GB2151538A - Process for producing porous polyolefin films - Google Patents
Process for producing porous polyolefin films Download PDFInfo
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- GB2151538A GB2151538A GB08431524A GB8431524A GB2151538A GB 2151538 A GB2151538 A GB 2151538A GB 08431524 A GB08431524 A GB 08431524A GB 8431524 A GB8431524 A GB 8431524A GB 2151538 A GB2151538 A GB 2151538A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/48—Wearing apparel
- B29L2031/4871—Underwear
- B29L2031/4878—Diapers, napkins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
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- Veterinary Medicine (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Prostheses (AREA)
- Polymerisation Methods In General (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The process comprises blending 100 parts by weight of a polyolefin resin with 50 to 500 parts by weight of barium sulfate preferably having an average particle diameter of 0.1 to 7 mu m melting the resulting resin composition and forming it into a film, and then stretching the film at least uniaxially by a factor of 1.5 to 7. The polyolefin resin preferably has a melt index of 0.5 to 7 and a density of 0.915 to 0.935; more preferably, it is a linear low-density resin having a melt index of 0.5 to 8.5 and a density of 0.915 to 0.935. As the linear low-density polyethylene resin, a copolymer of ethylene and hexene and/or octene is particularly preferred.
Description
SPECIFICATION
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, Japanese Patent Laid-Open Nos.
47334/'82 and 203520/'82 disclose a process for producing porous films which comprises melting a resin composition obtained by blending a polyolefin resin with a filler and liquid rubber or a hydroxylated poly-saturated-hydrocarbon, forming the molten resin composition into a sheet or film, and then stretching this sheet or film. Moreover, Japanese Patent Laid-Open No.
15538/'83 discloses a process for producing porous 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 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 relatively large thickness because of their low mechanical strength.
Furthermore, it is described in Japanese Patent Laid-Open No. 149303/'83 that such porous films can be used as a leakproof sheet in disposable 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, forming the resulting resin composition into a film, and then stretching this film at least uniaxially by 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 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.
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. However, the resulting sanitary napkins have the disadvantage of causing a disagreeable sensation during prolonged use because of their lack of permeability to water vapor.
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 invention to provide a process for producing porous films which have sufficiently high porosity and thereby 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" 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 (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 on the 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 Japanese Patent Laid-Open Nos. 47334/'82, 203520/'82, 1 5538/'83 and 149303/'83 should 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 unobtainable 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; preferably using a low-density polyethylene resin having a specific melt index and density and more 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 homopoloymers such as polypropylene, low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polybutylene, etc.; copolymers such as ethylene-propylene copolymer, ethylenebutylene 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 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 lowdensity 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-pressureprocessed 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 lienar 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 average particle diameter of 0.1 to 7 m and more preferably 0.5 to 5 elm If the average particle diameter is smaller than 0.1 ,um, well-defined pores cannot be obtained. On the contrary, if it is larger than 7 'lem, 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 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 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 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 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 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 pelletized. Subsequently, the film is at east unaxially stretched by a factor of 1.5 to 7 according 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 lowdensity polyethylene resin is used as the base resin, the resulting film will show very little reduction in strength. Thus, it is possible to produce porous films which are thinner (for example, approximately 10 jilm in thickness) than those produced by the prior-art processes.
Furthermore, since the resin composition 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 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 used as a filtering medium owing to their even distribution of pores.
The prsent invention is further illustrated by the following examples. However, these examples are given for purposes of illustration only and are 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.
Also in the examples, film properties were evaluated according to the following procedures: (1) Strength and elongation
Using a Tension 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:
a = Very soft and smooth
B = Rather soft and smooth
C = 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 twinscrew mixer, the resulting mixture was intimately blended 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.
Table 1
Base resin 1) Trade name Melt Density Type (manufacturer) index 3 /10 min (g/cm REXLON F-41 (Nippon Example 1 LDPE Petrochemicals Co., 5.0 0.923 Ltd.) " 2 " " " " 3 " " " MIRASON 45 (Mitsui II 4 " Polychemicals Co., 1.5 0.920 Ltd.) 5 " " " UBE POLYETHYLENE 6 6 F0191 (Ube Kosan 0.9 0.912 K.K.) Neo-zex 4330 (Mitsui Petrochemical Indus 7 7 ,, tries, Inc.)/UBE 3.0 0.940 POLYETHYLENE VF430 Ube Kosan K.K.) 0 2/1 8 L-LDPE NUCG-5511 (Nipon 1.0 0.920 Unicar Co., Ltd.) 9 " " " " Ultzex 2020L (Mitsui 10 Petrochemical Indus- 2.1 " tries, Inc.) 11 " " " 12 ..
13 " " " " Table 1 (Cont'd)
Filler Average 2) Stretching Film Type particle dia- Amount # factor thickness meter ( m) (phr) ( m) BaSO4 0.8 150 4 # 40 " " " 5 " " " " 2x2 " " 1.2 130 5 50 # 5.0 120 15 ..
.. 1.2 15 33) 51 " " 100 4 " " " " " 30 15 55 150 . 5 15 " 4.2 50 6.5 40 # 0.8 150 5 " 0.5 100 7 10 " " 300 3 40 Table 1 (Cont'd)
Strength Elongation (#) Moisture (kg/25 mm) permeability Soft ness MD TD MD TD (g/m/24 hr) 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 5.5 1.5 120 450 3,000 A 5.0 1.3 100 390 " A 3.9 1.0 855 390 1,100 B 4.5 " 50 200 2,000 C 3.5 1.2 100 420 3,900 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 0.7 40 120 8,500 A 5.3 1.5 78 360 5,500 A Table 1 (Cont'd)
Base resin Melt Trade name index Density Type) (manufacturer) (g/10 min) (g/cm ) Ultzex 3010F (Mitsui Example 14 L-LDPE Petrochemical Indus- 1.3 0.930 tries, Inc.) Ultzex 2020L (Mitsui 15 Petrochemical Indus- 2.1 0.920 tries, Inc.) Ultzex 20100J 16 (Mitsui Petrochemical 8.0 0.920 Industries, Inc.) Hi-zex HZ5000S " 17 HDPE (Mitsui Petrochemical 0.9 0.954 Industries, Inc.) MITSUI NOBLEN JS-G " 18 PP (Mitsui Toatsu 1.5 0.890 Chemicals, Inc.) MITSUI NOBLEN MjS-C 19 EPC (Mitsui Toaitsu " " Chemicals, Inc.) Table 1 (Cont'd)
Filler Average 2) Stretching Film Type particle dia- Amount factor thickness meter ( m) (Phr) (ism) BaSO4 5.0 150 5 50 " 0.5 500 2 40 " 0.8 200 3 " " " 150 5 " " " " " " " " " " "
Strength Elongation (%) Moisture (kg/25 mm) permeability Soft ness MD TD MD TD (g/m2 /24 hr) 5.1 1.4 110 400 6,700 A 5.0 1.0 35 20 5,000 A 5.5 1.4 105 420 4,700 A 8.0 2.2 70 400 4,500 C 10.3 2.5 90 350 4,900 C 9.1 2.3 88 520 4,000 C Table 1 (Cont5d)
Base resin Melt Density 1) Trade name index Type (manufacturer) (g/10 min) (g/cm ) Comparative Ultzex 2020L (Mitsui Example 1 L-LDPE Petrochemical Indus- 2.1 0.920 Example 1 tries, Inc.) " 2 " " " " " 3 " " " " .. 4 55 55 II " " 5 " " " " " 6 " NUCG-551 (Nippon 1.0 " Unicar Co., Ltd.) " 7 .. 55 55 II B " " " " PETROSEN 207 (Toyo " 9 LDPE Soda Manufacturing 8 0.924 Co., Ltd.
Notes: 1) LDPE = low-density polyethylene.
L-LDPE = linear low-density polyethylene.
PP = Polypropylene
EPC = ethylene-propylene copolymer.
2) Parts by weight of the filler per 100 parts by weight of tile base rein.
3), 5) & 7) The maximum value at which stretching
can be performed steadily.
4) & 6) No sampling was possible because of frequent
breakage during the stretching process.
Table 1 (Cont5d)
Filler Average 2) Stretching Film Type particle dia- Amount factor thickness meter ( m) (Phr) BaS04 0,8 150 Unstretch- 50 4 ed 55 55 600 Unstretch ed I, " 150 8 . ~ CaCO3 1.0 " 4 70 Glass BaSO4 BaSO4 " 30 5 40 " " 100 86) Glass " " 37) 60 beads BaSO4 " 130 Unstretch ed Table 1 (Cont'd)
Strength Elongation (%) Moisture (kg/25 m) Elongation (@) Moisture permeability soft ness MD TD MD TD (g/m/24 hr) 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 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 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 superposed 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 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 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 side edges to prevent leakage.
Disposable diapers are made by placing a 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, 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 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 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 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 amount given in Table 2, 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 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, 1 3 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).
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 yam. 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 cm. Properties of this porous film were evaluated and the results are shown in
Table 2.
On the outer side of this porous film was superposed a LDPE film of 70 itm thickness having apertures of 1 mm diameter (20/cm2) 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.
Table 2
Base resin Filler Amount Amount Type (parts by Type (parts by weight) weight) Example 20 LDPE 100 BaSO4 150 21 " " " " " 22 L-LDPE 55 " 200 23 LDPE " " 150 " 24 L-LDPE IS " 200 Comparative " " " Example 10 150 11 " " " 600 12 " " " 150 13 " " CaCO3 " 14 " " Glass 120 beads *) 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.
Table 2 (Cont'd)
Strength Moisture Stretching iMD/TD ] permeability Softness factor 2 (kg/25 mm) (g/m /24 hr) 4 6.0/1.5 3,500 5 6.5/1.3 4,200 @ 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 1 A Unstretch- 2.3/2.2 15 A ed Uns tretch- ed 8*) 4 4.3/0.8 3,000 C 2**) 1.5/0.7 30 C Comparative Example 15
120 parts by weight of calcium carbonate having an average particle diameter of 1.2 m and 20 parts by weight of a hydroxylated poly-saturated-hydrocarbon (Liquid Polybutadiene GI2000; 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 mmf 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. Thus, there were obtained films having a thickness of 50 lim. These porous films exhibited surface tackiness and varied in moisture permeability according to the location. Disposable diapers using 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 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 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 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 cayse no disagreeable sensation even during prolonged use.
The following examples illustrate the use of the porous film of the prsent 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 yam. 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 practically for prolonged periods of time, the sanitary napkins in accordance with the present invention did not cause a disagreeable, stuffy sensation.
Table 3
Base resin Filler Strength Moisture Stretching [MD/TD] permeability Soft Amount Amount factor ness Type (parts by Type (parts by weight) weight) (kg/25 mm) (g/m/24 hr) Example 25 L-LDPE 100 BaSO4 100 6 3.2/1.0 5,200 A Example 26 " " " 150 5 3.0/0.9 4,800 A Example 27 " " " 400 3 2.5/0.8 4,200 A
Claims (19)
1. In a process for producing porous films which comprises melting a resin composition consisting 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 non-compatible filler is barium sulfate, the barium sulfate 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 the average particle diameter of the barium sulfate is in the range of 0.1 to 7 jum.
3. A process as claimed in claim 2 wherein the average particle diameter of the barium sulfate 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 amount of 100 to 400 parts by weight per 100 parts by weight of the polyolefin resin.
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.
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 the polyethylene resin is a low-density polyethylene resin having a melt index of 0.5 to 7 and a density of 0.915 to 0.935.
8. A process as claimed in claim 7 wherein 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.
10. A process as claimed in claim 7 wherein the melt index is in the range of 1 to 5.
11. A process as claimed in claim 6 wherein the polyethylene resin is a linear low-density polyethylene resin.
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 and a density of 0.915 to 0.935.
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. The process for producing porous films substantially as hereinbefore described with reference to any one of the foregoing examples of the invention.
18. A porous film substantially as hereinbefore described with reference to any one of the foregoing examples of the invention.
19. The use of a porous film substantially as hereinbefore described with reference to any one of the foregoing examples of the invention.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58236333A JPS60129240A (en) | 1983-12-16 | 1983-12-16 | Porous film and its manufacture |
JP59040440A JPS60185803A (en) | 1984-03-05 | 1984-03-05 | Disposable diaper |
JP5357784A JPS60199037A (en) | 1984-03-22 | 1984-03-22 | Porous film and manufacture thereof |
JP5357684A JPS60199036A (en) | 1984-03-22 | 1984-03-22 | Porous film and manufacture thereof |
Publications (3)
Publication Number | Publication Date |
---|---|
GB8431524D0 GB8431524D0 (en) | 1985-01-23 |
GB2151538A true GB2151538A (en) | 1985-07-24 |
GB2151538B GB2151538B (en) | 1987-04-29 |
Family
ID=27460900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB08431524A Expired GB2151538B (en) | 1983-12-16 | 1984-12-13 | Process for producing porous polyolefin films |
Country Status (12)
Country | Link |
---|---|
KR (1) | KR870001966B1 (en) |
AU (1) | AU551948B2 (en) |
CA (1) | CA1245026A (en) |
CH (1) | CH666222A5 (en) |
DE (1) | DE3445771A1 (en) |
FR (1) | FR2556648B1 (en) |
GB (1) | GB2151538B (en) |
IT (1) | IT1179513B (en) |
NL (1) | NL187233C (en) |
NO (1) | NO171456B (en) |
NZ (1) | NZ210433A (en) |
SE (1) | SE465310B (en) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0214859A2 (en) * | 1985-09-09 | 1987-03-18 | E.I. Du Pont De Nemours And Company | Microporous polymeric films and process for their manufacture |
EP0226179A2 (en) * | 1985-12-11 | 1987-06-24 | MITSUI TOATSU CHEMICALS, Inc. | Resin composition for porous film and film prepared therefrom |
EP0227037A2 (en) * | 1985-12-23 | 1987-07-01 | MITSUI TOATSU CHEMICALS, Inc. | Process for producing a porous film |
EP0232060A2 (en) * | 1986-01-21 | 1987-08-12 | MITSUI TOATSU CHEMICALS, Inc. | Process for the preparation of porous polyolefin films |
EP0253667A2 (en) * | 1986-07-16 | 1988-01-20 | Sumitomo Chemical Company, Limited | Breathable film and process for production of the same |
EP0256717A2 (en) * | 1986-08-04 | 1988-02-24 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Process for the manufacture of microporous film |
EP0259003A2 (en) * | 1986-08-04 | 1988-03-09 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Process for the manufacture of microporous film |
US4778634A (en) * | 1986-08-04 | 1988-10-18 | El Paso Products Company | Process for the manufacture of porous film |
US4815714A (en) * | 1986-08-04 | 1989-03-28 | El Paso Products Company | Process for the manufacture of microporous film |
EP0311423A2 (en) * | 1987-10-08 | 1989-04-12 | Applied Extrusion Technologies, Inc. | Process for preparing uniaxially oriented filled films for controlled atmosphere packaging |
EP0352802A2 (en) * | 1988-07-27 | 1990-01-31 | Hercules Incorporated | Breathable microporous film and method for making it |
WO1999022930A1 (en) * | 1997-11-04 | 1999-05-14 | Tredegar Corporation | Textured, dimensionally stable microporous film and method of making same |
WO2000064968A1 (en) * | 1999-04-22 | 2000-11-02 | Dunlop Tire Corporation | Vulcanizable elastomeric compositions for use as tire treads |
EP1070736A1 (en) * | 1999-07-23 | 2001-01-24 | SK Corporation | Composition for air permeable film of high processability and permeability and production of air permeable film |
USH1955H1 (en) | 1996-07-31 | 2001-04-03 | Exxon Chemical Patents Inc. | Polyolefin/filler films having increased WVTR and method for making |
WO2001058809A2 (en) * | 2000-02-09 | 2001-08-16 | Sachtleben Chemie Gmbh | Barium sulphate, method for producing same and the use thereof |
WO2003074615A1 (en) * | 2002-03-06 | 2003-09-12 | Sachtleben Chemie Gmbh | Method for the production of coated, fine-particle, inorganic solids and use thereof |
US6776947B2 (en) | 1996-07-31 | 2004-08-17 | Exxonmobil Chemical Company | Process of adjusting WVTR of polyolefin film |
EP1201295A3 (en) * | 2000-10-30 | 2006-08-30 | Sumitomo Chemical Company, Limited | Porous film, separator for cell, and cell |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS61114701A (en) * | 1984-11-09 | 1986-06-02 | Terumo Corp | Flat film type permeable membrane and preparation thereof |
CA2116081C (en) | 1993-12-17 | 2005-07-26 | Ann Louise Mccormack | Breathable, cloth-like film/nonwoven composite |
US5843057A (en) † | 1996-07-15 | 1998-12-01 | Kimberly-Clark Worldwide, Inc. | Film-nonwoven laminate containing an adhesively-reinforced stretch-thinned film |
US6258308B1 (en) | 1996-07-31 | 2001-07-10 | Exxon Chemical Patents Inc. | Process for adjusting WVTR and other properties of a polyolefin film |
BE1012087A4 (en) * | 1998-07-24 | 2000-04-04 | Age S A | Microporous polyolefin films and tight gas liquid impermeables |
US6264864B1 (en) | 1998-10-16 | 2001-07-24 | Exxon Chemical Patents Inc. | Process for producing polyolefin microporous breathable film |
KR20020066110A (en) * | 2001-02-09 | 2002-08-14 | 주식회사 한진피앤씨 | Improvement radiation of far-infrared light of air permeability film |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5417789B1 (en) * | 1969-04-25 | 1979-07-03 | ||
GB1310430A (en) * | 1970-12-29 | 1973-03-21 | Sekisui Chemical Co Ltd | Process for producing a synthetic resin sheet |
JPS5933138B2 (en) * | 1977-09-22 | 1984-08-14 | 旭化成株式会社 | Film containing inorganic filler |
US4265960A (en) * | 1978-12-26 | 1981-05-05 | Mobil Oil Corporation | Films produced from LDPE encapsulated CaCO3 |
JPS5932492B2 (en) * | 1981-06-08 | 1984-08-09 | 東ソー株式会社 | agricultural film |
US4472328A (en) * | 1981-06-09 | 1984-09-18 | Mitsubishi Chemical Industries, Ltd. | Process for producing porous film or sheet |
DE3306843A1 (en) * | 1982-03-02 | 1983-09-15 | Kao Corp., Tokyo | ABSORBENT PRODUCT |
-
1984
- 1984-12-03 AU AU36221/84A patent/AU551948B2/en not_active Ceased
- 1984-12-04 SE SE8406114A patent/SE465310B/en unknown
- 1984-12-04 NZ NZ210433A patent/NZ210433A/en unknown
- 1984-12-11 CH CH5894/84A patent/CH666222A5/en not_active IP Right Cessation
- 1984-12-13 GB GB08431524A patent/GB2151538B/en not_active Expired
- 1984-12-13 CA CA000470090A patent/CA1245026A/en not_active Expired
- 1984-12-14 NL NLAANVRAGE8403798,A patent/NL187233C/en not_active IP Right Cessation
- 1984-12-14 DE DE19843445771 patent/DE3445771A1/en active Granted
- 1984-12-14 IT IT24069/84A patent/IT1179513B/en active
- 1984-12-14 FR FR8419186A patent/FR2556648B1/en not_active Expired
- 1984-12-14 NO NO845047A patent/NO171456B/en unknown
- 1984-12-15 KR KR1019840007995A patent/KR870001966B1/en not_active IP Right Cessation
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0214859A2 (en) * | 1985-09-09 | 1987-03-18 | E.I. Du Pont De Nemours And Company | Microporous polymeric films and process for their manufacture |
US4698372A (en) * | 1985-09-09 | 1987-10-06 | E. I. Du Pont De Nemours And Company | Microporous polymeric films and process for their manufacture |
EP0214859A3 (en) * | 1985-09-09 | 1989-02-22 | E.I. Du Pont De Nemours And Company | Microporous polymeric films and process for their manufacture |
EP0226179A3 (en) * | 1985-12-11 | 1988-06-15 | Mitsui Toatsu Chemicals, Incorporated | Resin composition for porous film and film prepared therefrom |
EP0226179A2 (en) * | 1985-12-11 | 1987-06-24 | MITSUI TOATSU CHEMICALS, Inc. | Resin composition for porous film and film prepared therefrom |
US4699733A (en) * | 1985-12-11 | 1987-10-13 | Mitsui Toatsu Chemicals, Inc. | Resin compostion for porous film and film prepared therefrom |
EP0227037A2 (en) * | 1985-12-23 | 1987-07-01 | MITSUI TOATSU CHEMICALS, Inc. | Process for producing a porous film |
EP0227037A3 (en) * | 1985-12-23 | 1988-07-06 | Mitsui Toatsu Chemicals Inc. | Process for producing a porous film |
US4921652A (en) * | 1985-12-23 | 1990-05-01 | Mitsui Toatsu Chemicals, Inc. | Process for producing a porous film |
AU595565B2 (en) * | 1985-12-23 | 1990-04-05 | Mitsui Toatsu Chemicals Inc. | Process for producing a porous film |
EP0232060A2 (en) * | 1986-01-21 | 1987-08-12 | MITSUI TOATSU CHEMICALS, Inc. | Process for the preparation of porous polyolefin films |
EP0232060A3 (en) * | 1986-01-21 | 1988-06-22 | Mitsui Toatsu Chemicals, Incorporated | Porous polyolefin films and preparation process thereof |
US4814124A (en) * | 1986-01-21 | 1989-03-21 | Mitsui Toatsu Chemicals Inc. | Preparation of gas permeable porous film |
EP0253667A2 (en) * | 1986-07-16 | 1988-01-20 | Sumitomo Chemical Company, Limited | Breathable film and process for production of the same |
EP0253667A3 (en) * | 1986-07-16 | 1988-06-15 | Sumitomo Chemical Company, Limited | Breathable film and process for production of the same |
US4815714A (en) * | 1986-08-04 | 1989-03-28 | El Paso Products Company | Process for the manufacture of microporous film |
EP0259003A3 (en) * | 1986-08-04 | 1989-07-12 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Process for the manufacture of microporous film |
EP0256717A3 (en) * | 1986-08-04 | 1989-07-26 | El Paso Products Company | Process for the manufacture of microporous film |
US4778634A (en) * | 1986-08-04 | 1988-10-18 | El Paso Products Company | Process for the manufacture of porous film |
EP0259003A2 (en) * | 1986-08-04 | 1988-03-09 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Process for the manufacture of microporous film |
EP0256717A2 (en) * | 1986-08-04 | 1988-02-24 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Process for the manufacture of microporous film |
EP0311423A3 (en) * | 1987-10-08 | 1990-08-22 | Hercules Incorporated | Uniaxially oriented filled films for controlled atmosphere packaging |
EP0311423A2 (en) * | 1987-10-08 | 1989-04-12 | Applied Extrusion Technologies, Inc. | Process for preparing uniaxially oriented filled films for controlled atmosphere packaging |
EP0352802A2 (en) * | 1988-07-27 | 1990-01-31 | Hercules Incorporated | Breathable microporous film and method for making it |
EP0352802A3 (en) * | 1988-07-27 | 1990-08-16 | Hercules Incorporated | Breathable microporous film and method for making it |
USH1955H1 (en) | 1996-07-31 | 2001-04-03 | Exxon Chemical Patents Inc. | Polyolefin/filler films having increased WVTR and method for making |
US6776947B2 (en) | 1996-07-31 | 2004-08-17 | Exxonmobil Chemical Company | Process of adjusting WVTR of polyolefin film |
WO1999022930A1 (en) * | 1997-11-04 | 1999-05-14 | Tredegar Corporation | Textured, dimensionally stable microporous film and method of making same |
WO2000064968A1 (en) * | 1999-04-22 | 2000-11-02 | Dunlop Tire Corporation | Vulcanizable elastomeric compositions for use as tire treads |
EP1070736A1 (en) * | 1999-07-23 | 2001-01-24 | SK Corporation | Composition for air permeable film of high processability and permeability and production of air permeable film |
WO2001058809A2 (en) * | 2000-02-09 | 2001-08-16 | Sachtleben Chemie Gmbh | Barium sulphate, method for producing same and the use thereof |
WO2001058809A3 (en) * | 2000-02-09 | 2002-04-11 | Sachtleben Chemie Gmbh | Barium sulphate, method for producing same and the use thereof |
EP1201295A3 (en) * | 2000-10-30 | 2006-08-30 | Sumitomo Chemical Company, Limited | Porous film, separator for cell, and cell |
WO2003074615A1 (en) * | 2002-03-06 | 2003-09-12 | Sachtleben Chemie Gmbh | Method for the production of coated, fine-particle, inorganic solids and use thereof |
US7341625B2 (en) | 2002-03-06 | 2008-03-11 | Sachtleben Chemie Gmbh | Method for the production of coated, fine-particle, inorganic solids and use thereof |
Also Published As
Publication number | Publication date |
---|---|
NO845047L (en) | 1985-06-17 |
AU551948B2 (en) | 1986-05-15 |
NO171456B (en) | 1992-12-07 |
NL187233B (en) | 1991-02-18 |
GB2151538B (en) | 1987-04-29 |
DE3445771A1 (en) | 1985-07-04 |
FR2556648A1 (en) | 1985-06-21 |
NL187233C (en) | 1991-07-16 |
FR2556648B1 (en) | 1987-11-20 |
SE8406114L (en) | 1985-06-17 |
SE8406114D0 (en) | 1984-12-04 |
IT1179513B (en) | 1987-09-16 |
CH666222A5 (en) | 1988-07-15 |
NL8403798A (en) | 1985-07-16 |
CA1245026A (en) | 1988-11-22 |
KR850004599A (en) | 1985-07-25 |
DE3445771C2 (en) | 1990-06-07 |
GB8431524D0 (en) | 1985-01-23 |
SE465310B (en) | 1991-08-26 |
NZ210433A (en) | 1987-05-29 |
AU3622184A (en) | 1985-06-20 |
IT8424069A0 (en) | 1984-12-14 |
KR870001966B1 (en) | 1987-10-23 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19951213 |