapel's glass doors were opened and the air flow inside was adjusted to operate eight (8) cycles of the chapel volume per hour. Unless otherwise stated, the temperature in the chapel was maintained at 25 ° C ± 5 ° C. The humidity inside the chapel was ambient. The test tanks were regularly weighed in the chapel. The calculated weight loss of benzyl acetate, in combination with the elapsed time and the surface area of the microporous sheet exposed to the inside of the test reservoir, were used to determine the transfer speed of the volatile material from the sheet.
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8/63 microporous, in units of mg / (hour * cm ² ).
[0014] As used in this report and the claims, the percentage increase in the transfer rate of volatile material of the microporous material of the present invention from 25 ° C to 60 ° C was determined for separate, though substantially equivalent, sheet samples of microporous material at 25 ° C and 60 ° C, according to the method described above. The reservoirs were placed in a large glass hood and a 50% aqueous solution of potassium chloride also contained in the hood. The bell with all its contents was placed in an oven heated to 60 ° C. The reservoirs were maintained under these conditions for a period of 7 to 10 hours. The reservoirs were then returned to the chapel under environmental conditions overnight and the process repeated for several days. Each reservoir was weighed before being placed in and after being removed from the hood. When the bell was removed, the weight of each reservoir was collected after the reservoir returned to room temperature.
[0015] As used in this report and in the claims, if the vapor release surface of the microporous material is substantially free of volatile material in liquid form this has been determined according to the description below. When the test reservoirs were weighed, as described above, the vapor release surface of the microporous sheet was visually examined with the naked eye to determine whether drops and / or liquid film were present on it. If by visual observation any evidence of drops (ie, a single drop) and / or liquid film on the
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9/63 vapor release surface, but which has not been drained (o), the microporous sheet should be considered acceptable. If the drops have run off the surface, the microporous sheet should be considered a failure. If no evidence of droplets (ie, no droplets) and / or of a liquid film on the vapor-release surface is found by visual observation, the microporous sheet should be considered substantially free of volatile material in liquid form .
[0016] Unless otherwise specified, all ranges described herein should be understood as covering any and all sub-ranges included herein. For example, a range quoted from 1 to 10 should be considered to include any and all sub-ranges between (and inclusive) the minimum value of 1 and the maximum value of 10; that is, all sub-bands that start with a minimum value of 1 or more and end with a maximum value of 10 or less, for example, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, etc.
[0017] Unless otherwise specified, all numbers or expressions, such as those expressing structural dimensions, quantities of ingredients, etc., as used in the report and in the claims, are understood to be modified in all cases by the term about.
[0018] The term volatile material, as used herein and in the claims, means a material capable of conversion to a gaseous or vapor form (ie capable of vaporization) at ambient temperature and pressure, in the absence of additional or supplementary energy supplied (eg in the form of heat and / or agitation). The volatile material may comprise an organic volatile material, which may include the materials
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10/63 volatiles comprising a solvent-based material, or those dispersed in a solvent-based material. The volatile material can be in a liquid and / or solid form, and can be naturally occurring or synthetically formed. When in solid form, the volatile material typically sublimates from a solid form to a vapor form, in the absence of an intermediate liquid form. The volatile material can be optionally combined or formulated with non-volatile materials, such as a carrier (eg, water and / or non-volatile solvents). In the case of a solid volatile material, the non-volatile carrier may be in the form of a porous material (eg, an inorganic porous material) in which the solid volatile material is kept. Likewise, the volatile material
solid can be in the form of a gel semi-solid.[0019] O material volatile can be a material in fragrance, such as an oil for occurrence perfume natural or synthetic. Examples in perfume oils From
which liquid volatile material can be selected include, but is not restricted to bergamot oil, bitter orange, lemon, mandarin orange, caraway, cedar leaf, clove leaf, cedar stick, geranium, lavender, orange, oregano, orange ( petitgrain), white cedar, patchouli, neroli, apricot rose, and their combinations. Examples of solid fragrance materials from which the volatile material can be selected include, but are not limited to, vanillin, ethyl vanillyl, coumarin, tonalid, calone, heliotropene, musk xylol, cedrol, musk ketone benzophenone, raspberry ketone, methyl naphthyl ketone beta, phenyl ethyl salicylate, veltol, maltol, maple lactone, proeugenol acetate, evemil and their combinations.
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11/63 [0020] The transfer rate of volatile material from microporous material can be equal to or less than 0.7 mg / (hour * cm ² ), or equal to or less than 0.6 mg / (hour * cm ² ) , or less than or equal to 0.55 mg / (hour * cm ² ), or less than or equal to 0.50 mg / (hour * cm ² ). The transfer rate of volatile material from the microporous material can be equal to or greater than 0.02 mg / (hour * cm ² ), or equal to or greater than 0.04 mg / (hour * cm ² ), or equal to or greater than 0.30 mg / (hour * cm ² ), or equal to or greater than 0.35 mg / (hour * cm ² ). The rate of transfer of volatile material from the microporous material can vary between any combination of these maximum and minimum values. For example, the transfer rate of volatile material from microporous material can be from 0.04 to 0.6 mg / (hour * cm ² ), or from 0.2 to 0.6 mg / (hour * cm ² ), or from 0.30 to 0.55 mg / (hour * cm ² ) or from 0.35 to 0.50 mg / (hour * cm ² ), in each case, including the mentioned values.
[0021] Without intending to be bound by any theory, when the volatile material is transferred from the contact surface of volatile material to the vapor release surface of the microporous material, it is believed that the volatile material is in a selected form of liquid, steam and a combination thereof. In addition, and without being bound by any theory, it is believed that the volatile material, at least in part, travels through the network of interconnected pores that communicate substantially throughout the microporous material.
[0022] The microporous material can have a density of at least 0.7 g / cm ³ , or at least 0.8 g / cm ³ . As used herein and in the claims, the density of the microporous material is determined by measuring the weight and volume of a sample of the microporous material. The maximum density limit
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12/63 of microporous material can vary widely, as long as it has a transfer rate of target material, for example, from 0.04 to 0.6 mg / (hour * cm ² ), and the vapor release surface is substantially free of volatile material in liquid form when the volatile material is transferred from the contact surface of volatile material to said vapor release surface. Typically, the density of the microporous material is equal to or less than 1.5 g / cm ³ , or equal to or less than 1.0 g / cm ³ . The density of the microporous material can vary between any of the above values, including the values mentioned. For example, the microporous material can have a density of 0.7 g / cm ³ to 1.5 g / cm ³ , such as 0.8 g / cm ³ to 1.2 g / cm ³ , including values cited.
[0023] When the microporous material has a density of at least 0.7 g / cm ³ , such as at least 0.8 g / cm ³ , the contact surface of volatile material and the vapor release surface of the microporous material can be free of coating material on it. When free of coating material, the contact surface of volatile material and the vapor release surface are each defined by the microporous material.
[0024] When the microporous material has a density of at least 0.7% g / cm ³ , such as at least 0.8 g / cm ³ , at least a portion of the volatile material contact surface of the microporous material can optionally having a first coating on it, and / or at least a portion of the vapor-release surface of the microporous material can optionally have a second coating on it. The first coating and the second
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13/63 coating can be the same or different. When at least a portion of the volatile material contact surface has a first coating on it, the volatile material contact surface will be defined, at least in part, by the first coating. When at least a portion of the vapor release surface has a second
coating regarding the same, the surface of release of steam it will be defined, fur less in part, for the second coating . [0025] O first coating and the second coating
they can each be formed by a coating selected from liquid coatings and solid particulate coatings (eg powder coatings). Typically, the first and second coatings are each independently formed with a coating selected from liquid coatings which may optionally include a solvent selected from water, organic solvents and combinations thereof. The first and second coatings can each be independently selected from crosslinkable coatings (eg thermosetting coatings and photocurable coatings) and non-crosslinkable coatings (eg air-dried coatings). The first and second coatings may be applied to the respective surfaces of the microporous material according to methods recognized in the prior art, such as spray application, curtain coating techniques, dip coating, and / or stretch coating (eg leveling blade or drawbar).
[0026] The first and second coat compositions may each include independently additives
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14/63 recognized in the state of the art, such as antioxidants, ultraviolet light stabilizers, flow control agents, dispersion stabilizers (ex: in the case of aqueous dispersions), and dyes (ex: dyes and / or pigments). Typically, the first and second coat compositions are free of dyes, and, as such, are substantially colorless or opaque. Optional additives can be present in the coating compositions in individual amounts, for example, from 0.01 to 10 weight percent, based on the total weight of the coating composition.
[0027] The first coating and said second coating can each be formed with an aqueous coating composition that includes dispersed organic polymeric material. The aqueous coating composition can have a particle size of 200 to 400 nm. The solids of the aqueous coating composition can vary widely, for example, from 0.1 to 30 weight percent, or from 1 to 20 weight percent, in each case based on the total weight of the aqueous coating composition. Organic polymers comprising aqueous coating compositions can have numerical average molecular weights (Mn), for example, from 1000 to 4,000,000, or from 10,000 to 2,000,000.
[0028] The aqueous coating composition can be selected from aqueous dispersions of poly (meth) acrylate, aqueous dispersions of polyurethane, aqueous dispersions in silicone oil (or silicon), and combinations thereof. Poly (meth) acrylate polymers of aqueous poly (meth) acrylate dispersions can be prepared according to methods recognized in the prior art. For example, polymers of
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15/63 poly (meth) acrylates can include residues (or monomeric units) of alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group. Examples of alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( met) propyl acrylate, (meth) 2-hydroxypropyl acrylate, (meth) isopropyl acrylate, (meth) butyl acrylate, (meth) isobutyl acrylate, (meth) butyl acrylate, (meth) acrylate 2 ethylhexyl, (meth) lauryl acrylate, (meth) isobornyl acrylate, (meth) cyclohexyl acrylate, and 3,3,5-trimethylcyclohexyl (meth) acrylate. For purposes of the non-restrictive illustration, an example of aqueous dispersion of poly (meth) acrylate from which the compositions of the first and second coatings can each be independently selected is HYCAR 26138, supplied by Lubrizol Advance Materials, Inc.
[0029] The polyurethane polymers of the aqueous polyurethane dispersions, of which the first and second coatings can, each independently, be selected include any of those known in the art. Typically, polyurethane polymers are prepared with materials with isocyanate functionality having two or more isocyanate groups, and materials with active hydrogen functionality, having two or more active hydrogen groups. Active hydrogen groups can be selected, for example, from hydroxyl groups, thiol groups, primary amines, secondary amines, and combinations thereof. For the purpose of non-restrictive illustration, an example of aqueous polyurethane dispersion of
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16/63 which first and second coating compositions can be selected, each independently selected is WITCOBOND W240, which is supplied by Chemtura Corporation.
[0030] Silicon polymers of aqueous dispersions in silicone oil can be selected from aqueous dispersions in silicone oil known and recognized in the prior art. For the purposes of non-restrictive illustration, an example of an aqueous silicon dispersion from which the first and second coating compositions can each be independently selected is MOMENTIVE LE-410, supplied by Momentive Performance Materials.
[0031] The first coating and the second coating, each independently, can be applied in any appropriate thickness, as long as the microporous material has a target volatile material transfer rate, for example, from 0.04 to 0.6 mg / (hour * cm ² ) and the vapor release surface is substantially free of volatile material in liquid form when the volatile material is transferred from the volatile material contact surface to said vapor release surface. Likewise, the first coating and the second coating can each independently have a coating weight (that is, the weight of the coating that covers the
material microporous) from 0.01 to 5.5 g / m ² , such as from 0.1 to 5.0 g / m ² , or from 0.5 to 3 g / m ² , or 0.7 5 a 2.5 g / m ² , or from 1 to 2 g / m ² .[0032] O material microporous can have one density
less than 0.8 g / cm ³ , and at least a portion of the volatile material contact surface of the microporous material may have a first coating on it, and / or at least
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17/63 a portion of the vapor release surface of the microporous material may have a second coating on it. The first coating and the second coating may be the same or different, and are each independently as previously described herein in relation to the optional first and second coatings of the microporous material with a density of at least 0.8 g / cm ³ .
[0033] When less than 0.8 g / cm ³ , the density of the microporous material of the present invention can have any suitable minimum limit, as long as the microporous material has a target volatile material transfer rate, for example, 0, 04 to 0.6 mg / (hour * cm ² ), and the vapor release surface is substantially free of volatile material in liquid form when the volatile material is transferred from the volatile material contact surface to said vapor release surface . With this specific embodiment of the present invention, the density of the microporous material can be from 0.6 to a maximum of 0.8 g / cm ³ , or from 0.6 to 0.75 g / cm ³ (ex: 0, 60 to 0.75 g / cm ³ ), or 0.6 to 0.7 g / cm ³ (ex: 0.60 to 0.70 g / cm ³ ) or 0.65 to 0.70 g / cm ³ .
[0034] In addition, at least a portion of the volatile material contact surface of the microporous material may have a first coating on it, and / or at least a portion of the vapor release surface of the microporous material may have a second coating on it, in which the first and second coatings, each independently, are selected from a coating composition comprising a polyvinyl alcohol.
[0035] With the embodiment coated with alcohol
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18/63 polyvinyl material of the present invention, when the microporous material (i.e., the microporous material coated with polyvinyl alcohol) is exposed to a temperature increase of 25 ° C to 60 ° C, its transfer rate of volatile material increases by one percentage equal to or less than 150 percent. When microporous material coated with polyvinyl alcohol is exposed to a temperature rise (eg from an ambient temperature of 25 ° C to 60 ° C) the transfer rate of volatile material typically increases, and typically does not decrease unless, for example , the microporous material has been damaged by exposure to a higher ambient temperature. Therefore, and as stated in this report and the claims, the quote that the transfer speed of volatile material increases by a percentage equal to or less than a percentage (quoted) (eg 150 percent), includes a limit minimum of 0 percent, although it does not include a lower limit of less than 0 percent.
[0036] For purposes of illustration, when the microporous material coated with polyvinyl alcohol has a volatile material transfer rate of 0.3 mg / (hour * cm ² ) at 25 ° C, when the microporous material is exposed to a temperature at 60 ° C, the transfer rate of volatile material increases to a value equal to or less than 0.75 mg / (hour * cm ² ).
[0037] In one embodiment, when the microporous material (that is, the microporous material coated with polyvinyl alcohol) is exposed to a temperature increase of 25 ° C to 60 ° C, its transfer speed of volatile material increases at a percentage equal to or less than 125 percent.
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19/63
For example, when the microporous material coated with polyvinyl alcohol has a volatile material transfer rate of 0.3 mg / (hour * cm2) at 25 ° C, when the microporous material is exposed to a temperature of 60 ° C, the transfer rate of volatile material increases to 0.68 mg / (hour * cm2) or less.
[0038] In addition, when microporous material (i.e. microporous material coated with polyvinyl alcohol) is exposed to a temperature rise of 25 ° C to 60 ° C, its transfer rate of volatile material increases by a percentage equal to or less than 100 percent. For example, when microporous material coated with polyvinyl alcohol has a volatile material transfer rate of 0.3 mg / (hour * cm ² ) at 25 ° C, when the microporous material is exposed to a temperature of 60 ° C, the transfer rate of volatile material increases to a value equal to or less than 0.6 mg / (hour * cm2).
[0039] The first and second coatings of polyvinyl alcohol can each be independently present in any appropriate coating weight, provided that the microporous material has a target volatile material transfer rate, for example, of at least 0.04 mg / (hour * cm2), and when the microporous material (i.e., microporous material coated with polyvinyl alcohol) is exposed to a temperature increase of 25 ° c to 60 ° C, its material transfer speed increases by a percentage equal to or less than 150 percent. Typically, the first polyvinyl alcohol coating and the second polyvinyl alcohol coating each independently have a coating weight of 0.01 to 5.5
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20/63 g / m ² or from 0.1 to 4.0 g / m ² , or from 0.5 to 3.0 g / m ² , or from 0.75 to 2.0 g / m ² .
[0040] The rate of transfer of volatile material from microporous material coated with polyvinyl alcohol can be at least 0.02 mg / (hour * cm ² ). The transfer rate of volatile material from microporous material coated with polyvinyl alcohol may be equal to or greater than 0.04 mg / (hour * cm ² ), or equal to or greater than 0.1 mg / (hour * cm ² ), or equal to or greater than 0.2 mg / (hour * cm ² ), equal to or greater than 0.30 mg / (hour * cm ² ), or equal to or greater than 0.35 mg / (hour * cm ² ). The transfer rate of volatile material from microporous material coated with polyvinyl alcohol can be equal to or less than 0.7 mg / (hour * cm ² ) or less than or equal to 0.6 mg / (hour * cm ² ), or equal or less than 0.55 mg / (hour * cm ² ), or less than or equal to 0.50 mg / (hour * cm ² ). The rate of transfer of volatile material from microporous material coated with polyvinyl alcohol can vary between any combination of these maximum and minimum values, including the mentioned values. For example, the transfer rate of volatile material from microporous material coated with polyvinyl alcohol can be at least 0.02 mg / (hour * cm ² ), such as from 0.04 to 0.70 mg / (hour * cm ² ), or from 0.04 to 0.60 mg / (hour * cm ² ), or from 0.20 to 0.60 mg / (hour * cm ² ), or from 0.30 to 0.55 mg / (hour * cm ² ), or 0.35 to 0.50 mg / (hour * cm ² ), in each case, including the quoted values.
[0041] The density of the microporous material of the microporous material coated with polyvinyl alcohol of the present invention can vary widely, as long as the microporous material coated with alcohol
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21/63 polyvinyl has a transfer rate of target volatile material, for example, at least 0.04 mg / (hour * cm ² ), and when the microporous material (ie the microporous material coated with polyvinyl alcohol) is exposed to a temperature rise of 25 ° C to 60 ° C, its transfer rate of volatile material increases by a percentage equal to or less than 150 percent.
[0042] In addition, the density of the microporous material of the microporous material coated with polyvinyl alcohol, can be at least 0.7 g / cm ³ , as well as at least 0.8 g / cm ³ (ex: 0, 8 to 1.2 g / cm ³ ), including the mentioned values. In one embodiment of the present invention, the density of the microporous material coated with polyvinyl alcohol (i.e., the density of the microporous material before applying the polyvinyl alcohol coating) is less than 0.8 g / cm ³ . For example, the density of microporous material, microporous material coated with polyvinyl alcohol can be 0.6 to a maximum of 0.8 g / cm ³ , or 0.6 to 0.75 g / cm ³ (eg 0.60 to 0.75 g / cm ³ ), or 0.6 to 0.7 g / cm ³ (ex: 0.60 to 0.70 g / cm ³ ), or 0.65 to 0.70 g / cm ³ , including the values quoted.
[0043] With the microporous material coated with polyvinyl alcohol of the present invention, when the volatile material is transferred from the contact surface of volatile material to the vapor release surface, the vapor release surface is substantially free of volatile shaped material liquid.
[0044] The polyvinyl alcohol coating can be selected from liquid coatings that can optionally include a solvent selected from water, organic solvents
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22/63 and their combinations. The polyvinyl alcohol coating can be selected from crosslinkable coatings (eg, thermosetting coatings), and non-crosslinkable coatings (eg, air-dried coatings). The polyvinyl alcohol coating can be applied to the respective surfaces of the microporous material according to methods recognized in the prior art, such as spray application, curtain coating, or stretch coating (eg by means of a leveling blade or drawing bar) ).
[0045] In one embodiment, the first and second coatings of polyvinyl alcohol are each independently formed from aqueous polyvinyl alcohol coating compositions. The solids of the aqueous polyvinyl alcohol coating composition can vary widely, for example, from 0.1 to 15 weight percent, or from 0.5 to 9 weight percent, in each case based on the total weight of the composition aqueous coating. The polyvinyl alcohol polymer of the polyvinyl alcohol coating compositions can have numerical average molecular weights (Mn), for example, from 100 to 1,000,000 or from 1000 to 750,000.
[0046] The polyvinyl alcohol polymer of the polyvinyl alcohol coating composition can be a homopolymer or copolymer. The comonomers from which the polyvinyl alcohol copolymer can be prepared include those which are copolymerizable (by means of radical polymerization) with vinyl acetate, and known in the art. For the purposes of the illustration, comonomers from which the polyvinyl alcohol copolymer can be prepared include, but are not limited to: (meth) acrylic acid, maleic acid,
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Fumaric acid, crotonic acid, metal salts thereof, alkyl esters thereof (eg C2-C10 alkyl esters thereof), polyethylene glycol esters thereof, and polypropylene glycol esters thereof; vinyl chloride; tetrafluoroethylene; 2-acrylamido-2-methyl-propane sulfonic acid and its salts; acrylamide; N-alkyl acrylamide; acrylamides substituted with N, N-dialkyl; and N-vinyl formamide.
[0047] For the purpose of non-restrictive illustration, an example of a polyvinyl alcohol coating composition that can be used to form the microporous material coated with polyvinyl alcohol of the present invention, is CELVOL 325, supplied by Sekisui Specialty Chemicals.
[0048] The compositions of the first and the second coating of polyvinyl alcohol can each independently include additives recognized in the prior art, such as antioxidants, ultraviolet light stabilizers, flow control agents, dispersion stabilizers (eg no aqueous dispersions), and dyes (eg dyes and / or pigments). Typically, the first and second coat compositions are free of dyes, and, as such, are substantially colorless or opaque. Optional additives can be present in the polyvinyl alcohol coating compositions in individual amounts, for example, from 0.01 to 10 weight percent, based on the total weight of the coating composition.
[0049] The matrix of the microporous material is composed of thermoplastic organic polymer substantially insoluble in water. The numbers and types of such polymers suitable for use as a matrix are large. In general, you can use
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24/63 any thermoplastic organic polymer substantially insoluble in water that can be extruded, calendered, pressed or wrapped in film, sheet, strip or blanket. The polymer can be a simple polymer or it can be a mixture of polymers. The polymers can be homopolymers, copolymers, random copolymers, block copolymers, graft copolymers, atactic polymers, isotactic polymers, syndiotactic polymers, linear polymers, or branched polymers. When polymer mixtures are used, the mixture can be homogeneous or can comprise two or more polymeric phases.
[0050] Examples of suitable classes of substantially water-insoluble thermoplastic organic polymers include thermoplastic polyolefins, poly (halo-substituted olefins), polyesters, polyamides, polyurethanes, polyureas, poly (vinyl halides), poly (vinylidene halides), polystyrenes , poly (vinyl esters), polycarbonates, polyethers, polysulfides, polyimides, polysilanes, polysiloxanes, polycaprolactones, polyacrylates, and polymethacrylates. Hybrid classes from which water-insoluble thermoplastic organic polymers can be selected include, for example, thermoplastic poly (urethanoureas), poly (ester-amides), poly (silanosiloxanes), and poly (ether-ester). Other examples of substantially thermoplastic water-insoluble organic polymers include high density thermoplastic polyethylene, low density polyethylene, ultra-high molecular weight polyethylene, polypropylene (atactic, isotactic or syndiotactic), poly (vinyl chloride), polytetrafluoroethylene, copolymers of ethylene and acid
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25/63 acrylic, copolymers of ethylene and methacrylic acid, poly (vinylidene chloride), copolymers of vinylidene chloride and vinyl acetate, copolymers of vinylidene chloride and vinyl chloride, copolymers of ethylene and propylene, copolymers of ethylene and butene, poly (vinyl acetate), polystyrene, poly (omega-aminoundecanoic acid) poly (hexamethylene adipamide), poly (epsilon-caprolactam) and poly (methyl methacrylate). The citation of these classes and example of thermoplastic organic polymers substantially insoluble in water is not exhaustive and is provided for purposes of illustration.
[0051] Thermoplastic organic polymers substantially insoluble in water include, in particular, for example, poly (vinyl chloride), vinyl chloride copolymers, or mixtures thereof. In one embodiment, the water-insoluble thermoplastic organic polymer includes an ultra-high molecular weight polyolefin selected from: ultra-high molecular weight polyolefin (eg, essentially linear ultra-high molecular weight polyolefin), having an intrinsic hair viscosity minus 10 deciliters / gram; or ultra-high molecular weight polypropylene (eg, essentially linear ultra-high molecular weight polypropylene) having an intrinsic viscosity of at least 6 deciliters / gram; or a mixture of them. In a specific embodiment, the water-insoluble thermoplastic organic polymer includes ultra-high molecular weight polyethylene (eg, ultra-high linear molecular weight polyethylene) with an intrinsic viscosity of at least 18 deciliters / gram.
[0052] Ultra-high molecular weight polyethylene (UHMWPE) is not a thermoset polymer with infinite molecular weight, it is
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26/63 technically classified as thermoplastic. However, due to the fact that the molecules have substantially very long chains, the UHMWPE softens when heated, although it does not flow like a molten liquid in a normal thermoplastic form. It is believed that the very long chains and the peculiar properties they provide for UHMWPE contribute to a large extent with the desirable properties of microporous materials prepared with this polymer.
[0053] As previously indicated, the intrinsic viscosity of UHMWPE is about at least 10 deciliters / gram. Generally, the intrinsic viscosity is about at least 14 deciliters / gram. Often, the intrinsic viscosity is about at least 18 deciliters / gram. In many cases, the intrinsic viscosity is about at least 19 deciliters / gram. Although there is no specific restriction on the upper limit of intrinsic viscosity, it is often in the range of about 10 to about 39 deciliters / gram. The intrinsic viscosity is often in the range of about 14 to about 39 deciliters / gram. In most cases, the intrinsic viscosity is in the range of about 18 to about 39 deciliters / gram. An intrinsic viscosity in the range of about 18 to about 32 deciliters / gram is preferred.
[0054] The nominal molecular weight of UHMWPE is empirically related to the intrinsic viscosity of the polymer according to the equation:
M (UHMWPE) = 5.3 x 10 ⁴ [η] ^1.37 where M (UHMWPE) is the nominal molecular weight and [η] is the intrinsic viscosity of UHMW polyethylene expressed in deciliters / gram.
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27/63 [0055] As used in this report and the claims, the intrinsic viscosity is determined by extrapolating to zero concentration the reduced viscosities or the inherent viscosities of several diluted solutions of the UHMWPE, in which the solvent is freshly distilled decahydronaphthalene and which 0.2 percent by weight of 3,5-di-ter-butyl-4-hydroxyhydrocinamic acid neopentanotetrail ester [CAS Registry No. 6683-19-8] was added. The intrinsic viscosities or inherent viscosities of the UHMWPE are determined from relative viscosities obtained at 135 degrees Celsius, using the Ubbelohde No. 1 viscometer according to the general procedures of ASTM D 4020-81, except that several diluted solutions of different concentration are employed. ASTM D 4010-81 is incorporated herein in its entirety by reference.
[0056] In one embodiment, the matrix comprises a mixture of substantially linear ultra-high molecular weight polyethylene having an intrinsic viscosity of at least 10 deciliters / gram, and lower molecular weight polyethylene with a melting index according to ASTM D 1238 Condition E less than 50 grams / 10 minutes and a melting index according to ASTM D 1238-86 Condition F of at least 0.1 gram / 10 minutes. The nominal molecular weight of the lower molecular weight polyethylene (LMWPE) is less than that of UHMW polyethylene. LMWPE is thermoplastic and many different types are known. One classification method is through density, expressed in grams / cubic centimeter and rounded to the nearest thousandth, according to ASTM D 1248-84 (re-approved 1989), as summarized below:
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28/63
Type Abbreviation Density (g / cm ³ ) Low density polyethylene LDPE 0.910-0.925 Medium density polyethylene MDPE 0.926-0.940 High density polyethylene HDPE 0.941-0.965
[0057] Any or all of these polyethylenes can be used as the LMWPE in the present invention. For some applications, HDPE can be used as it generally tends to be more linear than MDPE or LDPE. ASTM 1248-84 (re-approved 1989) is, in its entirety, incorporated by reference.
[0058] The processes for preparing the various LMWPEs are well known and well documented. They include the high pressure process, the Phillipis Petroleum Company process, the Standard Oil Company process (Indiana) and the Ziegler process.
[0059] The melting index according to ASTM D 1238-86 Condition E (ie 190 ° C and 2.16 kg of load) of the LMWPE is less than about 50 grams / 10 minutes. Often, the melting index of Condition E is less than about 25 grams / 10 minutes. Preferably, the melt index of condition E is less than about 15 grams / 10 minutes.
[0060] The melting index according to ASTM D 1238-86 Condition E (ie 190 ° C and 2.16 kg of load) of the LMWPE is at least 0.1 gram / 10 minutes. In many cases, the melting index of Condition F is less than about 0.5 grams / 10 minutes. Preferably, the melt index of condition F is about at least 1.0 gram / 10 minutes.
[0061] ASTM D 1238-86 is, in its entirety, incorporated herein by reference.
[0062] Sufficient UHMWPE and LMWPE must be present in the
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29/63 matrix to transmit its properties to the microporous material. Another thermoplastic organic polymer can also be present in the matrix, as long as its presence does not adversely affect the properties of the microporous material in an adverse way. The other thermoplastic polymer can be another thermoplastic polymer or it can be more than one other thermoplastic polymer. The amount of the other thermoplastic polymer that may be present depends on the nature of that polymer. Examples of thermoplastic organic polymers that may optionally be present include poly (tetrafluoroethylene), polypropylene, copolymers of ethylene and propylene, copolymers of ethylene and acrylic acid, and copolymers of ethylene and methacrylic acid. If desired, all or a portion of the carboxyl groups of carboxyl-containing copolymers can be neutralized with sodium, zinc or the like.
[0063] In most cases, UHMWPE and LMWPE together make up at least 65 percent by weight of the matrix polymer. Often, UHMWPE and LMWPE together make up at least 85 percent by weight of the matrix polymer. Preferably, the other thermoplastic organic polymer is substantially absent, so that UHMWPE and LMWPE together constitute substantially 100 weight percent of the matrix polymer. [0064] UHMWPE can make up at least one weight percent of the matrix polymer, and UHMWPE and LMWPE together make up substantially 100 weight percent of the matrix polymer.
[0065] When UHMWPE and LMWPE together constitute 100 percent by weight of the material matrix polymer
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30/63 microporous, the UHMWPE can constitute a percentage equal to or greater than 40 weight percent of the matrix polymer, such as equal to or greater than 45 weight percent, or equal to or greater than 48 weight percent, or equal or greater than 50 weight percent, or equal to or greater than 55 weight percent of the matrix polymer. Likewise, UHMWPE can constitute a percentage equal to or less than 99 percent by weight of the matrix polymer, such as equal to or less than 80 percent by weight, or equal to or less than 70 percent by weight, or equal to or less than 65 weight percent, or equal to or less than 60 weight percent of the matrix polymer. The level of UHMWPE comprising the matrix polymer can vary between any of these values, including the quoted values.
[0066] Similarly, when UHMWPE and LMWPE together constitute 100 percent by weight of the matrix polymer of the microporous material, the LMWPE may constitute a percentage equal to or greater than 1 percent by weight of the matrix polymer, such as equal to or greater than 5 percent by weight, equal to or greater than 10 percent by weight, or equal to or greater than 15 percent by weight, or equal to or greater than 20 percent by weight, or equal to or greater than 25 percent by weight, or equal to or greater than 30 percent by weight, or equal to or greater than 35 percent by weight, or equal to or greater than 40 percent by weight, or equal to or greater than 45 percent by weight, or equal to or greater than 50 weight percent, or equal to or greater than 55 weight percent of the matrix polymer. Likewise, the LMWPE may constitute a percentage equal to or less than 70 percent by weight of the matrix polymer, such as equal to or less than 65 percent by weight, or equal to or less than 60 percent by weight, or equal to or less than 55 percent
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31/63 by weight or less than or equal to 50 percent by weight or less than or equal to 45 percent by weight of the matrix polymer. The LMWPE level can vary between any of these values, including the values quoted.
[0067] It should be noted that for any of the microporous materials previously described in the present invention, the LMWPE can comprise high density polyethylene.
[0068] The microporous material also includes a finely divided particulate charge material and is substantially insoluble in water. The particulate charge material may include an organic particulate material and / or an inorganic particulate material. The particulate charge material is typically not colored, for example, the particulate charge material is a white or off-white particulate charge material, such as a silica or clay particulate material.
[0069] The finely divided and substantially water-insoluble filler particles may comprise 20 to 90 weight percent of the microporous material. For example, such filler particles can comprise 20 to 90 percent by weight of the microporous material, such as 30 percent to 90 percent by weight of the microporous material, or 40 to 90 percent by weight of the microporous material, or from 40 to 85 percent by weight of the microporous material, or from 50 to 90 percent by weight of the microporous material and from 60 percent to 90 percent by weight of the microporous material.
[0070] The finely divided particulate charge and substantially insoluble in water may be in the form of final particles, aggregates of final particles, or a combination of both. At least about 90 weight percent
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32/63 of the charge used in the preparation of the microporous material has crude particle sizes in the range of 0.5 to about 200 micrometers, such as 1 to 100 micrometers, as determined by the use of a laser-sized diffraction instrument. particle, Beckman Coulter's LS230, capable of measuring particle diameters as small as 0.04 micrometers. Typically, at least 90 weight percent of the particulate charge has crude particle sizes in the range of 10 to 30 micrometers. The sizes of load pellets can be reduced during the processing of ingredients
used in preparation of material microporous. Consequently, the distribution of sizes particle gross in the material microporous can be less than that itself gross cargo.[0071] Examples non-restrictive of materials particulates
Suitable organic and inorganic materials that can be used in the microporous material of the present invention include those described in U.S. Patent No. 6,387,519 B1 column 9, line 4 to column 13, line 62, the portions of which are incorporated herein by reference.
[0072] In a specific embodiment of the present invention, the particulate charge material comprises siliceous materials. Non-restrictive examples of silicon fillers that can be used to prepare the microporous material include silica, mica, montmorillonite, kaolinite, nano-clay, such as cloisite from Southern Clay Products, talc, diatomaceous earth, vermiculite, natural and synthetic zeolites, calcium silicate, aluminum silicate, aluminum sodium silicate, aluminum polysilicate, silica alumina gels and glass particles. In addition to loads
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33/63 silicas, other finely divided particulate fillers and substantially insoluble in water can also optionally be employed. Non-restrictive examples of such optional particulate charges include carbon black, charcoal, graphite, titanium oxide, iron oxide, copper oxide, zinc oxide, antimony oxide, zirconia, magnesia, alumina, molybdenum disulfide, sulfide zinc, barium sulfate, strontium sulfate, calcium carbonate, and magnesium carbonate. In a non-restrictive embodiment, the silicon filler can include silica and any of the aforementioned clays. Non-restrictive examples of silica include precipitated silica, silica gel, fumed silica, and combinations thereof.
[0073] Silica gel is generally produced commercially by acidifying an aqueous solution of soluble metal silicate, for example, sodium silicate at a low pH with acid. The acid used is generally a strong mineral acid such as sulfuric acid or hydrochloric acid, although carbon dioxide can be used. Since there is essentially no difference in density between the gel phase and the surrounding liquid phase, although the viscosity is low, the gel phase does not deposit, that is, it does not precipitate. Consequently, silica gel can be described as a non-precipitated, cohesive, rigid three-dimensional lattice of continuous particles of amorphous colloidal silica. The subdivision status varies from large, solid masses to submicroscopic particles, and the degree of hydration from almost amorphous silica to soft gelatinous masses containing the order of 100 parts of water per part of silica by weight.
[0074] Precipitated silica is generally produced
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34/63 commercially combining an aqueous solution of a soluble metal silicate, usually alkaline metal silicate, such as sodium silicate, and an acid so that colloidal silica particles grow in a weakly alkaline solution and are coagulated by alkali metal ions of the resulting soluble alkali metal salt. Various acids can be used, including but not restricted to mineral acids. Non-restrictive examples of acids that can be used include hydrochloric acid and sulfuric acid, although carbon dioxide can also be used to produce precipitated silica. In the absence of a coagulant, silica is not precipitated from the solution at any pH. In a non-restrictive embodiment, the coagulant used to effect silica precipitation can be the soluble alkali metal salt produced during the formation of colloidal silica particles, or it can be an added electrolyte, such as soluble inorganic or organic salt, or it can be a combination of both.
[0075] Precipitated silicas are available in many grades and forms, and are supplied by PPG Industries, Inc. These silicas are sold under the brand name Hi-Sil®.
[0076] For the purposes of the present invention, the finely divided and substantially water-insoluble particulate silicon load may comprise at least 50 percent by weight (e.g. at least 65, at least 75 percent by weight) or at least 90 percent by weight of the loading material substantially insoluble in water. The silicon filler can comprise 50 to 90 weight percent (eg 60 to 80 percent by weight) of the particulate filler material, or the silicon filler can comprise substantially all of the filler material
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35/63 particulate substantially insoluble in water.
[0077] The particulate filler (eg, the silicon filler) typically has high oil absorption allowing the filler to transport much of the plasticizer processing composition used in the production of the microporous material of the present invention. The filler particles are substantially insoluble in water and can also be substantially insoluble in any organic processing liquid used in preparing the microporous material. This can facilitate the retention of the particulate charge within the microporous material.
[0078] The microporous material of the present invention may also include small amounts (eg, less than or equal to 5 percent by weight, based on the total weight of the microporous material) of other material used in processing, such as lubricant, processing plasticizer , organic extraction liquid, water and the like. Other materials introduced for specific purposes such as thermal, ultraviolet and dimensional stability, can optionally be present in the microporous material in small amounts (eg, equal to or less than 15 percent by weight, based on the total weight of the microporous material). Examples of such other materials include, but are not restricted to antioxidants, ultraviolet light absorbers, reinforcement fibers, such as cut glass fiber filament and the like. The balance of the microporous material, excluding filler and any coating, printing ink, or impregnant applied for one or more special purposes, is essentially the thermoplastic organic polymer.
[0079] The microporous material of the present invention also
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36/63 includes a network of interconnected pores that communicate substantially across all microporous material. In a coating, printing ink and impregnant free base, pores typically constitute 35 to 95 percent by volume, based on the total volume of microporous material, when prepared through the processes, as described below. The pores can constitute 60 to 75 percent by volume of the microporous material, based on the total volume of the microporous material. As used here and in the claims, the porosity (also known as empty volume) of the microporous material, expressed as a percentage by volume, is determined according to the following equation:
Porosity = 100 [1-d ₁ / d ₂ ] where d ₁ is the density of the sample, which is determined from the weight of the sample and the volume of the sample based on the measurements of the sample dimensions; and d2 is the density of the solid portion of the sample, which is determined from the weight of the sample and the volume of the solid portion of the sample. The volume of the solid portion of the microporous material is determined using a Quantachrome stereopicnometer (Quantachrome Corp.) according to the operating manual that comes with the instrument.
[0080] The average pore volumetric diameter of the microporous material is determined by means of mercury porosimetry using an Autoscan mercury porosimeter (Quantachrome Corp.) according to the operations manual accompanying the instrument. The average pore volumetric radius for a simple scan is automatically determined by the porosimeter. When operating the porosimeter, a scan is performed in the high pressure range (from 139 kilopascals
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37/63 absolute to 227 absolute megapascals). If 2 percent or less of the total volume introduced occurs at the minimum point (138 to 250 absolute kilopascals) of the high pressure range, the average pore volumetric diameter is considered to be twice the average pore volumetric radius determined by the porosimeter. On the other hand, an additional sweep is performed in the minimum (low) pressure range (from 7 to 165 absolute kilopascals) and the average volumetric pore diameter is calculated according to the equation:
d = 2 [v ₁ r ₁ / w ₁ + v ₂ r ₂ / w ₂ ] / [v ₁ / w ₁ + v ₂ / w ₂ ] where d is the average pore volumetric diameter; v1 is the total volume of mercury introduced in the high pressure range; ri is the average pore volumetric radius determined from the high pressure scan; r2 is the average pore volumetric radius determined from low pressure scanning; wi is the weight of the sample subjected to scanning under high pressure; and w2 is the weight of the sample subjected to scanning under high pressure.
[0081] Generally, on a coating, printing ink and impregnant free base, the average pore volumetric diameter of the microporous material is at least 0.02 micrometer, typically at least 0.04 micrometer, and more typically at least 0.05 micrometers. On the same basis, the average pore volumetric diameter of the microporous material is also typically equal to or less than 0.5 micrometer, more typically equal to or less than 0.3 micrometer, and still typically equal to or less than 0.25 micrometer. The average volumetric diameter of the pores, on the same basis, can vary between any of these values, including the values mentioned. For example, the average volumetric diameter
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38/63 of the pores of the microporous material can vary from 0.02 to 0.5 micrometer, or from 0.04 to 0.3 micrometer, or from 0.05 to 0.25 micrometer, in each case, including the values quoted .
[0082] When determining the average pore volumetric diameter using the procedure described above, the maximum pore radius detected can also be determined. Such determination is made from the sweep in the low pressure range, if this is done; on the other hand, it is determined from the sweep in the high pressure range. The maximum pore diameter of the microporous material is typically twice the maximum pore radius.
[0083] The coating, printing and impregnation processes can result in the filling of at least some pores of the microporous material. In addition, such processes can also irreversibly compress the microporous material. Consequently, parameters related to porosity, average volumetric diameter of the porous, and maximum pore diameter are determined for the microporous material before the application of one or more of these processes.
[0084] Numerous processes recognized in the state of the art can be used to produce the microporous materials of the present invention. For example, the microporous material of the present invention can be prepared by mixing the filler particles, the thermoplastic organic polymer powder, processing plasticizer and minimal amounts of lubricant and antioxidant, until a substantially uniform mixture is obtained. The weight ratio of particulate charge to polymer powder used in the formation of the mixture is essentially the same as that of the microporous material at
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39/63 be produced. The mixture, together with additional processing plasticizer, is typically introduced into the heated barrel of a screw extruder. At the end of the extruder is a sheet forming matrix. A web formed by the die is directed without stretching to a pair of heated calender cylinders acting cooperatively to form a web of less thickness than the web that ejects from the die. The level of the processing plasticizer present in the web at this point in the process can vary widely. For example, the level of processing plasticizer present in the web, prior to extraction, as described below, can be equal to or greater than 30 percent by weight of the web, such as equal to or greater than 40 percent by weight, or equal to or greater than 45 weight percent of the web before extraction. Likewise, the amount of processing plasticizer present in the web before extraction can be equal to or less than 70 percent by weight of the web, such as equal to or less than 65 percent by weight, or equal to or less than 60 weight percent, or less than or equal to 55 weight percent of the web before extraction. The level of processing plasticizer present in the web at this point in the process, prior to extraction, can vary between any of the quoted values, including the quoted values.
[0085] The continuous sheet of the calender is then passed to a first extraction zone where the processing plasticizer is substantially removed by extraction with an organic liquid that is a good solvent for the processing plasticizer, a poor (weak) solvent
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40/63 for the organic polymer and one more volatile than the processing plasticizer. Generally, although not necessarily, both the processing plasticizer and the organic extraction liquid are substantially immiscible with water. The web then passes to a second extraction zone where the residual organic extraction liquid is substantially removed by steam and / or water. The web is then passed through a forced air dryer to remove substantial residual water and the remaining residual organic extraction liquid. From the dryer the continuous sheet, which is microporous material, is passed to a recovery cylinder.
[0086] The processing plasticizer is a liquid at room temperature and generally a processing oil such as paraffinic oil, naphthenic oil, or aromatic oil. Suitable processing oils include those that meet the requirements of ASTM D 2226-82, Types 103 and 104. More typically, processing oils with a pour point below 220 ° C, in accordance with ASTM D 97-66 (approved in 1978), are used to produce the microporous material of the present invention. Processing plasticizers useful in preparing the microporous material of the present invention are discussed in more detail in U.S. Patent No. 5,326,391, column 10, lines 26 to 50, the description of which is incorporated herein by reference.
[0087] In one embodiment of the present invention, the processing plasticizer composition used in the preparation of the microporous material has a small solvating effect on the polyolefin at 60 ° C, and a solvation effect only moderate at elevated temperatures of the order
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41/63 of 100 ° C. The processing plasticizer composition is generally a liquid at room temperature. Non-restrictive examples of processing oils that can be used can include SHELLFLEX® 412 oil, SHELLFLEX®371 oil (Shell Oil Co.) which are solvent-refined and hydrotreated oils derived from crude naphthenic oils, ARCOprime® 400 oil (Atlantic Richfield Co .) and KAYDOL® oil (Witco Corp.), which are white mineral oils. Other non-restrictive examples of processing plasticizers can include phthalate ester plasticizers, such as dibutyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, and ditridecyl phthalate. Mixtures of any of the processing plasticizers mentioned above can be used in preparing the microporous material of the present invention.
[0088] There are many organic extraction liquids that can be used in the preparation of microporous material from
gift invention. Examples of other liquids in extraction organic appropriate include the described at patent American No. 5,326,391, column 10, lines 51 The 57, whose
description is hereby incorporated by reference.
[0089] The extraction fluid composition may comprise halogenated hydrocarbons, such as chlorinated hydrocarbons and / or fluorinated hydrocarbons. In particular, the extraction fluid composition can include halogenated hydrocarbon (s) and have a solubility parameter coulomb (occlb) term ranging from 4 to 9 (Jcm ³ ) ^1/2 . Non-restrictive examples of halogenated hydrocarbon (s) suitable as an extraction fluid composition for use in the production of the microporous material of the present invention can
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42/63 include one or more azeotropes of halogenated hydrocarbons selected from trans-1,2-dichlorethylene, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, and / or 1,1, 1,3,3 pentafluorobutane. These materials are available on the market under the trade names of VERTREL MCA (a binary azeotrope of 1,1,1,2,2,3,4,5,5,5-dihydrodecafluoropentane and trans-1,2-dichlorethylene: 62% / 38%) and VERTREL CCA (a ternary azeotrope of 1,1,1,2,2,3,4,5,5,5 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane, and trans-1,2 -dichlorethylene: 33% / 28% / 39%) both from MicroCare Corporation.
[0090] The residual processing plasticizer content of microporous material according to the present invention is generally less than 10 weight percent, based on the total weight of the microporous material, and that amount can be further reduced through additional extractions using the same or a different organic extraction liquid. Often, the residual processing plasticizer content is less than 5 weight percent, based on the total weight of the microporous material, and that amount can be further reduced by additional extractions.
[0091] The microporous material of the present invention can also be produced in accordance with the general principles and procedures of US Patent Nos. 2,772,322; 3,696,061; and / or 3,862,030. These principles and procedures are particularly applicable when the matrix polymer is either predominantly poly (vinyl chloride), or a copolymer containing a large proportion of polymerized vinyl chloride.
[0092] Microporous materials produced through
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43/63 processes described above can optionally be stretched. The stretching of the microporous material typically results in both an increase in the void volume of the material and the formation of regions of increased or improved molecular orientation. As is known in the art, many physical properties of molecularly oriented thermoplastic organic polymer, including tensile strength, tensile modulus, Young's modulus and others, differ (for example, considerably) from those of the corresponding thermoplastic organic polymer with little or no molecular orientation. The drawing is typically carried out after substantial removal of the processing plasticizer, as described above.
[0093] Various types of stretching apparatus and processes are well known in the art and can be used to stretch the microporous material of the present invention. The stretching of microporous materials is described in more detail in U.S. Patent No. 5,326,391, in column 11, line 45 to column 13, line 13, the description of which is incorporated herein by reference.
[0094] The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations will be evident to those skilled in the art. Unless otherwise specified, all parts and percentages are by weight. EXAMPLES [0095] In Part 1 of the examples below, the materials and methods used in preparing the Example and Comparative mixtures prepared in the pilot plant and presented in Table 1 and the Example mixtures prepared are described
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44/63 according to the industrial scale process and the comparative commercial samples presented in Table 2. In Part 2, the methods used to extrude, calender and extract the sheets prepared with the mixtures of Part 1 are described. In Part 3, they are described the methods used to determine the physical properties reported in Tables 3 and 4. In Parts 4A and 4B, the coating formulations used are listed in Tables 5 and 7 and the properties of coated sheets are listed in Tables 6 and 8. In Part 5 , the results of the Benzyl Acetate Test for the products in Tables 1, 2, 6 and 8, are shown in Tables 9, 10, 11 and 12.
PART 1 - MIXING PREPARATION [0096] The dry ingredients are weighed in a FM-130D Littleford plow blade mixer with a high intensity cutter-style mixing blade in the order and quantities (grams (g)) specified in Table 1. The ingredients dried were pre-mixed for 15 seconds using only plow type blades. The process oil was then pumped through the hand pump through a spray nozzle on the top of the mixer, with only the plow type blades operating. The pumping time for the examples varied between 45-60 seconds. The high intensity cutter blade was switched on, together with the plow type blades and mixing was performed for 30 seconds. The mixer was turned off and its internal sides scraped to ensure that all ingredients were uniformly mixed. The mixer was restarted with the high intensity cutting blades and the plow type blades connected, and the mixing was carried out for another 30 seconds. The mixer was turned off and
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45/63 the mixture discharged into a storage container.
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Table 1
Samples Ex.1 Ex.2 Ex. 3 Ex.4 Ex. 5 Ex. 6 Ex. 7 Ex.8 Ex. 9 CE1 CE2 CE3 CE4 CE5 HiSil silica135 (a) 1393 1393 1393 1393 0 0 1814 1814 1814 1393 1393 2270 2270 2270 SilicaInhibisil (b) 0.0 0.0 0.0 0.0 1816 1816 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaCOa © 544.3 544.3 544.3 544.3 709.0 709.0 0.0 0.0 0.0 544.3 544.3 0.0 0.0 0.0 ^TiO 2 (d) 90.7 90.7 90.7 97.0 118.0 118.0 87.3 87.3 87.3 90.7 90.7 91.0 91.0 91.0 UHMWPE (e) 515.3 515.3 515.3 515.3 581.0 671.0 592.0 592.0 515.3 515.3 515.3 560.0 285.0 654.0 HDPE (f) 475.4 475.4 475.4 475.4 710.0 619.0 129.0 0.0 0.0 475.4 475.4 560.0 654.0 654.0 LDPE (g) 0.0 0.0 0.0 0.0 0.0 0.0 664.5 793.5 793.5 0.0 0.0 0.0 0.0 0.0 Antioxidant(H) 14.5 14.5 14.5 14.5 18.9 18.9 20.1 20.1 20.1 14.5 14.5 7.7 7.7 7.7 Lubricant(i) 14.5 14.5 14.5 14.5 18.9 18.9 21.6 21.6 21.6 14.5 14.5 22. 22.7 22.7 Polypropylene(j) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 185.0 370.0 0.0 CFA (k) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 194.7 Nanoargila MB(l) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 194.7 Mixing oil (m) 2841 2841 2841 2841 931 885 2836 2836 2836 2841 2841 3655 3851 3850 Process oil (%) 47.8% 48.0% 49.8% 52.6% 47.8% 47.2% 53.3% 56.0% 52.4% 55.9% 57.4% 60.5% 59.6% 57.7%
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The. HI-Sil®135 precipitated silica from PPG Industries, Inc.
B. INHIBSIL75 precipitated silica from PPG Industries, Inc.
ç. Camel White calcium carbonate
d. Titanium dioxide TIPURE® R-103 from E.I. du Pont de Nemours and Company
and. Ultra-high molecular weight polyethylene (UHMWPE) from Ticona Corp.
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f. Total Petrochemicals FINA® 1288 High Density Polyethylene (HDPE)
g. LDPE Petrothene®NA206000 from Lyondell Basel
H. CYANOX®1790 Antioxidant from Cytec Industries, Inc.
i. Technical grade calcium stearate lubricant
j. The PRO-FAX®7523 Polypropylene Copolymer from Ashland Distribution was used
k. PE MB foam, a foaming chemical agent from Amacet Corporation
l. Standard lot of Nanocor HDPE NanoMax® nano clay
m. Tufflo®6056 process oil from PPC Lubricants
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48/63 [0097] Examples 10-18 on an industrial scale were prepared using production scale equipment similar to the equipment and procedures described above. The samples were prepared with a mixture of ingredients listed in Table 2 as the percentage by weight of the total mixture.
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Table
Ingredients
HiSil ®
135 (a)
CaCO3 ©
TiO2 (d)
UHMWPE (e)
Ex.10
23.66
9.24
1.54
8.75
HDPE (f)
Antioxidant (h)
0.25
Ex.11
23.66
9.24
1.54
8.75
8.07
0.25
Ex. 12
23.66
Ex. 13
23.66
Ex.14
24.77
Ex.15
Ex.16
Ex.17
24.77
24.77
24.77
Lubricant (i) Mixing oil (m)
0.25
0.25
48.24
48.24
9.24
1.54
8.75
8.07
9.24
1.54
8.75
8.07
0.25
0.25
48.24
48.24
9.68
1.61
9.16
8.45
0.26
0.26
9.68
1.61
9.16
8.45
0.26
0.26
9.68
1.61
9.16
8.45
0.26
0.26
9.68
1.61
8.45
9.16
0.26
0.26
45.81 45.81 45.81 45.81
Ex.18
24.77
9.68
1.61
8.45
9.16
0.26
0.26
45.81
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PART 2 - EXTRUSION, CALENDERING AND EXTRACTION [0098] The mixtures of Examples 1-9 and Comparative Examples 1-5 were extruded and calendered in the form of a final sheet using an extrusion system that includes a feed, extrusion and calendering system, described below. A weight loss gravimetric feeding system (K-Tron model # K2MLT35D5) was used to feed each of the respective mixtures in a 27 mm twin screw extruder (the model number was the Leistritz Micro-27gg). The extruder barrel comprised eight temperature zones and a heated adapter for the sheet forming die. The extrusion mix feed port was located just before the first feed zone. A vent was installed in the third temperature zone. A vacuum breather was installed in the seventh temperature zone.
[0099] The mixture was fed into the extruder at a speed of 90g / minute. Additional processing oil was injected into the first atmospheric zone, as needed, to obtain the desired total oil content in the extruded sheet. The oil contained in the extruded (extruded) sheet discharged from the extruder is here referred to as the weight percentage of extruded oil.
[0100] The extrudate from the barrel was discharged in a 15 cm wide Masterflex® sheet forming matrix provided with a 1.5 mm discharge opening. The extrusion melting temperature was 203-210 ° C and the productivity of 7.5 kilograms per hour.
[0101] The calendering process was carried out using a set of three-cylinder vertical calender with an opening tip and a cooling cylinder. Each cylinder had a chrome surface. The cylinder dimensions were
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51/63 approximately 41 cm long and 14 cm in diameter. The temperature of the upper (top) cylinder was maintained between 135 ° C and 140 ° C. The temperature of the intermediate cylinder was maintained between 140 ° C and 145 ° C. The bottom cylinder was a cooling cylinder in which the temperature was maintained between 10-21 ° C. The extrudate was calendered as a sheet and passed over the water-cooled lower cylinder and rolled up.
[0102] A cut sheet sample up to 25.4 cm wide and 305 cm long was rolled up and placed in a container and exposed hot liquid 1,1,2-trichlorethylene for approximately 7-8 hours to extract oil from the sample. leaf. Then, the extracted leaf was air dried and subjected to the test methods described below.
[0103] Mixtures of Samples 10-18 were extruded and calendered in the form of a final sheet using an extrusion system and oil extraction process that was a scaled version for production of the system described above, conducted as described in U.S. Patent 5,196. 262, column 7, line 52, to column 8, line 47. The final sheets were tested for physical parameters using the test methods described above in Part 3. Comparative Examples 6-10 were commercial microporous products identified below: CE6 era TESLIN® Digital; CE7 was TESLIN® SP 10 mil; CE8 was TESLIN®SP 14 mil; and CE9 was TESLIN® SP 12 mil.
PART 3 - TEST AND RESULTS [0104] The physical properties measured in the extracted and dried films and the results obtained are listed in Tables 3 and 4. The weight percentage of extruded oil was measured using a Soxhlet extractor. The determination of the weight percentage of extruded oil used a sheet specimen
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52/63 extruded without prior extraction. A sample specimen of approximately 2.25 x 5 inches (5.72 cm x 12.7 cm) was weighed and recorded to ten decimal places. Each specimen was then rolled into a cylinder and placed in a Soxhlet extraction apparatus and extracted for approximately 30 minutes using trichlorethylene (TCE) as a solvent. The specimens were then removed and dried. The extracted and dried specimens were then weighed. The percentage values by weight of oil (extruded) was calculated as follows:% oil weight = (starting weight - extracted weight) x 100 / starting weight.
[0105] The thickness was determined using an Ono Sokki EG-225 thickness gauge. Two specimens of 4.5 x 5 inches (11.43 cm x 12.7 cm) were cut from each sample and the thickness for each specimen was measured in nine locations (at least 3/4 inch (1 , 91 cm) from any edge). The arithmetic mean of the readings was recorded in mils to 2 decimal places and converted to microns.
[0106] The density of the examples described above was determined by dividing the average anhydrous weight of two specimens measuring 4.5 x 5 inches (11.43 cm x 12.7 cm) that were cut from each sample by the volume average of those specimens. The average volume was determined by boiling the two specimens in deionized water for 10 minutes, removing and placing the two specimens in deionized water at room temperature, weighing each specimen suspended in deionized water. after equilibration to room temperature and weighing each specimen again in the air after the surface water has been stained. The average volume of the specimens was calculated as follows:
[0107] Volume (average) = [(weight of specimens slightly
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53/63 airborne stains - sum of immersed weights) x 1.002] / 2 [0108] The anhydrous weight was determined by weighing each of the two species on an analytical balance and multiplying that weight by 0.98 since the specimens were presumed to have 2 percent moisture.
[0109] The porosity reported in Tables 3 and 4 was determined using a Gurley densometer, model 4340, manufactured by GPI Gurley Precision Instruments of Troy, New York. Reported porosity was a measure of the rate of air flow through a sample or its resistance to air flow through the sample. The unit of measurement is a second Gurley and represents the time in seconds for 100cc of air to pass through an area of 1 square inch using a pressure differential of 4.88 inches of water. Lower values equate to less resistance to airflow (more air can pass freely). The measurements were completed using the procedure listed in the manual, Model 4340 Automatic Densometer and Smoothness Tester, Instruction Manual. The TAPPI T460 om-06-Paper air resistance method can also be considered as the basic measurement principles.
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Table 3
Property Ex. 1 Ex.2 Ex. 3 Ex.4 Ex. 5 Ex. 6 Ex.7 Ex.8 Ex. 9 CE1 CE2 CE3 CE4 CE5 Sheet thickness (pm) 262 264 264 262 371 419 173 155 173 260 246 174 160 169 % weight of extruded oil 47.8% 48.0% 49.8% 52.6% 47.8% 47.2% 53.5% 56.0% 52.4% 55.9% 57.4% 60.5% 59.6% 57.7% Density (g / cc) 0.764 0.828 0.755 0.707 0.892 0.901 0.646 0.612 0.701 0.750 0.695 0.584 0.659 0.620 Porosity (sec. Gurley) 2148 2161 2009 1988 1685 1730 3787 3735 4155 1842 1517 1473 1309 1410
Table 4
Property Ex.10 Ex.11 Ex. 12 Ex. 13 Ex.14 Ex. 15 Ex.16 Ex.17 Ex.18 CE6 CE7 CE8 CE9 CE10 Sheet thickness (pm) 291 293 269 286 289 288 278 277 284 284 157 250 359 306 % weight of extruded oil 58.0% 57.6% 58.0% 57.1% 55.0% 53.5% 54.0% 54.0% 53.0% - - - - - Density (g / cc) 0.795 0.804 0.809 0.815 0.818 0.882 0.835 0.835 0.862 0.719 0.607 0.677 0.691 0.672 Porosity (sec. Gurley) 2877 3017 3395 3208 2800 2872 3048 2849 3102 5983 1867 3659 4110 4452
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PART 4 - COAT FORMULATIONS AND COATED PRODUCTS [0110] The coatings 1-5 listed in Table 5 were prepared by dispersing CELVOL® 325 polyvinyl alcohol in cold water under slight agitation in a 600 ml beaker. The slight agitation was provided by a 1 (2.54 cm) paddle agitator driven by an electric agitation motor. The mixture was heated to 190 ° F (87.8 ° C) and stirred for 20-30 minutes. The resulting solution was allowed to cool to room temperature during stirring. Specific quantities of mixture and resulting measured solids are shown in Table 5.
Table 5 - Coating Formulations
Coating# CELVOL® 325, (grams) Deionized water, (grams) Measured solids,% by weight 1 7.5 292.5 2.5 ± 0.3 2 11.3 288.7 3.8 ± 0.3 3 13.5 286.5 4.5 ± 0.3 4 18.0 282.0 6.0 ± 0.3 5 15.0 285.0 5.0 ± 0.3
[0111] The coatings, free of visible undissolved particles, were applied to TESLIN® HD microporous substrate sold by PPG Industries, Pittsburgh, Pa. The coatings were applied to 8.5 x 11 (21.59 cm x substrate sheets) 27.94 cm) 11 mils thick, each being weighed on a scale before being placed on a transparent glass surface and using tape to glue the top corners of the sheet to the glass. A piece of transparent 11 mils thick polyester 11 x 3 (27.94 cm x 7.62 cm) was positioned across the top edge of the sheet, covering 1/2 (1.27 cm) from the top edge of the sheet down . The polyester was fixed to the glass surface with adhesive tape. A measuring rod wrapped in wire from Diversified Enterprises was placed 1-2 inches above the sheet, parallel to the top edge, close
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56/63 to the upper edge of the polyester. A 10-20 ml amount of coating was deposited in the form of a bead strip (approximately 1/4 (0.64 cm) wide) directly next to or in contact with the measuring rod using a disposable pipette. The bar was stretched completely through the sheet at a continuous / constant speed. The resulting wet sheet was removed from the glass surface, placed immediately on the weighed scale, weighed, the weight of the wet coating recorded, then the coated sheet was placed in a forced air oven and dried at 95 ° C for 2 minutes. The dried sheet was removed from the oven and the same coating procedure repeated on the same coated sheet surface. The two wet coating weights were used to calculate the final dry coating weight in grams per square meter. The coated sheets of Examples 19-23 are described in Table 6.
Table 6- Final Coated Sheets
Ex.# No. CoatingO%Solids Rod wrapped in No. wire Weight 1 ^the coated. moist, grams Weight 2 ^the coated. moist, grams Coated weighttotal wet, grams Coated weightFinal calc. gsm 19 1 3 0.6 0.65 1 0.5 ± 0.1 20 2 3 0.61 0.59 1.20 0.75 ± 0.1 21 3 3 0.70 0.64 1.34 1.0 ± 0.2 22 4 3 0.76 0.64 1.40 1.5 ± 0.1 23 5 10 1.18 1.20 2.38 2.1 ± 0.2
[0112] The following formula was used to calculate the final dry coating weight.
[0113] Final dry coating weight calculated in grams per square meter = ((coating solids x 0.01) x (wet first coating weight + wet second coating weight)) / (8.5 x 10.5) x 1550
PART 4B - COATING FORMULATIONS AND COATED PRODUCTS [0114] The procedure in Part 4A was followed by preparing the
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57/63 coating formulations of Coatings 6-12, with the exception of Coat 7 which was mixed for 2 days before use. The coating formulations are listed in Table 7.
[0115] The substrate used in this part 4B was the microporous substrate TESLIN® SP1000 sold by PPG Industries, Pittsburgh, Pa. The same procedure used in Part 4A was followed, except that some sheets were coated on both sides, drying the first coated side before applying the second on the opposite side, using a number 9 measuring rod for all coatings. Information on the final coated sheets is included in Table 8.
Table 7 - Coating formulations with related quantities in grams
Ingredients 6 7 8 9 10 11 12 Witcobond W240 _(n) 8 8 8 8 16 0 0 Aerosil® 200 _(o) 2.5 0 0 0 0 0 0 CaCO3 (c) 0 2.5 0 0 0 0 0 HiSil® T700 (p) 0 0 2.5 0 0 0 0 Lo-Vel® 6200 (q) 0 0 0 2.5 0 0 0 MOMENTIVE LE-410 _(r) 0 0 0 0 0 0.54 0 HYCAR 26138 (s) 0 0 0 0 0 0 10 Deionized water 39.5 39.5 39.5 39.5 34.0 49.5 40 Total, grams 50 50 50 50 50 50 50 Solids,% 10 10 10 10 10 0.4 10
(n) WITCOBOND W-240, an aqueous dispersion of polyurethane from
Chemtura Corporation.
(o) Aerosil® 200 fumed silica from Degussa (p) HiSil®T200 precipitated silica from PPG Industries, Inc.
(q) Lo-Vel®6200 precipitated silica from PPG Industries, Inc.
(r) MOMENTIVE LE-410 is an aqueous silicon dispersion from Momentive
Performance Materials.
(s) HYCAR 26138, an aqueous dispersion of poly (meth) acrylate from
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Lubrizol Advanced Materials, Inc.
Table 8 - Final Coated Sheets
Ex. # Revest.# Typecoating Wet coating weight (grams) Final coating weight (gsm) 24 10 simple 0.95 1.7 25 10 on both sides 2.0 3.5 26 11 on both sides 2.0 0.14 27 12 on both sides 2.1 3.9 CE 11 11 simple 0.9 0.07 CE 12 12 simple 1.1 1.9 CE 13 6 on both sides 2.2 3.8 CE 14 7 on both sides 2.5 4.4 EC 15 8 on both sides 2.3 3.9 CE 16 9 on both sides 2.3 4.0
PART 5 - BENZILA ACETATE TEST [0116] The support set used for the evaporation speed and performance test of a membrane consisted of a front fixer with an annular gasket, rear clamp, test reservoir cup and four screws. The test reservoir cup was manufactured with transparent thermoplastic polymer with internal dimensions defined by a circular diameter at the edge of the open side of approximately 4 centimeters and a depth of at most 1 centimeter. The open side was used to determine the transfer speed of volatile material.
[0117] Each clamp in the support assembly had a circular opening 1.5 (3.8 cm) in diameter to accommodate the test reservoir cup and provide an opening to expose the membrane under test. When placing the membrane under test, that is, a sheet of microporous material with 6 to 18 mils of thickness, the posterior clamp of the support set was positioned on top of a cork ring. The test reservoir cup was placed on the posterior clamp and loaded with approximately 2ml of benzyl acetate. A disk approximately 2 (5.1 cm) in diameter was
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59/63 cut from the membrane sheet and placed directly on and in contact with the edge of the reservoir cup so that 12.5 cm ² of the contact surface of volatile material of the microporous sheet were exposed to the inside of the reservoir.
[0118] The front clamp of the support was carefully positioned over the whole set, with the screw holes aligned so as not to interfere with the membrane disk. When using a coated microporous sheet, the coated surface was placed in the direction of the reservoir or facing the atmosphere as indicated in the table below. The screws were fixed and tightened enough to prevent leakage. The annular gasket created a seal / seal. The support was labeled to identify the membrane sample under test. 5 to 10 replicates of each test were prepared. Five replicates of a Control (uncoated sample) were included for the coated Examples. For the Examples in Table 11, there were 5 controls for each Example and the average evaporation speed for each Control was reported with the corresponding Example, as well as the percentage reduction in the example evaporation speed, compared to the corresponding Control. The coated surface of Example 19-23 in Table 11 was facing the atmosphere.
[0119] Each support set was weighed to obtain an initial weight of the entire set loaded. The set was then placed in an upright position in a chemical laboratory hood (hood) with dimensions of approximately 5 feet (height) x 5 feet (width) x 2 feet (depth). With the test vessel in an upright position, benzyl acetate was in direct contact with at least a portion of the volatile material contact surface of the microporous sheet. The glass doors of the chapel were opened and the air flow inside was adjusted to operate eight
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60/63 (8) chapel volume cycles per hour. Unless otherwise stated, the temperature in the chapel was maintained at 25 ° C ± 5 ° C. The humidity inside the chapel was ambient. The test tanks were regularly weighed in the chapel. The calculated weight loss of benzyl acetate, in combination with the elapsed time and the surface area of the microporous sheet exposed to the inside of the test reservoir, were used to determine the transfer speed of volatile material from the microporous sheet, in units of mg / (hour * cm ² ). The average evaporation speed (mg / h) of the replicas for the entire set is shown in the Tables below. These two values are related by the following formula:
Average evaporation speed (mg / h) / 12.5 cm ² = volatile Material transfer speed (mg / (hour * cm ² )) [0120] Marginal (marg.) Indicates that there were both approved and failed samples or that the test showed no flaws as described by potting and dripping benzyl acetate on the membrane surface, but that there were a few drops of benzyl acetate forming granules (beads) on the membrane surface, which was also unacceptable.
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Table 9
Samples Ex. 1 Ex.2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex.8 Ex.9 CE 1 CE 2 EC 3 CE 4 EC 5 Results5 days appr. appr. appr. appr. appr. appr. appr. appr. appr. fail. fail. fail. fail. fail. Rateevaporation 2.8 2.8 2.6 2.8 2.7 4.3 3.2 3.3 3.2 3.0 3.1 2.9 2.6 2.8
Table 10
Samples Ex.10 Ex.11 Ex.12 Ex.13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex.18 EC 6 EC 7 EC 8 EC 9 EC 10 Results 5 days marg. marg. marg. marg. appr. appr. appr. appr. appr. fail. fail. fail. fail. fail. Rateevaporation 3.4 3.3 3.2 3.2 3.7 3.9 3.7 3.8 3.7 2.9 3.0 3.0 3.3 3.1
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Table 1
Samples Ex.19 Control Ex.20 Control Ex.21 Control Ex.22 Control Ex.23 Control Results 5 days appr. appr. appr. appr. appr. appr. appr. appr. appr. fail. Evaporation rate 4.09 4.65 3.61 4.69 2.05 4.10 2.68 4.69 1.25 4.03 Percentage reduction in evaporation rate 1223504669
Table 12
Samples Control ⁽¹⁾ Ex.2 4 Ctr ⁽²⁾ Ex.2 4 Cta ⁽³⁾ Ex. 2 5 Control ⁽⁴⁾ Ex. 2 6 Ex. 2 7 CE 11 Cta ⁽³⁾ CE 12 Cta ⁽³⁾ CE 13 CE 14 EC 15 CE16 Results5 days fail. approve approve approve fail. approve approve reprove reprove reprove reprove reproveEvaporation rate 2.64 2.64 2.61 2.83 3.4 3.3 3.4 3.3 3.2 2.64 2.63 2.56 2.65
i. Control of uncoated TESLIN®HD microporous material that was included with Examples 24, 25, CE 13-16.
ii. Coated surface facing the volatile material reservoir.
iii. Coated surface facing the atmosphere.
iv. Control of uncoated TESLIN®HD microporous material that was included with Examples 26, 27, CE 11-12.
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63/63 [0121] Although the specific embodiments of the present invention have been described above for purposes of illustration, it will be apparent to those skilled in the art that numerous variations of the details of the present invention can be made without departing from the scope of the invention, as defined in the following claims.

权利要求:
Claims (10)
[1]
1. Microporous material, characterized by the fact that it comprises:
(a) a water-insoluble thermoplastic organic polymer matrix comprising polyolefin;
(b) finely divided particulate charge and insoluble in water, said particulate charge being distributed throughout the matrix and constituting 20 to 90 weight percent, based on the total weight of said microporous material; and (c) a network of interconnected pores that communicate through all said microporous material;
being that said microporous material has,
- a contact surface of volatile material,
- a vapor release surface, said volatile material contact surface and said vapor release surface are opposed to each other, and where (i) at least a portion of said volatile material contact surface has a first coating on it, and / or (ii) at least a portion of said vapor-release surface has a second coating on it, and the first and second coatings can each independently be formed from a coating composition aqueous which includes dispersed organic polymeric material.
[2]
2. Microporous material, characterized by the fact that it comprises:
(a) a water-insoluble thermoplastic organic polymer matrix comprising polyolefin;
(b) particulate charge finely divided and insoluble in water, said particulate charge being distributed throughout the aforementioned matrix and constituting 20 to 90 percent by weight, based on
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2/4 in the total weight of said microporous material; and (c) a network of interconnected pores that communicates through all said microporous material;
being mentioned microporous material has,
- a contact surface of volatile material,
- a vapor release surface, said volatile material contact surface and said vapor release surface are opposed to each other, with (i) at least a portion of said volatile material contact surface having a first coating on it, and / or (ii) at least a portion of said vapor-release surface has a second coating on it, said first coating and said second coating being each independently selected from a coating composition comprising polyvinyl alcohol.
[3]
3. Microporous material, according to claim 2, characterized by the fact that the microporous material:
- have a density of less than 0.8 g / cm ³ , preferably from 0.6 g / cm ³ to less than 0.8 g / cm ³ , more preferably from 0.6 g / cm ³ to 0.7 g / cm ³ .
[4]
Microporous material according to either of claims 1 or 2, characterized in that said volatile material transfer rate is 0.1 to 0.6
mg / (hour * cm ² ), if the claim 4 is dependent gives claim 2 or 0.30 to 0 , 55 mg / (hour * cm ² ) if The claim 4 is dependent gives claim 1, preferably from 0.35 to 0.50 mg / (hour * cm ² ). 5. Microporous material, according with the claim 1, characterized by the fact of said first coating and
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3/4 said second coating are each independently formed from an aqueous coating composition selected from the group consisting of aqueous poly (meth) acrylate dispersions, aqueous polyurethane dispersions, aqueous dispersions in silicon oil, and combinations the same.
[5]
6. Microporous material according to claim 5, characterized in that each aqueous coating composition has a particle size of 200 to 400 nm.
[6]
7. Microporous material according to either of claims 1 or 2, characterized in that (a) said polyolefin comprises ultra-high molecular weight polyethylene having an intrinsic viscosity of at least 10 deciliters / gram, preferably at least 18 deciliters / gram, more preferably in the range of 18 to 39 deciliters / gram; or (b) said polyolefin comprises a mixture of linear ultra-high molecular weight polyethylene having an intrinsic viscosity of at least 10 deciliters / gram and lower molecular weight polyethylene having a melt index according to ASTM D 1238-86 Condition It is less than 50 grams / 10 minutes and a melting index according to ASTM D 1238-86 Condition F of at least 0.1 gram / 10 minutes, where preferably said linear ultra-high molecular weight polyethylene constitutes at least one weight percent of said matrix and said linear ultra-high molecular weight polyethylene and said lower molecular weight polyethylene together constitute 100 percent by weight of the matrix polymer and preferably said lower molecular weight polyethylene comprises polyethylene high density.
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4/4
[7]
8. Microporous material according to either of claims 1 or 2, characterized in that said particulate load constitutes 20 to 90 weight percent of said microporous material, based on the total weight of said microporous material, where said load particulate material comprises siliceous particles comprising particulate silica, where preferably said particulate silica comprises particulate precipitated silica.
[8]
Microporous material according to either of claims 1 or 2, characterized in that said pores constitute 35 to 95 percent by volume of said microporous material, based on the total volume of said microporous material.
[9]
10. Microporous material according to claim 2, characterized in that said microporous material is exposed to a temperature increase from 25 ° C to 60 ° C, said rate of transfer of volatile material increasing to a percentage equal to or less than 125 percent, preferably less than or equal to 100 percent.
[10]
11. Microporous material according to claim 2, characterized in that said polyvinyl alcohol is a homopolymer.

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同族专利:

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CA2796293A1|2011-10-20|

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TW201139543A|2011-11-16|

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WO2011129928A1|2011-10-20|

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KR20130030262A|2013-03-26|

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AU2011241039A1|2012-11-08|

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EP2558520A1|2013-02-20|

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EP2558520B1|2018-08-08|

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PT2558520T|2018-10-31|

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CA2796293C|2015-06-16|

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CN102933639A|2013-02-13|

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KR20140097399A|2014-08-06|

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HK1181799A1|2013-11-15|

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JP2014095096A|2014-05-22|

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CN102933639B|2015-01-14|

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KR101557254B1|2015-10-02|

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US8435631B2|2013-05-07|

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US20110256364A1|2011-10-20|

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JP2013527865A|2013-07-04|

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TWI447161B|2014-08-01|

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PH12014501102B1|2015-07-06|

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PH12014501102A1|2015-07-06|

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AU2011241039B2|2013-09-26|

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ZA201207552B|2014-03-26|

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ES2689874T3|2018-11-16|

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MX368141B|2019-09-19|

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MX2012011814A|2012-11-29|

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2019-11-19| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-01-21| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US12/761,020|US8435631B2|2010-04-15|2010-04-15|Microporous material|

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PCT/US2011/027471|WO2011129928A1|2010-04-15|2011-03-08|Microporous material|

---