NZ210433A

NZ210433A - Process for producing porous film

Info

Publication number: NZ210433A
Application number: NZ210433A
Authority: NZ
Inventors: Ito Keiko; Ito Michiyasu; Tsuji Shoichi; Suzuki Hisatosi; Ito Shoichi
Original assignee: Mitsui Toatsu Chemicals
Priority date: 1983-12-16
Filing date: 1984-12-04
Publication date: 1987-05-29
Also published as: KR870001966B1; NL187233C; FR2556648B1; GB2151538B; IT1179513B; AU3622184A; CA1245026A; NO171456B; DE3445771A1; SE8406114L; NO845047L; NL187233B; FR2556648A1; IT8424069A0; NL8403798A; SE8406114D0; GB2151538A; CH666222A5; AU551948B2; SE465310B

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £10433 2 10433 Priority Date(s): Complete Specification Filed: Class: Publication Date: DAT. P.O. Journal, No: / « ■ y* • ■ • * NEW ZEALAND PATENTS ACT, 1953 N.Z. PATENT OFFICE - 4 DEC 1984 RECEIVED No.: Date: COMPLETE SPECIFICATION PROCESS FOR PRODUCING POROUS FILMS tyWe, MITSUI TOATSU CHEMICALS, INCORPORATIED, of 2-5, Kasumigaseki 3-chome, chiyoda-ku, Tokyo, Japan hereby declare the invention for which >1 / we pray that a patent may be granted to.tffe/us, and the method by which it is to be performed, to be. particularly described in and by the following statement:- - 1 - (followed by page la) a - 1 - 210433 SPECIFICATION Title of the Invention: Process for Producing Porous Films Background of the Invention; a) Field of the Invention: This invention relates to an improved process for producing porous films. More particularly, it relates to a process for producing porous films which comprises blending a polyolefin resin with barium sulfate as a filler, melting the resulting resin composition and forming it into a film, and then stretching the film at least uniaxially. b) Description of the Prior Art: Conventionally, there are a large number of well-known processes for producing porous films by forming a resin composition comprising a polyolefin resin and any of various noncompatible fillers into a film and then stretching this film. For example, there is known ; 1 films which comprises melting a resin composition a process for producing porous obtained by blending afin |r and liquid rubber or a hydroxylat fin resin with a filler aturated- "f - 2 - 210433 O hydrocarbon, forming the molten resin composition into a sheet or film, and then stretching this sheet or film. Moreover, there is known a process for producing porous 5 films which comprises melting a resin composition obtained by blending a linear low-density polyethylene resin with a filler and a liquid or waxy hydrocarbon polymer, forming the molten resin composition into a sheet or film, and then stretching this sheet or 10 film. However, the films produced by these processes are disadvantageous in that they exhibit surface tackiness due to the aforesaid component contained in addition to the polyolefin resin and the filler and in that they can only be practically used in 15 relatively large thickness because of their low mechanical strength. Furthermore, it is known —— that such porous films can be used as a leakproof sheet in disposable 20 diapers. Porous films for use as the leakproof sheet of a disposable diaper are produced by blending 100 parts by weight of a polyolefin resin with 28 to 200 parts by weight of a filler and 10 to 70 parts by weight of a liquid or waxy hydrocarbon polymer, 25 forming the resulting resin composition into a film, and then stretching this filj& at least uniaxja^pLy by - 3 - a factor of 1.2 or greater. However, this process for producing porous films has the disadvantages that some types of fillers give poor stretchability and hence fail to provide fully uniform pores and 5 that the resulting film tends to produce a disagreeable noise. Moreover/ the concurrent use of a hydrocarbon polymer makes this process unsatisfactory because the hydrocarbon polymer tends to bloom to the film surface and causes a sticky sensation. 10 Such porous films are also useful as a leakproof sheet in sanitary napkins. Conventionally, a sheet of paper which has been rendered liquid-impermeable by means of a synthetic resin such as polyethylene has been used for this purpose. How-15 ever, the resulting sanitary napkins have the disadvantage of causing a disagreeable sensation during prolonged use because of their, lack of permeability to water vapor. 20 Summary of the Invention; Accordingly, it is an object of the present invention to provide an improved process for producing porous films. It is another object of the present inven-25 tion to provide a process for producing porous films which have sufficiently high porosity and thereby 210433 - 4 - exhibit high moisture permeability and gas permeability while retaining excellent water resistance. It is still another object of the present invention to provide a process for producing porous films which are free from surface tackiness, have excellent softness and show little reduction in strength. It is a further object of the present invention to provide an improved leakproof sheet for use in disposable diapers. It is a further object of the present invention to provide an improved leakproof sheet for use in sanitary napkins. Other objects of the present invention will be apparent from the following description. According to the present invention, there is provided a process for producing porous films which comprises melting a resin composition consisting essentially of 100 parts by weight of a polyolefin resin and 50 to 500 parts by weight of barium sulfate, forming the molten resin composition into a film, and then stretching the film at least uniaxially by a factor of 1.5 to 7. The expression "a resin composition consisting essentially of 100 parts by weight of a polyolefin resin and 50 to 500 parts by weight of barium sulfate" m - 5 - 210433 as used herein means that the resin composition may further contain (1) at least one additive selected from common stabilizers, antioxidants, colorants, ultraviolet light absorbents and laubricants and/or ' 5 (2), in addition to the barium sulfate, other inorganic fillers (such as calcium carbonate and the like) or common inorganic and organic modifiers in an amount less than that of barium sulfate used (for example, not greater than 20% based oil the 10 amount of barium sulfate used), but the addition of liquid rubber, a hydroxylated poly-saturated-hydrocarbon or a hydrocarbon polymer as described in the aforementioned prior art should 15 be positively avoided in order to obtain a porous film free from surface tackiness. According to the present invention, porous films which are free from surface tackiness and have excellent properties and which have been un-20 obtainable in the prior art can be produced without using any of the above-described additives used in the prior art. This can be accomplished simply by specifying the type of the filler, its amount used and preferably its average particle diameter; 25 preferably using a low-density polyethylene^resin having a specific melt index and density and mo preferably a linear low-density polyethylene resin (in particular, a linear low-density polyethylene resin comprising a copolymer of ethylene and hexene and/or octene) which most preferably has a specific melt index and density; and stretching the film by a specific factor. Detailed Description of the Invention: The polyolefin resins which can be used in the present invention include homopolymers such as polypropylene, low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polybutylene, etc.; copolymers such as ethylene-propylene copolymer, ethylene-butylene copolymer, ethylene-vinyl acetate copolymer, etc.; and blends thereof. Among these resins, low-density polyethylene resins having a melt index of 0.5 to 7 (0.5 to 8.5 for linear low-density polyethylene resins) and a density of 0.915 to 0.935 are preferred. Although it is preferable to use a single resin, any blend of polyethylene resins having different densities may be used. More preferably, the melt index is in the range of 1 to 5. If the melt index is less than 0.5 or greater than 7 (8.5 for linear low-density polyethylene resins) , the resin will have significantly 2 104 - 7 - decreased formability into a film and may fail to yield a film of small and uniform thickness. On the other hand, if the density is lower than 0.915 or higher than 0.935, the resin will have decreased stretchability and increased rigidity and may fail to yield a soft film. Particularly preferred polyolefin resins are linear low-density polyethylene resins. Linear low-density polyethylene resins are copolymers of ethylene and one or more a-olefins, and differ from low-density polyethylene resins prepared by the conventional high-pressure process. Linear low-density polyethylene resins are prepared by the low-pressure process, and useful a-olefins include butene, hexene, octene, decene and the like. The difference between high-pressure-processed low-density polyethylene resins and low-pressure-processed low-density polyethylene resins lies in the fact that, when seen from the viewpoint of chemical structure, the former ones are highly branched polymers while the latter ones are straight-chain polymers. Among such liear low-density polyethylene resins, copolymers of ethylene and hexene and/or octene are particularly preferred. In the practice of the present invention, it is preferable to use barium sulfate having an 2\0i - 8 - average particle diameter of 0.1 to 7 ym and more preferably 0.5 to 5 ym. If the average particle diameter is smaller than 0.1 ym, well-defined pores cannot be obtained. On the contrary, if it is larger than 7 ym, the resulting film will have poor stretchability and, therefore, well-defined pores can hardly be obtained just as in cases where the average particle diameter is too small. The barium sulfate is used in an amount of 50 to 500 parts by weight, and preferably 100 to 400 parts by weight, per 100 parts by weight of the polyolefin resin. If the amount of barium sulfate used is less than 50 parts by weight, sufficiently high porosity cannot be obtained, while if it is greater than 500 parts by weight, the resulting film cannot be fully stretched because of its increased rigidity and, therefore, will show a reduction in porosity. It is preferable to subject the barium sulfate to surface treatment with a fatty acid or a metallic salt thereof, silicone, silane, a resin acid or the like, because this treatment is effective in improving its dispersibility in the resin and producing well-defined pores. So far as the effects of the present invention are not impaired, other inorganic fillers such as 33 - 9 - 210433 calcium carbonate and the like or common inorganic and organic modifiers may be used in addition to the barium sulfate. However, these additives should be used in an amount of not greater than 20% based 5 on the amount of barium sulfate used. Now, the present process for producing porous films will be specifically described hereinbelow. According to the need, at least one additive 10 selected from stabilizers, antioxidants, colorants, ultraviolet light absorbents and lubricants is added to a polyolefin resin and barium sulfate. These ingredients are mixed with a Henschel mixer, super-mixer or tumbling mixer. Thereafter, using an 15 ordinary single-screw or twin-screw extruder, the resulting mixture is blended and pelletized. Then, using an inflation extruder or T-die extruder, these pellets (alone or in admixture with polyolefin resin pellets) are melted at a temperature higher 20 than the melting point of the polyolefin resin (preferably, by 20°C or more) and lower than the decomposition temperature thereof, and formed into a film. In some cases, the aforesaid mixture may be directly formed into a film with an extruder, instead of being 25 pelletized. Subsequently, the film is at least unaxially stretched by a factor of 1.5 to 7 according i i 2104 33 - 10 - to a conventional technique such as roll stretching, tentering or the like. This stretching may be performed in steps and/or in two or more directions. In the case of biaxial stretching, however, it is preferable to stretch the film simultaneously in the two directions. In order to enhance the morphological stability of pores, the stretched film may be annealed by heating. The porosity is determined by the amount of barium sulfate used, the stretching factor and the like. If the stretching factor is less than 1.5, sufficiently high porosity cannot be obtained, while if it is greater than 7, a porous film cannot be steadily produced because of its frequent breakage during the stretching process. Porous films produced by the process of the present invention are characterized by high porosity, excellent softness and little reduction in strength. Moreover, since the good affinity between the polyolefin resin and barium sulfate provides good stretchability, not only good workability but also an even distribution of pores can be achieved and, therefore, a porous film can be produced steadily. Especially when a linear low-density polyethylene resin is used as the base resin, the resulting film will show very little reduction in strength. Thus, it 0* u Q 21 - 11 - is possible to produce porous films which are thinner (for example, approximately 10 ym in thickness) than those produced by the prior-art processes. Furthermore, since the resin composition 5 does not contain any of the liquid rubber, hydroxylated poly-saturated-hydrocarbons and hydrocarbon polymers used in the prior-art processes, the resulting porous film is free from surface tackiness. Thus, the porous films of the present 10 invention have sufficiently high porosity and hence exhibit good moisture permeability and gas permeability while retaining excellent water resistance, so that they can be used in clothing and sanitary applications. In addition, they can also be 15 used as a filtering medium owing to their even distribution of pores. The present invention is further illustrated by the following examples. However, these examples are given for purposes of illustration only and are 20 not to be construed to limit the scope of the invention. In the examples, melt index (MI) was determined according to ASTM D-1238 and density was determined according to ASTM D-1505. 25 Also in the examples, film properties were evaluated according to the following procedures: 210433 - 12 - (1) Strength and elongation Using a Tensilon tensile testing machine, a piece of film measuring 25 mm (wide) x 100 mm (long) is tested at a straining rate of 200 mm/min. Its strength and elongation at breakage are determined with respect to the machine direction (MD) and the transverse direction (TD). (2) Moisture permeability Moisture permeability is tested according to ASTM E96(Method D). (3) Softness Softness is evaluated by the feel and rated according to the following cristeria: Very soft and smooth Rather soft and smooth Hard and rough Examples 1-19 and Comparative Examples 1-9 Each of the fillers given in Table 1 was added to the corresponding base resin in the amount given in Table 1, and mixed therewith by means of a Henschel mixer. Thereafter, using a twin-screw mixer., the resulting mixture was intimately blended A = B = C = 210433 - 13 - and formed into pellets. Then, using a T-die extruder, these pellets were melted at a temperature 80°C higher than the melting point of the base resin and formed into a film. This film was uniaxially or biaxially (Example 3) stretched by the factor given in Table 1 to obtain a porous film having the thickness given in Table 1. However, the film was not stretched in Comparative Example 1 and could not be stretched into a porous film in Comparative Examples 2 and 9. In Comparative Examples 5 and 8, the film could only be stretched by a factor of up to 2. In Comparative Examples 3 and 7, no sampling was possible because of frequent breakage during the stretching process. The strength, elongation, moisture permeability and softness of the porous films thus obtained were evaluated according to the above-described procedures and the results are shown in Table 1. 2104 33 - 14 - Table 1 Base resin 1) Type Trade name (manufacturer) Melt index (g/10 min) Density (g/cm3) Example 1 LDPE REXLON F-41 (Nippon Petrochemicals Co., Ltd.) 5.0 0.923 2 II II II fl " 3 11 II It fl " 4 11 MIRASON 45 (Mitsui Polychemicals Co., Ltd.) 1.5 0.920 " 5 If fl «l II 6 If UBE POLYETHYLENE F0191 (Ube Kosan K.K.) 0.9 0.912 " 7 If Neo-zex 43 30 (Mitsui Petrochemical Industries , Inc.)/UBE POLYETHYLENE VF430 (Ube Kosan K.K.)=2/1 3.0 0.940 8 L-LDPE NUCG-5511 (Nippon Unicar Co., Ltd.) 1.0 0.920 9 If If If •• o H / / II Ultzex 2020L (Mitsui Petrochemical Industries, Inc.) 2.1 II 11\^ ft II H II 12 \ II II If If 13 \ II II II II \ 210433 - 15 - Table 1 (Cont'd) /—N o Filler Stretching factor Film thickness (ym) Type Average particle diameter (ym) 2) Amount (phr) BaSO. 4 o • 00 150 4 40 fl fl II 5 II fl fl II 2X2 II If 1.2 130 5 50 It 5.0 120 II II II 1.2 II 33> II II II 100 4 II ft fl II fl 30 It II 150 5 15 II 4.2 50 6.5 40 •1 o • CD 150 5 ft II 0.5 100 7 10 II If 300 3 40 - 16 - 2104 Table 1 (Cont'd) Strength (kg/25 nun) Elongation (%) Moisture permeability Soft MD TD MD TD (g/m^/24 hr) ness 6.0 1.5 80 350 3,500 A 6.5 1.3 60 300 4,200 A 4.9 4.5 200 200 3,900 A in • m 1.5 120 450 3,000 A 5.0 1.3 100 390 M A 3.9 1.0 55 390 1,100 B 4.5 If 50 200 2,000 ' c 3.5 1.2 100 420 3,900 c /; 2.5 0.8 80 400 5,000 A 7.8 1.4 65 170 2,800 A 6.5 1.8 130 510 7,500 A 2.3 j 0.7 40 ! 120 i 8,500 A « in 1.5 78 360 ! 5,500 ! A - 17 - 2 104 33 Table 1 (Cont'd) Base resin Type 1) Trade name (manufacturer) Melt index (g/10 min) Density (g/cm3) Example 14 L-LDPE Ultzex 3010F (Mitsui Petrochemical Industries, Inc.) 1.3 0.930 15 Ultzex 2020L (Mitsui Petrochemical Industries , Inc.) 2.1 0.920 16 Ultzex 20100J (Mitsui Petrochemical Industries, Inc.) 8.0 0.920 17 HDPE Hi-zex HZ5000S (Mitsui Petrochemical industries, Inc.) 0.9 0.954 18 PP MITSUI NOBLEN JS-G (Mitsui Toatsu Chemicals, Inc.) 1.5 0.890 19 EPC MITSUI NOBLEN MJS-G (Mitsui Toatsu Chemicals, Inc.) o - 18 - 2, ^ 04* ^ ^ Table 1 (Cont'd) Filler Type BaSO, Average particle diameter (ym) 5.0 0.5 0.8 2) Amount (Phr) 150 500 200 150 Stretching factor Film thickness (ym) 50 40 o Table 1 (Cont'd) O Strengrth (kg/25 jnm) Elongation (%) Moisture permeability Soft MD TD MD TD (g/m^/24 hr) ness 5.1 1.4 110 400 6,700 A o • in 1.0 35 20 5,000 A 5.5 1.4 105 420 4,700 \ ' A o • CO 2.2 70 400 4,500 c 10.3 2.5 90 350 4,900 C : 9.1 1 2.3 | 88 520 4,000 ■ i U O ■Mm*niwi>wmun*ininni i (C Jl. u Sx <J - 20 - Table 1 (Cont'd) Base resin Type 1) Trade name (manufacturer) Melt index (g/10 min) Density (g/cm3) Comparative Example 1 L-LDPE Ultzex 2020L (Mitsui Petrochemical Industries, Inc.) 2.1 0.920 NUCG-5511 (Nippon Unicar Co., Ltd.) 1.0 8 LDPE PETROSEN 207 (Toyo Soda Manufacturing Co., Ltd. 0.924 Notes: 1) LDPE = low-density polyethylene. L-LDBE = linear low-density polyethylene. PP = Polypropylene EPC = ethylene-propylene copolymer. 2) Parts by weight of the filler per 100 parts by weight of the base rein. 3) , 5) & 7) The maximum value at which stretching can be performed steadily. 4) & 6) No sampling was possible because breakage during the stretching process. of (M -9 MAR 1987! V V. 21043 - 21 - Table 1 (Cont'd) Filler Stretching factor Film thickness (ym) Type Average particle diameter (ym) 2) Amount (Phr) BaS04 0.8 150 Unstretch-ed 50 II II 600 Unstretched - II II 150 84) - CaC03 1.0 II 4 70 Glass beads 1.2 120 25' 50 BaS04 II 30 5 40 II II 100 86> - Glass beads II II 27' 60 BaSO^ II 130 Unstretch-ed - - 22 - 2104 33 Table 1 (Cont'd) O Strength (kg/25 nan) Elongation (%) Moisture permeability Soft MD TD MD TD (g/m2/24 hr) ness 2.5 2.3 570 480 15 A - - - - - - - - - - - - 4.3 0.8 20 100 3,000 C 1.5 0.7 140 290 30 c 4.5 1.0 105 430 15 c - - - - - - 1.0 0.5 40 100 40 . C i - - - - . . 1 f 1 1 G 210433 - 23 - Porous films produced by the process of the present invention have high porosity and excellent softness and, moreover, show little reduction in strength, so that they are very suitable for use as a 5 leakproof sheet in disposable diapers. Although such a leakproof sheet is generally used as the outermost layer of a disposable diaper, a material (such as a common punched film or sterically embossed sheet) not impairing its moisture permeability may be super-10 posed on the outer side of the leakproof sheet to impart a cloth-like appearance thereto. In such disposable diapers, there may be used any of common liquid absorbers including fluff composed of pulp fibers, such fluff wrapped in 15 absorbent paper or the like, polymeric absorbers having high water absorbency, and the like. As the liquid-permeable sheet which will be in direct contact with the skin, there may preferably be used a non-woven fabric composed of 20 polyester fibers, nylon fibers, polyolefin fibers or the like. In addition, there may be used pressure-sensitive tapes for fastening the diaper, and elastic members (such as rubber members) provided along the 25 side edges to prevent leakage. Disposable diapers are made by placing a 2104 3 3 - 24 - liquid absorber on the aforesaid leakproof sheet, and stacking a liquid-permeable sheet thereon. In disposable diapers using the porous film of the present invention as the leakproof sheet, 5 the outermost leakproof sheet has a large number of pores. Since these pores allow water vapor to pass therethrough while retaining water droplets, the skin of the infant is not dampened but kept in a dry state, resulting in little tendency to develop diaper 10 rash. Moreover, they also have the advantages of being hardly torn because of their high strength and being soft enough to produce no disagreeable noise. The following examples illustrate the use of the porous film of the present invention as a 15 leakproof sheet in disposable diapers. Examples 20-22 and Comparative Examples 10-14 Barium sulfate having an average particle diameter of 1.5 ym or each of the other fillers given 20 in Table 2 was added to 100 parts by weight of low-density polyethylene (LDPE) having a melt index (MI) of 3 (Examples 20 and 21) or linear low-density polyethylene (L-LDPE) having a melt index (MI) of 5 (Example 22 and Comparative Examples 10-14) in the 25 amount given in Table 2, and mixed therewith by means of a Henschel mixer. Thereafter, using a 2 104-33 - 25 - twin-screw mixer, the resulting mixture was intimately blended and formed into pellets. Then, using a T-die extruder, these pellets were melted at 130°C and formed into a film. This film was uniaxially stretched between a preheating roll heated to 50°C and a stretching roll by the factor given in Table 2 to obtain a porous film having a thickness of 50 ym. Properties of the porous films thus obtained were evaluated and the results are shown in Table 2. Disposable diapers were made by placing a filling of fluffy pulp and a non-woven polyester fabric on each of the porous films obtained in Examples 20-22 and Comparative Examples 10, 13 and 14, and then providing it with pressure-sensitive tapes and rubber members. The disposable diapers of Examples 20-22 were superior in strength, moisture permeability and softness to those of "Comparative Examples 10, 13 and 14, so that they produced only a slight rustling noise during use and felt comfortable to the touch. When these disposable diapers were tested by using them practically in infants, those of Examples 20-22 caused no rash on the skin of the wearer. In contrast, the disposable diapers of Comparative Examples 10, 13 and 14 caused an extensive rash or a slight rash (Comparative Example 13). 2104 - 26 - Example 23 Using a biaxial stretching machine heated to 70°C, the unstretched film formed in Example 20 was simultaneously stretched in both the machine and the transverse direction (by factors of 2 x 2) to^ obtain a porous film having a thickness of 50 ym. Properties of this porous film were evaluated and the results are shown in Table 2. Disposable diapers using this porous film as the leakproof sheet exhibited as good performance as those of Example 20. Example 24 The same resin composition as used in Example 22 was formed into a film. Using a roll heated to 50°C, this film was uniaxially stretched by a factor of 4 to obtain a porous film having a thickness of 15 ym. Properties of this porous film were evaluated and the results are shown in Table 2. On the outer side of this porous film was i superposed a LDPE film of 70 ym thickness having 2 apertures of 1 mm diameter (20/cm ) all over its surface. Disposable diapers using this composite material as the leakproof sheet also exhibited as good performance as those of Examples 20-23. 21043 - 27 - Table 2 Base resin Filler Type Amount (parts by weight) Type Amount (parts by weight) Example 20 LDPE 100 BaSO^ 150 21 It II if tl 22 L-LDPE fl it 200 23 LDPE II ii 150 24 1-LDPE II ii 200 Comparative Example 10 fl II II 150 11 II It II 600 12 II ' 'II II 150 13 If H CaC03 ft i 1 14 II II Glass beads 120 *) An attempt was made to stretch the film by a factor of 8, but no sampling'was possible because of frequent breakage during the stretching process. **) The film could not be stretched by a factor of more than 2. 21043 - 28 - Table 2 (Cont'd) Stretching factor Strength IMD/TD] (kg/25 mm) Moisture permeability (g/m2/24 hr) Softness 4 6.0/1.5 3,500 A 5 6.5/1.3 4,200 A 3 5.5/1.3 4,600 A 2 X 2 4.9/4.5 3,900 A 4 6.7/0.9 4,700 A Unstretch-ed 2.3/2.2 15 A Unstretch-ed - - - *) 8 ; - - - 4 4.3/0.8 3,000 C 2 ' 1.5/0.7 30 C 210433 - 29 - Comparative Example 15 120 parts by weight of calcium carbonate having an average particle diameter of 1.2 ym and 20 parts by weight of a hydroxylated poly-saturated-hydrocarbon (Liquid Polybutadiene GI-2000; Nippon Soda Co., Ltd.) were added to 100 parts by weight of linear low-density polyethylene (L-LDPE) having a melt index (MI) of 5, and mixed therewith by means of a Henschel mixer. Thereafter, using a twin-screw mixer, the resulting mixture was intimately blended and formed into pellets. Then, using a 40 mmjrf inflation extruder, these pellets were formed into a film. This film was roll stretched at 80°C by a factor of 3.0 to obtain a porous film having a thickness of 50 ym. This porous film varied in moisture permeability according to the location and exhibited a slight degree of surface tackiness. Disposable diapers using this porous film as the leakproof sheet caused a slight rash on the skin of infants. Comparative Example 16 The procedure of Comparative Example 15 was repeated except that liquid polybutadiene (Nisso PBG; Nippon Soda Co., Ltd.) or rubbery EPR (Toughmer P0480; Mitsui Petrochemical Industries, Inc.) was used as the hydroxylated poly-saturated-hydrocarbon. 2 13 - 30 - 0 O Thus, there were obtained films having a thickness of 50 ym. These porous films exhibited surface tackiness and varied in moisture permeability according to the location. Disposable diapers using 5 each of these porous films as the leakproof sheet caused a slight rash on the skin of infants. Porous films obtained by the process of the present invention have high porosity and excellent softness and, moreover, show little reduction in 10 strength in spite of their small thickness, so that they are very suitable for use as a leakproof sheet in sanitary napkins. Conventional sanitary napkins are so constructed that a liquid absorber such as fluffy pulp, cotton, absorbent resin or the like is 15 partially covered with a film of paper having been rendered liquid-impermeable by treatment with a synthetic resin such as polyethylene or the like and the resulting structure is then wrapped in a non-woven fabric. In sanitary napkins using the porous 'w' 20 film of the present invention as the leakproof sheet, this leakproof sheet has a large number of pores which allow water vapor to pass therethough. Accordingly, they can keep the skin of the user in a dry state and cause no disagreeable sensation even during 25 prolonged use. The following examples illustrate the use of - 31 - 11 04- 33 the porous film of the present invention as a leakproof sheet in sanitary napkins. Examples 25-27 Barium sulfate having an average particle diameter of 0.8 ym was added to 100 parts by weight of linear low-density polyethylene (L-LDPE) having a melt index (MI) of 2.1 in the amount given in Table 3, and mixed therewith by means of a Henschel mixer. Thereafter, using a twin-screw mixer, the resulting mixture was intimately blended and formed into pellets. Then, using a T-die extruder, these pellets were melted at 230°C and formed into a film. This film was uniaxially stretched between a preheating roll heated to 80°C and a stretching roll by the factor given in Table 3 to obtain a porous film having a thickness of 20 ym. Properties of this porous film were evaluated and the results are shown in Table 3. Sanitary napkins were made by covering a filling of fluffy pulp partially with each of the porous films obtained in Examples 25-27, wrapping the resulting structure in a non-woven fabric and then heat sealing its overlapping portions. When these sanitary napkins and commercially available ones having a liquid-impermeable film of polyethylene-coated paper were comparatively tested by using them - 32 - 210433 practically for prolonged periods of time, the sanitary napkins in accordance with the present invention did not cause a disagreeable, stuffy sensation. </div>

Claims

<div class="application article clearfix printTableText" id="claims"> c o O 0 Table 3 Base resin Filler Stretching factor Strength [MD/TD] (kg/25 tnm) Moisture permeability (g/m2/24 hr) Softness Type Amount (parts by weight) Type Amount (parts by weight) Example 25 L-LDPE 100 BaSO. 4 100 6 ^ 3.2/1.0 5,200 A Example 26 II II ft 150 5 3.0/0.9 4,800 A Example 27 II n It 400 3 2.5/0.8 4,200 A © - 34 - HATHr/WE CLAIM WVnf in rlnimn^ i g •

1. In a process for producing porous films which comprises melting a resin composition consisting 5 essentially of a polyolefin resin and a filler non-compatible therewith, forming the molten resin composition into a film, and then stretching the film at least uniaxially, the improvement in which the ■ Hon-compatible filler is barium sulfate, the barium sulfate 10 is used in an amount of 50 to 500 parts by weight per 100 parts by weight of the polyolefin resin, and the film is stretched by a factor of 1.5 to 7.

2. A process as claimed in claim 1 wherein 15 the average particle diameter of the barium sulfate is in the range of 0.1 to 7 ym.

3. A process as claimed in claim 2 wherein the average particle diameter of the barium sulfate CD 20 is in the range of 0.5 to 5 ym.

4. A process as claimed in claim 1 wherein the barium sulfate is used in an cimount of 100 to 400 parts by weight per 100 parts by weight of the 25 polyolefin resin. m 210433 - 35 -

5. A process as claimed in claim 1 wherein the barium sulfate has been subjected to surface treatment with a fatty acid or a metallic salt thereof, silicone, silane or a resin acid. 5 '

6. A process as claimed in claim 1 wherein the polyolefin resin is a polyethylene resin.

7. A process as claimed in claim 6 "wherein 10 the polyethylene resin is a low-density polyethylene resin having a melt index of 0.5 to 7 g/10 min. and a density of 0.915 to 0.935 cj/cm3. .

8. A process as claimed in claim 7 wherein 15 the low-density polyethylene resin is a single resin.

9. A process as claimed in claim 7 wherein the low-density polyethylene resin is a blend of polyethylene resins having different densities. 20

10. A process as claimed in claim 7 wherein the melt index is in the range of 1 to 5. 9^10 min. <3

11. A process as claimed in claim 6 wherein 25 the polyethylene resin is a linear 1-ow-density:- ethylene resin. </. Q XV /7 V : 1 5 APR 1987"! /•*;_ // .-*7 ? v;.' - 36 - 210433

12. A process as claimed in claim 11 wherein the linear low-density polyethylene resin has a melt index of 0.5 to 8.5 jgf/10 min. and a density of 0.915 to 0.935 g/cm3. 6

13. A process as claimed in claim 11 wherein the linear low-density polyethylene resin is a copolymer of ethylene and hexene and/or octene.

14. A porous film having water resistance, moisture permeability and gas permeability which has been produced by a process as claimed in any one of claims 1 to 13.

15. The use of the porous film of claim 14. as a leakproof sheet in disposable diapers..

16. The use of the porous film of claim 14 as a leakproof sheet in sanitary napkins.

17. A process as claimed in any one of claims 1 to 13 substantially as herein described with reference to the Examples.

18. A porous film as claimed in claim 14 substantially as herein described with reference to the Examples. </div>