2) United States Patent oy os) 0) o an @ 6s) (60) Gt (2) 68) Clarke et al. RMEABLE MEMBRANE Inventors: Raymond Clarke, Los Altos, CA (US Charles B. Derringer, Morgan Hil, cA) Assignee: Aplo, Ine, Guadalupe, CA (US) Notice: Subject to any disclaimer, the team ofthis patent is extended of adjusted under 35 USC. 154(b) by 198 days Appl. Nos 10/742,548 Filed: Dee. 19, 2003 Prior Publication Data US 2004)0131810.A1 Jul. 8, 2004 Related Us ion Data 7 filed on Dev. APE Provisional aplication No, 643 20, 2002, Im. Cl. Cosy 9/36 (2006.01), BOSD 81724 (200601) US. Cl. 428/137; 428/35,7; 428/138 Field of Classification Search “226/131 428/137, 138, 357 search history Se application file for complet 'US007329452B2 3294: (10) Patent No. (4s) Date of Patent: US 7,329,452 B2 Feb. 12, 2008 66) References Cited US. PATENT DOCUMENTS S284381 A 101993 Stowart 4261106, S876 A ‘911908 Chie cal 28333 857.607 BL 62003 Gorka oa. ax 20030009832 AL $2003 Borehardk 28.402 FOREIGN PATENT DOCUMENTS wo WO 9912825 4199 * cited by examiner (74) Atiomes: Agent, or Firm Mak Rose & Anderson PC Alicia Chevalier ‘elltey G. Sheldon: Sheldon on ABSTRACT Gas-permeable metbranes comprising a microporous film ‘and a coating on the micropormus film, the coating being joblained by coating the microporous film with aliquid ‘coating composition comprising s polymer and hollow poh ‘meric particles dispersed i the composition, and then Solidi fying the coating. The gas-permeable membrane has a redneed ratio of carbon dioxide permeability to oxygen permeability 18 Claims, 1 Drawing SheetU.S. Patent Feb. 12, 2008 US 7,329,452 B2 FIGUREUS 7,329,452 B2 1 GAS-PERMEABLE MEMBRANE CROSS REFERENCE TO RELATED APPLICATION, ‘This application claims the benefit under 38 USC 119 () (1) of US. provisional patent application No. 60/435,567, filed by Raymond Clarke and Charles B. Derringer on 20 Dee. 2002, BACKGROUND ‘The invention relates to gas-permesble membranes suite able for use in the packaging of respiring biological mate- rials Respiring biological materials, eg. fruits and vegetables, ‘consume oxyzen (O;) and produce earbon dioxide (CO.) at rates which depend upon the stage of their development, the ‘atmosphere surrounding them and the temperature. In modi fie atmosphere packaging (MAP), the objective isto pro- ‘duce a desired atmosphere around respiring materials by placing them ina sealed container shose permeability tO. ‘and CO, is conelated with (i) the partial pressures of O, and ‘CO, inthe air outside the package, and (i) the temperature, 'o produce a desired atmosphere within the container. In many eases, the container includes an atmosphere control member (ACM) having a high O, tcansmission rate (OTR) and CO, transmission mie (COTR). In controlled atimo- sphere packaging (CAP), the objective is 10 produce ‘desire atmosphere around respiring materials by displacing some oF all of the air within a container by one or more ‘gases, ©. nitrogen, O,, COs and ethylene, in desired pro- Portions. For frther details of MAP an CAP, reference may bbe made, for example, to U.S. Pat, No. 3,360,380 (Bedro- sian), US. Pat. No. 3,450,542 (Badran), US. Pat. No. 3,450,544 (Badran et al). US. Pat. No. 3.798.333 (Cummin ‘eta, U.S. Pat. No. 3,924,010 (Fr), US. Pat. No. 4,003,728, (Rath), US. Pat. No. 4.734.324 (Hill), US. Pat. No. 4.79, 524 (Wada), US, Pat, No, 4,890,863 (Jones), US, Pat. No 4842,875 (Anderson), US. Pat. No. 4.879.078 (Antoon), US. Pat, No. 4,910,032 (Antoon), US. Pat. No, 4,923,708 (Anioon), US, Pat. No, 4,987,745 (Has), USS. Pat. No. 5,041,290 (Wallace et al.) U.S. Pat. No. 5,045,331 (Antoon), US. Pat, No, 5,063,753 (Woodrull), U.S. Pat. No, 5,160,768 (Antoon), US. Pat, No, 5,254,354 (Stewart), US. Pat. No. 5,333,394 (Herdemun), USS. Pat. No. $433,335 (Raudalus tal), US. Pat, No. 5,460,841 (Herdeman), US. Pat. No. 5,556,688 (Raudalus et al), U.S. Pat_No. 5,658,607 (Herde- man), U.S. Pat, No. $807,630 (Christie ot al), US. Pat. No. 6.013.293 (De Moor), US. Pat, No. 6.376.032 (Clarke et al), US. Pat. No. 6.548.132 (Clarke e al.) and US. Pat. No, 6,379,607 Gozukara et al.), copending. commonly signed U.S. patent application Set. No. 09°858,190 (Pubs Tication Number US2002/009045) and Ser, No, 09/989,682 (Publication Number US2002/0127308) Publication Num- ber US2003/0099832, published 29 May, 2003, Interna- tional Publication Nos. WO 94/12040 (Fresh Wester), WO 96/38495 (Candee), WO 99/33838 (Gozukara et al), WO ‘00104787 (Landee) and WO 01/92118 (Lande), and Puro- pean Patent Applications Nos. 0351,115 and 0.351,116 (Courtauld). The disclosure of each of those patents, appli ‘cations and publications is incorporated herein by reference Tor all purposes "The profered packaging atmosphere fora respiring mate rial often depends on the material and the changes (if ny) jn the material which are desired. In some cases, itis “desirable for the packaging atmosphere to have a relatively, 0 o 2 CO, content and a relatively low O, content In order to obtain such a packaging atmosphere in a modified stmo- sphere package itis desirable to make use of an ACM whieh has a felatively low COTRIOTR ratio (often refered t0 herein asthe R ratio). US. Pat. No. $807,630 (Christe et al), U.S. Pat. No 6,579,607 (Gozvkara et al.) and Publication Number US 2003/0099832 (Borchardt), published May 29, 2008, di lose self-supporting films of controlled permeability which ‘comprise film-forming polymer and a porous filler. The filler has a particle size greater than the intinsic film thickness of the film-foming polymer, und is present in ‘amount suficient to reduce the R ratio of the film, SUMMARY OF THE INVENTION ‘We have discovered that novel and useful gas-permeable membeanes, suitable for use as ACM's in packaging respi jing materials, can he obtained by coating a microporous polymeric film with a liguid coating composition compris- ing (@) a polymer, and () hollow polymeric particles dispersed in dhe compos sion, ‘The presence ofthe hollow polymere particles inthe liquid coating composition results ina membrane having a reduced Ratio, In a first aspect, ths invention provides a method of preparing a gas-permeable membrane which comprises a ‘ieroporous flat and a solid eoating on the aieroporous film, the method comprising (A) Forming Tiguid coating onthe microporous fil, che Jiquid coating being composed of Tiguid coating compos sion which comprises (a) first polymer, and (b) hollow particles which (i are dispersed in the coating ‘composition, and (ji) are composed of a polymeric ‘composition comprising a sevond polymer, the second polymer being different from the first polymer, and (8) solidifying the liquid coating on the microporous film, TIn.a second aspect, this invention provides « gat-perme- able membrane which comprises (1) @ miieroporous film, and (2) solid coating on the microporous film, the coating comprising (2) matrix comprising a first polymer, and (b) hollow particles which ()) are composed of a poly ‘meric composition comprising a socond polymer, ( are dispersed in the matrix, and (fii) have maximum ‘mension which is at most 50% ofthe thickness of the solid coating, the second polymer being different fom the fist polymer In third aspect, this invention provides a gas-permeble membrane which comprises (a mieroporous film, and 2) solid costing on the microporous film, the coating comprising (2) a matrix comprising a first polymer, and (b) a plurality of microscopic voids which (provide continuous pathways for the transmission of ‘oxygen and carbon dioxide throug the coating, and (i) area east parly defined by walls composed of the second polymer ‘The gus-permeable membranes of the second and third aspects of the invention can be prepared by the method of the first aspect of the invention, The membranes of the thirdUS 7,329,452 B2 3 aspect of the invention are obtained when the soliditiato sep (B) involves heating which at least partially melts at Feast some ofthe hollow polymere partiles so tht they fuse together to form a plurality of microscopic woids. Thus, i is possible for the solid coating of the membranes of the Second and third aspect of the invention to include both () hollow polymerie particles which are the same as or similar to the hollow polymeric particles in the eoating composition and (i) microscopic voids formed by sion of hollow polymeric particles. Tn founh aspect, this invention provides # container ‘which can be sealed around a respiring biological material and which includes one ar more ACM's, at least one of the ACM’s comprising gas-permeable membrane prepared by the method of the fist aspect of the invention andlor as ‘defined in the second and/or third aspect of the invention, ‘Geaerally, the container is suc that, afer the container has been sealed around the biological material, at least 50%, ‘offen at least 75%, of the oxygen Which enters the interior ‘of the sealed package passes through the one or more ACM's In a fourth aspect, this invention provides a package whet comprises (a) a sealed container, and () within the sealed container, « respiring biological ‘material and a packaging atmosphere arsund the bio- logical material the scaled container including one or more, ACM's a least ‘one of said ACM's comprising a gas-permeable membrane Prepared by the method of the first aspect of the invention ‘and/or as defined in the second andlor thitd aspect of the invention. Generally, the package is such that atleast S0%, ‘often at least 75%, ofthe oxygen which enters the packaging, fstmosphere passes through the one oF more atmosphere ‘control meaabers BRIBE DESCRIPTION OF THE DRAWINGS “The invention sillusteated ia the accompanying drawing in which the FIGURE is a graph of R ratio (R) against volume fraction of panicles (VFN) in Examples 1-4 below. DETAILED DESCRIPTION OF THE INVENTION. In the Summary of the Iavention above and in the Detailed Description ofthe Invention, the Examples, and the Statements below, reference is made to particula features (cluding method steps) ofthe invention. It isto be under stood that the disclosure of the invention inthis specification includes all appropriate combinations of suck particular features. For example, where «particular feature is disclosed in the context of particular aspect or embodiment ofthe invention, ora particular Statement or claim, that feature can also be used, to the extent appropriate, in combination with andor in the context of other particular aspects and embod mens of the invention, aad i the invention generally In describing and claiming the invention below, the fol- lowing abbreviations, definitions, and methods of measure- ment (in addition to those already given) are used ‘OTR is O. permeability. COTR is CO. permenbily. OTR ‘and COTR values are given in ce/100 inet atm. 24 hrs, and ‘ean be measured using pemeability cell (supplied by Millipore) in which a mixture of O;, CO, and helium is applic tothe sample, using a pressure of 0035 kien (0.5 psi) and the gases passing through the sample are analyzed 0 o 4 {or O, and CO, by a gas chromatograph, The cell ould be placed in a water bath Yo control the temperature, The abbreviation Ps used to mean the ratio of the peemeabi ity, 10, oF CO, as specified, at a frst temperature, ¢ to the permeability at second temperature Ts, where Tis (y-10)° C. T, heing 10°C. and T, being 0° C. unless otherwise noted. The abbreviation R of R ratio is used 10 ‘mca the ratio of COTR to OTR, both permeabilities being ‘measured at 20° C. unless otherwise noted. Pore sizes are measured by mercury porosimety. Pars and percentages are by weight, except for percentages of gases, which are by volume, Tempeniture are in degrees Centigrade. Por erys- fallin polymers, the abbreviation T, is used t0 mean the ‘onset of melting, the abbreviation Tis used t0 mean the enysalline melting point, and the abbreviation AH is used t0 vean the heat of fision. T,, I, and AFI are measured by’ ‘means ofa differential scanning calorimeter (DSC) at arate ‘of 10" C/minute and on the second heating eyce, I, and T, are measured in the conventional way well known fo those sailed in sear. Thus T, ithe temperature at the peak of the DSC curve, and, isthe temperature atthe intersection of the baseline of the BSC peak and the onset ine the onset line being defined asthe tangent to the steepest part of the DSC curve below T,, ‘The term “comprises” and grammatical equivalents thereat are used herein to mean that ether elements (ie components, ingredients, steps ete.) are optionally present. For example, composition “comprising” (or “which com: prises") ingredionts A, B and C can contain only ingredients A, B and C, or ean contain not only ingredients A, B and C bit also one oF more other ingredients, The term “consisting essentially of” and grammatieal equivalents thereof are used brcin to mean that other elements may be present which de ‘ot materially alte the claimed invention. Where reference is made herein to # method comprising two or more defined the defined steps ean be carried out in any order or taneously (except where the context excludes that ity), and the method can inelude one oF more other Stops which are carried aut before any of the defined steps between two of the defined steps, oF afterall the defined steps (except where the context excludes that possibilty. The ferm “atleast” followed by a number is used herein to denote the start of a range beginning with that number (hich may be a range having an upper limit or no upper limit, depending on he variable being defined), For example “at least 1" means 1 oF more than 1, and “at leas 80%" scans 80% oF more than 80%, The term “at most” Followed by a number is used herein to denote the end of a range ending with that umber (which may he a range having 1 oF 0 as its Tower limit, or a range baving no lower limi depending upon the variable being defined). For example, “atmost 4° means 4 or les than 4, and “at most 4094" means 40% or less than 40%, When, inthis specification, a range js given as “(a fist number) to (a second number)" oF "(a first number)-(a second number)”, this means a range whose lower limit is the first number and whose upper limit i the second number. For example, “from 8 to 20 carbon stoms” ‘oF "8-20 carbon atoms” means a range whose lower limit is 8 carbon atoms, and whose upper lit is 20 carbon a The numbers given herein should be construed with the Jatitude appropriate to their context and expression ‘Where reference is made herein to sealed packages and sealed containers, and to sealing bags and other containers containing biological materials, itis to be understood that the sealing can be, but need not be, hermetic sealing, (Conventional methods for sealing bags and other containers can conveniently be used in this invention, Ifthe bag isUS 7,329,452 B2 5 sealed hermetically, it will generally be desirable to inelude ‘one or more pinholes inthe bag, 1 achieve equilibration of the pressures inside and outside the bag. "The method of the fist aspect of the invention may’ ‘optionally have one oF more of the following features: (6) the hollow polymerie panicles have one or more ofthe following characteristics (a) maximum dimension D of most 0.5, for example O11 to O44 t, where tis the thickness ofthe solid coating ()anaverape sizeof 0.210 08 micron, forexample 04 10 0.7 micro: and (©) at Teast 90% of the panicles have a maximum ‘dimension of 0.2 t0 0:8 micron, for example Ot 10 0.7 micron: ) the hollow particles dispersed in the Figuid eoating ‘composition are such that, at atleast one temperature between 0 ad 22° C., the gas-permesble membrane prepared by the method has an Rratio which is at most O85 times, preferably at most 0.75 times, the R ratio of 2 4 gas-permeable membrane which is produced by 2 :method which is identical except thatthe Figuid coating composition docs nat contain the particles; i) the hollow particles are hollow microspheres or hollow microfilaments composed of a homopolymer or copolymer of styrene, eg. a copolymer of styrene and at Teast one acrylic monomer, iv) the average size ofthe hollow particles dispersed in tho coating. composition is 0.2 t0 0.8 micron, for example 0 0 0.7 micron; (0) at least 90% of the hollow paticles dispersed in the coating composition have a maximum dimension of 0.2 {0 08 micron, for example Oat to 0.7 micron, (4) the evating composition contains 5 to 50%, preferably 10 to 40%, for example 20 10 35%, by weight of the hollow particles, based on the combined weight of the polymer and the paricles (vi) the volume ofthe hollow particles dispersed in the Tiguid coating composition is (@) atleast 11%, preferably at least 12%, for example at Teast 13%, of the volume of the solid coating, andor () less than 30%, for example less than 20%, ofthe ‘volume of the solid coating, and/or (©) 11 to 20%, preferably 12 (6 18%, ofthe volume of the solid coating: (Gil) the polymer comprises a crystalline polymer () having a peak melting temperature T, of 5 to 40° ., for example 0 to 25° C,, and a heat of fasion of at least Jig, preferably least 10 Jig, especially at least 20 4g, andlor (b) having an onset of melting temperature, such that (LT) isles than 10° C., preferably fess than 8° C. fof example 5-10? C., andor (©) comprising atleast one side chain erytalline (SCC) polymer, for example an SCC polymer which con- {sins ethylenically unsatorated repeating unis; {the polymer a anorpons polymer, pose (x) the polymer becomes crosslinked during the step (B); (i) the coating eomposition comprises liquid cari, for ‘example an aqueous liguid (including water) having the polymer and the hollow particles uniformly dispersed ‘therein, preferably a mixture of an aqueous emulsion of the polymer and an aqueous emulsion of the hollow particles; and (it) step (B) comprises heating the coating, for example to remove a liquid carrier therefrom and/or to crosslink 0 o 6 the polymeric mtix andor to eanse the hollow pat ticle to fise to each olber andlor to the polymeric ‘mtv; the heating can be carried out as a separate step ‘ora part of @continaous operation; the coating ean for ‘example be heated at a temperature of 50 10 85° C ‘Membranes prepared by the method of the first aspect of the invention may optionally have one or more of the following characteristics (@)an OTR at 20° C.of atleast 30,000, preferably atleast, 50,000, c£/100 in® stm 24 hrs ()an oxygen Pio ratio ofa least 2, proferably atleast 2, ‘over at least one 10° C. temperature range between 0 land 25°C. (©) carbon dioxide Py ratio of at least 2, preferably at least 2.5 over af east one 10° C. temperate range between O and 25° C3 and (2) aa R ratio of less than 4, preferably less than particular less than 2.5. at at least one tempera between O and 22°C. If higher OTR and COTR values are desitod, the coating ‘weight ofthe coating composition can be reduced, but this will sult in lower Py values ‘The gns-permeable membranes of the second and third aspects of the invention may optionally have one or more of the following characteristis: ) ihe solid polymeric coating comprises microscopic ‘ids andlor hollow polymeric particles suc that, a at least one temperature between O and 22° C. the mem- bane has an Re ratio which is at most 0.85 times, preferably at most 0.75 times, the R ratio of a mem- brane whichis the same excep that the coating doesnot ‘contin the microscopic voide andor hollow polymeric particles; Gi) the hollow polymeric particles have one or more ofthe following characteristics (@) maximum dimension D of most 0. , for example 0.110 O44 {, where Cs the thickness of the solid costing: ()anaverage sizeof 0.2 100.8 micron, forexample 0.4 1 0.7 micron; and (6) at least 90% of the particles have a maximum ‘dimension of 0.2 t0 08: Gil) the sod coating contains $ to 50%, preferably 100 40%, for example 20 10 35%, by weight of the Second polymer, (Gv) the hollow polymeric particles andor the microscopic ‘oids resulting from sion of hollow polymeric par tiles define vokumes which constivate (@)at least 11%, preferably at least 12%, for example at least 13%, of the volume of the solid coating, andior (b) less than 30% for example less than 20%, of the ‘volume of the Solid coating, andior (6) 11 0 20%, preferably 12 0 18%, ofthe volume of the solid costing: () the polymeric mucix compris fs defined in subparagraph (vi (the polymeric mati is crosslinked: (vi) the membrane has at least one of the following, characteristics {@) aa OTR at 20° C, of at least 30,000, preferably at Teast $0,000, co!100 in? atm. 24 hrs; (©) an oxygen Pyp ratio of atleast 2, preferably atleast 2.5, over at least one between 0 and 25° Cs «crystalline polymer above;US 7,329,452 B2 7 (©)a carbon dioxide Prato of atleast 2, preferably at least 2.5, over a least one 10° C. temperature range Tetween O and 25° Cand (@) an R rato of less than 4, preferably less than 3, particular less than 2.5, at atleast one temperature Therween O and 22° C. “The microporous polymere film, which serves a 8 sup= port for the polymeric coating, comprises a network of Jnercomnected pores such that gases can pass through the film, Preferably the pores have an average pore size of Tess than 0.24 micron. Other optional features of the microporous ‘lm include (9) a least 70%, eg, at Teast 9096, of the pores having 9 pore size of less than 0.24 micro: (atleast 80% ofthe pores havea pore size less than 0.15 (6) less than 20% of the pores have a pore size less than 0.014 micron; (4) the pores constitute 38 10 80% by volume of the ‘microporous film; (6) the micropotous film comprises a polymeric matrix ‘comprising () an essentially linear lirahigh molecular ‘weight polyethylene having an intrinsic viscosity of at least 18 deciliters or (i) an essentially linear ultra high molecular weight polypropylene having an intrin- sie viseosty of at least 6 deciiters/g, oF (ii) a mitre of Gi) and (i) (the microporous film contains 30 ta 90% by weight, ‘based on the weight of the film, of a finely divided particulate substantially insoluble filler, preferably 2 ‘Slicous illr, which i istbuted throughout the films (2) the mieroporous film is prepared by a process com= rising (A) preparing a uniform mixture comprising the poly- ‘meric mateix material in the form of a powder, the filler, and a processing ol: (B) extruding the mixture asa continuous sheet; (©) forwarding the continuous sheet, without drawing, 1 a pair of heated calender rolls; (D) passing the continuous sheet through the calender rolls to form a shect of lesser thickness (©) passing the shect from step (D) toa first extraction zone in which the processing oil i substantially removed by extrcton with an omzunic extraction Tiguid whieh isa good solvent for the processing oil, ‘poor solveat forthe polymerie matrix material, and more volatile than the processing ol (P) passing the sheet from step (B)to-8 second extrac- tion zone in which the ommanic extraction liquid is substantially removed by team or water or both and (G) passing the sheet from step (F) through a forced “dyer to remove a residual ater andl organic ext tion liquid. As indicated above, the polymeric matrix ofthe coating ‘on the microporous film preferably comprises, and may ‘consist essentially of, 3 erystalline polymer, preferably an SCC polymer. The use of a erystalline polymer results in an increase in the Py» values in the melting region of the polymer. The SCC polymer can comprise, and optionally ‘can consist of, units derived from (i) atleast one n-alkyl aerglate or methacrylate (or equivalent monomer, for ‘example an amide) in which the malky! group contains at Jeast 12 carbon atoms, for example in amount 35-100%, 0 o 8 preferably 50-100%, offen 80-100%, and optionally i) one ‘or more comonomer selected from acrylic acid, methacrylic acid, and esters of aerylic or methacrylic acid in whic the esterifing group contains less than 10 carbon atoms. The SSC polymer can also include units derived from a diaeey- late or other crosslinking monomer. The prefered number of carbon atoms inthe alkyl group of the units derived from (}) depends upon the desired melting point ofthe polymer. For the packaging of biological materials, it soften preferred 10 vse # polymer having a relatively low melting point, for ‘example a polymer in which the alkyl groups in dhe units erived fiom () contain 12 and/or 14 carbon a SSC polymer can be a block copolymer in which one of blocks is a crystalline polymer as defined and the other bloek(s) is erystalline or amorphous, for example a block copolymer comprising (i) polysiloxane polymeric blocks, and (i) erystaline polymer blocks having aT, of ~5t0 40° C. Preferred SCC polymers are those prepared by emulsion polymerization, particularly those prepared in aecordance ‘with the disclosure of US. Pat, No. 6,199,318 (Stewart et al) and US. Pat. No. 6,540,984 (Stewart et al), the entire disclosures of which are incorporated herein by reference ‘The polymeric matrix ean also consist of or contain other enysalline and amorphous polymers. Examples of such ‘other polymers include cis-polybutadiene, poly (4-methyl- pentene), polysiloxanes including polyimethyl siloxane, and ethiylene-propylene rubber The preferred hollow polymeric particles for use in this invention ate hollow microspheres of an organic polymer. Sueh microspheres canbe consist essentially of, for ‘example, homopolymers of styrene; copolymers of styrene ‘and one or more other monomers, for example styrene acrylic copolymers, styrene divinylbenzene copolymers styrene maleic anhydride copolymers and styrene butadiene copolymers; polyvinyl toluene; and polymethyl methuery- late, Such particles are commercially available in a wide range of sizes as apacifers for paints and for use in eyom- ety. For example, serylie/stynene copolymers are available under the tradename Ropaque from Rohm & Faas: poly- styrene and carboxyl microspheres are available under the tradename Polybead from Polyseiences Ine. and polysty- ene and styrene copolymer mierospheres are available from Bangs Laboratories Inc. For use in this invention, the particles of preferably in the form of an aqueous emulsion that blends easily with an agueous emulsion of the matrix polymer to be costed onta the microporous fi. The permeability of the containers and packages of the invention ean be influenced by perforating the container in forr to make a plurality of pinholes therein, EXAMPLES The invention is illustrated in the following Examples, Examples C1-C4 being comparative Examples. In the Examples, the SCI, SCC2 and SCCS aerylate polymers used to provide the polymeric matrix in the coatings were prepared by emulsion polymerizing the monomers and parts by weight theroof shown in Table I to give emulsion polymers having the % solid, particle sizes, I, and AH also shown in Table 1. In Table 1. MAA is methacrylic acid, CDA is hexyldincrylte, C12A is dodecyl serylate, and C14A js tetradeeyl acrylateUS 7,329,452 B2 9 TABLE 1 scr AMS mG NS HO 8aS ser 407 M22 HAL 4S 106 88 (0P96 is an aqueous emulsion containing about 36.6% oF bout 47.2% by weight of hollow polyasee spheres having an average particle size of 580 am. Its availabe from Robin & Has under the trafename Ropaque OP96. Tesin is a microporous polyethylene film available commercially from PG under the tradename Testi SP7. I eontains abou 60% silica, fas a thickness of about 0.18 mm (0.007 inch), 2 porosity of about 65%, an average pore size of about 0.1 micron and a largest pore size of 4-10 microns, The diste- bution of pore sizes in Tesin SP7 is set out in Table 2 below. 0 10 TABLE 2 for ees)_013 O16 026 OM 0 08 AN AS 24366 per rere In each of the Pxamples, the coating composition was coated onto Teslin using a #10 wire-wound rod, and was then dried at 82° C, Tor 2 hours, resulting in 8 crosslinked coating on the surface ofthe Teslin. The OTR and COTR of the resulting product were measured at different temper tures. Examples C1 and 1-4 Examples Cl and 1-4 are summarized in Table 3 below Ineach ofthese Examples, the coating composition (e) was prepared by mixing polymer SCCT and the indieated per centage by weight (based on the weight ofthe mixture) of ‘0P96 (36.6% solids), followed by dilution to about 3% solids ia Examples I-f and to about 7% solide in Example C1. The dried coating (de) containing the indicated percent ‘ges by weight and by volume of the hollow polymeric spheres TABLES ‘a na aw oa 3m det Sie ant 387 Ss Tea ples C2 and § Examples C2 and 5 are summarized in Table 4 below. In each of these Examples, the coating composition (ce) was prepared by mixing polymer SCC2 und the indicated per ‘entage by weight (based on weight ofthe mixtire) of OP (55% solids), followed by dilution to about 5% solids in Example C2 and about 12% solids in Example 5, The dri coating (de) containing the indicated percentages by weight and by volume of hollow polymeric panicles. TABLE 4 we wth wl Tepes he Pa x OP pte tere eyUS 7,329,452 B2 Examples C3, C4 and 6 are summarized in Table 5 below. In Fxample C3, the coating composition (ce) contained only polymer SCC3 and was coated at 11% solids, In Examples ‘C4, the coating composition contained a S0/S0 mixture of polymers SCC2 and SCS, and was coated at 10% solids. In Example 6, the coating composition was made by mixing 76% of a 50/50 mixture of polymers SCC2 and SCC3, and 24% of OP96 (36.6%) followed by dilution to about 12% Solids. The dred eoating (de) contain the indiated pereent- ‘ages by weight and by volume of hollow polymer spheres 12 TABLE 6 Wy Gator 82 Cater #6, 2h TABLE $ we ae lee eae wes wee I “Repent we MN wm Ea Ex OMG ples pices 1S Ie c fo ore 38) ont | ge) aici Examples C5, C6, 7 and In Examples C5, C6, 7 and 8, packages containing 3 16 (2.28 kg) of whole stawherries were used. In Example CS, the package was open, In Example C6, the package was scaled and was composed of Mylar except for a known imosphere contol member having an area of 2.5 inch? (1610 mm") and composed of Teslin having costing thereon of an SCC polymer containing units derived from, tetradecyl acrylate (57 parts), hexadecyl acrylate (40 pars) ‘and aeryli acid ( parts), Ia Example 7, the package was the same as in Example C6, except thatthe atmosphere control member was composed of the coated film of Example 5. In Example 8 the package was the same as in Example 7, ss ‘except thatthe area ofthe atmosphere control member Was 440 inch* (2580 mm") Faeh package in Examples C6, 7 and 8 had a 26 g pinhole to eqllize the pressures inside and ‘ouside the sealed package. The packages wore stored at 2° C. for 72 hours, then at 4 10° C. for 48 hours, and finally a 2°C. for 120 hours, alter ‘which the sealed packages were opened. Table 6 below shows the Weight loss ofthe strwhemies atthe end of the storage period and the O, and CO, contents of the aimo- sphere within the sealed packages at 10° C. after 120 hours 6s Ge at theend of the 10°C. storage period) and at °C. ater 14 hours ‘The invention claimed is 1. A gus-pommeable membrane which comprises (1) 2 mieroporous film, and 2) solid coating on the microporous film, the coating ‘comprising (@) a matrix comprising fist polymer, and (6) a plurality of microscopic voids which (@ provide eontinsous pathways forthe transmission ‘of oxygen and carbon dioxide through the coating, ‘and i) ace at least partly defied by walls composed of ‘a second polymer, the second polymer being different from the frst polymer and the solid coating containing 10 to 40% by weight ofthe second polymer, based on the weight of the solid coating. 2. Amembrane aeconting to claim 1 which has an oxygen permeability (OTR) of ut least 30,000 ee! 00 in*atm.24 hrs at 20° C,, a ratio of carbon dioxide permeability to oxygen permeability (R ratio) of less than 4 atleast one teaper- ture between O and 22° C. 3. A membrane according to claim 1 wherein i the first polymer consists essentially of at Teast one side chain tnystalline polymer having a peak melting temperature T, of 5 0 40° C. and a heat of sion of at least 10 Jig, and Gi) the second polymer consists essentially of a homopolymer or copolymer of styreneUS 7,329,452 B2 13 4.4 membrane according to claim 1 whieh (@) hus an oxyzen permeability (OTR) at 20° C.of at least, '30,000 ce/100 in tm.24 ob for and concentrate on my phone hrs () has an oxygen Pio ratio of at least 2 over at feast one 10" C. temperature range between 0 and 25° C. (6) has carbon dioxide Pg ratio ofa least 2 over at east fone 10° C. temperature range between O and 25° C and (2) has am R ratio less than 4 at atleast oe temperature ‘between 0 and 22° C, 5. A container which ean be sealed around a respiring biological material and whieh includes one or more aimo- sphere control members, at least one of the atmosphere ‘control members comprising a gas-permeable membrane as ‘defined in claim 1 6. A package which comprises (@)a sealed container, and () within the sealed container, 2 respiring biological ‘material and a packaging almosphere around the bio- logical materia: the sealed container including one or more atmosphere ‘control members, at least ane of the atmosphere contol members comprising a gas-permeable membrane as defined in claim 1 7. Amembrane according to claim 1 wherein the coating ‘comprises hallow particles which (i) are composed of polymeric composition comprising the second polymer, i) dispersed in the matrix, and (ii) have @ maximum mension which is at most 026 of the thickness of he solid ‘esting: and the hollow polymeric particles and the micro= scopic voids define volumes which constitute II to 20% of the volume of the slid costing. 8, A membrane according (claim 7 wherwin the hollow particles are hollow microspheres or hollow microfilaments ‘composed of homopolymer or copolymer of styrene, 9. \ gas-pemeable membrane which comprises (1) mioporous film, and (Q) a solid coating on the microporous film, the coating ‘comprising (@) 8 matrix comprising o fist polymer, and (b) hollow panicles which (i) are composed of polymeric composition comprising « second poly= ‘er, (i) ae dispersed in the matrix, and (i) have & ‘maximum dimeasion which is at most 50% of the thickness of the solid coating, the second polymer Iheing different from the fist polymer and being present in amount 5 to 50% by weight, based on the ‘Weight of the solid coating, and wherein () the coating contains 10 10 40% by weight ofthe hollow panicles, based on the combined weight of the fist polymer and the particles, and at Teast 90% ofthe particles have a maximum dimen- ‘Sion of 0.2 to 0.8 micron, 0 14 10, A membrane according to claim 9 which also com- prises a plurality of microscopic voids which ) provide continuous pathways forthe transmission of ‘oxygen and carbon dioxide through the coating, and Gi are at least parly defined by walls composed of the second polymer 11. A membrane according to claim 9 which has an oxygen permeability (OTR) of at least 30.000 ce/100 intatm24 hs at 20° C., and a ratio of earbon dioxide permebility to oxygen permeability (R ratio) of Tes than 4 At at Teast one temperature between O and 22°C. 12, A membrane according to claim 9 wherein () the frst polymer consists essentially of at least one side chain enysalline polymer having a peak melting temperature T, of S40 40° Cand a heat of fsion of at lest 10 J, an the second polymer consists essentially of « homopolymer ‘or copolymer of styrene 13. A membrane according to claim 9 which (has an oxygen permeability (OTR) at 20°C. of atleast, 30,000 ce/100 in atm 24 hes (has un oxygen Py rato of ut lest 2 over at least one 10° C. temperature range between O and 25°C. () has carbon dioxide P, ratio ofa least 2 over at least ‘one 10° C. temperature range between 0 and 25° C.; and (8) has @ mtio of carbon dioxide permeability o oxygen permeability (R ratio) of Jess than 4 at at Feast one temperature between 0 and 22° C. 14, A container which can be sealed around a respiring biological material and which inelides one or more stmo- sphere control members, at least one of the atmosphere ‘cnrol members comprising a gns-permeable membrane as Sefine i claim 9, 15, A package which comprises (@) a sealed container, anal () within the sealed container, a respiring biological material and a packaging atmosphere around the bio logical material: the sealed! container including one or more atmosphere contro members al least one of the atmosphere contol members comprising a gas-permeable membrane as defined in claim 9 16, A package according to elaim 18 wherein the respiring biological material is fresh berries, Fresh cut fit, or a vegetable. 17. Amembrane aeconding to claim 9 wherein the volume ‘of the hollow particles dispersed inthe coating is 11 to 20% ‘of the Volume of the solid coating 18, A membrane according wo claim 9 wherein the hollow particles are hollow microspheres or hollow microfilaments composed of a homopolymer or copolymer of styrene