SPECIFICATIONAbsorbent articleThis invention relates to an absorbent article which is improved and integrally formed, such as adisposable nappy or diaper and a sanitary towel or napkin. More particularly, it relates to an absorbentarticle in which a liquid-impermeable, but vapor-permeable, porous film is used as a leakproof backingsheet.
The disposable diaper will be first described in the specification and then the sanitary napkin willbe disclosed.
Hitherto, as the leakproof backing sheet for disposable diapers, there has been used a sheetproduced by mixing low-density polyethylene with 3 to 5 wt.% of titanium oxide, molding the mixture toform a film having a basis weight of 20 to 30 g/m2 and then embossing said film. However, because ofits vapor impermeability, such a sheet causes a so-called clammy state around the wearer's buttocks because the inside of the diaper becomes exceedingly damp during long-time use. Such a clammy statecauses red skin irritation, like prickly heat, on the wearer's skin surface, and if the diaper is worn for alonger time in such a state, the wearer may suffer from a serious case of diaper rash.The necessity of avapor-permeable leakproof layer for a diaper has been pointed out and proposals have been madeconcerning utilisation of porous films, but there is not yet available a vapor-permeable, liquidimpermeable film which is fully satisfactory in respect of film strength, particularly tear strength,flexibility, economy and moisture permeation.
As a result of extensive studies for solving these problems, the present inventors have discoveredthe present invention.
Figure 1 is a cross-sectional view of a disposable diaper of the invention.
Figures 2 and 3 are each cross-sectional views of sanitary napkins of the invention.
Briefly, the present invention provides a disposable diaper comprising an integral assembly of avapor-permeable, liquid-impermeable, backing sheet 1, an absorbent layer 2 placed thereon and aliquid-permeable sheet 3 overlying said absorbent layer, in which the vapor-permeable, liquidimpermeable, backing sheet is composed of a film produced by mixing 100 parts by weight of apolyolefin resin, 28 to 200 parts by weight of a filler and 10 to 70 parts by weight of a liquid or wax-likehydrocarbon polymer, molding the mixture to form a film and then stretching the film laterally and/orlongitudinally until it has a dimension of more than 1.2 times its original dimension in that direction,whereby to form fine pores in the film.
As examples of polyolefin resins usable in this invention, there can be mentioned high-densitypolyethylene, polypropylene and linear low-density polyethylene resins. These resins can be used eithersingly or in mixtures of two or more of them, but it is preferred to use a linear low-density polyethyleneresin alone or a high-density polyethylene resin alone.
As the filler used in this invention, it is possible to employ both inorganic and organic fillers.
Examples of suitable inorganic fillers are calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth,magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate,aluminum hydroxide, zinc oxide, magnesium hydroxide, calcium oxide, magnesium oxide, titaniumdioxide, alumina, mica, asbestos powder, glass powder, "Shirasu" (white sandy deposit), zeolite,siliceous china clay and the like. Among them, calcium carbonate, talc, clay, silica, diatomaceous earthand barium sulfate are preferred.
As examples of organic fillers, cellulose powder, such as woodflour or pulp powder, can be usedeither singly or as a mixture of two or more of them.
The average particle size of the filler used in this invention is preferably less than 30 microns, morepreferably less than 10 microns, and most preferably, from 1 to 5 microns. An excessively large particlesize causes a poor pore density of the stretched film, while an excessively small particle size results in abad dispersibility of the filler in the resin and, hence, poor workability.
It is desirable to perform a surface treatment of the filler for the purposes of achieving betterdispersibility of the filler in the resin and, also, better stretchability of the film. A treatment of the fillerwith a fatty acid or a metal salt thereof gives an especially favorable result.
The liquid or wax-like hydrocarbon polymer used in this invention can be selected from liquidpolybutadiene, liquid polybutene and hydrogenates of liquid polybutadiene, among which saturated pojyhydroxy-substituted hydrocarbons obtained by hydrogenating hydroxy-terminated liquidpolybutadienes are preferred.
The saturated polyhydroxy-substituted hydrocarbons are hydrocarbon polymers in which the mainchain has at least 1.5 hydroxyl groups per one molecule and which has been saturated or substantiallysaturated by hydrogenation. Such polymers preferably have a number-average molecular weight (asmeasured by the vapor pressure method within the range of 400 to 48,000, preferably 500 to 20,000.
An excessively low number-average molecular weight cannot provide satisfactory weather resistance,while an excessively high number-average molecular weight leads to poor fluidity of the polymer whichmakes it difficult to properly treat the polymer. The average number of hydroxyl groups per onemolecule should be 1.5 or more preferably 1.8 or more, most preferably 2.0 to 5.0. It is desirable thatthe hydroxyl groups are present at the one or both terminals of the main chain or at the terminal of a  long side chain.
Such saturated polyhydroxy-substituted hydrocarbons can be obtained by a known method, for example, by hydrogenating a butadiene-based liquid polymer obtained by the radical polymerization of butadiene alone or together with a copolymerizable monomer, by using hydrogen peroxide or the like as polymerization initiator. Isoprene, chloroprene, styrene, methyl acrylate, methyl methacrylate, methyl vinyl ether or the like can be used as the copolymerizable monomer.
Hydrogenation can be accomplished in the usual way by using a nickel catalyst (such as reduced nickel or Raney nickel), a cobalt catalyst, a platinum catalyst, a palladium catalyst, a rhodium catalyst, a ruthenium catalyst or a mixture or an alloy catalyst thereof.
It is considered that the introduction of said hydrocarbon polymer having a polar hydroxyl group at the terminal thereof gives a favorable result in improving the compatibility of the components of the film with each other.
The polyolefin resin can be mixed with a heat and/or ultraviolet stabilizer, a pigment, an antistatic agent, a fluorescent agent and the like according to a conventional method.
As for the proportions of the polyolefin resin, the filler and the liquid or wax-like hydrocarbon polymer, it is recommended that the filler is blended in an amount of 28 to 200 parts by weight and the liquid or wax-like hydrocarbon polymer is blended in an amount of 10 to 70 parts by weight, both based on 100 parts by weight of the polyolefin resin.
 If If the proportion of the filler is less than 28 parts by weight, sufficient pores are not formed if Z the stretched film, whereas if the amount of filler exceeds 200 parts by weight, poor kneadability, poor dispersibility and poor film or sheet moldability are obtained, and, also, the stretched product proves to be low in its surface strength.
In producing the leakproof sheet according to this invention, the above-mentioned three materials are mixed and the mixture is molded to form a film or sheet in a known way. Then the film or sheet is stretched more than 1.2 times its original dimension in at least one direction to form fine pores in the film or sheet. In the case of uniaxially stretching said film or sheet, usually roll stretching is preferably employed, but tubular stretching can be used to place particular stress in one direction (take-up direction).
Such stretching can be accomplished in a single stage or in two or more stages.
Usually, the stretch ratio that can provide the desired porosity and uniform stretch is more than 1.2 times, preferably 1.2 to 4.0 times, more preferably 1.2 to 2.0 times, the original dimension in at least one direction of the film.
In the cases of both uniaxial and biaxial stretching, it is possible to precisely stabilize the film by conducting a heat treatment after stretching. It is also possible to perform a known surface treatment, such as corona discharge or flame treatment.
The film or sheet thus obtained is excellent in water vapor and gas permeability, because it has interconnected pores. In use of such a film or sheet as a backing sheet for a disposable diaper, consideration must be given to flexibility, strength and economy, and such factors are greatly affected by the basis weight of the film or sheet. The basis weight is preferably within the range of 20 to 50 g/m2, most preferably 25 to 40 g/m2. From the economical viewpoint, it is desirable that such a basis weight is less than 20 g/m2, but with the presently available techniques, such a low basis weight cannot provide sufficient film or sheet strength for practical use. From the aspect of strength, a basis weight of greater than 50 g/m2 is desirable, but such a high basis weight is impractical in terms of economy and flexibility.
Other constituents of the disposable diaper according to this invention will now be described.
Regarding the absorbent medium, there has long been used a laminate of sheets of tissue paper.
More recently, a fluff pulp web wrapped with tissue paper or wet strength tissue paper has become popular for the reasons of mass production and economy. These prior art absorbent media can be employed in the disposable diaper of this invention, but in order to enhance the effect, it is desirable to adopt a new design in which a super absorbent polymer is incorporated in the absorbent medium so that the urine absorbed by said medium will be retained therein, even when the wearer's body weight is loaded thereon. As the super absorbent polymer, it is advantageous to use, for example, Aquakeep bySeitetsu Kagaku KK.
A non-woven fabric is commonly used as the liquid-permeable sheet 3 forming the diaper surface layer that touches wearer s skin. In order to accomplish the object of this invention, it is desirable to employ a liquid-permeable sheet which is so designed as to be capable of preventing the absorbed liquid from again seeping out from the absorbent medium. For this purpose, it is recommended to employ a hydrophobic non-woven fabric principally composed of polyester fiber or polyolefin fiber.
Other known techniques, such as those disclosed in Japanese Utility Model Laid-Open No. 1 1212/1981 and Japanese Patent Laid-Open No. 123745/1977, can be advantageously applied for this purpose.
In addition to the above-mentioned basic structural features, it is also possible to employ other known features such as a pressure sensitive tape as a diaper fixing means and attaching an elastic member for preventing leaking. These means can be readily applied to the disposible diaper of this invention.
The invention will be further described in detail hereinbelow by reference to specific illustrative  examples thereof, but these examples do not limit the scope of the invention. In the Examples, the term "%" means percent by weight, unless otherwise noted.
PREPARATION 1(Preparation of saturated polyhydroxy-substituted hydrocarbon)3 kg of commercially available polyhydroxy-polybutadiene (R-45 HT produced by Arco Inc.,number-average molecular weight (Mn) = 3,1000; OH group = 0.82 meq/g; cis-1,4 = 15%; trans 1,4 = 58%; vinyl = 27%),3 3 kg of cyclohexane and 300 g of a catalyst of ruthenium (5%) supported on carbon (a product by Japan Engelhard Co.) were fed to an autoclave having a capacity of 10 liters, and,after purging the inside of the system with purified argon gas, high-purity hydrogen gas was supplied to the autoclave, with heating being started simultaneously. The steady-state conditions (internal temperature = approx. 1 000C; internal pressure = approx. 50 kg/cm2) were reached in about 30minutes.The reaction system was left standing under these conditions for about 1 5 hours and then thehydrogenation reaction was stopped, following which the polymer was refined and dried in the usual way.
The obtained polymer was waxy and IR absorption spectral analysis of it established that it was a saturated hydrocarbon polymer substantially free of double bonds. The -OH group content of thehydrogenate was 0.8 meq/g.
 ÇREPARATION 2 Preparation of saturated polyhydroxy-substituted hydrocarbon)Hydrogenation was carried out in the same way as described in Preparation 1 except that a liquidpolybutadiene G-2000 (produced by Nippon Soda KK, molecular weight = 2,000) was used as the polyhydroxypolybutadiene. The obtained polymer was liquid and had an iodine value of 5 g/100 g, ahydroxyl value of 44 KOH mg/g and a viscosity of 775 poises at 300C.
EXAMPLE 120 kg of a high-density polyethylene resin (Novatek ER-002, "Novatek" being a registered trademark of Mitsubishi Kasei Kogyo KK) and 5 kg of saturated polyhydroxy-substituted hydrocarbon (the same as obtained in Preparation 2) were stirred and mixed in a Henschel mixer and then 25 kg of calcium carbonate (average particle size: 1.2 microns, treated with a fatty acid) was added thereto, followed by further mixing under stirring.
The mixture thus obtained was additionally mixed and granulated by a double screw mixer DM-65 (mfd. by Nippon Seikojo KK).
The product was subjected to blown-film extrusion using a 40 mm 6 extruder to form a 70 y thick film. The extrusion conditions were as follows:Cylinder temperatures: 170-190-21 0-2300C Die head temperature: 2300CTakeup rate: 8 m/min, blow ratio = 2.0,flat width = 314 mmThe obtained film was uniaxially stretched by a roll stretcher under the following stretching conditions:Stretching temperature: 800CDraw ratio: 2.7 times the original lengthStretching rate: 11.0 m/minThe stretched film was sufficiently porous and satisfactorily whitened. It was also uniformly stretched and had a beautiful surface appearance.
By using the obtained porous film as the back sheet, a disposable diaper was made in the following way. A highly absorbent polymer Aquakeep (produced by Seitetsu Kagaku KK) was spread uniformly between layers of fluff pulp at a rate of 70 g/m2, to form an absorbent medium having a basis weight of 300 g/m2. This laminate was wrapped with wet strength tissue paper. The wrapped laminate was placed on the back sheet and was covered by a non-woven fabric (basic weight: 20 g/m2) principally composed of hydrophobic fiber, especially ES fiber (a product of Chisso KK), and finally the components were integrated to form a unitary article with a fastening tape tab attached thereto.
EXAMPLE 220 kg of a linear low-density polyethylene resin (Ultzex 2021 -NF, "Ultzex" is a registered trademark of Mitsubishi Sekiyu Kagaku Kogyo KK) and 5 kg of saturated polyhydroxy-substituted hydrocarbon obtained in Preparation 1 were stirred and mixed by a Henschel mixer and then 25 kg of calcium carbonate (average particle size: 1.2 microns, treated with a fatty acid) was added thereto, followed by additional mixing under stirring.
The obtained mixture was further mixed and granulated by a double screw mixer DSM-65 (mfg.
by Nippon Seikojo KK).
The resulting product was subjected to blown-film extrusion using a 40 mm 0 extruder to form a 70 ,u thick film. The extrusion conditions were as follows:  Cylinder temperatures: 170-190-21 0-23O0C Die head temperature: 2000C Takeup rate: 8 m/min, blow ratio = 2.0,flat width = 314 mmThe film thus obtained was uniaxially stretched by a roll stretcher under the following conditions:Stretching temperature: 80CDraw ratio: 2.5 times the original lengthStretching rate: 11.0 m/minThe stretched film was porous, satisfactorily whitened and uniformly stretched and also had abeautiful surface appearance.
By using this porous film as a backing sheet, a disposable diaper was made in the same way asdescribed in Example 1.
EXAMPLES 3-7 Porous films were produced by following the procedure of Example 1, but by changing theproportions of high-density polyethylene, filler and saturated polyhydroxy-substituted hydrocarbon asshown in Table 1. By using these porous films as back sheets, disposable diapers were made in thesame manner as described in Example 1.
EXAMPLES 810 By using the hydrocarbon polymer obtained in Preparation 1, there were produced porous films in the same way as described in Example 1, except that the draw ratio was changed as shown in Table 1, and disposable diapers were formed in the same manner as described in Example 1 by using said respective porous films as back sheets.
EXAMPLES 1112 Porous films were obtained in the same manner as described in Example 1 except that talc (MSTalc, a product of Japan Talc Co.) or diatomaceous earth were used as fillers. Disposable diapers were formed in the same manner as Example 1 by using said porous films as back sheets.
EXAMPLES 1315 Porous films were obtained following the process of Example 1, but by changing the proportions of the linear low-density polyethylene, filler and hydrocarbon polymer as set forth in Table 1. Disposable diapers were made in the same way as described in Example 1 by using said porous films as back sheets.
 EXAMPLES 1618 Porous films were produced in the same manner as described in Example 2 by using iiquid polybutadiene (Nisso PB-G available from Nippon Soda KK) or liquid polybutene (Nisseki Polybutene He300 available from Nippon Sekiyu Kagaku KK) as the liquid hydrocarbon polymer, and using calcium carbonate or talc (MS Talc available from Nippon Talc KK) as the filler. Disposable diapers were formed in the same manner as described in Example 1 by using said porous films as back sheets.
COMPARATIVE EXAMPLES 1-3 Porous films were obtained in the same manner as that described in Example 1 except that nohydrocarbon polymer was blended in the mixture and that the stretching temperature and draw ratiowere changed. By using these porous films as back sheets, there were formed disposable diapers byfollowing the procedure of Example 1.
COMPARATIVE EXAMPLES 4-6 Porous films were obtained in the same way as described in Example 2 except that nohydrocarbon polymer was blended in the mixture and that the stretching temperature and draw ratiowere changed. Disposable diapers were produced in the same manner as described in Example 1 byusing said porous films as back sheets.
The properties of the films obtained in Examples 118 and Comparative Examples 1-6, diaperformability and the test results of usage thereof are shown in Table 1. Similar evaluations were alsomade on a disposable diaper made by using a commercially available back sheet and another disposablediaper made by using two sheets of commercially available ring-shaped diaper of bleached cotton clothwith a commercially available wool flannel and a diaper cover. The results thereof were also shown inTable 1 (Comparative Examples 7 and 8).
The signs used in the column headed "Composition" in Table 1 are defined in Table 2.
The data given in Table 1 were determined by the following methods.
1) Strength a) Tensile strength:A test piece measuring 10 x 140 m/m was placed in the CD direction (iateral direction) of the sample film and pulled at a rate of 300 mm/min at pulling intervals of 100 m/m by using a Tensilon tensile tester, and the maximum load was given as tensile strength.
b) Tear strength:A 30 x 60 mm test piece was placed in the stretching direction of the sample film and, by providing a 30 mm slit at the middle part of the shorter side of the test piece, its tensile strength was measured by using the Tension tensile tester. The tearing rate was set at 300 mm/min.
2) Moisture permeability40 g/m2 fluffed pulp was wrapped with a tissue paper and molded into a 10 x 10 cm sheet. This sheet was placed on an aluminum plate and then 20 ml of a physiological saline solution was dropped thereonto so that it was spread uniformly over the entire sheet. Then the aluminum plate and sheet were covered with a 12 x 12 cm sample film and the four sides were secured by a vinyl tape. The prepared test piece was fixed to the wall (acrylic plate) of a constant-temperature water tank kept at 300C and, 2 hours later, the changes in the weight was measured. The measurement was conducted under conditions of 200C and 60% RH.
3) Use testThe finished disposable diapers were used by seven baby test subjects for one week continuously (per one test), and the condition of diaper rash and other troubles which developed during the test period were observed. When the test subjects suffered from a diaper rash because of ill health (such as diarrhea attack) in the course of the test, such test subjects were eliminated from the test results. The tests were conducted during the period from June to October.
 TABLE 1Composition (A) Stretching conditions StrengthFilm Tensile TearPolyoefin Hydrocarbon Temperature Stretch thickness Strength Strengthresin Filler polymer (C) ratio (ii) (g) (g)1 A-1 B-1 C-240 60 10 80 2.7 48 220 10.82 A-2 B-1 C-140 50 10 80 2.5 28 140 14.03 A-1 B-1 C-245 50 5 80 2.7 38 240 9.54 A-1 B-1 C-230 50 20 80 2.7 36 136 5.45 A-1 B-1 C-270 20 10 80 2.7 35 256 18.36 A-1 B-1 C-266 35 10 80 2.7 37 233 12.6 (*): part by weight  TABLE 1 (continued)Moisturepermeability Disposable diaperg/100 formability andcm2.2hr Flexibility use test Remarks 1 1.6 One out of seven subjectssuffered from slight prickly heat.
2 1.7 All seven subjects showedno abnormality.
3 1.2 Two out of seven subjectssuffered from slight prickly heat.
4 1.5 5 0.2 Three out of seven subjectshad a diaper rash likeprickly heat.
6 0.5 (*): part by weight  TABLE 1 (continued)Composition (A) Stretching conditions StrengthFilm Tensile TearPolyoefin Hydrocarbon Temperature Stretch thickness Strength Strengthresin Filler polymer (C) ratio (ii) (g) (g)7 A-1 B-1 C-230 60 10 80 2.7 33 148 4.88 A-1 B-1 C-140 50 10 80 2.7 35 215 99 A-1 B-1 C-140 50 10 80 1.5 45 241 12.510 A-1 B-1 C-1 80 1.2 50 289 13.311 A-1 B-2 C-240 50 10 80 2.7 35 219 7.112 A-1 B-3 C-240 50 10 80 2.7 36 231 7.8 (*): part by weight  TABLE 1 (continued)Moisturepermeability Disposable diaperg/100 formability andcm2.2hr Flexibility use test Remarks 7 1.7 Half of the diapers tested were tornduring the use test.
8 1.4 9 0.6 Non-uniformlystretched.
10 0.2 Non-uniformlystretched.
11 1.3 12 1.4 (*): part by weight  TABEL 1 (continued)Composition (A) Stretching conditions StrengthFilm Tensile TearPolyoefin Hydrocarbon Temperature Stretch thickness Strength Strengthresin Filler polymer (C) ratio (ii) (g) (g)13 A-2 B-1 C-145 50 5 80 2.5 30 183 9.514 A-2 B-1 C-166 35 10 80 2.5 30 195 15.215 A-2 B-1 C-130 60 10 80 2.5 29 120 6.616 A-2 B-2 C-340 50 10 80 2.5 30 145 9.417 A-2 B-3 C-340 50 10 80 2.5 31 148 10.318 A-2 B-1 C-440 50 10 80 2.5 30 154 9.1 (*): part by weight  TABLE 1 (continued)Moisturepermeability Disposable diaperg/100 formability andcm2.2hr Flexibility use test Remarks 13 1.8 14 0.4 15 2.0 25% of the diapers testedwere torn during the usetest.
16 1.9 17 2.2 18 1.8 (*): part by weight  TABLE 1 (continued)Composition (A) Stretching conditions StrengthFilm Tensile TearPolyoefin Hydrocarbon Temperature Stretch thickness Strength Strengthresin Filler polymer (C) ratio (ii) (g) (g)1 A-1 B-1 --50 50 110 4.0 25 134 3.22 A-1 B-1 --50 50 110 4.0 36 165 4.53 A-1 B-1 --50 50 110 6.0 25 126 2.44 A-2 B-1 -50 50 100 6.0 25 102 3.35 A-2 B-1 --50 50 100 6.0 33 124 4.76 A-2 B-1 --50 50 100 6.0 37 143 4.8 (*): part by weight  TABLE 1 (continued)Moisturepermeability Disposable diaperg/100 formability andcm2.2hr Flexibility use test Remarks 1 1.5 The diaper was torn during itsforming work.
2 1.2 The diaper was torn duringits use test.
3 1.6 The diaper was torn duringits forming work.
4 1.7 The diaper was torn duringits forming work.
5 1.5 The diaper was torn duringits use test.
6 1.1 The diaper was torn during itsuse test.
(*): part by wieght  TABLE 1 (continued)Composition (A) Stretching conditions StrenghtFilm Tensile TearPolyolefin Hydrocarbon Temperature Stretch thickness Strength Strengthresin Filler polymer (C) ratio (ii) (g) (g) 7 - - - - - 26 250 50 8 - - - - - - -  (*): part by weight  TABLE 1 (continued)Moisturepermeability Disposable diaperg/100 formability andcm2.2hr Flexibility use test Remarks 7 0.03 Five out of seven subjects Using commerciallyhad a diaper rash like avaible leakproofprickly heast. film.
8 1.6 One out of seven subjects Using two sheets ofsuffered from slight wool flannel and aprickly heat. commerciallycover.
(*): part by weight TABLE 2Sign Meaning A-i High-density polyethylene, Novatek ER002(Mitsubishi Kasei Kogyo)A-2 Linear low-density polyethylene, Ultzex 2021 -NF(Mitsui Sekiyu Kagaku) B-i Calcium carbonate, average particlesize = 1.2 , treated with a fatty acidB-2 Talc, MS talc (Japan Talc) B-3 Diatomaceous earth C-l Wax-like hydrocarbon polymer prepared byhydrogenating hydroxyl-terminated polybutadiene (Preparation 1)C-2 Liquid hydrocarbon polymer prepared byhydrogenating hydroxyl-terminated polybutadiene (Preparation 2)C-3 Liquid polybutadiene, Nisso PBG(Nippon Soda)C-4 Liquid polybutene, Nisseki PolybuteneHV-300 (Nippon Sekiyu Kagaku)From Table 1, an obvious difference is seen in film flexibility between Example 1 of this invention and Comparative Examples 1-3. It is noted that in the case of the comparative examples (known paper diapers), troubles arise during their forming work and the diapers, even if well formed, become torn during use. Example 2 is a diaper made by using a linear low-density polyethylene resin. Its difference from Comparative Examples 4-6 in film flexibility is evident. The diapers of Examples 3-7 were made by using a high-density polyethylene and varying the proportions of the resin, filler and hydrocarbon polymer. The limit blending proportions of the respective three components can be deduced from theseExamples.In Examples 1 and 810, the film working conditions were varied to change the thickness of the produced porous film. In these examples, although an improvement of film strength is noted, both flexibility and moisture permeability are reduced. Thus, the allowable limits of film thickness can be determined from these results. Examples 11 and 12 are cases wherein talc and diatomaceous earth were used as filler. It is seen that the films obtained in these examples show properties equal to those of the film of Example 1. In Examples 2 and 1318, porous films were produced by using linear lowdensity polyethylene and diapers were similarly made by using these films. It is noted that linear lowdensity polyethylene is preferable to high-density polyethylene in flexibility and moisture permeability of the film.Comparative Example 7 is a disposable diaper made by using a commercially available back film. Five of the seven subjects who used this diaper had diaper rash in two days' use. Comparative Example 8 is a diaper (baby pants) made from commercially available wool flannel. In the use test thereof, two pieces of commercially available diaper of ring-shaped bleached cotton cloth were used therewith. In all the use tests, the timing of changing the diapers was left to the discretion of the test subjects' mothers.
As is apparent from the foregoing results, the disposable diaper according to this invention shows excellent practical utility.
The absorbent article according to the invention can apply also to a sanitary napkin. When the invention is utilized as a sanitary napkin, it is preferable that a liquid rubber is incorporated into a polyolefin resin for the backing sheet, instead of the liquid or wax-like hydrocarbon polymer.
The sanitary napkin is shown in Figs. 2 and 3. Fig. 2 is a rough sketch of a cross section showing an embodiment of the sanitary napkin of the present device. The napkin comprises (1) an absorbing layer which is a laminate consisting of a cotton-like pulp 13, a water-absorbing paper 14 and a rayon staple cotton 15, (2) a water-repellent sheet 12 which is a porous film prepared by melt-molding a composition comprising a polyolefin resin, a filler and a liquid rubber and then stretching the molded product, the bottom, sides and a part of the upper surface of the absorbing layer being covered with the water-repellent sheet 12, and (3) a surface sheet 11 covering the whole.
Fig. 3 is a rough sketch of a cross section showing another embodiment of the sanitary napkin of the present device. The napkin comprises (1) the absorbing layer which is a laminate of the cotton-like pulp 13, the water-absorbing paper 14 and the rayon staple cotton, (2) the surface sheet 11 covering the upper surface of the absorbing layer and (3) the water-repellent sheet 12 which is the abovementioned porous film covering the bottom, sides and ends of the absorbing layer, the water-repellent sheet 12 being bonded and fixed to the surface sheet 11 by means of a hot melt adhesive 16 on the inside of the ends of the surface sheet 11.
The absorbing layer used in the present device generally contains a polymer having high waterabsorbing properties as well as the cotton-like pulp 3, the water-absorbing paper 4, and the rayon staple cotton 5.
The present device is characterized by the use of a human secretion-impermeable, vaporpermeable film, more concretely a porous film obtained by melt-molding the composition comprising polyolefin resin, filler and liquid rubber and subjecting the molded product to stretching treatment as the water-repellent sheet. As the polyolefin resin and the filler, the before mentioned embodiments can be used. As the liquid rubber, there may be used, for example, liquid polybutadiene and liquid polybutene.
From the viewpoint of film-forming properties and strength of the stretched product, the mixing ratio is preferably 100 parts by weight of the polyolefin resin, 28 to 200 parts by weight of the filler and 10 to 70 parts by weight of the liquid rubber. In the stretching treatment of the film, the draw ratio is at least 1.2 in at least one direction. The porous film thus obtained has open pores and, therefore, it has high vapor-permeability and water pressure resistance and is free of a possibility of leakage of the human secretion therethrough. It is preferred that a large quantity of the human secretion is vaporized through the napkin surface not in contact with the body.A porous film having a water vapor transmission rate [according to ASTM E 2666  (E)j of at least 1000 (g/m2/24 h), preferably at least 2000 (g/m224 h), is used. If a film having a water vapor transmission rate of less than 1000 (g/m2 .24 h) is used, a large quantity of the human secretion is kept in the napkin. Consequently, such a film has a poor effect of reducing the stuffiness and the significance of using a porous film as the water-repellent sheet is reduced.
EXAMPLE 195 kg of liquid hydroxyl-terminated polybutadiene  [ trade name: Poly bd, R-45HT; a product of Idemitsu Sekiyu Kagaku KK. ]  was added to 20 kg of a high-density polyethylene resin [trade name:Novatec BR002; a product of Mitsubishi Kasei Kogyo KK.] and the mixture was stirred in a Henschel mixer. Then, 25 kg of calcium carbonate (average particle diameter: 1.2 , treated with a fatty acid) was added thereto and the whole was further stirred.
The resulting mixture was kneaded in a Double-Screw Mixer DSM-65 (a product of Nihon Seikosho KK.) and pelletized.
The pellets were inflation-molded by means of a 40 d extruder to form a 70 y thick film. The extrusion conditions were as follows:cylinder temperatures: 1 50-i 80-i 800C head, die temperature: 1 800C take-off speed: 4 m/min, blow-up ratio = 1.3,flat width = 300 mmThe resulting film was stretched monoaxially by means of a roll stretching machine.
The stretching conditions were as follows:stretching temperature: 1000C draw ratio: 2.2Stretching rate: 4.4 m/min.
Thus, a sufficiently whitened, porous film was obtained. The porous film had beautiful surfaces and was free of uneven stretchingA sanitary napkin as shown in Fig. 2 was prepared using the obtained porous film as the waterrepellent sheet.
EXAMPLES 20 to 25Porous films were obtained in the same manner as in Example 1 9 except that the stretching temperature and draw ratio were as shown in Table 3. Sanitary napkins were prepared using the obtained porous films as the water-repellent sheet.
COMPARATIVE EXAMPLES 4 AND 5Porous films were prepared in the same manner as in Example 19 except that the liquid rubber was not used and the stretching temperature and draw ratio were as shown in Table 3. Sanitary napkins were prepared in the same manner as in Example 19 using the obtained porous films as the waterrepellent sheet.
COMPARATIVE EXAMPLE 6Sanitary napkins were prepared in the same manner as in Example 19 using a sheet comprising a laminate of a paper and polyethylene film ("poly-lami water-repellent paper") as the water-repellent sheet.
Film thickness, water vapor transmission rate and flexibility of the films obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were measured to obtain the results shown in Table 3.
Unlike the conventional sanitary napkins, the sanitary napkins of the present device have advantages that a part of the human secretion is vaporized out through the water-repellent sheet of the napkin, since the human secretion-impermeable, vapor-permeable porous film is used as the waterrepellent sheet and, therefore, the users do not feel stuffy or unpleasant during the use. Further, troubles such as a rash and inflammation due to the stuffiness are reduced.
TABLE 3
  Stretching conditions Water vapor*  transmission  Temp. Draw Film rate   ( C)  ratio thickness  (y)   /m2.24  Hr Flexibility Remarks  Ex.19 100 2.2 35 2530 0  Ex.20 100 1.5 45 1920 A  Ex.21 100 1.2 50 1250 A  Ex. 22 85 2.2 36 2700 0  Ex.23 50 2.2 37 2910 0  Comp. Ex. 4  110 2.2 34 2170 X The films  were torn.  Comp. Ex. 5  110 3.0 30 2010 X The films  were torn. Comp. Ex. 6  -    -   30 330 A Water   repellent  sheet  of commercial  napkin
Note) *1 Water vapor transmission rate was determined according to ASTM E26-66 (E).