TW201520232A - Microporous material - Google Patents

Abstract

Microporous materials that include thermoplastic organic polyolefin polymer (e.g., ultrahigh molecular weight polyolefin, such as polyethylene), particulate filler (e.g., precipitated silica), and a network of interconnecting pores, are described. The microporous materials of the present invention possess controlled volatile material transfer properties. The microporous materials can have a density of at least 0.8 g/cm3; and a volatile material transfer rate, from the volatile material contact surface to the vapor release surface of the microporous material, of from 0.04 to 0.6 mg/(hour*cm2). In addition, when 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.

Description

Microporous material Cross-references for related applications

This application is a continuation-in-part application of U.S. Patent Application Serial No. 13/473,001, filed on May 16, 2012, which is filed on April 15, 2010. The continuation of the application No. 12/761,020 (now U.S. Patent No. 8,435,631), which is incorporated herein by reference.

Field of invention

The present invention is directed to microporous materials possessing controlled transfer properties of volatile materials. The microporous material comprises a thermoplastic organic polymer, a particulate filler, and an interconnected pore network.

Background of the invention

Delivery of a volatile material, such as a fragrance, such as an air freshener, can be accomplished by a delivery device that includes a reservoir containing volatile materials. The delivery device or delivery device typically includes a vapor permeable membrane that covers or encapsulates the reservoir. The volatile material in the reservoir passes through the vapor permeable membrane and is released to the atmosphere on the atmospheric side of the membrane, such as air. Vapor permeable membranes are typically fabricated from organic polymers and Porosity.

The rate at which volatile materials pass through the vapor permeable membrane is generally an important factor. For example, if the rate at which volatile materials pass through the vapor permeable membrane is too low, the properties associated with volatile materials such as fragrances will typically be undesirably low or undetectable. On the other hand, if volatile materials pass The rate of vapor permeable membranes is too high, the storage of volatile materials can be exhausted too quickly, and the properties associated with volatile materials such as fragrances can be undesirably high or, in some cases, too strong.

It is also generally desirable to minimize or avoid the formation of liquid volatile materials on the atmospheric side or outside of the vapor permeable membrane from which volatile materials are released into the atmosphere (e.g., into the air). The liquid volatile material passing over the outside of the vapor permeable membrane may be collected (e.g., coagulated) in or on the outside and leaked from the delivery device, causing, for example, articles in contact with the liquid volatile material (such as, Clothing or furniture) stained. In addition, the formation of a liquid volatile material on the outside of the vapor permeable membrane can result in uneven release of the volatile material from the delivery device.

A further increase in ambient temperature increases the rate at which volatile materials pass through the vapor permeable membrane to an undesirably high rate. For example, one of the delivery devices used in a passenger compartment of a car may be exposed to an increased ambient temperature. Thus, the increase in the rate at which volatile materials contained within the device pass through the vapor permeable membrane, which is a function of the increased ambient temperature, is minimally desired.

What is desired is the development of new microporous materials with controlled transfer properties of volatile materials. Further hope is when these newly developed microporous materials When used as a vapor permeable membrane as a delivery device, the microporous material minimizes the formation of liquid volatile materials on the outer or outer surface of the membrane. In addition, the rate at which volatile materials pass through such microporous materials needs to be minimized as the ambient temperature increases.

Summary of invention

According to the present invention, there is provided a microporous material comprising: (a) a substantially water-insoluble thermoplastic organic polymer matrix comprising a polyolefin; (b) a finely divided substantially water-insoluble particulate filler, the particulate filler Is distributed throughout the substrate and is from 40 to 90% by weight based on the total weight of the microporous material; and (c) an interconnected pore network substantially in the microporous material Communicating; wherein the microporous material has a density of at least 0.8 g/cm ³ , a volatile material contacting surface, a vapor releasing surface, wherein the volatile material contacting surface and the vapor releasing surface are substantially opposite each other, And a volatile material transfer rate from the volatile material contact surface to the vapor release surface from 0.04 to 0.6 mg/(hr*cm ² ), and wherein the volatile material is transferred from the volatile material contact surface to the The vapor release surface (at a rate of volatile material transfer from 0.04 to 0.6 mg / (hr * cm ² )), the vapor release surface is substantially free of volatile materials in liquid form.

Furthermore, the present invention provides a microporous material comprising: (a) a substantially water-insoluble thermoplastic organic polymer matrix comprising a polyolefin; (b) a finely divided substantially water-insoluble particulate filler, the particle a packing system distributed throughout the substrate and constituting from 40 to 90% by weight based on the total weight of the microporous material; and (c) an interconnected pore network which is attached to the substance of the microporous material Connected to each other; wherein the microporous material has a density of less than 0.8 g/cm ³ , a volatile material contacting surface, a vapor releasing surface, wherein the volatile material contacting surface and the vapor releasing surface are substantially each other In contrast, wherein (i) at least a portion of the volatile material contact surface has a first coating thereon, and/or (ii) at least a portion of the vapor release surface has thereon a second coating, from 0.04 to 0.6 mg / (hr * cm ² ) of the volatile material transfer rate from the volatile material contact surface to the vapor release surface, and wherein, when the volatile material is from the volatile Material contact surface transferred to the vapor release The surface (at a rate of volatile material transfer from 0.04 to 0.6 mg / (hr * cm ² )), the vapor-releasing surface is substantially free of volatile materials in liquid form.

Furthermore, the present invention provides a microporous material comprising: (a) a substantially water-insoluble thermoplastic organic polymer matrix comprising a polyolefin; (b) a finely divided substantially water-insoluble particulate filler, the particle a filler is distributed throughout the substrate and is comprised from 40 to 90% by weight based on the total weight of the microporous material; and (c) an interconnected pore network that is substantially throughout the microporous material Connected; wherein the microporous material has a volatile material contact surface, a vapor release surface, wherein the volatile material contact surface and the vapor release surface are substantially opposite each other, wherein (i) the volatile material contacts At least a portion of the surface having a first coating thereon, and/or (ii) at least a portion of the vapor release surface having a second coating thereon, wherein the first coating And the second coating layer is each independently from a coating composition comprising poly(vinyl alcohol) and at least 0.04 mg / (hour * cm ² ) from the volatile material contacting surface to the vapor Release a volatile material transfer rate of the surface, and wherein When the microporous material, i.e., the poly(vinyl alcohol) coated microporous material, is exposed to an increase in temperature from 25 ° C to 60 ° C, the rate of transfer of the volatile material is increased by less than or equal to 150%.

Detailed description of the invention

As used herein and in the context of the patent application, the term "volatile" "Material contact surface" means the facing of a microporous material and is typically associated with, for example, a surface in contact with a volatile material within one of the reservoirs as described in further detail below.

As used herein and in the context of the patent application, the term "vapor-releasing surface" means that the microporous material does not face and/or is in direct contact with the surface of the volatile material, and that the volatile material is in a gas or vapor form. The surface is released into an external atmosphere.

As used herein and in the context of the claims, the terms "(meth)acrylate" and similar terms such as "(meth)acrylic refers to acrylate and/or methacrylate.

As used herein and in the scope of the patent application, the "volatile material transfer rate" of the microporous material is determined in accordance with the following description. One of the internal volumes having a volatile material sufficient to hold 2 milliliters of a volatile material such as benzoate acetate is made from a pure thermoplastic polymer. The internal dimensions of the reservoir are defined by a circle diameter of about 4 cm of the opening edge and a depth of no more than 1 cm. The opening face is used to determine the rate of transfer of volatile materials. With the test reservoir placed flat (with the open side facing up), approximately 2 ml of benzoate was introduced into the test reservoir. The benzoate acetate was introduced into the test reservoir with a sheet of microporous material having a thickness of from 6 to 18 mils placed on the open side/side of the test reservoir such that the microporous sheet was 12.5 cm ² The volatile material contact surface is exposed to the interior of the reservoir. The test reservoir is weighed to obtain the starting weight of the entire shot assembly. Then, the test reservoir containing benzoate acetate and encapsulated in a sheet of microporous material was placed upright with 5 inches [1.52 meters] (height) x 5 inches [1.52 meters] (width) x 2 inches [0.61 meters] (depth) of approximately the size of a laboratory chemical fume hood. The test reservoir is upright and benzyl acetate is in direct contact with at least a portion of the volatile material contacting surface of the microporous sheet. The glass door of the fume hood is pulled down and the air flow through the cabinet is adjusted to have an eight (8) revolution (or turnaround) cabinet volume per hour. The temperature inside the cabinet was maintained at 25 °C ± 5 °C unless otherwise indicated. The humidity in the fume hood is environmentally friendly. The test reservoir is regularly weighed in this cabinet. The calculated weight loss of benzyl acetate combined with the elapsed time and the surface area of the microporous sheet exposed to the interior of the test reservoir were used to determine the rate of volatile transfer of the microporous sheet in milligrams per hour/cm ² .

As used herein and in the scope of the patent application, the percent increase in the rate of transfer of volatile materials from 25 ° C to 60 ° C of the present invention is for individual but substantially equal pieces of microporous material at 25 ° C and 60 ° C. The material samples were judged according to the above method. The reservoir is placed in a large glass dome and placed in a 50% aqueous solution of potassium chloride also contained within the bell jar. The entire bell jar with the contents was placed in a furnace heated to 60 °C. The reservoir is maintained for a period of 7 to 10 hours under these conditions. The reservoir is then returned to the cabinet in ambient conditions overnight and the process is repeated for several days. Each reservoir is weighed before being placed in the bell and removed from the bell jar. When removed from the bell jar, the weight of each reservoir is taken after the reservoir returns to ambient temperature.

As used herein and in the scope of the patent application, the following methods are used to determine whether the vapor-releasing surface of the microporous material is substantially free of volatile materials in liquid form. When the test reservoir is weighed as described above, the vapor release surface of the microporous sheet is visually inspected to determine the liquid drop and / or whether the film is present on it. A microporous sheet is considered acceptable if any evidence of liquid drops (i.e., a single drop) and/or a film is visually observed on the vapor release surface but not from the surface. If the droplets of the volatile material liquid flow on the vapor release surface, the microporous sheet is judged to be ineffective. If no evidence of liquid drops (i.e., no drops) and/or a film is visually observed on the vapor release surface, the microporous sheet is judged to be substantially free of volatile materials in liquid form.

All ranges disclosed herein are to be understood as being inclusive of any and all sub-ranges For example, the stated range of "1 to 10" shall be considered to include any and all subranges between the minimum 1 and the maximum 10 (and include such); that is, starting with a minimum of 1 or more and at a maximum All sub-ranges ending with 10 or less, for example, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like. However, any numerical value inherently contains certain errors necessarily caused by the deviation of the label found in its individual test measurements and is included in the test instrument finder.

All numbers, such as structural dimensions, component amounts, and the like, which are used in the specification and the scope of the claims, are understood to be modified by the term "about" unless otherwise indicated. Accordingly, the numerical parameters set forth in this specification and the appended claims are approximations, and may vary depending upon the desired results obtained by the present invention. At the very least, and without attempting to limit the application of the singularity to the scope of the patent application, each numerical parameter is required to be at least based on the number of reported effective digits and by the application of general rounding techniques. Furthermore, when used in the specification and the appended claims, unless the <RTIgt; "One" and "the" are intended to include a plurality of references.

The term "volatile material" as used herein and in the context of the patent application, is meant to mean ambient room temperature and pressure and can be converted into a lack of additional or supplemental energy (eg, in the form of heat and/or agitation). A gas or vapor type (ie, a volatilizable) material. The volatile material may comprise an organic volatile material which may comprise a volatile material comprising a solvent based material or may be dispersed in a solvent based material. Volatile materials may be in liquid form and/or solid form and may be naturally occurring or synthetically formed. When in solid form, the volatile material is typically sublimed from the solid form to the vapor form without passing through the intermediate liquid form. The volatile material can be selectively combined or formulated with a non-volatile material such as a carrier, such as water and/or a non-volatile solvent. In the case of solid volatile materials, the non-volatile carrier can be in the form of a porous material, for example, a porous inorganic material in which the solid volatile material is retained. Further, the solid volatile material may be in a semi-solid gel form.

The volatile material can be a fragrance material such as a naturally occurring or synthetic essential oil. Examples of essential oils which may be selected as liquid volatile materials include, without limitation, bergamot, bitter orange, lemon, orange, geranium, cypress, eucalyptus, cedar, geranium, lavender, orange, oregano, bitter orange , white fir, patchouli, orange blossom, rose pure oil, and a combination of these oils. Examples of solid fragrance materials which may be selected as volatile materials include, without limitation, vanillin, ethyl vanillin, coumarin, tortoise, watermelon ketone, sunflower, xylene musk, cedarol, musk ketone diphenyl Ketone, raspberry ketone, methyl naphthyl ketone β, phenylethyl salicylate, meat flavor, maltitol, maple syrup Ester, raw eugenol acetate, oakmoss, and combinations of these.

The volatile material transfer rate of the microporous material may be less than or equal to 0.7 mg / (hour * cm ² ), or less than or equal to 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 volatile material transfer of the microporous material may 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 / (hours * cm ² ). The volatile material transfer rate range of the microporous material can be between any combination of the above values and the lower values. For example, the volatile material transfer rate of the microporous material can be from 0.04 to 0.6 mg / (hr * ² cm ² ), or from 0.2 to 0.6 mg / (hr * cm ² ), or from 0.30 to 0.55 mg / (hr * The centimeters ² ), or from 0.35 to 0.50 mg / (hours * cm ² ), in each case, contain the stated values.

While not intending to be bound by any theory, it is believed that when the volatile material is transferred from the volatile material contacting surface of the microporous material to the vapor releasing surface, it is believed that the volatile material is in a form selected from the group consisting of liquids, vapors, and combinations thereof. In addition, and without intending to be limited by any theory, it is believed that the volatile material is at least partially connected through interconnected pore networks throughout substantially the microporous material. Typically, the transfer of volatile materials occurs from 15 ° C to 40 ° C, for example, from 15 or 18 ° C to 30 or 35 ° C, and at ambient atmospheric pressure.

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 scope of the patent application, the density of the microporous material is determined by measuring the weight and volume of the sample of the microporous material. The upper limit of the density of the microporous material may be in a wide range as long as it has, for example, a target volatile material transfer rate of from 0.04 to 0.6 mg / (hr * cm ² ), and when the volatile material is transferred from the contact surface of the volatile material to When the vapor releases the surface, the vapor release surface is substantially free of volatile materials in liquid form. Typically, the microporous material has a density of less than or equal to 1.5 g/cm ³ , or less than or equal to 1.0 g/cm ³ . The density of the microporous material can be between any of the above values, including the stated values. For example, the microporous material can have a density from 0.7 g/cm ³ to 1.5 g/cm ³ , such as from 0.8 g/cm ³ to 1.2 g/cm ³ , including the recited values.

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 volatile material contacting surface of the microporous material and the vapor releasing surface can each have no coating material thereon. When there is no coating material thereon, the volatile material contacting surface and the vapor releasing surface are each defined by a microporous material.

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 selectively has a first coating thereon, And/or at least a portion of the vapor releasing surface of the microporous material can have a second coating thereon. The first coating and the second coating may be the same or different. When at least a portion of the volatile material contacting surface has a first coating thereon, the volatile material contacting surface is at least partially defined by the first coating, and at least a portion of the vapor releasing surface has a portion thereon The second coating, the vapor release surface, is at least partially defined by the second coating.

The first coating and the second coating each may be formed from a coating selected from the group consisting of a liquid coating and a solid particle coating (eg, a powder coating). Typically, The first and second coatings are each independently formed from a coating selected from the group consisting of a liquid coating, which may optionally contain a solvent selected from the group consisting of water, organic solvents, and combinations thereof. The first and second coatings can each independently be selected from crosslinkable coatings, such as thermoset coatings and photocurable coatings; and non-crosslinkable coatings, such as air dried coatings. The first and second coatings can be applied to individual surfaces of the microporous material, such as spray coating, curtain coating, dip coating, and/or pull down coating, in accordance with methods known in the art, for example, By scraper or pull-bar technology.

The first and second coating compositions each independently optionally contain additives known in the art, such as antioxidants, UV stabilizers, flow control agents, dispersion stabilizers, for example, in the case of aqueous dispersions. And coloring agents, for example, dyes and/or colorants. Typically, the first and second coating compositions are free of colorants and are therefore substantially transparent or opaque. The selective additive may be present in the coating composition, for example, in an amount from 0.01 to 10% by weight, based on the total weight of the coating composition.

The first coating and the second coating are each independently formed from an aqueous coating composition comprising the dispersed organic polymeric material. The aqueous coating composition can have a particle size of from 200 to 400 nm. The solids of the aqueous coating composition can vary widely, for example from 0.1 to 30% by weight, or from 1 to 20% by weight, based on the total weight of the aqueous coating composition, in each case. The organic polymer comprising this aqueous coating composition may have, for example, an average molecular weight (Mn) of from 1,000 to 4,000,000, or from 10,000 to 2,000,000.

The aqueous coating composition may be selected from aqueous poly(meth)acrylic acid An ester dispersion, an aqueous polyurethane dispersion, an aqueous polyoxo (or hydrazine) oil dispersion, and combinations thereof. The poly(meth)acrylate polymer of the aqueous poly(meth)acrylate dispersion can be prepared according to methods known in the art. For example, the poly(meth)acrylate polymer may be included in a residue (or monomer unit) of an alkyl (meth) acrylate having an alkyl group of from 1 to 20 carbon atoms. Examples of the alkyl (meth) acrylate having from 1 to 20 carbon atoms in the alkyl group include, without limitation, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate 2-hydroxyethyl ester, propyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate , (butyl) (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate. For the purposes of non-limiting illustration, one example of an aqueous poly(meth)acrylate dispersion that can be independently selected as one of each of the first and second coating compositions is HYCAR 26138, which is commercially available from Lubrizol. Advanced Materials, Inc.

Polyurethane polymers which may be independently selected as the aqueous polyurethane dispersion of each of the first and second coatings comprise any of those known to those skilled in the art. Typically, the polyurethane polymer is prepared from an isocyanate functional material having two or more isocyanate groups, and an active hydrogen functional material having two or more active hydrogen groups. The active hydrogen group can be selected, for example, from a hydroxyl group, a thiol group, a primary amine, a secondary amine, and combinations thereof. For non-limiting purposes, it may be independently selected as one of the first and second coating compositions, an aqueous polyurethane dispersion One example is WITCOBOND W-240, which is commercially available from Chemtura Corporation.

The rhodium polymer of the aqueous polyoxosulfan dispersion can be selected from aqueous polyoxo oil dispersions known and known in the art. For purposes of non-limiting illustration, an example of an aqueous hydrazine dispersion that can be independently selected as one of each of the first and second coating compositions is MOMENTIVE LE-410, which is commercially available from Momentive Performance Materials.

The first coating and the second coating each independently can be applied in any suitable thickness as long as the microporous material has, for example, a target volatile material transfer rate of from 0.04 to 0.6 mg / (hr * cm ² ), and When the volatile material is transferred from the volatile material contacting surface to the vapor releasing surface, the vapor releasing surface is substantially free of volatile materials in liquid form. Furthermore, the first coating and the second coating each independently may have from 0.01 to 5.5 g/meter ² , such as from 0.1 to 5.0 g/meter ² , or from 0.5 to 3 g/meter. ² , or a coating weight of from 0.75 to 2.5 g/ ^m2 , or from 1 to 2 g/ ^m2 , i.e., the coating weight on the microporous material.

The microporous material can have a density of less than 0.8 g/cm ³ and at least a portion of the volatile material contacting surface of the microporous material can have a first coating thereon and/or a vapor of the microporous material At least a portion of the release surface can have a second coating thereon. The first coating and the second coating may be the same or different, and each independently is such a selective first and second coating having a microporous material having a density of at least 0.8 g/cm ³ As usual.

When less than 0.8 g/cm ³ , the density of the microporous material of the present invention may have any suitable lower limit as long as the microporous material has, for example, a target volatile material transfer of from 0.04 to 0.6 mg / (hr * cm ² ) The rate, and when the volatile material is transferred from the contacting surface of the volatile material to the vapor releasing surface, the vapor releasing surface is substantially free of volatile material in liquid form. In this particular embodiment of the invention, the density of the microporous material can be from 0.6 to at least 0.8 g/cm ³ , or from 0.6 to 0.75 g/cm ³ , for example, from 0.60 to 0.75 g/cm ³ , or from 0.6 to 0.7 g / cm ³ , for example, from 0.60 to 0.70 g / cm ³ , or from 0.65 to 0.70 g / cm ³ .

Furthermore, at least a portion of the contact surface of the volatile material of the microporous material may have a first coating thereon, and/or at least a portion of the vapor releasing surface of the microporous material has one of The second coating, wherein the first and second coatings are each independently selected from a coating composition comprising one of poly(vinyl alcohol).

In the poly(vinyl alcohol) coated embodiment of the present invention, when the microporous material, that is, the poly(vinyl alcohol) coated microporous material is exposed to a temperature increase from 25 ° C to 60 ° C, the volatile material thereof The transfer rate increases by less than or equal to 150%. When the poly(vinyl alcohol) coated microporous material is exposed to an increase in temperature from ambient temperature, for example, from 25 ° C to 60 ° C, the rate of volatile material transfer typically increases and typically does not decrease unless, for example, Microporous materials have been damaged by exposure to higher ambient temperatures. Therefore, and as used herein and in the scope of the patent application, "the rate of increase in the rate of transfer of volatile materials is less than or equal to [the] percentage", for example, 150%, the statement contains a lower limit of 0%, but not Contains a lower limit of less than 0%.

For illustrative purposes, when the poly(vinyl alcohol) coated microporous material has a volatile material transfer rate of 0.3 mg/(hour*cm ² at 25 ° C, and when the microporous material is exposed to a temperature of 60 ° C, The rate of transfer of the volatile material is increased by at least or equal to a value of 0.75 mg / (hr * cm ² ).

In one embodiment, when the microporous material, ie, the poly(vinyl alcohol) coated microporous material, is exposed to a temperature increase from 25 ° C to 60 ° C, the rate of volatile material transfer increases by less than or equal to 125. %. For example, when the poly(vinyl alcohol) coated microporous material has a volatile material transfer rate of 0.3 mg/(hr*cm ² ) at 25 ° C, and when the microporous material is exposed to a temperature of 60 ° C, the volatility The material transfer rate is increased by at least or equal to a value of 0.68 mg / (hr * cm ² ).

Furthermore, when the microporous material, i.e., the poly(vinyl alcohol) coated microporous material, is exposed to an increase in temperature from 25 ° C to 60 ° C, its volatile material transfer rate is increased by less than or equal to 100%. For example, when the poly(vinyl alcohol) coated microporous material has a volatile material transfer rate of 0.3 mg/(hr*cm ² ) at 25 ° C, and when the microporous material is exposed to a temperature of 60 ° C, the volatility The material transfer rate is increased by at least equal to or equal to 0.6 mg / (hour * cm ² ).

The first and second poly(vinyl alcohol) coatings can each independently be present at any suitable coating weight as long as the microporous material has, for example, at least 0.04 mg / (hr * cm ² ) of the target volatile material transfer The rate, and when the microporous material, i.e., the poly(vinyl alcohol) coated microporous material, is exposed to a temperature increase from 25 ° C to 60 ° C, its volatile material transfer rate is increased by less than or equal to 150%. Typically, the first poly(vinyl alcohol) coating and the second poly(vinyl alcohol) coating each independently have from 0.01 to 5.5 g/meter ² , or from 0.1 to 4.0 g/m ² , or A coating weight of from 0.5 to 3.0 g/meter ² or from 0.75 to 2.0 g/m ² .

The volatile material transfer rate of the poly(vinyl alcohol) coated microporous material can be at least 0.02 mg / (hr * cm ² ). The volatile material transfer rate of the poly(vinyl alcohol) coated microporous material 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 More than 0.2 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 poly(vinyl alcohol) coated microporous material may have a volatile material transfer rate of less than or equal to 0.7 mg / (hour * cm ² ), or less than or equal to 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 volatile material transfer rate of the poly(vinyl alcohol) coated microporous material can range between any combination of the upper value and the lower value, inclusive. For example, the poly(vinyl alcohol) coated microporous material may have a volatile material transfer rate of 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 / (hr * cm ² ), or from 0.20 to 0.60 mg / (hr * cm ² ), or from 0.30 to 0.55 mg / (hr * cm ² ), or from 0.35 to 0.50 mg / (hr * The centimeters ² ) contain the stated values in each case.

The density of the microporous material of the poly(vinyl alcohol) coated microporous material of the present invention can vary widely as long as the poly(vinyl alcohol) coated microporous material has, for example, at least 0.04 mg / (hr * cm ² The target volatile material transfer rate, and when the microporous material, that is, the poly(vinyl alcohol) coated microporous material, is exposed to a temperature increase from 25 ° C to 60 ° C, its volatile material transfer rate increases less. At or equal to 150%.

Further, the microporous material coated with the poly(vinyl alcohol) microporous material may have a density of at least 0.7 g/cm ³ , such as at least 0.8 g/cm ³ , for example, from 0.8 to 1.2 g/cm ³ , all All include the stated values. In one embodiment of the invention, the density of the poly(vinyl alcohol) coated microporous material, i.e., the density of the microporous material prior to application of the poly(vinyl alcohol) coating, is less than 0.8 g/cm ³ . For example, the microporous material density of the poly(vinyl alcohol) coated microporous material can be from 0.6 to at least 0.8 g/cm ³ , or from 0.6 to 0.75 g/cm ³ , for example, from 0.60 to 0.75 g/cm. ³ , or from 0.6 to 0.7 g/cm ³ , for example, from 0.60 to 0.70 g/cm ³ , or from 0.65 to 0.70 g/cm ³ , the owner includes the stated value.

With respect to the poly(vinyl alcohol) coated microporous material of the present invention, when the volatile material is transferred from the volatile material contacting surface to the vapor releasing surface, the vapor releasing surface is substantially free of volatile material in liquid form.

The poly(vinyl alcohol) coating may be selected from liquid coatings which may optionally contain a solvent selected from the group consisting of water, organic solvents, and combinations thereof. The poly(vinyl alcohol) coating may be selected from crosslinkable coatings, such as thermoset coatings; and non-crosslinkable coatings, such as air dried coatings. The poly(vinyl alcohol) coating can be applied to individual surfaces of the microporous material, such as spray coating, curtain coating, or pull down coating, for example, by a doctor blade or a drawdown rod, according to methods known in the art. .

In one embodiment, the first and second poly(vinyl alcohol) coatings are each formed separately from an aqueous poly(vinyl alcohol) coating composition. The solids of the aqueous poly(vinyl alcohol) coating composition can vary widely, for example, in each case, with water The basis weight of the coating composition is from 0.1 to 15% by weight, or from 0.5 to 9% by weight. The poly(vinyl alcohol) polymer of the poly(vinyl alcohol) coating composition may have, for example, an average molecular weight (Mn) of from 100 to 1,000,000, or from 1000 to 750,000.

The poly(vinyl alcohol) polymer of the poly(vinyl alcohol) coating composition can be a homopolymer or a copolymer. Co-monomers from which the poly(vinyl alcohol) copolymer can be prepared comprise copolymerizable with vinyl acetate (by free radical polymerization) and are known to those skilled in the art. For illustrative purposes, the comonomer from which the poly(vinyl alcohol) copolymer can be prepared includes, without limitation, (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, metal salts thereof, and the like, alkyl groups thereof Esters, for example, C ₂ -C ₁₀ alkyl esters thereof, etc., polyethylene glycol esters thereof, and the like, polypropylene glycol esters thereof; vinyl chloride; tetrafluoroethylene; 2-propenyl decylamino-2- Methyl-propanesulfonic acid and salts thereof; acrylamide; N-alkyl acrylamide; acrylamide substituted with N,N-dialkyl; and N-vinylformamide.

For purposes of non-limiting illustration, one example of a poly(vinyl alcohol) coating composition that can be used to form the poly(vinyl alcohol) coated microporous material of the present invention is CELVOL 325, which is commercially available from Sekisui Specialty Chemicals. .

The first and second poly(vinyl alcohol) coating compositions each independently comprise an additive known in the art, such as an antioxidant, an ultraviolet stabilizer, a flow control agent, a dispersion stabilizer, for example, in aqueous dispersion. In the case of liquids, and coloring agents, for example, dyes and/or colorants. Typically, the first and second poly(vinyl alcohol) coating compositions are free of colorants and are therefore transparent or opaque. Selective addition based on the total weight of the coating composition The agent may be, for example, present in a poly(vinyl alcohol) coating composition in an amount from 0.01 to 10% by weight.

The matrix of microporous material consists of a substantially water-insoluble thermoplastic organic polymer. The amount and type of such polymers suitable as the matrix are large. In general, any substantially water-insoluble thermoplastic organic polymer that can be extruded, calendered, pressed, or rolled into a film, sheet, strip, or web can be used. The polymer can be a single polymer or it can be a polymer mixture. The polymer can be a homopolymer, a copolymer, a random copolymer, a block copolymer, a graft copolymer, a random polymer, a tactic polymer, a syndiotactic polymer, a linear polymer, or a branched polymer. When a polymer mixture is used, the mixture may be homogeneous or it may comprise two or more polymer phases.

Examples of suitable types of thermoplastic organic polymers that are substantially water-insoluble include thermoplastic polyolefins, poly(halogen-substituted olefins), polyesters, polyamines, polyurethanes, polyureas. Class, poly(ethylene halide), poly(vinylidene halide), polystyrene, poly(vinyl ester), polycarbonate, polyether, polysulfide, polyimine, Polydecanes, polyoxyalkylenes, polycaprolactones, polyacrylates, and polymethacrylates. Hybrid species contemplated for use as substantially water-insoluble thermoplastic organic polymers include, for example, thermoplastic poly(urethane-urea)s, poly(ester-decylamines), poly(decane-oxime) Oxylkanes, and poly(ether-esters). Further examples of suitable substantially water-insoluble thermoplastic organic polymers include thermoplastic high density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, polypropylene (non-standard, regular, or syndiotactic), poly( Vinyl chloride), Copolymer of polytetrafluoroethylene, ethylene and acrylic acid, copolymer of ethylene and methacrylic acid, copolymer of poly(vinylidene chloride), vinylidene chloride and vinyl acetate, copolymerization of vinylidene chloride and vinyl chloride , copolymer of ethylene and propylene, copolymer of ethylene and butene, poly(vinyl acetate), polystyrene, poly(ω-aminoundecanoic acid), poly(hexamethylene hexamethylenediamine) , poly(ε-caprolactam), and poly(methyl methacrylate). The description of these types and examples of substantially water-insoluble thermoplastic organic polymers is not exhaustive and is provided for illustrative purposes only.

The substantially water-insoluble thermoplastic organic polymer specifically comprises, for example, a poly(vinyl chloride), a copolymer of vinyl chloride, or a mixture thereof. In one embodiment, the water-insoluble thermoplastic organic polymer comprises an ultrahigh molecular weight polyolefin selected from the group consisting of ultrahigh molecular weight polyolefins having an intrinsic viscosity of at least 10 metrics per gram, for example, substantially linear ultrahigh molecular weight poly An olefin; or an ultrahigh molecular weight polypropylene having an intrinsic viscosity of at least 6 metrics per gram, for example, a substantially linear ultrahigh molecular weight polypropylene; or a mixture of such. In a particular embodiment, the water-insoluble thermoplastic organic polymer comprises an ultra high molecular weight polyethylene having an intrinsic viscosity of at least 18 metrics per gram, for example, a linear ultra high molecular weight polyethylene.

Ultrahigh molecular weight polyethylene (UHMWPE) is not a thermoset polymer with an infinite molecular weight, but the technology is classified as a thermoplastic. However, because the molecular system is substantially extremely long chain, UHMWPE softens upon heating but does not flow in a generally thermoplastic manner as a molten liquid. The extremely long chains and the special properties provided to UHMWPE are believed to be a substantial aid to the desirable properties of the microporous materials made using this polymer.

As indicated earlier, the inherent viscosity of UHMWPE is at least about 10 com/g. Typically, the intrinsic viscosity is at least about 14 com/g. Typically, the intrinsic viscosity is at least about 18 com/g. In many cases, the intrinsic viscosity is at least about 19 com/g. Although the upper limit of the intrinsic viscosity is not particularly limited, the intrinsic viscosity is usually in the range of from about 10 to about 39 com/g, for example, in the range of from about 14 to about 39 com/g. In most cases, the inherent viscosity of UHMWPE ranges from about 18 to about 39 com/g, typically from about 18 to about 32 com/g.

The nominal molecular weight of UHMWPE is empirically related to the inherent viscosity of the polymer according to the following equation: M(UHMWPE)=5.3x10 ⁴ [η] ^1.37 wherein M(UHMWPE) is the nominal molecular weight and [η] is UHMW polyethylene Intrinsic viscosity, expressed in gram/gram.

When used herein and in the scope of the patent application, the intrinsic viscosity is determined by extrapolating the specific viscosity or intrinsic viscosity of several UHMWPE dilute solutions to a concentration of 0, wherein the solvent is added by 0.2% by weight of 3,5. - Distillation of di-tert-butyl-4-hydroxyhydrocinnamic acid, neopentyl tetraester [CAS Accession No. 6683-19-8]. The specific viscosity or intrinsic viscosity of UHMWPE was determined using the Ubbelohde No. 1 viscometer except for the use of several dilute solutions of different concentrations in accordance with the general procedure of ASTM D 4020-81, from the relative viscosity obtained at 135 °C. ASTM D 4020-81 is hereby incorporated by reference in its entirety.

In a particular embodiment, the matrix comprises substantially linear ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 10 metric/g, and an ASTM D 1238-86 condition E melt index of less than 50 g/10 min and at least 0.1克/10 minutes of ASTM D 1238-86 Condition F Melt Index of a mixture of lower molecular weight polyethylene (LMWPE). The nominal molecular weight of LMWPE is lower than that of UHMW polyethylene. LMWPE is thermoplastic and many different types are known. A classification method is based on ASTM D 1248-84 (reapproved 1989) by density expressed in grams per cubic centimeter, and rounded to approx. to the thousands, which is summarized as follows: Any or all of these polyethylenes can be used as the LMWPE in the present invention. For some applications, HDPE can be used because it is generally more linear than MDPE or LDPE. ASTM D 1248-84 (Reapproved 1989) is hereby incorporated by reference in its entirety.

Methods for making various LMWPEs are known and well documented. They include high pressure processes, the Phillips Petroleum Company process, the Standard Oil Company (Indiana) process, and the Ziegler process.

The ASTM D 1238-86 condition E of LMWPE (i.e., 190 ° C and 2.16 kg load) has a melt index of less than about 50 g/10 minutes. Typically, the Condition E melt index is less than about 25 grams/10 minutes. Typically, the Condition E melt index is less than about 15 grams/10 minutes.

The ASTM D 1238-86 condition F of LMWPE (i.e., 190 ° C and 21.6 kg load) has a melt index of at least 0.1 g/10 min. In many cases, the condition F melt index is at least about 0.5 g/10 minutes. Typically, the Condition F melt index is at least about 1.0 g/10 minutes. ASTM D 1238-86 is hereby incorporated by reference in its entirety.

Sufficient UHMWPE and LMWPE need to be present in the matrix to provide their properties to the microporous material. Other thermoplastic organic polymers may also be present in the matrix as long as their presence does not substantially affect the properties of the microporous material in a detrimental manner. One or more other thermoplastic polymers may be present in the matrix. The amount of other thermoplastic polymer that may be present will depend on the nature of the polymer. Examples of selectively present thermoplastic organic polymers include, without limitation, poly(tetrafluoroethane), polypropylene, copolymers of ethylene and propylene, copolymers of ethylene and acrylic acid, and copolymerization of ethylene and methacrylic acid. Things. If desired, all or a portion of the carboxyl groups of the carboxyl group-containing copolymer may be neutralized by sodium, zinc or the like.

In most cases, UHMWPE and LMWPE together comprise at least about 65% by weight of the polymer of the matrix. Typically, UHMWPE and LMWPE together comprise at least about 85% by weight of the polymer of the matrix. Typically, there are substantially no other thermoplastic organic polymers such that UHMWPE and LMWPE together comprise substantially 100% by weight of the polymer of the matrix.

UHMWPE may constitute at least 1% by weight of the polymer of the matrix. If UHMWPE and LMWPE together comprise 100% by weight of the polymer of the matrix of the microporous material, UHMWPE may constitute greater than or equal to 40% by weight of the polymer of the matrix, such as greater than or equal to 45% by weight of the polymer of the matrix, or Greater than or equal to 48% by weight, or greater than or equal to 50% by weight, or greater than or equal to 55% by weight. Furthermore, the UHMWPE may constitute less than or equal to 99% by weight of the polymer of the matrix, such as less than or equal to 80% by weight of the polymer of the matrix, or less than or equal to 70% by weight, or less than or equal to 65% by weight. %, or less than or equal to 60% by weight. The amount of UHMWPE comprising the polymer of the matrix can be between any of these values, inclusive of the stated values.

Similarly, if UHMWPE and LMWPE together comprise 100% by weight of the polymer of the matrix of the microporous material, LMWPE may constitute greater than or equal to 1% by weight of the polymer of the matrix, such as greater than or equal to 5% by weight of the polymer of the matrix. Or greater than or equal to 10% by weight, or greater than or equal to 15% by weight, or greater than or equal to 20% by weight, or greater than or equal to 25% by weight, or greater than or equal to 30% by weight, or greater than or equal to 35% by weight, or Greater than or equal to 40% by weight, or greater than or equal to 45% by weight, or greater than or equal to 50% by weight, or greater than or equal to 55% by weight. Furthermore, the LMWPE may constitute less than or equal to 70% by weight of the polymer of the matrix, such as less than or equal to 65% by weight of the polymer of the matrix, or less than or equal to 60% by weight, or less than or equal to 55% by weight. %, or less than or equal to 50% by weight, or less than or equal to 45% by weight. The amount of LMWPE can range between any of these values, including the stated values.

It is noted that for any of the aforementioned microporous materials of the present invention, the LMWPE may comprise high density polyethylene.

The microporous material also comprises a finely divided particulate filler material that is substantially water insoluble. The particulate filler material may comprise an organic particulate material and/or an inorganic particulate material. Granular filler materials are typically uncolored, for example, The particulate filler material is a white or off-white particulate filler material, such as a tantalum or clay particulate material.

The finely divided substantially water-insoluble filler particles may constitute from 20 to 90% by weight of the microporous material. For example, such filler particles may comprise from 30% to 90% by weight of the microporous material, or from 40 to 90% by weight of the microporous material, or from 40 to 85% by weight of the microporous material, for example, from 45 to 80% by weight. %, or from 50 to 80% by weight of the microporous material, for example, 50 to 65, 70 or 75% by weight, and even from 60% to 90% by weight of the microporous material.

The finely divided substantially water-insoluble particulate filler may be in the form of a primary particle, an aggregate of primary particles, or a combination of the two. By using one of the Beckman Coulton laser diffraction particle size instruments capable of measuring particle diameters as small as 0.04 microns, at least about 90% by weight of the filler used to prepare the microporous material has a range from 0.5 to about 200 when determined by LS230. The coarse particle size of the micron, such as from 1 to 100 microns. Typically, at least 90% by weight of the particulate filler has a coarse particle size ranging from 5 to 40 microns, for example, from 10 to 30 microns. The size of the filler aggregates can be reduced during processing of the ingredients used to prepare the microporous material. Thus, the distribution of the coarse grain size within the microporous material can be less than the original filler itself.

Non-limiting examples of suitable organic and inorganic particulate materials useful in the microporous materials of the present invention are described in U.S. Patent No. 6,387,519, the disclosure of which is incorporated herein by reference. for reference.

In a particular embodiment of the invention, the particulate filler material comprises a tantalum material. Non-limiting examples of enamel fillers that can be used to prepare microporous materials Contains ceria, mica, montmorillonite, kaolin, nanoclay (such as cliosite available from Southern Clay Products), talc, diatomaceous earth, vermiculite, natural and synthetic zeolites, calcium citrate, aluminum citrate, Sodium aluminum citrate, aluminum polysilicate, alumina cerium oxide gel, and glass granules. In addition to the enamel filler, other finely divided granules which are substantially water-insoluble may also be optionally used. Non-limiting examples of such selective particulate fillers include carbon black, charcoal, graphite, titanium oxide, iron oxide, copper oxide, zinc oxide, cerium oxide, zirconium oxide, magnesium oxide, aluminum oxide, molybdenum disulfide, zinc sulfide, Barium sulfate, barium sulfate, calcium carbonate, and magnesium carbonate. Some of these selective fillers are color-filled fillers that, depending on the amount used, add to the color or color of the microporous material. In one non-limiting embodiment, the enamel filler can comprise cerium oxide and any of the foregoing clays. Non-limiting examples of cerium oxide include precipitated cerium oxide, cerium oxide gel, gas phase cerium oxide, and combinations thereof.

Cerium dioxide gels are generally commercially produced by acidifying an aqueous solution of a soluble metal silicate (e.g., sodium citrate) with an acid at a low pH. The acid used is generally a strong mineral acid such as sulfuric acid or hydrochloric acid, even though carbon dioxide can be used. Since the gel phase is substantially indistinguishable from the surrounding liquid phase in the density system at low viscosity, the gel phase does not settle, i.e., does not precipitate. Thus, the cerium oxide gel can be described as a non-precipitating adhesive rigid three-dimensional network adjacent to one of the colloidal non-crystalline cerium oxide particles. The subdivided state range is from a large solid material to a submicroscopic particle, and the hydration is from a geometric anhydrous cerium oxide to a soft gel material having a grade of 100 parts by weight water per part by weight of cerium oxide.

Precipitated cerium oxide is generally obtained by making a soluble metal ceric acid An aqueous salt solution, a general alkali metal ruthenate (such as sodium citrate), and an acid combination, such that the colloidal cerium oxide particles are grown in a weakly alkaline solution and formed by a soluble alkali metal salt of an alkali metal ion Coalesced and commercialized. Various acids can be used, including mineral acids without limitation. Non-limiting examples of acids that can be used include hydrochloric acid and sulfuric acid, but carbon dioxide can also be used to make precipitated cerium oxide. In the absence of a coagulant, cerium oxide does not precipitate from the solution at any pH. In one non-limiting embodiment, the coagulant used to produce the ceria precipitate may be a soluble alkali metal salt produced during the formation of colloidal ceria particles, or it may be an added electrolyte, such as a soluble inorganic Or an organic salt, or it may be a combination of the two.

Many different precipitated cerium oxides can be used as enamel fillers for the preparation of microporous materials. Precipitated cerium oxide is a known commercial material and its method of manufacture is described in detail in a number of U.S. patents, including U.S. Patent Nos. 2,940,830 and 4,681,750. The average elementary particle size of the precipitated ceria used to prepare the microporous material (whether or not the elementary particles are aggregated) is generally less than 0.1 micron, for example, less than 0.05 micron or by breakthrough electron microscopy. Less than 0.03 microns. Precipitated cerium oxide is available in a number of grades and versions from PPG Industries, Inc. These silicon dioxide sold under the Department of Hi-Sil ^® brand name.

For the purposes of the present invention, the finely divided granules may be substantially water insoluble, and the enamel filler may comprise at least 50% by weight of the substantially water insoluble filler material, for example, at least 65 or at least 75% by weight, or at least 90% by weight. The enamel filler may comprise from 50 to 90% by weight of the particulate filler material, for example from 60 to 80% by weight, or the enamel filler may comprise a water-insoluble particulate filler material. Essentially all.

Particulate fillers, for example, enamel fillers, typically have a high surface area which enables the filler to be loaded with a number of processing plasticizer compositions used to make the microporous materials of the present invention. High surface area fillers are materials having very small particle sizes, materials with high porosity, or materials exhibiting these two properties. When determined by the Brunauer, Emmett, Teller (BET) method in accordance with ASTM D 1993-91, the surface area of the particulate filler (eg, enamel filler particles) may range from 20 or 40 to 400 square meters per gram, for example, from 25 to 350 square meters per gram, or from 40 to 160 square meters per gram. The BET surface area can be determined by fitting five relative pressure points of nitrogen adsorption isotherm measurements using a Micromeritics TriStar 3000 ^(TM) instrument. A station FlowPrep-060 ^TM may be used to provide heat and continuous gas flow during the sample preparation. The cerium oxide sample was dried by heating to 160 ° C for 1 hour in flowing nitrogen (PS) before nitrogen adsorption. Generally, but not necessarily, the surface area of any non-ruthenium filler particles used is within one of these ranges. The filler particles are substantially water insoluble and are also substantially insoluble in any organic processing liquid used to prepare the microporous material. This promotes retention of the particulate filler within the microporous material.

The microporous material of the present invention may also contain minor amounts, for example, less than or equal to 5% by weight, based on the total weight of the microporous material, for other materials used in processing, such as lubricants, processing plasticizers, organic Extract liquid, water, etc. Additional materials introduced for special purposes such as heat, ultraviolet light and dimensional stability may optionally be present in microporous materials in small amounts, for example, less than or equal to 15 weights based on the total weight of the microporous material. %. Examples of such additional materials include, without limitation, antioxidants, UV absorbers, strong Chemical fibers (such as cut glass fiber strands) and the like. The balance of the microporous material other than the filler and any coating, printing ink, or impregnating agent applied for one or more special purposes is substantially a thermoplastic organic polymer.

The microporous material of the present invention also includes an interconnected pore network that communicates substantially throughout the microporous material. When manufactured by the methods described further herein, the pores typically comprise from 35 to 95 vol%, based on the total volume of the microporous material, on a non-coated, non-printing ink, and no impregnant basis. The pores may constitute from 60 to 75 vol% of the microporous material based on the total volume of the microporous material. As used herein and in the scope of the patent application, the porosity (also referred to as the pore volume) expressed by volume % of the microporous material is determined according to the following equation: porosity = 100 [1-d ₁ /d ₂ ] , d ₁ is the density of the sample, which is determined from the sample weight and sample volume when the sample size is confirmed; and the density of the solid portion of the d ₂ sample is the weight of the sample from the solid portion of the sample and Sample volume determination. The volume of the solid portion of the microporous material was determined using a Quantachrome stereometer (Quantachrome Corp.) in accordance with the operating manual accompanying the instrument.

The volume average diameter of the pores of the microporous material was determined by mercury porosimetry using an Autoscan mercury porosimeter (Quantachrome Corp.) according to the operating manual accompanying the apparatus. The volume average pore radius of a single scan is automatically determined by this porosity meter. For operating the porosimeter, the scanning was performed at a high pressure range (from 138 kPa absolute to 227 MPa absolute). If 2% or less of the total intrusion volume occurs at the lower order of this high pressure range (from 138 to 250 kPa absolute), the volume average pore diameter is twice the volume average pore radius as determined by the porosimeter. Otherwise, an additional scan is performed in the low pressure range (from 7 to 165 kPa absolute) and the volume average pore diameter is calculated according to the following equation: d = 2 [v ₁ r ₁ /w ₁ +v ₂ r ₂ / w ₂ ]/[v ₁ /w ₁ +v ₂ /w ₂ ] wherein d is the volume average pore diameter; v ₁ is the total volume of mercury invaded in the high pressure range; v ₂ is the mercury invading in the low pressure range Total volume; r ₁ is the volume average pore radius determined from the high pressure scan; r ₂ is the volume average pore radius determined from the low pressure scan; w ₁ is the weight of the sample subjected to the high pressure scan; and w ₂ is The weight of the sample subjected to low pressure scanning.

Typically, the pores of the microporous material have a volume average diameter of at least 0.02 microns, typically at least 0.04 microns, and more typically at least 0.05 microns, on a non-coated, non-printing ink, and no impregnant basis. On the same basis, the volume average diameter of the pores of the microporous material is also typically less than or equal to 0.5 microns, more typically less than or equal to 0.3 microns, and more typically less than or equal to 0.25 microns. Based on this, the volume average diameter of the pores can range between any of these values, including the stated values. For example, the pores of the microporous material may have a volume average diameter ranging from 0.02 to 0.5 microns, or from 0.04 to 0.3 microns, or from 0.05 to 0.25 microns, in each case comprising the stated values.

The maximum pore radius detected during the determination of the volume average pore diameter by the above procedure can also be determined. This is taken from the low pressure range scan if it is carried out; otherwise it is taken from the high pressure range scan. The maximum pore diameter of the microporous material is typically twice the maximum pore radius.

Coating, printing, and dipping methods result in at least some of the pores filling the microporous material. In addition, these methods can also irreversibly compress the microporous material. Thus, parameters relating to porosity, volume average diameter of pores, and maximum pore diameter are determined by determining the microporous material prior to application of one or more of such methods.

Several methods of this art are known for making the microporous materials of the present invention. For example, the microporous material of the present invention can be prepared by mixing filler particles, a thermoplastic organic polymer powder, a processing plasticizer, and a small amount of a lubricant and an antioxidant together to obtain a substantially homogeneous mixture. The weight ratio of the particulate filler to the polymer powder used to form the mixture is substantially the same as that of the microporous material to be manufactured. This mixture, together with another processing plasticizer, is typically introduced into a heating sleeve of a screw extruder. Attached to the terminal of the extruder is a tableting die. One continuous sheet formed by the mold is advanced without stretching to a pair of heated calender rolls which cooperate to form a continuous sheet having a thickness that is less than the continuous sheet exiting the mold. The amount of processing plasticizer present in the continuous sheet at this point in the process can vary and affect the density of the final microporous sheet. For example, prior to extraction as described herein below, the amount of processing plasticizer present in the continuous sheet may be greater than or equal to 30% by weight of the continuous sheet, such as greater than or greater than the continuous sheet prior to extraction. Equal to 40% by weight, or greater than or equal to 45% by weight. Furthermore, the amount of processing plasticizer present in the continuous sheet prior to extraction may be less than or equal to 70% by weight of the continuous sheet, such as less than or equal to 65% by weight of the continuous sheet before extraction, Or less than or equal to 60% by weight, or less than or equal to 57% by weight. Before extraction, this side The amount of processing plasticizer present in the continuous sheet at this time may range between any of these values, including the stated values. Generally, the amount of processing plasticizer can vary from 57 to 62 weight percent in one embodiment and less than 57 weight percent in another embodiment.

Then, the continuous sheet from the calender is sent to a first extraction zone, during which the plasticizer is processed by an organic liquid (which is a good solvent for processing the plasticizer, which is bad for the organic polymer system) The solvent, which is more volatile than the processing plasticizer, is extracted and substantially removed. Typically, but not necessarily, both the processing plasticizer and the organic extraction liquid are substantially immiscible with water. The continuous sheet is then sent to a second extraction zone during which the residual organic extract system is substantially removed by steam and/or water. The continuous sheet is then sent to a forced air dryer to substantially remove residual water and leave residual organic extract liquid. From this dryer, a continuous sheet of microporous material is fed to a take-up roll.

The processing plasticizer is liquid at room temperature and is typically a processing oil such as paraffin oil, naphthenic oil, or aromatic oil. Suitable processing oils include those meeting the requirements of ASTM D 2226-82, 103 and 104. More typically, processing oil having a pour point of less than 220 ° C in accordance with ASTM D 97-66 (Reapproved 1978) is used to make the microporous materials of the present invention. Processed plasticizers useful in the preparation of the microporous materials of the present invention are discussed in further detail in column 10, lines 26 to 50 of U.S. Patent No. 5,326,391, the disclosure of which is incorporated herein. reference.

In one embodiment of the present invention, the processed plasticizer composition for preparing a microporous material has a very small melting effect on polyolefin at 60 ° C and an intermediate melting effect at a high temperature of 100 ° C. The processing plasticizer composition is typically a liquid at room temperature. Non-limiting examples of processing oils that may be used may include SHELLFLEX ^® 412 oil, SHELLFLEX ^® 371 oil (Shell Oil Co.), solvent refining and hydrogen treatment oils derived from naphthenic crude oil, ARCOprime ^® 400 oil. (Atlantic Richfield Co.) and KAYDOL ^® oil (Witco Corp.), such as a white mineral oil-based. Other non-limiting examples of processing plasticizers may include phthalate plasticizers such as dibutyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, bicyclo ruthenate Hexyl ester, butyl benzyl phthalate, and di-tridecanoic acid. Mixtures of any of the foregoing processing plasticizers can be used to prepare the microporous materials of the present invention.

There are many organic extraction liquids that can be used to prepare the microporous materials of the present invention. Examples of suitable organic extraction liquids are described in column 10 of the U.S. Patent No. 5,326,391, the entire disclosure of which is incorporated herein by reference.

The extract fluid composition may comprise halogenated hydrocarbons such as chlorinated hydrocarbons and/or fluorinated hydrocarbons. In particular, the extraction fluid composition may comprise a halogenated hydrocarbon and have a calculated solubility parameter Coulomb term (δclb) ranging from 4 to 9 (Jcm ³ ) ^1/2 . Non-limiting examples of halogenated hydrocarbons suitable as the extract fluid composition for use in making the microporous materials of the present invention may comprise selected from the group consisting of trans-1,2-dichloroethylene, 1,1,1,2,2. One or more azeotropes of halogenated hydrocarbons of 3,4,5,5,5-decafluoropentane, and/or 1,1,1,3,3-pentafluorobutane. These materials are the binary azeotrope of VERTREL MCA (1,1,1,2,2,3,4,5,5,5-dihydrodecafluoropentane and trans-1,2-dichloroethylene). : 62%/38%), and VERTREL CCA (1,1,1,2,2,3,4,5,5,5-dihydrodecafluoropentane, 1,1,1,3,3-five Fluorane, and a ternary azeotrope of trans-1,2-dichloroethylene: 33%/28%/39%) are commercially available, both available from MicroCare Corporation.

The residual processed plasticizer content of the microporous material according to the present invention is usually less than 10% by weight based on the total weight of the microporous material, and the content can be further reduced by additional extraction using the same or different organic extract liquids. . Typically, the residual processing plasticizer content is less than 5% by weight based on the total weight of the microporous material, and this level can be further reduced by extra-extraction.

The microporous materials of the present invention can also be made in accordance with the general principles and procedures of U.S. Patent Nos. 2,772,322, 3,696,061, and/or 3,862,030. These principles and procedures are particularly useful when the polymer system of the matrix is predominantly poly(vinyl chloride) or a copolymer containing a large proportion of polymerized vinyl chloride.

The microporous material produced by the above method can be selectively stretched. Stretched microporous materials typically result in an increase in the pore volume of the material and the formation of regions with increased or enhanced molecular orientation. As is known in the art, many of the physical properties of molecularly oriented thermoplastic organic polymers (including tensile strength, tensile modulus, Young's modulus, etc.) are related to thermoplastic organic polymers having minimal or no molecular orientation. , for example, quite different. Stretching is typically accomplished after substantially removing the processing plasticizer as described above.

Various types of stretching implements and methods are known to those skilled in the art and can be used to accomplish the stretching of the microporous materials of the present invention. The stretching of the microporous material is in the 11th column of the US Patent No. 5,326,391, line 45 to 13 Further details are set forth in column 13 of the column, the disclosure of which is incorporated herein by reference.

The invention is described more specifically in the following examples, which are intended to be illustrative only, as many modifications and variations are apparent to those skilled in the art. All parts and percentages are by weight unless otherwise stated.

example

In the first part of the following examples, the exemplary mixtures and comparative mixtures prepared in the test plant and presented in Table 1, and the sample mixtures prepared in the amplification method are compared with the materials of the commercial samples presented in Table 2. And methods. In Part 2, a method for extruding, calendering and extracting a sheet prepared from a mixture of Part 1 and Part 2 is described. In Section 3, the method used to determine the physical properties reported in Tables 3 and 4 is illustrated. In Sections 4A and 4B, the series of coating formulations used are shown in Tables 5 and 7, and the series of properties of the coated sheets are shown in Tables 6 and 8. The results of the test results for benzyl acetate of the products of Tables 1, 2, 6 and 8 in Table 5 are shown in Tables 9, 10, 11 and 12.

Part 1 - Mixture Preparation

The dry ingredients were weighed into a FM-130D Littleford coulter mixer with a high strength chopper type mixing knife in the order and amount specified in Table 1 (grams (g)). The dry ingredients were premixed for 15 seconds using only a coulter. then. The processing oil (mixed oil) is taken in via a spray nozzle pump at the top of the mixer by a hand pump and operated only with a coulter. The pumping time for these examples varied between 45 and 60 seconds. High-strength chopper knife and coulter It was started and the mixture was mixed for 30 seconds. The mixer is turned off and the inside of the mixer is scraped to ensure that all ingredients are evenly mixed. The mixer was turned on again and both the high intensity chopper and the coulter were turned on and the mixture was mixed for another 30 seconds. The mixer was turned off and the mixture was poured into a storage container.

(a) HI-SIL® 135 precipitated cerium oxide from PPG Industries, Inc.

(b) INHIBISIL75 precipitated calcium citrate from PPG Industries, Inc.

(c) Calcium carbonate from Camel White

(d) TIPURE® R-103 Titanium Dioxide from E.I.du Pont de Nemours and Company

(e) GUR® 4130 Ultra High Molecular Weight Polyethylene (UHMWPE) from Ticona Corp.

(f) FINA® 1288 High Density Polyethylene (HDPE) from Total Petrochemicals

(g) Petrothene® NA206000 LDPE from Lyondell Basel

(h) CYANOX® 1790 Antioxidant from Cytec Industries, Inc.

(i) Calcium stearate lubricant, technical grade

(j) Use of PRO-FAX® 7523 polypropylene copolymer from Ashland Distribution

(k) Foam PE MB from Amacet Corporation, a chemical blowing agent

(l) NanoMax® HDPE Masterbatch Nano Clay from Nanocor

(m) Tufflo® 6056 processing oil from PPC Lubricants

Amplification Example 10-18 is prepared in a factory scaled batch size using equipment of similar specifications to the equipment and procedures described above. These magnified samples were prepared from a mixture of the ingredients listed in Table 2 as a weight percent of the total mixture.

Part 2 - Extrusion, Calendering, and Extraction

The mixtures of Examples 1-9 and Comparative Examples 1-5 were extruded and calendered into the final sheet form using an extrusion system comprising a feed, extrusion and calendering system as described below. The weight loss of the weight feed system (K-tron model K2MLT35D5) was used to supply each individual mixture to a 27 mm twin screw extruder (model Leistritz Micro-27gg). The sleeve of the extruder contains eight temperature zones and a heated joint to one of the tableting dies. The extrusion mixture feed port is located in front of the first temperature zone. A vent is located in the third temperature zone. A vacuum hole is located in the seventh temperature zone.

The mixture was supplied to the extruder at a rate of 90 g/min. Various additional processing oils are also injected at the first temperature zone as needed to achieve a desired total oil content in the extruded sheet. The oil contained in the extruded sheet (extrudate) discharged from the extruder is referred to herein as "extrudate oil" or "process oil" and is based on the total weight of the extruded sheet. It is reported in Table 1 as a weight percentage. According to an embodiment of the present invention, the microporous sheet having a density of more than 0.8 g/cm ³ is obtained when the content of the processing oil (extrudate oil) in the extruded sheet is less than 57% by weight. While not wishing to be bound by any particular theory, it is believed that by experimental evidence at hand, reducing the amount of processing oil in the extruded microporous sheet increases the density of the microporous sheet, for example, to greater than 0.8 g/cm ³ , and The surface of the sheet is altered such that the volatile material transferred to the vapor release surface is more dispersed and does not initially collect into a drop on the surface.

The extrudate from the sleeve is discharged to a 15 cm wide tablet Masterflex® mold with a 1.5 mm discharge opening. The temperature of the extruded melt was 203-210 ° C, and the throughput was 7.5 kg / hr.

The calendering process is accomplished using a three-roll vertical calendering unit having a pinch point and a chill roll. Each of these rolls has a chrome surface. The roll size is about 41 cm in length and 14 cm in diameter. The top roll temperature is maintained between 135 ° C and 140 ° C. The intermediate roll temperature is maintained between 140 ° C and 145 ° C. The bottom roll is a chill roll in which the temperature is maintained between 10 and 21 °C. The extrudate is calendered into a sheet form and passed through a bottom cooling water roll and wound.

A sheet sample cut to a width of up to 25.4 cm and a length of 305 cm was rolled up and placed in a can, and exposed to hot liquid 1,1,2-trichloroethylene for about 7-8 hours. The sheet sample is extracted for oil. Thereafter, the extracted sheet was air dried and subjected to the test method described later.

The mixture of the enlarged examples 10-18 shown in Table 2 is an extrusion system and an oil extraction method using the above-mentioned system for producing a dimensional type, in US 7,196,262, column 7, line 52 to column 8, line 47. The above, which is incorporated herein by reference, is carried out and extruded and calendered into the final sheet form. The final sheet was tested for physical parameters using the test methods described in Section 3. Comparative Examples 6-10 are commercial microporous products as indicated below: CE 6 series TESLIN ^® Digital 10 mil; CE 7 series Teslin ^® SP 6 mil; CE 8 series TESLIN ^® SP 10 mil; CE 9 series TESLIN ^® SP 14 mil; and CE 10 is TESLIN ^® SP 12 mil.

The extrudate oil (% by weight) used in the commercial products of Comparative Examples 6-10 was varied from 57 to 62%.

Part 3 - Tests and Results

The physical properties measured on the extruded and dried film and the results obtained are shown in Tables 3 and 4. The weight percentage of the extrudate oil was measured using a Soxhlet extractor. The weight percentage of the extrudate oil was determined using a sample of the extrudate sheet which was not previously extracted. A sample of approximately 2.25 inches x 5 inches (5.72 cm x 12.7 cm) was weighed and recorded to four decimal places. Each sample was then rolled into a cylinder and placed in a Soxhlet extraction tool and extracted with trichloroethylene (TCE) as a solvent for about 30 minutes. The sample is then removed and dried. The extracted and dried samples were then weighed. The oil weight percentage value (extrudate) was calculated as follows: oil weight % = (starting weight - weight after extraction) x 100 / starting weight.

The thickness was determined using an Ono Sokki thickness gauge EG-225. Two 4.5 inch x 5 inch (11.43 cm x 12.7 cm) samples were cut from each sample and the thickness of each sample was measured at nine positions (at least 3⁄4 inch (1.91 cm) from any end edge). . The arithmetic mean of the readings is recorded in mils to Two digits below the decimal and converted to microns.

The density of the above examples was determined by dividing the average anhydrous weight of two samples measured from each sample by 4.5 inches x 5 inches (11.43 cm x 12.7 cm) by the average volume of the samples. The average volume was obtained by boiling the two samples in deionized water for 10 minutes, removing the two samples and placing them in deionized water at room temperature, and equilibrating at room temperature to weigh each sample suspended in deionized water. And after the surface water is wiped off, it is judged by weighing each sample again in the air. The average volume of the sample is calculated as follows: volume (average) = [(weight of the sample that is lightly rubbed in air - sum of impregnation weight) x 1.002] / 2

The waterless weight is determined by weighing each of the two samples on an analytical scale and multiplying the weight by 0.98, since these samples are assumed to contain 2% moisture.

The porosity reported in Tables 3 and 4 was determined using a Gurley densitometer manufactured by GPI Gurley Precision Instruments of Troy, New York, Model 4340. The reported porosity is the rate at which a sample flows through a sample or its impedance to the flow of air through the sample. The unit of measurement is "Gurley seconds" and represents the time in seconds that 100 cc of air is passed through an area of 1 inch square (6.4 x 10 ^-4 m ² ) using water of 4.88 inches (12.2 x 10 ² Pa). The lower value is equal to less airflow impedance (allowing more air to pass freely). The measurement system is completed using the procedure listed in the MODEL 4340 Automatic Densometer and Smoothness Tester Instruction Manual. The TAPPI method T 460 om-06-Air Resistance of Paper can also be referred to as the basic principle of this measurement.

Part 4A - Coating formulations and coated products

The coatings 1-5 listed in Table 5 were prepared by dispersing CELVOL ^® 325 polyvinyl alcohol in cold water in a 600 ml beaker with gentle agitation. The mild agitation was provided by a 1" (2.54 cm) paddle stirrer driven by an electric stirring motor. The mixture was heated to 190 °F (87.8 °C) and stirred for 20-30 minutes. The resulting solution was cooled to room temperature while stirring. The specific blending amounts and the measured solids formed are shown in Table 5.

Acknowledgment-based coating of no undissolved particles seen TESLIN ^® HD is applied to the microporous substrate sold by the PPG Industries, Pittsburgh, Pa. The coating was applied to a sheet of 8.5 inches x 11 inches (21.59 cm x 27.94 cm), 11 mil thick substrate, each weighing the hair on a one day scale, after which the sheet was placed in a Clean the glass surface and use tape to adhere the corners of the sheet to the glass. A piece of transparent 10 mil thick polyester 11 inches x 3 inches (27.94 cm x 7.62 cm) was placed over the upper edge of the sheet, covering 1⁄2 inch (1.27 cm) from the upper edge of the sheet. The polyester is taped to the glass surface. One of the Diversified Enterprises' wire-wound rods was placed on the sheet 1-2 inches (2.5-5.1 cm) parallel to the upper edge and near the upper edge of the polyester. A disposable pipette was used to deposit a coating of 10-20 milliliters in a bead strip (about 1⁄4 inch (0.64 cm) wide) directly adjacent to and in contact with the metering rod. This rod is attempted to be pulled across the sheet at a continuous/fixed rate. The formed wet sheet was removed from the glass surface, immediately placed on the previous gross weight scale, weighed, and the wet coating weight was recorded. Then, the coated sheet was placed in a forced air oven and dried at 95 ° C. 2 minutes. The dried sheets were removed from the furnace and the same coating procedure was repeated for 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.

The following equation was used to calculate the final dry coating weight.

Calculate the final dry coating weight, g. / m ^ 2 = ((coating solid x 0.01) x (1 wet coat weight + 2nd wet coat weight) / (8.5x10.5) x 1550

Part 4B - Coating formulations and coated products

The procedure of Section 4A was followed by the coating formulation for the preparation of Coatings 6-12, except that the coating 7 was mixed for 2 days prior to use. The coating formulation series is shown in Table 7.

This substrate is based on the use of portions 4B are sold by PPG Industries, Pittsburgh, Pa TESLIN ^® SP1000 the microporous substrate. The same procedure for Part 4A was followed except that some of the sheets were applied on both sides, the first coated surface was allowed to dry before the second applied to the opposite side, and a 9 gauge rod was Used for all coatings. The information on the final coated sheet is contained in Table 8.

(n) WITCOBOND W-240, an aqueous polyurethane dispersion from Chemtura Corporation

(o) Aerosil ^® 200, gas phase cerium oxide from Degussa

(p) HiSil ^® T700, precipitated cerium oxide from PPG Industries, Inc.

(q) Lo-Vel ^® 6200, precipitated cerium oxide from PPG Industries, Inc.

(r) MOMENTIVE LE-410, aqueous hydrazine dispersion from Momentive Performance Materials

(s)HYCAR 26138, an aqueous poly(meth)acrylate dispersion from Lubrizol Advanced Materials, Inc.

Part 5 - Benzoyl acetate test

The gripper assembly for film evaporation rate and performance testing consists of a front clamp having a ring gasket, a rear clamp, a test reservoir cup, and four screws. The test reservoir cup is fabricated from a transparent thermoplastic polymer having an inner diameter defined by a circular diameter at the end edge of the open face of about 4 cm and a depth of no more than 1 cm. The opening face is used to determine the rate of transfer of volatile materials.

Each clamp of the holder assembly has a 1.5 inch (3.8 cm) diameter circular opening for receiving the test reservoir cup and providing an opening for the film exposure test. When a film is placed under test, i.e., a sheet of microporous material having a thickness of from 6 to 18 mils, the holder is placed on top of a cork ring after the holder assembly. The test reservoir cup was placed in the back jig and about 2 ml of benzyl acetate was injected. A disk of about 2 inches (5.1 cm) in diameter is cut from the film sheet and directly on the end edge of the reservoir cup and brought into contact therewith, so that the microporous sheet has a volatile material of 12.5 cm ² The contact surface is exposed to the interior of the reservoir.

Prior to the holder, the clamp is carefully placed over the entire assembly and the screw holes are aligned without disturbing the film disc. When a coated microporous sheet is used, as shown in the table below, the coated surface is placed toward the reservoir or toward the atmosphere. Attach and lock the screws enough to avoid leakage. The annular gasket creates a seal. The gripper is marked to identify the film mold under test. Five to ten replicates were prepared for each test line. For the coated example, five replicates of a control (uncoated sample) were included. For the example in Table 11, there are five control groups for each of the sample lines, and the average evaporation rate of each control group is reported with the corresponding example, and this example is lower than the evaporation rate of the corresponding control group. Percentage reported. The coated surfaces of Examples 19-23 in Table 11 are directed to the atmosphere.

Each gripper assembly is weighed to obtain the starting weight of the entire shotcrete assembly. The assembly is then placed upright in a laboratory chemical fume hood with 5 inches [1.52 meters] (height) x 5 inches [1.52 meters] (width) x 2 inches [0.61 meters) The approximate size of the ruler] (depth). In a test reservoir standing up, benzyl acetate is in direct contact with at least a portion of the contact surface of the volatile material of the microporous sheet. The glass door of the fume hood is pulled down and the air flow through the cabinet is adjusted to have an eight (8) revolution (or turn) cabinet volume per hour. The temperature inside the cabinet was maintained at 25 °C ± 5 °C unless otherwise indicated. The humidity in the fume hood is environmentally friendly. The test reservoir is regularly weighed in this cabinet. The test was implemented for five (5) days. The calculated weight loss of benzyl acetate combined with the elapsed time and the surface area of the microporous sheet exposed to the interior of the test reservoir were used to determine the rate of volatile transfer of the microporous sheet in milligrams per hour/cm ² . The average evaporation rate (mg/hr) of the replicates is reported in the table below for the entire assembly. These two values are linked by the following equation: average evaporation rate (mg/hr) / 12.5 cm ² = volatile material transfer rate (mg/hr * cm ² )

The tolerance (Marg.) indicates a replication with a pass and failure, or the test does not have the failure to "collect" and "drop" the surface of the membrane with benzyl acetate, but with some acetic acid on the surface of the membrane. The bead droplets formed by benzyl ester are also considered unacceptable relatives for the results of the "pass". However, there is a clear performance difference between the FAIL test results and the Marg. test results, as discussed here, the latter is clearly preferred.

The data of Examples 10-18 and Comparative Examples 6-10 of Tables 2, 4 and 10 are illustrative of microporous sheets manufactured by production scale equipment, and it was confirmed that the sheet density was increased (by lowering the extruded sheet) The amount of the extrudate oil was achieved) and the correlation between the tests by benzyl acetate. The data series are summarized in Table 13.

(1) The uncoated microporous material TESLIN ^® HD control group, which is contained in the sample line 24, 25, Comparative Examples 13-16.

(2) The coated surface is oriented toward a reservoir of volatile material.

(3) The coated surface is directed toward the atmosphere.

(4) Uncoated TESLIN ^® HD microporous material control group, which is included in Examples 26, 27 and Comparative Examples 11-12.

While the invention has been described with respect to the preferred embodiments of the present invention, it will be apparent to those skilled in the art Go on.

Claims (35)

A vapor permeable microporous material comprising: (a) a substantially water-insoluble thermoplastic organic polymer matrix comprising a polyolefin; (b) a finely divided substantially water-insoluble particulate filler, the particulate filler distribution Between the substrates and based on the total weight of the microporous material, from 40 to 90% by weight; and (c) an interconnected pore network interconnected substantially at the microporous material Wherein the microporous material has (1) a density of at least 0.8 g/cm ³ , (2) a volatile material contacting surface, and a vapor releasing surface, the volatile material contacting surface and the vapor releasing surface being substantially each other Upper opposite, and (3) when the volatile material contact surface of the vapor permeable microporous material is placed in contact with a volatile material and the vapor release surface is not in direct contact with the volatile material, from 0.04 to 0.6 The rate of transfer of volatile material from the contact surface of the volatile material to the vapor release surface of milligrams per hour (cm ² ), the density of the microporous material being such that when the volatile material is transferred from the contact surface of the volatile material to The vapor release When the surface of the vapor release surface is substantially free of a liquid-based version of the liquid volatile material. The microporous material of claim 1, wherein the microporous material has a density of from 0.8 to 1.2 g/cm ³ . The microporous material of claim 1, wherein the volatile material transfer rate is from 0.30 to 0.55 mg / (hr * cm ² ). The microporous material of claim 1, wherein the volatile material transfer rate is from 0.35 to 0.50 mg / (hr * cm ² ). The microporous material of claim 1, wherein the volatile material contact surface and the vapor release surface each have no coating material. The microporous material of claim 1, wherein at least a portion of the volatile material contact surface has a first coating thereon and/or at least a portion of the vapor release surface has thereon a second coating. The microporous material of claim 6, wherein the first coating layer and the second coating layer are each independently selected from the group consisting of aqueous poly(meth)acrylate dispersions, aqueous polyurethane dispersions, The aqueous eucalyptus dispersion, and one of the groups of such combinations, is formed from an aqueous coating composition. The microporous material of claim 7, wherein the particles of the dispersion of each of the aqueous coating compositions have a particle size of from 200 to 400 nm. The microporous material of item 8 of the request, wherein the first coating and the second coating layer each independently has a coating from 0.01 to 5.5 g / m ² of weight. The microporous material of claim 1, wherein the polyolefin of the water-insoluble thermoplastic organic polymer comprises ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 10 metric/g. The microporous material of claim 10, wherein the ultrahigh molecular weight polyolefin has an ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 18 metric/g. The microporous material of claim 11, wherein the ultrahigh molecular weight polyethylene has There is an intrinsic viscosity ranging from 18 to 39 com/g. The microporous material of claim 1, wherein the polyolefin of the thermoplastic organic polymer comprises substantially linear ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 10 metric/g and an ASTM having less than 50 g/10 min D 1238-86 Condition E Melt Index and a mixture of lower molecular weight polyethylene of at least 0.1 g/10 min ASTM D 1238-86 Condition F Melt Index. The microporous material of claim 13, wherein the substantially linear ultrahigh molecular weight polyethylene constitutes at least 1% by weight of the matrix, and the substantially linear ultrahigh molecular weight polyethylene and the lower molecular weight polyethylene together constitute the matrix The polymer is substantially 100% by weight. The microporous material of claim 14, wherein the lower molecular weight polyethylene comprises high density polyethylene. The microporous material of claim 1, wherein the particulate filler comprises enamel particles comprising particulate cerium oxide. The microporous material of claim 16, wherein the particulate cerium oxide comprises particulate precipitated cerium oxide. The microporous material of claim 1, wherein the pores constitute from 35 to 95% by volume of the microporous material based on the total volume of the microporous material. A vapor permeable microporous material comprising (a) a substantially water-insoluble thermoplastic organic polymer matrix comprising a polyolefin; (b) a finely divided substantially water-insoluble particulate filler, the particulate filler being distributed The substrate is constructed from 40 to 90% by weight based on the total weight of the microporous material; and (c) an interconnected pore network that is substantially interconnected throughout the microporous material; Wherein the microporous material has (1) a density of less than 0.8 g/cm ³ , (2) a volatile material contact surface, and a vapor release surface, the volatile material contact surface and the vapor release surface are substantially each other Upper opposite, and (3) when the volatile material contact surface of the vapor permeable microporous material is placed in contact with a volatile material and the vapor release surface is not in direct contact with the volatile material, from 0.04 to 0.6 a rate of volatile material transfer from the contact surface of the volatile material to the vapor release surface of milligrams per hour (i.e., centimeter ² ), and wherein (i) at least a portion of the contact surface of the volatile material has thereon a first coating, and/or (ii) the At least a portion of the vapor release surface has a second coating thereon, the first coating and the second coating each being independently selected from the group consisting of aqueous poly(meth)acrylate dispersions, aqueous Forming an aqueous coating composition of a polyurethane dispersion, an aqueous eucalyptus dispersion, and a combination of such combinations, when volatile materials are transferred from the volatile material contact surface to the vapor release surface, The vapor release surface is substantially free of liquid volatile materials. The microporous material of claim 19, wherein the microporous material has a density of from 0.4 g/cm ^{3 to} at least 0.8 g/cm ³ . The microporous material of claim 19, wherein the microporous material has a density of from 0.4 g/cm ³ to 0.7 g/cm ³ . The microporous material of claim 19, wherein the volatile material transfer rate is from 0.30 to 0.55 mg / (hr * cm ² ). The microporous material of claim 19, wherein the particles of the dispersion of each of the aqueous coating compositions have a particle size of from 200 to 400 nm. The microporous material of item 23 of the request, wherein the first coating and the second coating layer each independently has a coating from 0.1 to 3 g / m ² of weight. The microporous material of claim 19, wherein the polyolefin comprises ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 10 metric/gram. The microporous material of claim 25, wherein the ultrahigh molecular weight polyolefin is an ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 18 metric gram per gram. The microporous material of claim 26, wherein the ultrahigh molecular weight polyethylene has an intrinsic viscosity ranging from 18 to 39 com/g. The microporous material of claim 19, wherein the matrix comprises substantially linear ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 10 metric/g and ASTM D 1238-86 condition E melting of less than 50 g/10 min An index and a mixture of lower molecular weight polyethylene having a melt index of at least 0.1 g/10 min ASTM D 1238-86. The microporous material of claim 28, wherein the substantially linear ultrahigh molecular weight polyethylene constitutes at least 1% by weight of the matrix, and the substantially linear ultrahigh molecular weight polyethylene and the lower molecular weight polyethylene together comprise the matrix The polymer is substantially 100% by weight. The microporous material of claim 29, wherein the lower molecular weight polyethylene comprises high density polyethylene. The microporous material of claim 19, wherein the particulate filler comprises enamel particles comprising particulate cerium oxide. The microporous material of claim 35, wherein the particulate cerium oxide comprises particulate precipitated cerium oxide. The microporous material of claim 19, wherein the pores constitute from 35 to 95% by volume of the microporous material based on the total volume of the microporous material. A vapor permeable microporous material comprising: (a) a substantially water-insoluble thermoplastic organic polymer matrix comprising ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 10 metric/gram; (b) the essence of finely divided a water-insoluble particulate cerium oxide distributed throughout the matrix and having a composition of from 40 to 90% by weight based on the total weight of the microporous material; and (c) An interconnected pore network interconnected substantially throughout the microporous material, the interconnected pores constituting from 35 to 95% by volume of the microporous material, based on the total volume of the microporous material, The microporous material has (1) a density of from 0.8 to 1.2 g/cm ³ , (2) a volatile material contact surface, and a vapor release surface, the volatile material contact surface and the vapor release surface being substantially each other In contrast, and (3) when the volatile material contact surface of the vapor permeable microporous material is placed in contact with a volatile material and the vapor release surface is not in direct contact with the volatile material, from 0.04 to 0.6 mg. / (hours * cm ² ) from the volatile material a rate of transfer of the volatile material from the contact surface to the vapor release surface, the density of the microporous material being such that when the volatile material is transferred from the contact surface of the volatile material to the vapor release surface, the vapor release surface is substantially absent Liquid volatile material in liquid form. The vapor permeable microporous material of claim 34, wherein (a) the thermoplastic organic polymer comprises substantially linear ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 10 metric gram per gram and having less than 50 grams per 10 minutes ASTM D 1238-86 Condition E melt index and a mixture of at least 0.1 g/10 min ASTM D 1238-86 condition F melt index lower molecular weight polyethylene; (b) the particulate filler is precipitated ceria; c) The volatile material transfer rate of the microporous material is from 0.30 to 0.55 mg / (hr * cm ² ).