CN105745010A

CN105745010A - Microporous material

Info

Publication number: CN105745010A
Application number: CN201480060547.9A
Authority: CN
Inventors: J·L·博伊尔; C·加德纳; C·L·诺克斯; L·M·帕里尼洛; R·斯威舍
Original assignee: PPG Industries Inc
Current assignee: PPG Industries Inc
Priority date: 2013-10-04
Filing date: 2014-09-26
Publication date: 2016-07-06
Also published as: MX2016004289A; KR20160064225A; HK1221431A1; JP2016531965A; EP3052220A1; CA2925895A1; WO2015050784A1; AU2014329889A1; BR112016007432A2; TW201520232A

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

Poromerics

The cross reference of related application

The application is the U.S. Patent Application No. 13/473 in submission on May 16th, 2012 (now abandoning), the part continuation application of 001, it is the U.S. Patent Application No. 12/761 submitted on April 15th, 2010,020 (is now United States Patent (USP) 8,435,631) continuity case, they are all incorporated herein by this.

Invention field

The present invention relates to the poromerics having controlled volatile material transfer character.This poromerics includes thermoplastic organic polymer, particulate filler and interconnected pores network.

Background of invention

Volatile material (such as, aromatic, for instance, air aromatic agent) delivery can be realized by delivery apparatus, this device includes the reservoir containing volatile material.This delivery apparatus or delivery device typically comprise the vapor permeable membrane covering or encapsulating this reservoir.Volatile material in reservoir passes through vapor permeable membrane, and in the air (such as, air) discharged to the atmospheric side of this film.Vapor permeable membrane is manufactured by organic polymer typically and is porous.

Volatile material is usually important factor by the speed of vapor permeable membrane.Such as, if volatile material is too low by the speed of vapor permeable membrane, the character relevant with volatile material (such as, aromatic) can be typically make us low undesirably or can not discover.On the other hand, if volatile material is too high by the speed of vapor permeable membrane, the storage of volatile material can exhaust too quickly, and with volatile material (such as, aromatic) relevant character can make us high undesirably, or too strong (overpowering) in some cases.

Generally it is also expected to make the formation of the liquid volatile material on the atmospheric side of vapor permeable membrane (volatile material in its release to air (such as, to air)) or outside minimize or avoid the formation of.Can be collected (such as by the liquid volatile material outside vapor permeable membrane, coagulation (puddle)) in or beyond this film on side, and spill from delivery device, cause, such as, the goods (such as, medicated clothing or furniture) contacted with this liquid volatile material stain.Volatile material can be caused from the uneven release of delivery device additionally, form liquid volatile material on outside vapor permeable membrane.

Ambient temperature increase further can make volatile material pass through the speed increase of vapor permeable membrane to making us undesirably high speed.Such as, the ambient temperature of increase can be exposed to for the delivery device that car occupant is indoor.Therefore, the increase making to be contained in the speed (it is as the function of the ambient temperature increased) by vapor permeable membrane of the volatile material in this device minimize typically it is desirable that.

It is desirable to exploitation and has the new poromerics of controlled volatile material transfer character.Being desirable to when such poromerics newly developed is used as the vapor permeable membrane of delivery device further, this poromerics makes the formation of the liquid volatile material on the outside of this film or outer surface minimize.Additionally, volatile material should be increased and minimally increase along with ambient temperature by the speed of such poromerics.

Summary of the invention

According to the present invention, it is provided that a kind of poromerics, comprise:

A the substrate of () substantially water-insoluble thermoplastic organic polymer, described organic polymer includes polyolefin；

B substantially water-insoluble particulate filler that () is finely divided, described particulate filler is distributed in whole described substrate, and based on the gross weight gauge of described poromerics, constitutes 40 to 90 weight %；With

C () interconnected pores network, it substantially connects in whole described poromerics；

Wherein, described poromerics has

At least 0.8g/cm³Density,

Volatile material contact surface,

Steam release surface, wherein said volatile material contact surface is mutually substantially relative with described steam release surface, and

0.04 to 0.6mg/ (hour * cm²) described volatile material contact surface to the volatile material transfer rate of described steam release surface, and

Wherein it is transferred to described steam release surface (with 0.04 to 0.6mg/ (hour * cm when volatile material contacts surface from described volatile material²) volatile material transfer rate), described steam release surface is substantially free of the volatile material in liquid form.

Further, the invention provides a kind of poromerics, comprise_:

Wherein said poromerics has

Less than 0.8g/cm³Density,

Volatile material contact surface,

Steam release surface, wherein said volatile material contact surface is mutually substantially relative with described steam release surface, wherein, first coating having at least partially above on (i) described volatile material contact surface, and/or second coating having at least partially above of (ii) described steam release surface

Additionally, the invention provides a kind of poromerics, comprise:

B substantially water-insoluble particulate filler that () is finely divided, described particulate filler is distributed whole described substrate, and based on the gross weight gauge of described poromerics, constitutes from 40 to 90 weight %；With

Wherein said poromerics has,

Volatile material contact surface,

Steam release surface, wherein, described volatile material contact surface is mutually substantially relative with described steam release surface, wherein first coating having at least partially above on (i) described volatile material contact surface, and/or second coating having at least partially above of (ii) described steam release surface, wherein said first coating and described second coating are each independently selected from coating composition (it comprises poly-(vinyl alcohol)), and

At least 0.04mg/ (hour * cm²) described volatile material contact surface to the volatile material transfer rate of described steam release surface, and

Wherein when described poromerics, i.e. through the poromerics that poly-(vinyl alcohol) is coated with, being exposed to the temperature from 25 DEG C to 60 DEG C increases, and described volatile material transfer rate adds less than or equal to 150%.

Detailed description of the invention

As herein with in claim use, term " volatile material contact surface " mean poromerics in the face of and the surface that contacts with volatile material typically, this volatile material such as, is contained in reservoir, describes in detail further below.

As herein with in claim use, term " steam release surface " mean poromerics not in the face of and/or be not directly contacted with the surface of volatile material, and volatile material is to discharge to outside atmosphere with gas or vaporous form surface since then.

As herein with in claim use, the term similar of term " (methyl) acrylate " and such as " (methyl) acrylic acid ester " means acrylate and/or methacrylate.

As herein with in claim use, " the volatile material transfer rate " of poromerics according to following description measure.There is the test reservoir of internal volume of the volatile material (such as benzyl acetate) being enough to hold 2 milliliters by transparent (clear) thermoplastic polymer manufacture.The inside dimension of this reservoir is to limit in the circular diameter of the edge substantially 4 centimetres of the face of opening (openface) and the degree of depth being not more than 1 centimetre.The face of opening is to measure volatile material transfer rate.When testing reservoir and keeping flat (make to open and face up), the benzyl acetates of about 2 milliliters are introduced in test reservoir.After benzyl acetate being introduced in test reservoir, the poromerics sheet with 6 to 18 mil thickness is placed on the face of the opening/side of test reservoir so that the 12.5cm of microperforated sheet²Volatile material contact surface be exposed to inside reservoir.Test reservoir is weighed to obtain the starting weight of whole charging assembling.Then, containing benzyl acetate and with poromerics sheet encapsulating test reservoir by the laboratory chemical ventilating kitchen being erectly positioned over the size with substantially 5 feet of [1.52 meters] (highly) x5 feet [1.52 meters] (width) x2 foot [0.61 meter] (degree of depth).When testing reservoir and being upright, acetic acid Bian ester contacts at least some of directly contact on surface with the volatile material of microperforated sheet.The glass door of ventilating kitchen is pulled down, and adjusts the air stream through this kitchen (hood), so that having eight (8) the kitchen volumes turning (turn) (or turnover number (turnover)) per hour.Unless otherwise directed, in kitchen, temperature maintains 25 DEG C ± 5 DEG C.Humidity in ventilating kitchen is ambient humidity.Test reservoir routine weighing in this kitchen.The benzyl acetate loss in weight calculated is used to measure the volatility transfer rate of microperforated sheet in conjunction with the elapsed time with the microperforated sheet surface area being exposed within test reservoir, and unit is mg/ (hour * cm²)。

As herein with in claim use, the poromerics of the present invention is according to said method mensuration for the independence 25 DEG C and 60 DEG C but substantially equivalent poromerics samples of sheets from the percentage ratio that the volatile material transfer rate of 25 DEG C to 60 DEG C increases.Reservoir is placed in big glass bell jar, and is placed on 50% potassium chloride solution being also contained in this bell jar.The whole bell jar with content is placed in heating to the stove of 60 DEG C.Reservoir maintains the time period of 7 to 10 hours under these conditions.Then, make reservoir return in the kitchen of environmental condition and continue a whole night, and this process is repeated last from days.Each reservoir in being placed in clock and putting before and remove from bell jar and to weigh afterwards.When removing from bell jar, after reservoir returns to ambient temperature, weigh the weight of each reservoir.

As herein with in claim use, following methods is used to determine whether the steam release surface of poromerics " is substantially free of the volatile material in liquid form ".When testing reservoir and weighing as mentioned above, check the steam release surface of microperforated sheet is so that whether the drop and/or film determining liquid exists thereon by macroscopic visual.If by being visually observed the drop (that is, single drop) of liquid and/or any evidence of film but not at Surface runoff (runoff) on steam release surface, then it is assumed that microperforated sheet is acceptable.If the drop of volatile material liquid flows at steam release surface, then it is assumed that microperforated sheet lost efficacy.If not being visually observed the drop (namely, it does not have) of liquid and/or the evidence of film on steam release surface, then microperforated sheet is confirmed as being substantially free of the volatile material in liquid form.

Unless otherwise directed, all scopes disclosed herein are understood to contain any and all subrange comprised in it.Such as, the stated ranges of " 1 to 10 " should be believed to comprise between minima 1 and maximum 10 any and all subrange of (and comprising end value)；That is, with minima 1 or bigger beginning and with all subranges of maximum 10 or less end, for instance, 1 to 6.1,3.5 to 7.8,5.5 to 10 etc..But, any numerical value is substantially to contain some error that necessarily causes of standard deviation found in its each test is measured, including find in test instrunment those.

Unless otherwise directed, all numerals or statement (such as represent physical dimension, component amount etc. those) are in description and claims, it is thus understood that modified by term " about " in all cases.Therefore, unless contrary instructions, the numerical parameter shown in this specification and appended is approximation, and it can be depending on the present invention and seeks the results needed of acquisition and change.At least, and the application of doctrine of equivalents is limited to scope of the claims by non-attempt, each numerical parameter need at least in view of report number of significant digit and explain by applying the common technology of rounding up.Additionally, used in such specification and appended, unless clearly and be unambiguously limited to one to mention thing, singulative " ", " one " and " being somebody's turn to do " are intended to include plural number and mention thing.

Term " volatile material " as herein with in claim use, mean environmental chamber moderate pressure and be absent from give other or supplementary energy (such as, with heat and/or stir form) under can change into gas or the material of vaporous form (that is, can volatilize).Volatile material can comprise organic volatile material, and it can include those volatile materials containing solvent based materials, or is scattered in those in solvent based material.Volatile material can be liquid form and/or solid form, and for naturally occurring or can be synthetically formed.When in solid form, volatile material is typically sublimed into vaporous form from solid form, and without intermediate liquid form.Volatile material optionally with non-volatile materials (such as, carrier, for instance, water and/or non-volatile solvents) combination or allotment.When solid volatile material, nonvolatile vehicle can be porous material form, for instance, porous inorganic material, solid volatile material retains in the inner.Additionally, solid volatile material can be semi-solid gel form.

Volatile material can be fragrance material, such as, and the essential oil naturally occurring or synthesizing.The example being selected as the essential oil of liquid volatile material includes but not limited to Fructus Citri Sarcodactylis, bigarabe, Fructus Citri Limoniae, Citrus, Herba Coriandri, cedar leaf, Folium Caryophylli, cedar wood, Flos Pelargonii, Garden lavender, orange, Adeps Bovis seu Bubali, Petitgrain, white fir wood, Herba Pogostemonis, orange blossom oil, rose absolute and the oil of their combination.The example being selected as the solid aromatic agent material of volatile material includes but not limited to vanillin, ethyl vanillin, coumarin, tonalid, watermelon ketone (calone), Helianthi essence (heliotropene), musk xylene, cedrol, musk ketone benzophenone, raspberry ketone, methyl naphthyl ketone β, phenylethyl salicylate, meat flavor essence (veltol), maltol, maple lactone, former acetaminol (proeugenol) acetas, oak moss (evemyl) and their combination.

The volatile material transfer rate of poromerics may be less than or equal to 0.7mg/ (hour * cm²), or less than or equal to 0.6mg/ (hour * cm²), or less than or equal to 0.55mg/ (hour * cm²), or less than or equal to 0.50mg/ (hour * cm²).The volatile material transfer of poromerics can be equal to or more than 0.02mg/ (hour * cm²), or equal to or more than 0.04mg/ (hour * cm²), or equal to or more than 0.30mg/ (hour * cm²), or equal to or more than 0.35mg/ (hour * cm²).The volatile material transfer rate scope of poromerics can be between these higher limits and any combination of lower limit.Such as, the volatile material transfer rate of poromerics can be from 0.04 to 0.6mg/ (hour * cm²), or from 0.2 to 0.6mg/ (hour * cm²), or from 0.30 to 0.55mg/ (hour * cm²), or from 0.35 to 0.50mg/ (hour * cm²), include described value in either case.

Although being not intended to system limited by any theory, but when volatile material is transferred to steam release surface from the volatile material contact surface of poromerics, it is believed that volatile material is to be selected from liquid, steam, and the form of their combination.Additionally, and be not intended to system limited by any theory, it is believed that volatile material is moved through connecting the interconnected pores network of substantially whole poromerics at least partly.Typically, the transfer of volatile material is from 15 DEG C to 40 DEG C, for instance, from the temperature of 15 or 18 DEG C to 30 or 35 DEG C, and occur at environment atmospheric pressure.

Poromerics can have at least 0.7g/cm³Or at least 0.8g/cm³Density.As herein with in claim use, the density of poromerics is to measure by measuring the weight and volume of sample of poromerics.The upper limit of poromerics density can for being extensively varied, and condition is that it has, for instance, from 0.04 to 0.6mg/ (hour * cm²) target volatile material transfer rate, and when volatile material from volatile material contact surface be transferred to described steam release surface time, steam release surface is substantially free of the volatile material in liquid form.Typically, the density of poromerics is less than or equal to 1.5g/cm³, or less than or equal to 1.0g/cm³.The density of poromerics can be between any of above numerical value, including described value.Such as, poromerics can have 0.7g/cm³To 1.5g/cm³Density, such as, 0.8g/cm³To 1.2g/cm³, including described value.

When poromerics has at least 0.7g/cm³, such as, at least 0.8g/cm³Density time, poromerics volatile material contact surface and steam release surface each can thereon without coating material.When thereon without coating material, volatile material contact surface and steam release surface are individually and limit with poromerics.

When poromerics has at least 0.7g/cm³, such as, at least 0.8g/cm³Density time, at least some of of the volatile material contact surface of poromerics optionally can have the first coating thereon, and/or at least some of of the steam release surface of poromerics optionally can have the second coating thereon.First coating and the second coating can be identical or different.When volatile material contacts when having the first coating thereon at least partially of surface, volatile material contact surface is limited by the first coating at least partly.When having the second coating thereon at least partially of steam release surface, steam release surface is limited by the second coating at least partly.

First coating and the second coating each can be formed by the coating selected from liquid coating and solid particle coating (such as, powder coating).Typically, the first and second coatings are formed by the coating selected from liquid coating independently of one another, and this liquid coating optionally includes the solvent being selected from water, organic solvent and their combination.First and second coatings are selected from cross-linking coating independently of one another, for instance, thermoset coating and light curable coating；With non-crosslinkable coating, for instance, air drying coating.First and second coatings can be applied to each surface of poromerics according to the method for this area accreditation, such as, spraying, curtain coating, dip-coating, and/or blade coating (draw-downcoating), such as, by scraper or drawdown rod (draw-downbar) technology.

First and second coating compositions optionally include the additive of this area accreditation independently of one another, such as, antioxidant, UV light stabilizing agent, flow control agent, dispersion stabilizer are (such as, when aqueous dispersion), with coloring agent (such as, dyestuff and/or pigment).Typically, the first and second coating compositions are without coloring agent, and therefore substantial transparent or opaque.The gross weight gauge of coating based compositions, optional additive is passable, for instance, it is present in coating composition from the separate amount of 0.01 to 10 weight %.

First coating and described second coating can be formed by the water-based paint compositions of organic polymer material including being dispersed through independently of one another.Water-based paint compositions can have the particle size of 200 to 400nm.The solid of water-based paint compositions can be extensively varied, for instance, based on the gross weight gauge of water-based paint compositions in each case, from 0.1 to 30 weight %, or from 1 to 20 weight %.The organic polymer comprising water-based paint compositions can have, for instance, from 1000 to 4,000,000, or from 10,000 to 2, the number-average molecular weight (Mn) of 000,000.

Water-based paint compositions is selected from aqueous poly-(methyl) acrylate dispersoid, aqueous pu dispersions, waterborne organic silicon (or silicon) oil dispersion and their combination.Poly-(methyl) acrylate polymer of poly-(methyl) acrylate dispersoid of aqueous can be prepared according to the method for this area accreditation.Such as, poly-(methyl) acrylate polymer may be included in the residue (or monomeric unit) of (methyl) alkyl acrylate in alkyl group with 1 to 20 carbon atom.The example of (methyl) alkyl acrylate in alkyl group with 1 to 20 carbon atom includes but not limited to (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) propyl acrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 3, 3, 5-3-methyl cyclohexanol ester.Purpose for non-limitative illustration, the example of poly-(methyl) acrylate dispersoid (the first and second coating compositions can be each independently selected from it) of aqueous is HYCAR26138, it is available commercially from LubrizolAdvancedMaterials, Inc..

The polyether polyols with reduced unsaturation (the first and second coatings can be each independently selected from it) of aqueous pu dispersions include known to those skilled in the art any those.Typically, polyether polyols with reduced unsaturation is by the isocyanate-functional material with two or more isocyanate groups, and prepared by the reactive hydrogen functional material with two or more active hydrogen group.Active hydrogen group is selected from, for instance, oh group, thiol group, primary amine, secondary amine, and their combination.For the purpose of non-limitative illustration, the example of aqueous pu dispersions (the first and second coating compositions can be each independently selected from it) is WITCOBONDW-240, and it is available commercially from ChemturaCorporation.

The silicon polymer of aqueous silicone oil dispersion body is selected from known and this area accreditation aqueous silicone oil dispersion body.For the purpose of non-limitative illustration, the example of aqueous silicon dispersion (the first and second coating compositions can be each independently selected from it) is MOMENTIVELE-410, and it is available commercially from MomentivePerformanceMaterials.

First coating and the second coating can apply by any applicable thickness independently of one another, and condition is that poromerics has, for instance, from 0.04 to 0.6mg/ (hour * cm²) target volatile material transfer rate, and when volatile material from volatile material contact surface be transferred to described steam release surface time, steam release surface is substantially free of the volatile material in liquid form.Additionally, the first coating and the second coating can have 0.01 to 5.5g/m independently of one another², such as, from 0.1 to 5.0g/m², or from 0.5 to 3g/m², or from 0.75 to 2.5g/m², or from 1 to 2g/m²Coating weight, i.e. the coating weight on poromerics.

Poromerics can have less than 0.8g/cm³Density, and first coating can having at least partially above on the volatile material contact surface of poromerics, and/or second coating can having at least partially above of the steam release surface of poromerics.First coating and the second coating can be identical or different, and independently of one another as herein previously with respect to having at least 0.8g/cm³Density poromerics the first and second optional coatings described in.

When less than 0.8g/cm³Time, the density of the poromerics of the present invention can have any applicable lower limit, and condition is that poromerics has, for instance, from 0.04 to 0.6mg/ (hour * cm²) target volatile material transfer rate, and when volatile material from volatile material contact surface be transferred to described steam release surface time, steam release surface is substantially free of the volatile material in liquid form.In this particular implementation of the present invention, the density of poromerics can be from 0.6 to less than 0.8g/cm³, or from 0.6 to 0.75g/cm³, for instance, from 0.60 to 0.75g/cm³, or from 0.6 to 0.7g/cm³, for instance, from 0.60 to 0.70g/cm³, or from 0.65 to 0.70g/cm³。

In addition, first coating can having at least partially above on the volatile material contact surface of poromerics, and/or second coating having at least partially above of the steam release surface of poromerics, wherein, the first and second coatings are each independently selected from the coating composition comprising poly-(vinyl alcohol).

In the embodiment that the warp poly-(vinyl alcohol) of the present invention is coated with, work as poromerics, that is, when the poromerics being coated with through poly-(vinyl alcohol) is exposed to the temperature increase from 25 DEG C to 60 DEG C, its volatile material transfer rate increases less than or equal to 150%.When the poromerics being coated with through poly-(vinyl alcohol) is exposed to from ambient temperature, for instance, from the temperature of 25 DEG C to 60 DEG C increase time, volatile material transfer rate typically increases, and typically will not reduce, unless, such as, poromerics is impaired because being exposed to higher ambient temperature.Therefore, and as herein with in claim use, statement " its volatile material transfer rate increase less than or equal to [elaboration] percentage ratio ", for instance, 150%, including the lower limit of 0%, but do not include the lower limit less than 0%.

For illustrative purposes, it is 0.3mg/ (hour * cm that the poromerics being coated with when warp poly-(vinyl alcohol) has at 25 DEG C²) volatile material transfer rate time, and when poromerics is exposed to the temperature of 60 DEG C, volatile material transfer rate increases to less than or equal to 0.75mg/ (hour * cm²) value.

In one embodiment, poromerics is worked as, i.e. through the poromerics that poly-(vinyl alcohol) is coated with, when being exposed to the temperature increase from 25 DEG C to 60 DEG C, its volatile material transfer rate increases less than or equal to 125%.Such as, it is 0.3mg/ (hour * cm that the poromerics being coated with when warp poly-(vinyl alcohol) has at 25 DEG C²) volatile material transfer rate time, and when poromerics is exposed to the temperature of 60 DEG C, volatile material transfer rate increases to less than or equal to 0.68mg/ (hour * cm²) value.

Additionally, work as poromerics, i.e. through the poromerics that poly-(vinyl alcohol) is coated with, when being exposed to the temperature increase from 25 DEG C to 60 DEG C, its volatile material transfer rate increases less than or equal to 100%.Such as, it is 0.3mg/ (hour * cm that the poromerics being coated with when warp poly-(vinyl alcohol) has at 25 DEG C²) volatile material transfer rate time, and when poromerics is exposed to the temperature of 60 DEG C, volatile material transfer rate increases to less than or equal to 0.6mg/ (hour * cm²) value.

First and second poly-(vinyl alcohol) coatings each can exist with any applicable coating weight independently, and condition is that poromerics has, for instance, at least 0.04mg/ (hour * cm²) target volatile material transfer rate, and work as poromerics, i.e. through the poromerics that poly-(vinyl alcohol) is coated with, be exposed to from the temperature of 25 DEG C to 60 DEG C increase time, its volatile material transfer rate increases less than or equal to 150%.Typically, the first poly-(vinyl alcohol) coating and second poly-(vinyl alcohol) coating have 0.01 to 5.5g/m independently of one another², or from 0.1 to 4.0g/m², or from 0.5 to 3.0g/m², or from 0.75 to 2.0g/m²Coating weight.

The volatile material transfer rate of the poromerics being coated with through poly-(vinyl alcohol) can be at least 0.02mg/ (hour * cm²).Can be equal to or more than 0.04mg/ (hour * cm through gathering the volatile material transfer rate of the poromerics that (vinyl alcohol) is coated with²), or equal to or more than 0.1mg/ (hour * cm²), or equal to or more than 0.2mg/ (hour * cm²), or equal to or more than 0.30mg/ (hour * cm²), or equal to or more than 0.35mg/ (hour * cm²).Volatile material transfer rate through gathering the poromerics that (vinyl alcohol) is coated with may be less than or equal to 0.7mg/ (hour * cm²), or less than or equal to 0.6mg/ (hour * cm²), or less than or equal to 0.55mg/ (hour * cm²), or less than or equal to 0.50mg/ (hour * cm²).The volatile material transfer rate scope of the poromerics being coated with through poly-(vinyl alcohol) can between these higher limits and any combination of lower limit, including described value.Such as, the volatile material transfer rate of the poromerics being coated with through poly-(vinyl alcohol) can be at least 0.02mg/ (hour * cm²), such as, from 0.04 to 0.70mg/ (hour * cm²), or from 0.04 to 0.60mg/ (hour * cm²), or from 0.20 to 0.60mg/ (hour * cm²), or from 0.30 to 0.55mg/ (hour * cm²), or from 0.35 to 0.50mg/ (hour * cm²), include described value in each case.

The poromerics density through gathering the poromerics that (vinyl alcohol) is coated with of embodiment of the present invention can be widely varied, and condition is that the poromerics being coated with through poly-(vinyl alcohol) has, for instance, at least 0.04mg/ (hour * cm²) target volatile material transfer rate, and work as poromerics, i.e. through the poromerics that poly-(vinyl alcohol) is coated with, be exposed to from the temperature of 25 DEG C to 60 DEG C increase time, its volatile material transfer rate increases less than or equal to 150%.

Additionally, the poromerics density of the poromerics being coated with through poly-(vinyl alcohol) can be at least 0.7g/cm³, such as, at least 0.8g/cm³, for instance, from 0.8 to 1.2g/cm³, all include described value.In one embodiment of the present invention, the density of the poromerics being coated with through poly-(vinyl alcohol), i.e. apply the density of poromerics before poly-(vinyl alcohol) coating less than 0.8g/cm³.Such as, the poromerics density of the poromerics being coated with through poly-(vinyl alcohol) can be from 0.6 to less than 0.8g/cm³, or from 0.6 to 0.75g/cm³, for instance, from 0.60 to 0.75g/cm³, or from 0.6 to 0.7g/cm³, for instance, from 0.60 to 0.70g/cm³, or from 0.65 to 0.70g/cm³, all include described value.

About the poromerics being coated with through poly-(vinyl alcohol) of the present invention, when volatile material is transferred to steam release surface from volatile material contact surface, steam release surface is substantially free of the volatile material in liquid form.

Poly-(vinyl alcohol) coating is selected from liquid coating, and it optionally includes being selected from water, organic solvent and the solvent of their combination.Poly-(vinyl alcohol) coating is selected from crosslinkable coating, for instance, thermoset coating；With non-crosslinkable coating, for instance, air drying coating.Poly-(vinyl alcohol) coating can be applied to each surface of poromerics according to the method for this area accreditation, such as, spraying, curtain coating, or scraper coating, for instance, by scraper or drawdown rod.

In one embodiment, first and second poly-(vinyl alcohol) coatings are formed by poly-(vinyl alcohol) coating composition of aqueous independently of one another.The solid of poly-(vinyl alcohol) coating composition of aqueous can extensively change, for instance, in each case, based on the gross weight gauge of water-based paint compositions, it is 0.1 to 15 weight %, or from 0.5 to 9 weight %.Poly-(vinyl alcohol) polymer of poly-(vinyl alcohol) coating composition can have, for instance, from 100 to 1,000,000, or from 1000 to 750, the number-average molecular weight (Mn) of 000.

Poly-(vinyl alcohol) polymer of poly-(vinyl alcohol) coating composition can be homopolymer or copolymer.The comonomer of poly-(vinyl alcohol) copolymer can be prepared include closing (passing through radical polymerization) with vinyl acetate copolymerization and be those known to those skilled in the art.For illustrative purposes, the comonomer that can prepare poly-(vinyl alcohol) copolymer includes but not limited to: (methyl) acrylic acid, maleic acid, fumaric acid .beta.-methylacrylic acid, their slaine, their Arrcostab, for instance, their C₂-C₁₀Arrcostab, their macrogol ester, and their polypropylene glycol ester；Vinyl chloride；Tetrafluoroethene；2-acrylamido-2-methyl-propanesulfonic acid and salt thereof；Acrylamide；N-alkyl acrylamide；Through the acrylamide that N, N-dialkyl group replaces；With N-vinyl formamide.

Purpose for non-limitative illustration, may be used to form the example of poly-(vinyl alcohol) coating composition through gathering the poromerics that (vinyl alcohol) is coated with of the present invention is CELVOL325, and it is available commercially from SekisuiSpecialtyChemicals.

First and second poly-(vinyl alcohol) coating compositions each can include the additive of this area accreditation independently, such as, antioxidant, UV light stabilizing agent, flow control agent, dispersion stabilizer are (such as, when aqueous dispersion), with coloring agent (such as, dyestuff and/or pigment).Typically, first and second poly-(vinyl alcohol) coating compositions are without coloring agent, and are therefore transparent or opaque.The gross weight gauge of coating based compositions, optional additive is passable, for instance, it is present in poly-(vinyl alcohol) coating composition from the separate amount of 0.01 to 10 weight %.

The substrate of poromerics comprises substantially water-insoluble thermoplastic organic polymer.The value volume and range of product of this polymer being suitable for use as this substrate is big.Generally, can use and can be extruded, roll, suppress, or be rolled into (rollinto) film, sheet material, web or any substantially water-insoluble thermoplastic organic polymer of web material.Polymer can be single polymers, or it can be the mixture of polymer.Polymer can be homopolymer, copolymer, random copolymer, block copolymer, graft copolymer, atactic polymer, isotachyte, syndiotactic polymer, linear polymer, or branched polymer.When using the mixture of polymer, this mixture can be uniform or it can comprise two or more polymer phase.

The example of kind of the substantially water-insoluble thermoplastic organic polymer being suitable for includes thermoplastic polyolefin-like, poly-(through the alkene that halogen replaces) class, polyesters, polyamide-based, polyurethanes, polyureas, poly-(halogen ethylene) class, poly-(vinylidene halide) class, polystyrene type, poly-(vinyl acetate) class, polycarbonate-based, polyethers, multiple sulfides, polyimide, polysilanes, polysiloxane-based, polycaprolactone class, polyacrylate and polymethacrylate.The intended kind (substantially water-insoluble thermoplastic organic polymer is selected from it) that mixes includes, such as, thermoplastic poly (carbamate-urea) class, poly-(ester-acid amide) class, poly-(silane-siloxanes) class, and poly-(ether-ester) class.The further example of the substantially water-insoluble thermoplastic organic polymer being suitable for includes thermoplastic high density's polyethylene, Low Density Polyethylene, ultra-high molecular weight polyethylene, polypropylene (atactic, isotaxy, or syndiotaxy), poly-(vinyl chloride), politef, ethylene and acrylic acid copolymer, the copolymer of ethylene and methacrylic acid, poly-(vinylidene chloride), the copolymer of vinylidene chloride and vinyl acetate, the copolymer of vinylidene chloride and vinyl chloride, the copolymer of ethylene and propylene, the copolymer of ethylene and butylene, poly-(vinyl acetate), polystyrene, poly-(omega-amino undecanoic acid), poly-(hexamethylene adipamide), poly-(epsilon-caprolactams), with poly-(methyl methacrylate).These kinds of substantially water-insoluble thermoplastic organic polymer and example enumerate non-and limit, but be only used as descriptive purpose and provide.

Substantially water-insoluble thermoplastic organic polymer can include especially, for instance, the copolymer of poly-(vinyl chloride), vinyl chloride, or their mixture.In one embodiment, water-insoluble thermoplastic organic polymer includes being selected from following extrahigh-molecular weight polyolefins: have the extrahigh-molecular weight polyolefins of the intrinsic viscosity of at least 10 deciliter/gram, for instance, the extrahigh-molecular weight polyolefins of substantial linear；Or there is the ultrahigh molecular weight polypropylene of the intrinsic viscosity of at least 6 deciliter/gram, for instance, the ultrahigh molecular weight polypropylene of substantial linear；Or their mixture.In a specific embodiment, water-insoluble thermoplastic organic polymer includes the ultra-high molecular weight polyethylene with the intrinsic viscosity of at least 18 deciliter/gram, for instance, linear ultra-high molecular weight polyethylene.

Ultra-high molecular weight polyethylene (UHMWPE) is not the thermosetting polymer with infinite molecular weight, but technique classification is thermoplastic.But, because molecule is the chain substantially grown very much, UHMWPE softens when heated, but will not flow as melt liquid with general thermoplastic manner.This chain grown very much and they be supplied to the special nature of UHMWPE it is believed that the poromerics that contributes to using this polymer to a great extent it is desirable that character.

As previously indicated, the intrinsic viscosity of UHMWPE is at least about 10 deciliter/gram.Generally, intrinsic viscosity is at least about 14 deciliter/gram.Often, intrinsic viscosity is at least about 18 deciliter/gram.In many cases, intrinsic viscosity is at least about 19 deciliter/gram.Although the upper limit for intrinsic viscosity is not particularly limited, but intrinsic viscosity is usually in the scope of from about 10 to about 39 deciliter/gram, for instance, in the scope of from about 14 to about 39 deciliter/gram.In most cases, the intrinsic viscosity of UHMWPE is in the scope of from about 18 to about 39 deciliter/gram, and typically about 18 to about 32 deciliter/gram.

According to below equation, the nominal molecular weight of UHMWPE is rule of thumb relevant to the intrinsic viscosity of polymer:

M (UHMWPE)=5.3x10⁴[η]^1.37

Wherein, M (UHMWPE) is nominal molecular weight, and the intrinsic viscosity that [η] is UHMW polyethylene, represents with deciliter/gram.

As herein with in claim use, intrinsic viscosity is the reduced viscosity of the weak solution by making some UHMWPE or intrinsic viscosity is extrapolated to zero-dose and determines, wherein, solvent is added 0.2 weight % 3,5-di-t-butyl-4-hydroxyhydrocinnamic acid, neopentane four base ester [CAS accession number 6683-19-8] newly distill decahydronaphthalene.The reduced viscosity of UHMWPE or intrinsic viscosity are to use UbbelohdeNo.1 viscosimeter, are the general procedures according to ASTMD4020-81, the relative viscosity obtained at 135 DEG C confirm, except that some weak solutions with variable concentrations.ASTMD4020-81 is incorporated by with it by reference at this.

In a specific embodiment, substrate comprises the ultra-high molecular weight polyethylene of the substantial linear of the intrinsic viscosity with at least 10 deciliter/gram, and has less than 50 grams the/mixture of the lower molecular weight polyethylene (LMWPE) of the ASTMD1238-86 condition F melt index of the ASTMD1238-86 condition E melt index of 10 minutes and at least 0.1 gram/10 minutes.The nominal molecular weight of LMWPE is lower than the nominal molecular weight of UHMW polyethylene.LMWPE is thermoplastic, and many dissimilar be known.According to ASTMD1248-84 (1989 again check and approve), a kind of sorting technique is by with gram/cc density represented, and is rounded to immediate thousand points of positions, as outlined below:

Any or all of polyethylene of these polyethylene can be used as the LMWPE in the present invention.For some application, HDPE can be used, because it normally tends to more more linear than MDPE or LDPE.ASTMD1248-84 (again checks and approves 1989) and is incorporated by with it by reference at this.

For manufacture the method for various LMWPE be know and good record.They include high pressure method, PhillipsPetroleumCompany method, StandardOilCompany (Indiana) method and Ziegler method.

ASTMD1238-86 condition E (that is, 190 DEG C and the 2.16 kilograms of load) melt index of LMWPE was less than approximately 50 grams/10 minutes.Generally, condition E melt index was less than approximately 25 grams/10 minutes.Typically, condition E melt index was less than approximately 15 grams/10 minutes.

ASTMD1218-86 condition F (that is, 190 DEG C and the 21.6 kilograms of load) melt index of LMWPE is at least 0.1 gram/10 minutes.In many cases, condition F melt index is at least about 0.5 gram/10 minutes.Typically, condition F melt index is at least about 1.0 grams/10 minutes.ASTMD1238-86 is incorporated by with it by reference at this.

Enough UHMWPE and LMWPE should be present in substrate, so that their character is supplied to poromerics.Other thermoplastic organic polymer also is present in substrate, as long as the presence of which does not substantially affect the character of poromerics in harmful manner.One or more other thermoplastic polymers may be present in substrate.The amount of other thermoplastic polymer that can exist depends on the character of this polymer.The example of the thermoplastic organic polymer that may be optionally present includes but not limited to gather the copolymer of (tetrafluoroethene), polypropylene, ethylene and propylene, ethylene and acrylic acid copolymer and the copolymer of ethylene and methacrylic acid.If expectation, the carboxylic group of all or part of carboxylic copolymer can use sodium, zinc etc. to neutralize.

In most cases, UHMWPE and LMWPE constitutes at least about 65 weight % of the polymer of substrate together.Generally, UHMWPE and LMWPE constitutes at least about 85 weight % of the polymer of substrate together.Typically, other thermoplastic organic polymer it is substantially absent from so that UHMWPE and LMWPE constitutes the substantially 100 weight % of the polymer of substrate together.

UHMWPE may make up at least 1 weight % of the polymer of substrate.When UHMWPE and LMWPE constitutes the 100 weight % of polymer of substrate of poromerics together, UHMWPE may make up the polymer of substrate more than or equal to 40 weight %, such as, the polymer of substrate more than or equal to 45 weight %, or more than or equal to 48 weight %, or more than or equal to 50 weight %, or more than or equal to 55 weight %.Additionally, UHMWPE may make up the polymer of substrate less than or equal to 99 weight %, such as, the polymer of substrate less than or equal to 80 weight %, or less than or equal to 70 weight %, or less than or equal to 65 weight %, or less than or equal to 60 weight %.Comprise the polymer of substrate UHMWPE content can between these numerical value any, including described value.

Similarly, when UHMWPE and LMWPE constitutes the 100 weight % of polymer of substrate of poromerics together, LMWPE may make up the polymer of substrate more than or equal to 1 weight %, such as, the polymer of substrate more than or equal to 5 weight %, or more than or equal to 10 weight %, or more than or equal to 15 weight %, or more than or equal to 20 weight %, or more than or equal to 25 weight %, or more than or equal to 30 weight %, or more than or equal to 35 weight %, or more than or equal to 40 weight %, or more than or equal to 45 weight %, or more than or equal to 50 weight %, or more than or equal to 55 weight %.Additionally, LMWPE may make up the polymer of substrate less than or equal to 70 weight %, such as, the polymer of substrate less than or equal to 65 weight %, or less than or equal to 60 weight %, or less than or equal to 55 weight %, or less than or equal to 50 weight %, or less than or equal to 45 weight %.The content range of LMWPE can between these numerical value any, including described value.

It should be noted that for any aforementioned poromerics of the present invention, LMWPE can comprise high density polyethylene (HDPE).

Poromerics also includes finely divided substantially water-insoluble particulate filler material.This particulate filler material can include organic particulate material and/or particulate inorganic material.Particulate filler material is typically without painted, for instance, particulate filler material is white or canescence particulate filler material, such as, siliceous or small bits of clay material.

Finely divided substantially water-insoluble filler particles may make up 20 to 90 weight % of poromerics.Such as, this filler particles may make up 30% to 90 weight % of poromerics, or 40 to 90 weight % of poromerics, or 40 to 85 weight % of poromerics, for instance, 45 to 80 weight %, or 50 to 80 weight % of poromerics, for instance, 50 to 65,70 or 75 weight %, and or even 60% to 90 weight % of poromerics.

Finely divided substantially water-insoluble particulate filler can be the aggregation of fundamental particle (ultimateparticle), fundamental particle, or the form of combination.By using the laser diffraction particle size analyzer from BeckmanCoulton that can measure the little particle diameter to 0.04 micron, when LS230 determines, at least about 90 weight % for preparing the filler of poromerics have the overall particle size (grossparticlesize) of scope from 0.5 to about 200 micron, such as, from 1 to 100 micron.Typically, at least 90 weight % of particulate filler have scope from 5 to 40 microns, for instance, the overall particle size of 10 to 30 microns.During processing the composition in order to prepare poromerics, the size of filler aggregation can be lowered.Therefore, the distribution of the overall particle size in poromerics is smaller than original filler itself.

Can be used for organic and inorganic particulate material the non-limitative example being suitable for of the poromerics of the present invention and include at U.S.6,387,519B1 the 9th hurdles the 4th walk to those described in the 13rd hurdle the 62nd row, and its cited portion is incorporated by reference at this.

In a particular implementation of the present invention, particulate filler material comprises siliceous material.The non-limitative example that may be used to prepare the siliceous filler of poromerics includes silicon dioxide, Muscovitum, montmorillonite, kaolinite, nanoclay (such as, be available from the cloisite of SouthernClayProducts), Talcum, kieselguhr, Vermiculitum, natural and synthetic zeolite, calcium silicates, aluminium silicate, sodium aluminium silicate, aluminium silicate polymer, alumina silica gels, and glass particle.Except siliceous filler, the filler of the essentially insoluble property of other finely divided microgranule also optionally uses.The non-limitative example of such optional particulate filler includes white carbon black, Linesless charcoal, graphite, titanium oxide, ferrum oxide, copper oxide, zinc oxide, stibium oxide, zirconium oxide, magnesium oxide, aluminium oxide, molybdenum bisuphide, zinc sulfide, barium sulfate, strontium sulfate, calcium carbonate and magnesium carbonate.Some such optional fillers are the fillers producing color, and depend on the amount used, and color (hue) or color can be added into poromerics.In a non-limiting embodiment, siliceous filler can include silicon dioxide and any aforesaid clay.The non-limitative example of silicon dioxide includes precipitated silica, silica gel, fumed silica and their combination.

Silica gel is commercially produced typically by the aqueous solution acidifying at a low ph making soluble metal silicate (such as, sodium silicate) with acid.The acid used is usually strong inorganic acid, such as, and sulphuric acid or hydrochloric acid, although carbon dioxide can be used.Owing to when low-viscosity, density between gel phase and ambient liquid phase there is no difference, gel phase will not settle, i.e. will not precipitate.Therefore, silica gel can be described as the non-precipitating of contiguous colloid non-crystalline silica granule, stick together (coherent), rigidity, three-dimensional network.Finely divided state ranges for from big solid matter (mass) to submicroscopic granule, and degree of hydration is from almost anhydrous silicon dioxide to containing the soft gelatinous mass that every parts by weight of silica is about 100 weight parts waters.

Precipitated silica is typically by making the aqueous solution of soluble metal silicate, common alkali silicate (such as; sodium silicate); combine with acid so that colloidal silica particles can be grown in weakly alkaline solution and be condensed by the alkali metal ion of the soluble alkali metal salts of gained and commercially produce.Various acid can be used, include but not limited to mineral acid.The non-limitative example of spendable acid includes hydrochloric acid and sulphuric acid, but is used as carbon dioxide to produce precipitated silica.When being absent from coagulating agent, silicon dioxide will not from solution precipitation under any pH.In a non-limiting embodiment, can be the soluble alkali metal salts produced during forming colloidal silica particles in order to realize the coagulating agent of precipitation of silica, or it can be the electrolyte added, such as, inorganic or the organic salt of solubility, or it can be combination.

Many different precipitated silicas can as the siliceous filler in order to prepare poromerics.Precipitated silica is the commercial material known, and its production method is described in detail in many United States Patent (USP)s, including United States Patent (USP) 2,940,830 and 4, and 681,750.When being measured by transmission electron microscopy, the average fundamental particle size (no matter whether fundamental particle is aggregated) in order to prepare the precipitated silica of poromerics is typically smaller than 0.1 micron, for instance, less than 0.05 micron or less than 0.03 micron.Precipitated silica can obtain with form from PPGIndustries, Inc. with many grades.These silicon dioxide be withTrade (brand) name is sold.

For the purposes of the present invention, the substantially water-insoluble siliceous filler of finely divided microgranule can account at least 50 weight % of substantially water-insoluble filler material, for instance, at least 65 or at least 75 weight %, or at least 90 weight %.Siliceous filler can account for 50 to 90 weight % of particulate filler material, for instance, from 60 to 80 weight %, or siliceous filler can account for the substantially all of water insoluble microparticle filler material.

Particulate filler, for instance, siliceous filler, typically there is high surface, it can make filler load many processing plasticizing agent compositionss in order to manufacture poromerics of the present invention.High surface area fillers is to have the material of very little particle size, has highly porous material, or represents the material of these two kinds of character.Pass through Brunauer, Emmett, when Teller (BET) method is determined according to ASTMD1993-91, particulate filler is (such as, siliceous filler granule) surface area can be from 20 or 40 to 400 meters squared per gram, such as, from 25 to 350 meters squared per gram, or from 40 to 160 meters squared per gram.BET surface area can pass through from using MicromeriticsTriStar3000^TMThe Nitrogen adsorption isotherm that instrument carries out is measured five relative pressure points of matching and is determined.FlowPrep-060^TMStation may be used to provide heat and continuous flow during sample preparation.Before N2 adsorption, silica sample by flowing nitrogen (PS) heating to 160 DEG C continue 1 hour and dry.Generally, but inessential, and the surface area of any non-silicon filler particles of use is also within one of these scopes.Filler particles is substantially water-insoluble, and is also substantially insoluble in prepare any organic processing liquid of poromerics.This can promote particulate filler delay in poromerics.

Based on the gross weight gauge of poromerics, the poromerics of the present invention may also comprise on a small quantity other material for processing of (such as, less than or equal to 5 weight %), such as, and lubricant, processing plasticizing agent, organic extraction liquid, water etc..The other material introduced for special purpose (such as, heat, ultraviolet and dimensional stability) is optionally to be present in poromerics in a small amount, for instance, based on poromerics gross weight gauge, less than or equal to 15 weight %.The example of such other material includes but not limited to antioxidant, UV absorbers, reinforcing fiber (such as, the glass fiber strands of chopped) etc..Poromerics except the filler used for one or more special purposes and any coating, printing-ink, or the surplus outside impregnating agent is substantially thermoplastic organic polymer.

The poromerics of the present invention also includes interconnected pores network, and it connects substantially whole poromerics.When the method such as further illustrated manufactures herein, without coating, without printing-ink, to be benchmark without impregnating agent, based on poromerics entire volume, hole typically constitutes from 35 to 95 volume %.Based on poromerics entire volume, hole may make up 60 to 75 volume % of poromerics.As herein with in claim use, poromerics is determine according to below equation with the volume % porosity (also referred to as voidage) represented:

Porosity=100 [1-d₁/d₂]

Wherein, d₁The density of sample, its be by example weight and sample volume (as from the measurement of sample size confirm) determine；And d₂Being the density of the solid portion of sample, it is the example weight by the solid portion of sample and sample volume is determined.The volume of the solid portion of poromerics is to use Quantachrome solid gravimeter (stereopycnometer) (QuantachromeCorp.) to determine according to the workbook with this instrument.

The volume mean diameter of the hole of poromerics is by hydrargyrum hole method, uses Autoscan mercury porosimetry (QuantachromeCorp.) to determine according to the workbook with this instrument.The volume averaging hole radius of single scanning is to be automatically determined by this porosimeter.In operation porosimeter, scanning is to carry out in high pressure range (from 138 kPas (definitely) to 227 MPas (definitely)).If always invading the 2% of volume or less betiding the end portion (lowend) (from 138 to 250 kPas (definitely)) of this high pressure range, then volume averaging hole diameter is the twice taking the volume averaging hole radius determined by porosimeter.Otherwise, additionally scanning is to carry out at low pressure range (from 7 to 165 kPas (definitely)), and volume averaging hole diameter is to calculate according to below equation:

D=2 [v₁r₁/w₁+v₂r₂/w₂]/[v₁/w₁+v₂/w₂]

Wherein, d is volume averaging hole diameter；v₁It it is the cumulative volume of the hydrargyrum invaded in high pressure range；v₂It it is the cumulative volume of the hydrargyrum invaded in low-pressure scope；r₁It is scanned, by high pressure, the volume averaging hole radius determined；r₂It is scanned, by low-pressure, the volume averaging hole radius determined；w₁It is the weight of the sample standing high tension；And w₂It is the weight of the sample standing low pressure scanning.

Generally, based on without coating, without printing-ink, and the benchmark without impregnating agent, the volume mean diameter of the hole of poromerics is at least 0.02 micron, isatypically at least 0.04 micron, and is more typically at least 0.05 micron.Based on identical benchmark, the volume mean diameter of the hole of poromerics is also typically smaller than or equal to 0.5 micron, is more typically less than or equal to 0.3 micron, and is typically less than or equal to 0.25 micron further.Based on this benchmark, the volume mean diameter scope of hole can be between these numerical value any, including described value.Such as, the volume mean diameter scope of the hole of poromerics can be from 0.02 to 0.5 micron, or from 0.04 to 0.3 micron, or from 0.05 to 0.25 micron, include described value in each case.

During determined volume averaging hole diameter by said procedure, the maximum pore radius of detection also can be determined.This be taken from low pressure range scanning, if carried out words；Otherwise take from high pressure range scanning.The twice of the maximum pore diameter of poromerics maximum pore radius typically.

It is coated with, prints, and dipping method can cause at least some hole filling poromerics.Additionally, this kind of method also can irreversibly compact micro-porous material.Accordingly, with respect to the volume mean diameter of porosity, hole, and the parameter of maximum pore diameter be one or more in using these methods before poromerics is measured.

The method of many this areas accreditation may be used to produce the poromerics of the present invention.Such as, the poromerics of the present invention can pass through to make filler particles, thermoplastic organic polymer powder, processing plasticizing agent, and a small amount of lubricant and antioxidant mix until obtaining substantially uniform mixture and preparing.The particulate filler used for forming mixture is substantially the same with poromerics person to be produced with the weight rate of polymer powder.This mixture is directed to typically in the cartridge heater of extruser together with other processing plasticizing agent.That be attached with the terminal of extruder is sheet die (sheetingdie).The continuous sheet formed by this die head be tensionless winkler foundation advance to heated a pair stack, this stack cooperatively forms the continuous sheet with thickness less of the continuous sheet left from die head.The content of the processing plasticizing agent being present in continuous sheet at this point in the method can be different, and can affect the density of final microperforated sheet.Such as, before extraction as described below herein, the content of the processing plasticizing agent being present in continuous sheet can be continuous sheet more than or equal to 30 weight %, such as, before extraction, be continuous sheet more than or equal to 40 weight %, or more than or equal to 45 weight %.In addition, the amount of the processing plasticizing agent being present in continuous sheet before extraction can be continuous sheet less than or equal to 70 weight %, such as, be before extraction continuous sheet less than or equal to 65 weight %, or less than or equal to 60 weight %, or less than or equal to 57 weight %.Before extraction, the weight range of the processing plasticizing agent being present in continuous sheet at this point in the method can be between these numerical value any, including described value.Generally, the content of processing plasticizing agent can change from 57 to 62 weight % in one embodiment, and in another embodiment less than 57 weight %.

Then, continuous sheet from calender is delivered to the first extraction section, processing plasticizing agent is substantially removed by extracting with organic liquid (it is good solvent for processing plasticizing agent, is poor solvent for organic polymer, and than processing plasticizing agent more volatility) there.Generally, but not necessarily, processing plasticizing agent and organic extraction liquid both of which are substantially immiscible with water.Then, continuous sheet being delivered to the second extraction section, organic extraction liquid remaining there is substantially to be removed by steam and/or water.Then, make continuous sheet pass through to force air drier, substantially to remove residual water and remaining remaining organic extraction liquid.From this exsiccator, continuous sheet (it is poromerics) is delivered to takers-in.

Processing plasticizing agent is at room temperature liquid, and is usually processing oil, such as, and paraffin oil, naphthenic oil, or aromatic oil.The processing oil being suitable for includes meeting ASTMD2226-82, those of the requirement of Class1 03 and 104.More typically, have and according to ASTMD97-66 (again checking and approving 1978), there is the processing oil of the pour point less than 220 DEG C and be used to produce the poromerics of the present invention.Can be used for the processing plasticizing agent preparing the poromerics of the present invention at U.S. Patent number 5, the 326,391, the 10th hurdle, the 26th walks to and inquires in further detail in 50 row, and this disclosure is incorporated by reference at this.

In one embodiment of the present invention, at 60 DEG C polyolefin had few solvation effect for preparing the processing plasticizing agent compositions of poromerics, and at the high temperature of about 100 DEG C, there is moderate solvating effect.Processing plasticizing agent compositions is at room temperature usually liquid.The non-limitative example of spendable processing oil can include412 oil,371 oil (ShellOilCo.), they are derived from solvent refined and the hydrotreatment oil of cycloalkanes type crude oil,400 oil (AtlanticRichfieldCo.) andOil (WitcoCorp.), they are slab oils.Other non-limitative example of processing plasticizing agent can include phthalic acid ester plasticiser, such as, dibutyl phthalate, phthalic acid double; two (2-ethylhexyl) ester, diisooctyl phthalate, dicyclohexyl phthalate, phthalic acid fourth Bian ester, and double; two 13 esters of phthalic acid.The mixture of any aforementioned processing plasticizing agent can be used to the poromerics of the preparation present invention.

There is the much organic extraction liquid that may be used to prepare poromerics of the present invention.The example of the organic extraction liquid being suitable for includes at U.S. Patent number 5, and the 326,391, the 10th hurdle, the 51st walks to those described in 57 row, and the disclosure of which is incorporated by reference at this.

Extract fluid composition and can comprise the hydro carbons of halogenation, such as, the hydro carbons of chlorination and/or the hydro carbons of fluoride.Especially, extract fluid composition to include the hydro carbons of halogenation and there is scope from 4 to 9 (Jcm³)^1/2Calculating solubility parameter coulomb item (δ clb).It is adapted as the non-limitative example of hydro carbons of the halogenation extracting fluid composition for producing poromerics of the present invention and can include being selected from anti-form-1,2-dichloroethylene, 1,1,1,2,2,3,4,5,5,5-Decafluoropentanes, and/or 1,1, one or more azeotropic mixtures of the hydro carbons of the halogenation of 1,3,3-3-pentafluorobutane.This kind of material is available commercially from VERTRELMCA (1,1,1,2,2,3,4,5,5,5-dihydro Decafluoropentane and anti-form-1s, the binary azeotrope of 2-dichloroethylene: 62%/38%), and VERTRELCCA (1,1,1,2,2,3,4,5,5,5-dihydro Decafluoropentane, 1,1,1,3,3-3-pentafluorobutane, and anti-form-1, the ternary azeotrope of 2-dichloroethylene: 33%/28%/39%), the two is all available from MicroCareCorporation.

Based on the gross weight gauge of poromerics, it is typically smaller than 10 weight % according to the remaining processing plasticizing agent content of the poromerics of the present invention, and this content can pass through to use additionally extracting of identical or different organic extraction liquid to reduce further.Generally, based on the gross weight gauge of poromerics, remaining processing plasticizing agent content is less than 5 weight %, and this content can be reduced further by other extraction.

The poromerics of the present invention is also dependent on U.S. Patent number 2,772,322；3,696,061；And/or the General Principle of 3,862,030 and program manufacture.These principles and program at the polymer of substrate are or mainly poly-(vinyl chloride) or be applicatory especially containing the copolymer of the aggregated vinyl chloride of vast scale.

The poromerics produced by said method optionally can be stretched.Stretch poromerics and typically cause the increase of material pore volume, and form the region of the molecular orientation that tool increases or strengthens.As known in the art, through the thermoplastic organic polymer of molecular orientation many physical propertys (including hot strength, stretch modulus, Young's modulus etc.) to there is few or corresponding thermoplastic organic polymer without molecular orientation those, such as, considerably different.Stretch and complete after substantially removing processing plasticizing agent as mentioned above typically.

Various forms of stretching devices and method are well-known to those skilled in the art, and may be used to the stretching of poromerics of the present invention.Poromerics be stretching in U.S. Patent number 5,326,391 the 11st hurdle, the 45th walk in the 13rd hurdle the 13rd row further describe, the disclosure of which is incorporated by reference at this.

The present invention further illustrates in the examples below that, and this embodiment is intended only to be illustrative of, because many of which modifications and variations will be apparent to those skilled in the art.Except as otherwise noted, all numbers and percentage ratio are by weight.

Embodiment

Part 1 in following example, describe for preparing in pilot plant preparation and the embodiment mixture presented in Table 1 and comparing mixture, and in amplifying (scale-up) method the embodiment mixture of preparation and the material of the commercial sample of comparison presented in table 2 and method.In part 2, the method describing to extrude, roll and extract the sheet material prepared by the mixture of part 1 and part 2.In third portion, describe to measure the method for the physical property of report in table 3 and 4.In 4A and 4B part, the formulation for coating material of use is listed in table 5 and 7, and the character of coated sheet material is listed in table 6 and 8.In the 5th part, the acetic acid Bian ester test result of the product of table 1,2,6 and 8 is listed in table 9,10,11 and 12.

Prepared by part 1-mixture

Dry ingredient is the order to illustrate in Table I and measures in FM-130DLittleford plough type blade (ploughblade) blender that (gram (g)) is weighed into the mixing cutter with a high intensity chopper type.Dry ingredient is only to use plough type blade premixing 15 seconds.Then.Processing oil (miscella) is that manually pump pumps into via the spray nozzle at blender top, and only has the operation of plough type blade.The pump time of this embodiment changed in the 45-60 second.Make high intensity chopping machine knife start together with plough type blade, and mixture is mixed 30 seconds.Turn off blender, and inside blender, be scratched (scrappeddown), to guarantee all the components Homogeneous phase mixing.It is again started up blender, and high intensity chipper and plough type blade both are activated, and mixture is mixed other 30 seconds.Turn off blender, and mixture is dumped to hold-up vessel.

Table 2

Part 2-extrusion, calendering, and extraction

The mixture of embodiment 1-9 and comparative example 1-5 is to use the as described below extrusion system extrusion including charging, extrusion and calendaring system and be rolled into final sheet-form.By the loss in weight of gravimetric feed system (K-tron model #K2MLT35D5) in order to make each other mixture be fed in 27mm double screw extruder (model # is LeistritzMicro-27gg).The cylinder of extruder comprises eight humidity provinces and is connected to the heated joint of sheet die.Before extrusioning mixture charging aperture is placed exactly in the first humidity province.Passage is positioned at the 3rd humidity province.Vacuum hole is positioned at the 7th humidity province.

Mixture is that the speed supply with 90 gram/minute is to extruder.The other processing oil of various amounts is injected as needed in the first humidity province, to realize in extrusion sheet it is desirable that total oil content.Oil contained from the extrusion sheet (extrudate) that extruder is discharged is hereby incorporated by " extrudate oil " or " processing oil ", and is based on extrusion sheet gross weight gauge, is reported in table 1 with percentage by weight.According to an embodiment of the present invention, more than 0.8g/cm³The microperforated sheet of density is obtaining when measuring less than 57 weight % of processing oil (the extrudate oil) in extrusion sheet.Although without wishing to by any theoretical especially restriction, it is believed that by experimental evidence on hand, reduce the amount of processing oil in extrusion microperforated sheet and add the density of microperforated sheet, for instance, increase to more than 0.8g/cm³, and changing the surface of sheet material so that the volatile material being transferred to steam release surface is more disperseed and will not initially be accumulated drop on that surface.

Extrudate from cylinder is discharged to lamellar wide for 15cmDie head, it has the exhaust openings of 1.5 millimeters.Extrusion melt temperature is 203-210 DEG C, and handling capacity is 7.5 kgs/hr.

Calendering process is to use the vertical re-entrant trough profiled steel sheeting of three-roller type (stack) to complete, and it has a bite and a chill roll.Each in this roller has chromium surface.Roller size is about 41cm length and 14cm diameter.Top roller temperature is maintained between 135 DEG C to 140 DEG C.Intermediate calender rolls temperature is maintained between 140 DEG C to 145 DEG C.Lower roller is chill roll, and wherein temperature is maintained between l0-21 DEG C.Extrudate is rolled into sheet-form, and crosses bottom coohng damping roller and wind.

Roll being cut into the samples of sheets being up to 25.4cm width and 305cm length and be placed in tank, and be exposed to hot liquid 1,1,2-trichloro ethylene persistently about 7-8 hour, to extract fuel-displaced from samples of sheets.Thereafter, the sheet material through extracting is through air drying, and stands method of testing described afterwards.

The mixture of the amplification embodiment 10-18 shown in table 2 is to use extrusion system and oil extracting process (the production size version of said system) to extrude and be rolled into final sheet-form, with U.S.5,196,262 the 7th hurdles the 52nd walk to (it is incorporated by reference at this) described in the 8th hurdle the 47th row and carry out.Use the physical parameter as above testing final sheet material in the method for testing described in third portion.Comparative example 6-10 is the commercial cellular products of following instruction: comparative example 6 isDigital10 mil；Comparative example 7 isSP6 mil；Comparative example 8 isSP10 mil；Comparative example 9 isSP14 mil；And comparative example 10 isSP12 mil.

Extrudate oil (weight %) for the commercial product of comparative example 6-10 changes from 57 to 62%.

Third portion-test and result

Result in the physical property through extracting and measure on dry film and acquisition is listed in table 3 and 4.Soxhlet extractor is used to measure extrudate weight of oil percentage ratio.The extrudate sheet material sample not extracted in advance is used to measure extrudate weight of oil percentage ratio.The specimen sample of about 2.25 inches of x5 inches (5.72cmx12.7cm) is weighed and recorded to arithmetic point four.Then, each sample is rolled into cylinder, and is placed in Soxhlet extraction equipment, and use trichloro ethylene (TCE) as solvent extraction about 30 minutes.Then, sample removed and dry.Then, by through extracting and dry samples weighing.Weight of oil percent value (extrudate) is calculated as below: weight of oil %=(weight of starting weight-extraction) xl00/ starting weight.

OnoSokki calibrator EG-225 is used to determine thickness.Two 4.5 inches x5 inch (11.43cmx12.7cm) samples are cut from each sample, and measures the thickness of each sample at nine positions (from least 3/4 inch of any edge (1.91cm)).The arithmetic mean of instantaneous value of reading is with 2 figure places after mil record to decimal, and changes into micron.

The density of above-described embodiment is by making the average moisture free weight of two samples being measured as 4.5 inches of x5 inches (11.43cmx12.7cm) cut from each sample determine divided by the average external volume of those samples.Average external volume is by making two samples boil 10 minutes in deionized water, this two sample is removed and is placed in the deionized water of room temperature, to room temperature, each sample being suspended in deionized water is weighed in balance, and after wiping surface water, again weigh each sample in atmosphere and determine.The average external volume of sample is calculated as below:

Volume (on average)=[(weight of the sample through slight wiping weighed in atmosphere-dipping weight summation) x1.002]/2

Moisture free weight is by each in this this two samples of weighing on analytical balance and makes this weight be multiplied by 0.98 and determine, because it was assumed that this sample contains the moisture of 2%.

In table 3 and 4, the porosity of report is to use the Gurley densimeter manufactured by the GPIGurleyPrecisionInstruments of New York Troy, and model 4340 is determined.The porosity reported is that air flows through measuring of the speed of sample or the resistance of its air stream to flowing through this sample.Measuring unit is " Gurley second ", and represents the water (12.2x10 using 4.88 inches of pressure differentials²Pa) make 100cc air by 1 inches square (6.4x10^-4m²) area in time of second.Relatively low value is equal to less air flow resistance (allowing more air to pass freely through).Measurement is to be used in MODEL4340AutomaticDensometerandSmoothnessTesterInstructi onManual handbook the program listed to complete.TAPPI method T460om-06-AirResistanceofPaper also can be referenced the ultimate principle as this measurement.

4A part-formulation for coating material and coated product

The coating 1-5 listed in table 5 is by making under mild agitation in 600 ml beakers325 polyvinyl alcohol are dispersed in cold water to be prepared.Gentle agitation is by driven by electrical stirring motor 1 " offer of (2.54cm) dasher.Heat the mixture to 190 °F (87.8 DEG C) and stir 20-30 minute.Gained solution is cooled to room temperature stir simultaneously.The amount of actual mixt and the solid recorded of gained are summarized in table 5.

Table 5. formulation for coating material

Will confirm that the coating without visible non-dissolved particles is applied to by PPGIndustries, Pittsburgh, Pa saleHD microporous substrate.Coating is applied to 8.5 inches of x11 inches (21.59cmx27.94cm), the sheet material of 11 mil thick base materials, its each comfortable balance tares, thereafter, makes sheet material be placed in clean glass surface, and use adhesive tape to make the top corners of sheet material and glass stick together.A piece of 11 inches of x3 inches (27.94cmx7.62cm) of transparent 10 mil thick polyester are crossed sheet material top and are placed, and cover from sheet material top down 1/2 inch (1.27cm).With adhesive tape, polyester is fixed to glass surface.It is placed on sheet material by the measuring stick of the wire-wound (wirewrapped) from DiversifiedEnterprises 1-2 inch (2.5-5.1cm), parallel with top, close to the top of polyester.Disposable pipet is used to make the coating of 10-20 ml vol directly be close to as pearl strip (beadstrip) (about % inch (0.64cm) is wide) and contact measuring stick and deposit.Attempt this bar drawing completely across (across) sheet material with continuously/fixing speed.The wet-sheet of gained is removed from glass surface, is immediately placed on previous tare weight balance, weighs, record wet coating weight, then, coated sheet material is placed in forced air oven, and dry 2 minutes at 95 DEG C.The sheet material of drying is removed from this stove, and identical coated sheet surface is repeated identical coating program.Two wet coating weight are used to calculate final dry coating weights (in gram/m).The coated sheet material of embodiment 19-23 is described in table 6.

The sheet material that table 6. is finally coated

Below equation is used to calculate final dry coating weight.

The final dry coating weight that calculates (in gram/m)=((coat solid x0.01) x (the 1st wet coating weight the+the 2 wet coating weight))/(8.5xl0.5) x1550

4B part-formulation for coating material and coated product

In the formulation for coating material of preparation coating 6-12, it then follows the program of 4A part, except coating 7 mixes 2 days before use.Formulation for coating material is shown in table 7.

The base material used in 4B part is to be sold by PPGIndustries, Pittsburgh, PaSP1000 microporous substrate.Follow the same program for 4A part, except some sheet materials are coated with on both sides, before making the second coated side put on opposite side, dry first coated side, and No. 9 measuring sticks are used for all coatings.The information of finally coated sheet material includes in table 8.

Table 7. has a gram formulation for coating material for the amount listed

N () WITCOBONDW-240, from the aqueous pu dispersions of ChemturaCorporation

(0)200, from the fumed silica of Degussa

(p)T700, from the precipitated silica of PPGIndustries, Inc.

(q)6200, from the precipitated silica of PPGIndustries, Inc.

R () MOMENTIVELE-410, from the aqueous silicon dispersion of MomentivePerformanceMaterials

(s) HYCAR26138, poly-(methyl) acrylate dispersoid of aqueous from LubrizolAdvancedMaterials, Inc.

The sheet material that table 8 is finally coated

5 parts-acetic acid Bian ester test

Assemble by having the front jig of ring washer, rear jig, test reservoir cup for the evaporation rate of film and the clamper of performance test, and four screw compositions.Test reservoir cup is by transparent thermoplastic polymer manufacture, the inside dimension that its round diameter with the about 4cm by opening face edge limits, and is not more than the degree of depth of 1cm.The face of opening is to determine volatile material transfer rate.

Each fixture of clamper assembling has the circular open of 1.5 inches of (3.8cm) diameters, to hold test reservoir cup and to provide the opening making film be exposed under test.When making film (that is, having the poromerics sheet material of 6 to 18 mil thickness) be placed under test, the rear jig that clamper assembles is placed on the top of cork ring (corkring).Test reservoir cup is placed in rear jig, and loads the acetic acid Bian ester of about 2 milliliters.Cut the dish of about 2 inches of (5.1cm) diameters from this film sheet, and be placed directly within the edge of reservoir cup and be in contact with it so that the 12.5cm of microperforated sheet²Volatile material contact surface be exposed to inside reservoir.

The front jig of clamper is carefully placed in whole fit on, and makes screw align, and do not disturb this film disk like thing.When using coated microperforated sheet, coated surface is placed towards reservoir or towards air, as shown in the table.Screw attachment is made to be enough to prevent seepage with being tightly locked to.Ring washer produces to seal.Marking clip holder is to identify membrane sample under test.For each test, prepare 5 to 10 duplicates.For coated embodiment, including five duplicates of matched group (sample of uncoated).For the embodiment in table 11, for each embodiment, there are 5 matched groups, and the average evaporation rate of each matched group is for corresponding embodiment report, and reduce percentage ratio report with this embodiment compared to the evaporation rate of corresponding matched group.The coated surface of the embodiment 19-23 in table 11 is towards air.

Each clamper of weighing assembling starting weight to obtain whole loaded assembling.Then, this assembling is upwards erectly placed in laboratory chemical ventilating kitchen, and it has about size of 5 feet of [1.52 meters] (highly) x5 feet [1.52 meters] (width) x2 foot [0.61 meter] (degree of depth).When testing reservoir and being upright, acetic acid Bian ester contacts at least some of directly contact on surface with the volatile material of microperforated sheet.The glass door of drop-down ventilating kitchen, and adjust the air stream flowing through this kitchen, so that having eight (8) the kitchen volumes turning (or turnover number) per hour.Unless otherwise directed, in kitchen, temperature maintains 25 DEG C ± 5 DEG C.Humidity in ventilating kitchen is ambient temperature.Test reservoir routine weighing in this kitchen.Test carries out five (5) skies.In conjunction with the elapsed time and the acetic acid Bian ester loss in weight of calculating is exposed to the microperforated sheet surface area within test reservoir in order to determine the volatility transfer rate of microperforated sheet, and unit is mg/ (hour * cm²).Whole assembling is reported by the average evaporation rate (mg/ hour) of duplicate in the following table.The two numerical value is associated by following formula:

Average evaporation rate (mg/ hour)/12.5cm²=volatile material transfer rate (mg/ hour * cm²)

Critical (marginal) (Marg.) instruction exists by the duplicate with inefficacy, or test does not have the inefficacy described under the surface of film with acetic acid Bian ester " collecting " and " drippage ", but there are some acetic acid Bian ester drops forming pearl on the surface of the film, for being cited as " passing through " result, this is also regarded as unacceptable (face-to-face (vis-à-vis)).But, between (FAIL) test result and critical (Marg.) test result, there is clear and definite performance difference losing efficacy, the latter is clear and definite more excellent, as discussed here.

The data of the embodiment 10-18 and comparative example 6-10 of table 2,4 and 10, which illustrate the microperforated sheet produced on production scale equipment, it is thus identified that increase sheet density (it is the amount realization by reducing the extrudate oil in extrusion sheet) and by the dependency between the test of acetic acid Bian ester.This Data Generalization is set forth in table 13.

Table 13

Although the specific embodiment of the present invention is for purposes of illustration described above, but it will be apparent to those skilled in the art that the multiple change of details of the present invention can carry out when without departing from the such as present invention defined in the appended claims.

Claims

1. a vapor permeable poromerics, comprises:

Wherein said poromerics has

(1) at least 0.8g/cm³Density,

(2) volatile material contact surface and steam release surface, described volatile material contact surface is mutually substantially relative with described steam release surface, and

(3) it is placed as contacts with volatile material and when described steam release surface does not directly contact with described volatile material when the described volatile material of described vapor permeable poromerics contacts surface, 0.04 to 0.6mg/ (hour * cm²) described volatile material contact surface to the volatile material transfer rate of described steam release surface, the density of described poromerics makes when volatile material is transferred to described steam release surface from described volatile material contact surface, and described steam release surface is substantially free of the liquid volatile material in liquid form.

2. poromerics as claimed in claim 1, wherein said poromerics has 0.8 to 1.2g/cm³Density.

3. poromerics as claimed in claim 1, wherein said volatile material transfer rate is 0.30 to 0.55mg/ (hour * cm²)。

4. poromerics as claimed in claim 1, wherein said volatile material transfer rate is 0.35 to 0.50mg/ (hour * cm²)。

5. poromerics as claimed in claim 1, wherein said volatile material contact surface and described steam release surface are each without coating material.

6. poromerics as claimed in claim 1, first coating having at least partially above on wherein said volatile material contact surface, and/or second coating having at least partially above of described steam release surface.

7. poromerics as claimed in claim 6, wherein said first coating and described second coating are gathered (methyl) acrylate dispersoid, aqueous pu dispersions, aqueous silicone oil dispersion body by selected from aqueous independently of one another, and the water-based paint compositions of their combination is formed.

8. poromerics as claimed in claim 7, the granule of the dispersion of each of which water-based paint compositions has the particle size of 200 to 400nm.

9. poromerics as claimed in claim 8, wherein said first coating and described second coating have 0.01 to 5.5g/m independently of one another²Coating weight.

10. poromerics as claimed in claim 1, wherein the described polyolefin of water-insoluble thermoplastic organic polymer includes the ultra-high molecular weight polyethylene with the intrinsic viscosity of at least 10 deciliter/gram.

11. such as the poromerics of claim 10, wherein said extrahigh-molecular weight polyolefins is the ultra-high molecular weight polyethylene of the intrinsic viscosity with at least 18 deciliter/gram.

12. such as the poromerics of claim 11, wherein said ultra-high molecular weight polyethylene has the scope intrinsic viscosity from 18 to 39 deciliter/gram.

13. poromerics as claimed in claim 1, the mixture of the lower molecular weight polyethylene of the ASTMD1238-86 condition E melt index of ultra-high molecular weight polyethylene that wherein the described polyolefin of thermoplastic organic polymer includes having the substantial linear of the intrinsic viscosity of at least 10 deciliter/gram and have less than 50 grams/10 minutes and the ASTMD1238-86 condition F melt index of at least 0.1 gram/10 minutes.

14. the poromerics such as claim 13, the ultra-high molecular weight polyethylene of wherein said substantial linear constitutes at least 1 weight % of described substrate, and the ultra-high molecular weight polyethylene of described substantial linear constitutes the substantially 100 weight % of polymer of described substrate together with described lower molecular weight polyethylene.

15. such as the poromerics of claim 14, wherein said lower molecular weight polyethylene includes high density polyethylene (HDPE).

16. poromerics as claimed in claim 1, wherein said particulate filler includes siliceous particles, and described siliceous particles includes silica particle.

17. such as the poromerics of claim 16, wherein said silica particle includes particulate deposits silicon dioxide.

18. poromerics as claimed in claim 1, wherein based on the entire volume of described poromerics, described hole constitutes 35 to 95 volume % of described poromerics.

19. a vapor permeable poromerics, comprise

Wherein said poromerics has

(1) less than 0.8g/cm³Density,

(2) volatile material contact surface, and steam release surface, described volatile material contact surface is mutually substantially relative with described steam release surface, and

(3) it is placed as contacts with volatile material and when described steam release surface does not directly contact with described volatile material when the described volatile material of described vapor permeable poromerics contacts surface, 0.04 to 0.6mg/ (hour * cm²) described volatile material contact surface to the volatile material transfer rate of described steam release surface, and

Wherein first coating having at least partially above on (i) described volatile material contact surface, and/or second coating having at least partially above of (ii) described steam release surface, described first coating and described second coating are independently of one another by selected from poly-(methyl) acrylate dispersoid of aqueous, aqueous pu dispersions, aqueous silicone oil dispersion body, the water-based paint compositions of the combination with them is formed, and when volatile material is transferred to described steam release surface from described volatile material contact surface, described steam release surface is substantially free of liquid volatile material.

20. such as the poromerics of claim 19, wherein said poromerics has 0.4g/cm³To less than 0.8g/cm³Density.

21. such as the poromerics of claim 19, wherein said poromerics has 0.4g/cm³To 0.7g/cm³Density.

22. such as the poromerics of claim 19, wherein said volatile material transfer rate is 0.30 to 0.55mg/ (hour * cm²)。

23. such as the poromerics of claim 19, the granule of the dispersion of each of which water-based paint compositions has the particle size of 200 to 400nm.

24. as the poromerics of claim 23, wherein said first coating and described second coating have 0.1 to 3g/m independently of one another²Coating weight.

25. such as the poromerics of claim 19, wherein said polyolefin includes the ultra-high molecular weight polyethylene with the intrinsic viscosity of at least 10 deciliter/gram.

26. such as the poromerics of claim 25, wherein said extrahigh-molecular weight polyolefins is the ultra-high molecular weight polyethylene of the intrinsic viscosity with at least 18 deciliter/gram.

27. such as the poromerics of claim 26, wherein said ultra-high molecular weight polyethylene has the scope intrinsic viscosity from 18 to 39 deciliter/gram.

28. such as the poromerics of claim 19, the mixture of the lower molecular weight polyethylene of the ASTMD1238-86 condition E melt index of ultra-high molecular weight polyethylene that wherein said substrate includes having the substantial linear of the intrinsic viscosity of at least 10 deciliter/gram and have less than 50 grams/10 minutes and the ASTMD1238-86 condition F melt index of at least 0.1 gram/10 minutes.

29. the poromerics such as claim 28, the ultra-high molecular weight polyethylene of wherein said substantial linear constitutes at least 1 weight % of described substrate, and the ultra-high molecular weight polyethylene of described substantial linear constitutes the substantially 100 weight % of polymer of described substrate together with described lower molecular weight polyethylene.

30. such as the poromerics of claim 29, wherein said lower molecular weight polyethylene is high density polyethylene (HDPE).

31. such as the poromerics of claim 19, wherein said particulate filler includes siliceous particles, and described siliceous particles includes silica particle.

32. such as the poromerics of claim 35, wherein said silica particle includes particulate deposits silicon dioxide.

33. such as the poromerics of claim 19, wherein based on the entire volume of described poromerics, described hole constitutes 35 to 95 volume % of described poromerics.

34. a vapor permeable poromerics, comprise:

A () substantially water-insoluble thermoplastic organic polymer substrate, it comprises the ultra-high molecular weight polyethylene of the intrinsic viscosity with at least 10 deciliter/gram；

B substantially water-insoluble silica particle that () is finely divided, described silica particle is distributed in whole described substrate, and based on the gross weight gauge of described poromerics, constitutes 40 to 90 weight %；With

C () interconnected pores network, it substantially connects in whole described poromerics, and based on the entire volume of described poromerics, described interconnected pores constitutes 35 to 95 volume % of described poromerics；

Wherein said poromerics has

(1) 0.8 to 1.2g/cm³Density,

(3) it is placed as contacts with volatile material and when described steam release surface does not directly contact with described volatile material when the described volatile material of described vapor permeable poromerics contacts surface, 0.04 to 0.6mg/ (hour * cm²) described volatile material contact surface to the volatile material transfer rate of described steam release surface, the density of described poromerics makes when described volatile material is transferred to described steam release surface from described volatile material contact surface, and described steam release surface is substantially free of the volatile material in liquid form.

35. such as the vapor permeable poromerics of claim 34, wherein:

A () described thermoplastic organic polymer includes having the mixture of the lower molecular weight polyethylene of the ASTMD1238-86 condition E melt index of the ultra-high molecular weight polyethylene of the substantial linear of the intrinsic viscosity of at least 10 deciliter/gram and have less than 50 grams/10 minutes and the ASTMD1238-86 condition F melt index of at least 0.1 gram/10 minutes；

B () described particulate filler is precipitated silica；With

C the volatile material transfer rate of () described poromerics is 0.30 to 0.55mg/ (hour * cm²)。