WO2015186808A1 - Film perméable à l'humidité - Google Patents

Film perméable à l'humidité Download PDF

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Publication number
WO2015186808A1
WO2015186808A1 PCT/JP2015/066261 JP2015066261W WO2015186808A1 WO 2015186808 A1 WO2015186808 A1 WO 2015186808A1 JP 2015066261 W JP2015066261 W JP 2015066261W WO 2015186808 A1 WO2015186808 A1 WO 2015186808A1
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moisture
permeable film
parts
mass
film
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PCT/JP2015/066261
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English (en)
Japanese (ja)
Inventor
信之 山形
豊 川合
滋充 間野
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三菱樹脂株式会社
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Publication of WO2015186808A1 publication Critical patent/WO2015186808A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene

Definitions

  • the present invention relates to a moisture permeable film.
  • a moisture-permeable film made of a polyolefin resin and calcium carbonate is generally used for sanitary materials such as disposable diapers and sanitary treatment products, and is particularly used as a moisture-permeable and waterproof back sheet.
  • the moisture-permeable film used for such sanitary materials is required to have the following properties. First, in order to prevent stuffiness when wearing a paper diaper, it is required to have good air permeability and moisture permeability. Next, it is required to have a good texture and feel, and to be flexible so as not to hinder infant activities. Furthermore, it is required that the waterproof sheet is a film having high water resistance and liquid leakage resistance, and that troubles such as blocking and squeezing are not caused when a roll-like sample of a moisture permeable film is stored over time. Therefore, it is desired that the moisture permeable film has a heat shrinkage rate as small as possible in the machine flow direction (direction in which the moisture permeable film is stretched).
  • Patent Document 1 employs an orientable thermoplastic resin having a low elastic modulus and a hydrophobic surface as a base resin.
  • An example of such a matrix resin is ethylene / propylene / 1,4-hexadiene terpolymer. Rich in texture and flexibility.
  • Patent Document 2 discloses that an ethylene- ( ⁇ -olefin) copolymer having a density of 0.86 to 0.90 g / cm 3 and a melting point of 60 to 100 ° C. and a thermoplastic elastomer are resin components.
  • a porous film is disclosed.
  • porous film shown by patent document 3 uses the mixture of liquid polyester comprised from hardened castor oil, a C4-C4 or more polyhydric alcohol, and a fatty acid as a plasticizer of a 3rd component. Have gained texture, feel and flexibility.
  • the film is stretched at room temperature, and since the melting point of the base resin is low, it is not suitable for practical use because it is too soft and does not have an appropriate rigidity.
  • the porous film described in Patent Document 2 is rich in flexibility, but has poor shrinkage resistance and dimensional stability due to heat, and is particularly unsuitable for uses other than sanitary materials.
  • the resin used as the base material is softened or has a low melting point, the problems of heat resistance, heat shrinkage, and productivity are not satisfied. Also, depending on the chemical structure, type, etc.
  • the liquid polyester constituting the porous film shown in Patent Document 3 water resistance and liquid leakage resistance are greatly reduced due to the hydrophilicity of the film surface, which is not suitable for a waterproof sheet of a disposable diaper. There is a fear.
  • the liquid plasticizer has problems that cause production troubles such as foaming, jetting, bleed out, and blocking between films during film formation from a raw material blend.
  • the problem to be solved by the present invention is to provide a moisture permeable film that is excellent in flexibility, breathability and moisture permeability, yet satisfies heat shrinkage resistance and liquid leakage resistance.
  • linear low-density polyethylene having a specific density, high-pressure polymerization low-density polyethylene, metallocene ethylene- ⁇ olefin copolymer, inorganic having a specific particle size It was found that a moisture permeable film having an air permeability of 50 to 5,000 seconds / 100 mL can be obtained by using a resin composition containing a predetermined amount of a filler and a plasticizer. That is, this invention provides the following moisture-permeable films.
  • a resin component comprising 5 to 20 parts by mass of polyethylene and (C) a metallocene ethylene- ⁇ -olefin copolymer having a density of 0.875 g / cm 3 or more and less than 0.910 g / cm 3
  • the resin composition comprises 100 to 200 parts by weight of (D) inorganic filler with respect to 100 parts by weight of the resin component, and 1 to 20 parts by weight of (E) plasticizer with respect to 100 parts by weight of the resin component.
  • a moisture-permeable film having an air permeability of 50 to 5,000 seconds / 100 mL.
  • the present invention it is possible to provide a moisture permeable film that is excellent in flexibility, air permeability and moisture permeability, yet satisfies heat shrinkage resistance and liquid leakage resistance.
  • the moisture-permeable film of the present invention comprises (A) 30 to 85 parts by mass of linear low density polyethylene having a density of 0.910 to 0.940 g / cm 3 , and (B) a density of 0.910 to 0.930 g / cm 3. 5 to 20 parts by mass of cm 3 high-pressure polymerization low-density polyethylene, and 10 to 10 parts of (C) a metallocene ethylene- ⁇ -olefin copolymer having a density of 0.875 g / cm 3 or more and less than 0.910 g / cm 3.
  • the air permeability is 50 to 5,000 seconds / 100 mL.
  • the resin composition having the above structure may be referred to as a resin composition of the present invention.
  • the resin composition of the present invention may further contain components other than the components (A) to (E).
  • the following terms may be referred to as follows.
  • Linear low density polyethylene LLDPE (Linear Low Density Polyethylene) High pressure polymerization low density polyethylene: LDPE (Low Density Polyethylene) Metallocene ethylene- ⁇ olefin copolymer: m-EOC Machine flow direction: MD (Machine Direction) Direction perpendicular to the machine flow direction (including a substantially vertical range): TD (Transverse Direction)
  • MD Machine Direction
  • TD Transverse Direction
  • the linear low density polyethylene has a density of 0.910 to 0.940 g / cm 3 .
  • the density is a density measured by a pycnometer method (JIS K7112 B method).
  • the densities of other resins are values measured in the same manner.
  • the linear low density polyethylene (LLDPE) has a density of 0.910 to 0.940 g / cm 3 and is not particularly limited as long as it is a linear polyethylene. It is a copolymer with an ⁇ -olefin other than ethylene.
  • ⁇ such as ethylene-propylene, ethylene- (1-butene), ethylene- (1-hexene), ethylene- (4-methyl-1-pentene), ethylene- (1-octene), etc. -Olefin copolymers.
  • the linear low-density polyethylene as the component (A) has a density of 0.910 from the viewpoints of flexibility, breathability, moisture permeability, heat shrinkage resistance, liquid leakage resistance, appearance, hiding property, and the like of the moisture permeable film. ⁇ 0.940 g / cm 3 .
  • it is preferably 0.914 to 0.937 g / cm 3 , and preferably 0.918 to 0.8. More preferably, it is 935 g / cm 3 .
  • the density is preferably 0.913 to 0.933 g / cm 3 , and 0.915 to 0.927 g / cm 3. More preferably, it is cm 3 .
  • the melting point of the linear low density polyethylene (A) is preferably 110 to 135 ° C., more preferably 115 to 135 ° C., and further preferably 115 to 130 ° C. Preferably, it is 117 to 130 ° C, more preferably 120 to 127 ° C.
  • the melting point was about 10 mg of resin was heated from ⁇ 40 ° C. to 200 ° C.
  • the linear low density polyethylene preferably has a melt flow rate (MFR) of 0.5 to 10 g / 10 min.
  • MFR is a value measured according to JIS K7219, and the measurement conditions are 190 ° C. and 2.16 kg load.
  • the MFRs of other resins are values measured in the same manner.
  • the content of (A) linear low density polyethylene in 100 parts by mass of the resin component is 30 to 85 parts by mass, and the flexibility, breathability, moisture permeability, heat shrinkage resistance, and liquid leakage resistance of the moisture permeable film. From the viewpoint of properties, it is preferably 30 to 80 parts by mass, more preferably 35 to 70 parts by mass, and further preferably 40 to 65 parts by mass.
  • the moisture permeable film it is preferably 40 to 85 parts by mass, more preferably 45 to 80 parts by mass, and 50 to 70 parts by mass. More preferably, it is a part.
  • (A) As the linear low density polyethylene a commercially available product may be used. As long as the linear low-density polyethylene satisfying the above-described density and melting point, there are no limitations on the manufacturer, trade name, and grade of the commercial product. Examples of commercially available products include “NOVATEC LL”, “NOVATECH C6” (manufactured by Nippon Polyethylene Co., Ltd.), “Neozex”, “Ultzex”, “Moretech”, “Evolue” [above, Prime Co., Ltd. Polymer] and the like.
  • LDPE High pressure polymerization low density polyethylene
  • B High-pressure polymerization method
  • Low-density polyethylene (LDPE) is a branched polyethylene, and in the present invention, a resin having a density of 0.910 to 0.930 g / cm 3 is used. If it is polyethylene which has this characteristic, it will not restrict
  • Examples of commercially available products include “Novatech LD” (manufactured by Nippon Polyethylene Co., Ltd.), “Sumikasen EP”, “Sumikasen GMH” (manufactured by Sumitomo Chemical Co., Ltd.), “Suntech LD” (Asahi Kasei Chemicals Corporation). Manufactured] and the like.
  • the (B) component high-pressure polymerization method low density polyethylene has a density of 0.910 to 0 from the viewpoint of the flexibility, breathability, appearance, concealability, moisture permeability, heat shrinkage resistance and liquid leakage resistance of the moisture permeable film. 0.930 g / cm 3 , preferably 0.913 to 0.927 g / cm 3 , and more preferably 0.915 to 0.923 g / cm 3 .
  • the melting point of the (B) high-pressure polymerization method low-density polyethylene is preferably 100 to 120 ° C, more preferably 105 to 118 ° C, and further preferably 107 to 116 ° C. preferable.
  • the content of (B) high-pressure polymerization low-density polyethylene in 100 parts by mass of the resin component is 5 to 20 parts by mass.
  • the effect on a manufacture surface such as ensuring of melt tension at the time of carrying out the high-speed extrusion molding of the resin composition of this invention, thickness stability, and the fall of a resin pressure, can be anticipated.
  • the content of the (B) high-pressure polymerization low-density polyethylene in 100 parts by mass of the resin component is preferably 7 to 17 parts by mass, and more preferably 9 to 15 parts by mass. More preferred.
  • C) Metallocene-based ethylene- ⁇ olefin copolymer (m-EOC) is a highly active such as Kaminsky catalyst represented by zirconocene, titanocene and hafnocene (collectively, metallocene), and a stoke metallocene catalyst.
  • a variety of polyethylene resins having an ultra-low density or ultra-low melting point and a very narrow molecular weight distribution are on the market.
  • m-EOC Metallocene-based ethylene- ⁇ -olefin copolymer
  • m-EOC improves kneadability and uniform dispersibility when kneaded with an inorganic filler
  • m-EOC has a low density, and has a low melting point. It is used for the purpose of lowering the elastic modulus and suppressing unevenness of stretching due to the fact that it is, and the features are greatly different from the component (A).
  • a resin having a density of 0.875 g / cm 3 or more and less than 0.910 g / cm 3 is used, and preferably a density of 0.880 g / cm 3 or more and 0.910 g / cm 3 for the above-described features and purposes. Less than 3 resins are used.
  • the melting point of the (C) component metallocene ethylene- ⁇ -olefin copolymer is preferably 70 to 110 ° C., more preferably 70 to 100 ° C.
  • the density and melting point are within the numerical ranges, it is easy to obtain effects such as the texture and flexibility of the moisture-permeable film, and suppresses troubles such as film tensile strength reduction, film blocking, and fusion during molding. can do.
  • the density of the (C) metallocene ethylene- ⁇ -olefin copolymer is 0.883 to 0.908 g / cm 3.
  • the melting point of the (C) metallocene ethylene- ⁇ -olefin copolymer is more preferably 75 to 97 ° C, and further preferably 80 to 95 ° C.
  • the present invention it is preferable to use a resin having a molecular weight distribution of 1.0 to 3.0 as the (C) metallocene ethylene- ⁇ -olefin copolymer.
  • the molecular weight distribution is more preferably from 1.1 to 2.8, and even more preferably from 1.2 to 2.5. When the molecular weight distribution is within this range, it is possible to suppress a decrease in elastic modulus and stretching unevenness.
  • the MFR of the (C) metallocene ethylene- ⁇ olefin copolymer is preferably 0.5 to 10 g / 10 min.
  • the content of the (C) metallocene ethylene- ⁇ olefin copolymer in 100 parts by mass of the resin component is 10 to 50 parts by mass.
  • the moisture-permeable film has a sufficient texture and flexibility, and when it is 50 parts by mass or less, more preferably 40 parts by mass or less. Therefore, the moisture-permeable film has sufficient mechanical properties and heat resistance, which is advantageous in terms of production cost.
  • the metallocene ethylene- ⁇ olefin copolymer may be a commercially available product as long as it has the above-mentioned density and melting point, and the commercially available product / grade is not particularly limited.
  • Polyethylene Co., Ltd. “Kernel”, “Harmolex”, Prime Polymer Co., Ltd. “Evolue”, Sumitomo Chemical Co., Ltd. “Sumikasen E”, “Exelen FX”, Dow Chemical Company “ELITE”, “ENGAGE”, Exxon Mobile Chemical “Enable”, “Exceed”, etc. are mentioned.
  • the content of all resin components in the resin composition of the present invention is 20 to 60% by mass from the viewpoints of flexibility, breathability, moisture permeability, heat shrinkage resistance, and liquid leakage resistance of the moisture permeable film. It is preferably 25 to 50% by mass, more preferably 30 to 45% by mass. Further, the total amount of the components (A) to (C) in all the resin components is 70% by mass or more from the viewpoint of the flexibility, breathability, moisture permeability, heat shrinkage resistance, and liquid leakage resistance of the moisture permeable film. It is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.
  • the inorganic filler is contained in the resin composition in the range of 100 to 200 parts by mass with respect to 100 parts by mass of the resin component.
  • the inorganic filler (Filler) is a component that contributes to the formation of voids (micropores) in the moisture permeable film, and is a component that imparts breathability, moisture permeability and liquid leakage resistance to the moisture permeable film. is there.
  • Examples of the inorganic filler (D) include calcium carbonate, calcium sulfate, barium carbonate, barium sulfate, titanium oxide, magnesium hydroxide, silicon oxide, aluminum oxide, talc, clay, kaolinite, montmorillonite, and hydrotalcite. Fine particles and minerals can be mentioned, and these can be used alone or in combination. Among these, calcium carbonate and barium sulfate are preferred because they are excellent in the expression of voids (micropores), high versatility, low price, and abundant brands.
  • the inorganic filler may be either a heavy product obtained by grinding raw ore minerals or a light product obtained by chemical synthesis.
  • the average particle diameter (D50) of the inorganic filler is preferably 0.5 to 3 ⁇ m, more preferably 0.8 to 2 ⁇ m. When the average particle size is 0.5 ⁇ m or more, there is no poor distribution and distribution of the inorganic filler and secondary aggregation, and the particles can be more uniformly dispersed. On the other hand, by setting the average particle size to 3 ⁇ m or less, the size of the voids (micropores) becomes appropriate when the resin composition of the present invention is thinned, and the machine has excellent air permeability and moisture permeability.
  • an inorganic filler whose surface is coated with a metal soap such as fatty acid, fatty acid ester or fatty acid salt in advance, a silane coupling agent, an inorganic filler whose surface is coated with fine particles such as silica and alumina.
  • a metal soap such as fatty acid, fatty acid ester or fatty acid salt
  • a silane coupling agent such as silane coupling agent
  • fine particles such as silica and alumina.
  • the content of the (D) inorganic filler in the resin composition with respect to 100 parts by mass of the resin component is 100 to 200 parts by mass from the viewpoints of film appearance, concealability, moisture permeability, mechanical properties and water resistance. Furthermore, from the viewpoint of flexibility, breathability, moisture permeability, heat shrinkage resistance, and liquid leakage resistance of the moisture permeable film, the content of the (D) inorganic filler with respect to 100 parts by mass of the resin component is 120 to 190 parts by mass. Preferably, it is 140 to 180 parts by mass.
  • the plasticizer is contained in the resin composition in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the resin component. By being in this range, it is excellent in the balance of the stretch workability at the time of shape
  • a plasticizer is a component which contributes to the improvement of the stretch workability of a resin composition composition.
  • oligomers such as hydrogenated castor oil, hydrogenated castor oil, dehydrated castor oil, aromatic esters, aromatic amides, polyethers and polyesters are used.
  • At least one castor oil selected from the group consisting of castor oil, hydrogenated castor oil, hydrogenated castor oil, and dehydrated castor oil is preferable, hydrogenated castor oil is more preferable, and triglyceride consisting of 12-hydroxyoctadecanoic acid and glycerin is used. More preferred is hardened castor oil as the main component.
  • the hardened castor oil is in the form of a powder having a melting point of 80 to 90 ° C., so that it can be easily handled during production of a moisture permeable film, has an excellent plasticizing and spreading effect on the resin composition of the present invention, and has water resistance. In addition, it exhibits liquid leakage resistance.
  • a commercial item may be used as the plasticizer, and the grade of the commercial item is not particularly limited.
  • a commercial item of hydrogenated castor oil Ito Oil Co., Ltd. Products such as castor hydrogenated oil A, KEF Trading “Hima Hard”, “HCO-I”, Toyokuni Oil Co., Ltd. “Caster Wax”, and the like.
  • the content of the (E) plasticizer with respect to 100 parts by mass of the resin component is 2 to 15 parts by mass. Is preferably 4 to 10 parts by mass.
  • the resin composition of the present invention further comprises a compatibilizer, a processing aid, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antiblocking agent, an antiblocking agent, depending on the intended use of the moisture permeable film. It may contain a clouding agent, a matting agent, an antibacterial agent, a deodorant, an antistatic agent, a flame retardant, a colorant, a pigment, and the like.
  • the moisture-permeable film of the present invention has an air permeability of 50 to 5,000 seconds / 100 mL.
  • the air permeability of the moisture permeable film is 50 to 5,000 seconds / 100 mL, preferably 200 to 1,000 seconds / 100 mL.
  • the air permeability is 50 seconds / 100 mL or more, sufficient mechanical properties, water resistance and liquid leakage resistance of the moisture-permeable film can be secured, and when the air permeability is 5,000 seconds / 100 mL or less, ventilation is achieved.
  • the air permeability of the moisture permeable film is measured according to a method defined in JIS P8117 (Gurley test machine method) [for example, manufactured by Asahi Seiko Co., Ltd., Oken air permeability tester, EGO1. -55 type], and measured at 10 locations of the moisture-permeable film, and the arithmetic average value is measured.
  • the heat shrinkage rate of the moisture permeable film in the machine flow direction after heating the moisture permeable film at 60 ° C. for 1 hour is preferably less than 5.0%, more preferably less than 3.0%. When it is less than 5.0%, there is little blocking or squeezing when a roll-shaped sample of a moisture-permeable film is stored over time, which is suitable for practical use.
  • the heat shrinkage rate of the moisture permeable film is determined as follows. A test piece (MD: 200 mm, TD: 10 mm) is collected from the moisture permeable film, and is statically heated in a convection oven set at a bath temperature of 60 ° C. for 1.0 hour.
  • the length L (mm) in the machine flow direction (MD) is measured. Randomly select and measure three locations on the moisture-permeable film, obtain the respective heat shrinkage rate by the formula “(L-200) / 200 ⁇ 100 (%)”, and calculate the arithmetic average value of the heat-permeable film. Shrinkage rate.
  • the tensile elastic modulus in the machine flow direction (MD) of the moisture-permeable film is preferably 50 MPa or less, more preferably 5 to 40 MPa. By setting it to 50 MPa or less, the texture and flexibility after processing the moisture-permeable film into a paper diaper are secured, and the comfort is excellent.
  • the moisture-permeable film of the present invention preferably further has the following mechanical properties.
  • the tensile strength in the machine flow direction (MD) of the moisture permeable film is preferably 3 to 10 N / 25 mm, and more preferably 5 to 8 N / 25 mm. By setting it to 3N / 25mm or more, it has moderate tensile strength and excellent mechanical suitability, and by setting it to 10N / 25mm or less, texture and flexibility after processing into a paper diaper are ensured, and the comfort is excellent.
  • the tensile elongation in the machine flow (MD) direction of the moisture permeable film is preferably 100 to 400%, more preferably 150 to 300%. If it is within the above range, it has appropriate flexibility and tensile strength, and therefore, it is excellent in mechanical suitability during processing of a paper diaper.
  • the tensile strength and tensile elongation of the moisture-permeable film were measured three times at a test width of 25 mm and a tensile speed of 200 m / min according to JIS K7127, and the strength and elongation at the point at which the specimen of the moisture-permeable film was broken.
  • the tensile elastic modulus of the moisture-permeable film is first measured three times at a test width of 25 mm and a tensile speed of 200 m / min in accordance with JIS K7127, similarly to the measurement of tensile strength and tensile elongation.
  • the tensile elastic modulus is calculated from the strength and elongation behavior in the range where the test piece is extended by 0 to 10%, and is obtained as the arithmetic average value.
  • the total light transmittance of the moisture-permeable film is preferably 20 to 60%, more preferably 30 to 50%. When the total light transmittance is 20% or more, it can be identified even if an indicator drug is applied to the moisture-permeable film to notify urination. When the total light transmittance is 60% or less, the film is white and concealed. Rich in nature.
  • the total light transmittance of the moisture permeable film is determined according to JIS K7361, such as a haze meter (for example, Nippon Denshoku Industries Co., Ltd., haze meter, NDH5000SP) and a constant pressure thickness meter (for example, Mitutoyo Corporation, thickness gauge, 547). -055] is measured at five locations of the moisture-permeable film, and the arithmetic average value is measured.
  • the oozing area of the moisture permeable film is preferably less than 30%, more preferably less than 20%, and even more preferably less than 10%. By being less than 30%, it can be said that the moisture-permeable film has excellent water resistance and liquid leakage resistance, and the moisture-permeable film can be suitably used as a moisture-permeable and water-proof back sheet for disposable diapers and physiological treatment products. .
  • the oozing area of the moisture permeable film is measured as follows.
  • a test liquid is marketed by stacking a moisture permeable film and a commercial kitchen paper on the filter paper. Gently drop 2.0 mL with a dropper on the center of the kitchen paper. After dripping the test solution, a resin plate is placed on a commercially available kitchen paper, and a weight of 2 kg is further placed and left for 30 minutes. Next, the area of the portion of the filter paper colored in red due to the bleeding of the test liquid (colored portion shown in the filter paper after the test in FIG. 1) is measured, and the proportion of the area in the entire pressurized filter paper is calculated. The value obtained is taken as the oozing area. Examples of the filter paper include “FILTER PAPER No. 2 (trade name); (diameter: 70 mm)” manufactured by Advantech Co., Ltd.
  • the basis weight of the moisture permeable film is preferably 5 to 50 g / m 2 , more preferably 10 to 30 g / m 2 , and still more preferably 15 to 25 g / m 2 . It is preferable that the basis weight is 5 g / m 2 or more because the tensile strength, tear strength, and appropriate rigidity of the moisture-permeable film can be secured. Further, when the basis weight is 50 g / m 2 or less, a moisture-permeable film having a sufficient lightweight feeling, texture and flexibility can be obtained.
  • the basis weight of the moisture-permeable film is a value obtained by taking a test piece (MD: 250 mm, TD: 200 mm) from the moisture-permeable film, measuring the mass (g) with an electronic balance, and multiplying the numerical value by 20 times.
  • the thickness of the moisture permeable film is preferably 5 to 50 ⁇ m, more preferably 15 to 30 ⁇ m.
  • the thickness of 5 ⁇ m or more is preferable because the tensile strength and tear strength of the moisture-permeable film can be secured. Moreover, sufficient lightweight feeling, texture, and a softness
  • the thickness of the moisture-permeable film is obtained by taking a test piece (MD: 100 mm, TD: 100 mm) from the moisture-permeable film and then measuring with a constant pressure thickness meter [eg, Mitutoyo Corporation, thickness gauge, model 547-055]. Is measured as 9 points, and is obtained as the arithmetic average value.
  • the moisture permeability of the moisture permeable film is preferably 1,000 to 20,000 g / (m 2 ⁇ 24 h), more preferably 2,000 to 15,000 g / (m 2 ⁇ 24 h), and still more preferably 5,000 to 15 000 g / (m 2 ⁇ 24 h).
  • Moisture permeability is 1,000g / (m 2 ⁇ 24h) or more, so it can be worn comfortably without stuffiness and skin irritation when used as a paper diaper, and at 20,000g / (m 2 ⁇ 24h) or less. As a result, sufficient mechanical properties, water resistance, and liquid leakage resistance of the moisture permeable film are ensured.
  • the moisture permeability of the moisture permeable film is measured by a method based on JIS Z0208 (cup method). Specifically, the measurement was performed in a constant temperature and humidity environment at a temperature of 40 ° C. and a relative humidity of 90%, and in the presence of 15 g of calcium chloride as a hygroscopic agent. It is a value calculated as an arithmetic average value by randomly selecting and measuring three locations of the moisture-permeable film.
  • the moisture-permeable film of the present invention may be a film having a multilayer structure having two or more moisture-permeable films using the resin composition of the present invention, depending on applications, purposes and the like.
  • the moisture-permeable film of the present invention can be obtained by forming the resin composition of the present invention into a thin film by a method such as melt extrusion. Therefore, the production method is not limited, and a film can be obtained by applying a known method. However, from the viewpoint of production efficiency, cost, etc., after the resin composition of the present invention is melt-extruded, inflation, tubular, T-die, etc. A method of forming a thin film according to the method is preferable. Moreover, in order for the moisture-permeable film of this invention to have the above-mentioned physical property, it is preferable that a moisture-permeable film is a stretched film.
  • the moisture-permeable film of the present invention is preferably produced by the following method for producing a moisture-permeable film of the present invention.
  • the moisture-permeable film of the present invention comprises a step (1) (A) 30 to 85 parts by mass of linear low density polyethylene having a density of 0.910 to 0.940 g / cm 3 , and (B) a density of 0.910 to High-pressure polymerization method of 0.930 g / cm 3 5 to 20 parts by mass of low density polyethylene, and (C) a metallocene ethylene- ⁇ -olefin copolymer having a density of 0.875 g / cm 3 or more and less than 0.910 g / cm 3
  • step (1) the above-described resin composition of the present invention is formed into a film.
  • the resin composition used in the method for producing a moisture-permeable film of the present invention is the resin composition of the present invention described above. Therefore, the structure of the resin composition used in the method for producing the moisture-permeable film of the present invention is the same as the structure of the resin composition of the present invention, and the preferred embodiment is also the same.
  • step (1) in addition to the components (A) to (E) contained in the resin composition of the present invention, components that may be included as necessary are mixed in the amounts described above, and then kneaded. It is preferable to melt and knead with a machine (extruder).
  • each component may be mixed by a mixer such as a tumbler mixer, a mixing roll, a Banbury mixer, a ribbon blender, or a super mixer.
  • the melt kneading of the mixture is preferably performed using a kneader such as a different-direction twin screw extruder or a same-direction twin screw extruder to promote uniform dispersion and distribution of the resin composition.
  • a mixer such as a mixer.
  • the resin composition melt-extruded from the kneader is preferably pelletized by a method such as strand cutting or die cutting after cooling. It is also possible to extrude from a kneader die to a cooling roller, a cooling belt or the like and directly form a thin film.
  • Step (2)-Drawing step- the resin composition molded into a film is stretched.
  • the method of stretching the film obtained in the step (1) is generally a stretch opening method, but the method is not particularly limited as long as the temperature condition and the stretch ratio are in the above ranges.
  • a known stretching method represented by a biaxial stretching method such as a roll stretching method, a tenter method, simultaneous biaxial stretching, or sequential biaxial stretching can be applied.
  • the resin composition molded into a film shape may be performed at least once in the uniaxial direction or twice or more in consideration of stretching unevenness and air permeability, and the appearance and moisture permeability are improved. Therefore, it may be performed in two stages.
  • the stretching condition is that the stretching temperature is 0 to 100 ° C., and the stretching ratio is preferably 1.5 to 4.0 times as a total ratio, and more preferably 2.0 to 3.5 times. By setting the stretching ratio to 1.5 times or more in total, a moisture-permeable film stretched uniformly without stretching unevenness can be obtained. On the other hand, by setting the stretching ratio to 4.0 times or less in total, a moisture permeable film satisfying the balance between moisture permeability, water resistance and liquid leakage resistance can be obtained.
  • the moisture-permeable film can be made thinner and lighter, and it has excellent breathability, moisture permeability, mechanical properties of machine direction flow, liquid resistance Leakage and heat resistance can be imparted in a well-balanced manner, and the conditions can be appropriately selected according to desired performance. For example, as the draw ratio is increased, air permeability is improved (air permeability is decreased), while water resistance and liquid leakage resistance tend to decrease, and tensile modulus and tensile strength are increased. While excellent mechanical suitability in the production line can be obtained, hardness tends to develop.
  • heat setting may be performed after stretching.
  • the heat setting refers to preliminarily applying heat to the film and intentionally shrinking the film to suppress shrinkage of the product roll.
  • the draw ratio ratio of winding side roll speed / unwinding side roll speed
  • the tenter stretching method the film is contracted by heating the film in the vicinity of the tenter outlet and making the clip width at both ends narrower than the width after stretching.
  • the heat-setting temperature in the present invention is preferably 60 to 100 ° C, more preferably 60 to 90 ° C. .
  • the negative draw ratio is preferably ⁇ 20 to ⁇ 5% in total, and if it is within the specified range, heat fixation can be performed without any trouble in production, and sufficient thermal dimensional stability can be obtained.
  • Example and comparative example of this invention are specified, this invention is not limited to these.
  • all the raw materials shown in Table 1 were put into a super mixer, mixed and dispersed for 10 minutes, melt-kneaded at a set extrusion temperature of 180 ° C. with a unidirectional twin screw extruder, and strand cut Compound pellets were obtained in this manner.
  • stretching is performed once in the machine flow direction (MD) at a stretching temperature of 65 ° C. and a stretching ratio of 2.50 times using a roll type longitudinal stretching machine.
  • MD machine flow direction
  • Table 1 shows the raw materials and compositions of Examples 1-2 and Comparative Examples 1-2.
  • (C) m-EOC having a separation amount distribution of 1.8 was used.
  • Example 3 to 4 and Comparative Examples 3 to 4 all the raw materials shown in Table 1 were put into a super mixer, mixed and dispersed for 10 minutes, melt-kneaded at a set extrusion temperature of 180 ° C. with a unidirectional twin screw extruder, and strand cut Compound pellets were obtained in this manner. Thereafter, the film was formed into a film shape using a single-screw extruder and an inflation bracket / die and stretched using a roll-type stretching machine. In Example 3 and Comparative Examples 3 to 4, the film was stretched once in the machine flow direction (MD) (temperature 65 ° C., magnification 2.60 times), heat fixed at 95 ° C., and relaxed.
  • MD machine flow direction
  • Example 4 the film was stretched once in the machine flow direction (MD) (temperature 65 ° C., magnification 2.80 times), heat fixed at 95 ° C., and relaxed.
  • MD machine flow direction
  • Example 3 to 4 and Comparative Examples 3 to 4 are shown in Table 1.
  • Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated on the following items.
  • the evaluation results are shown in Table 3.
  • items (1) to (9) were evaluated, and for Examples 3 and 4 and Comparative Examples 3 and 4, items (1) and (3) , (4), (7) to (10) were evaluated.
  • Thickness ( ⁇ m) After collecting a test piece (MD: 100 mm, TD: 100 mm) from the obtained moisture-permeable film, the thickness was measured at 9 points with a constant-pressure thickness meter (manufactured by Mitutoyo Corporation, thickness gauge, model 547-055). The arithmetic average value was defined as the thickness.
  • Air permeability (sec / 100mL) Using an air permeability measuring device (Asahi Seiko Co., Ltd., Oken air permeability measuring device, EGO1-55 type) according to the method specified in JIS P8117 (Gurley Tester Method), 10 samples Measured and the arithmetic average value was defined as air permeability.
  • Moisture permeability [g / (m 2 ⁇ 24h)]
  • the moisture permeability was measured by a method based on JIS Z0208 (cup method). Specifically, the measurement was performed under conditions of a constant temperature and humidity environment of a temperature of 40 ° C. and a relative humidity of 90% under the condition of 15 g of calcium chloride as a hygroscopic agent. The sample was measured at three points at random, and the arithmetic average value was obtained.
  • Tensile modulus (MPa) in the machine flow direction (described as MD tensile modulus in the table)
  • MD tensile modulus in the table Tensile modulus in the machine flow direction
  • the tensile modulus was calculated from the strength and elongation behavior in the range where the test piece was extended by 0 to 10%, and the arithmetic average value was obtained.
  • Heat shrinkage rate (%) (heat shrinkage rate in the machine flow direction after heating at 60 ° C. for 1 hour)
  • a test piece (MD: 200 mm, TD: 10 mm) was taken from the moisture permeable film, and was statically heated for 1.0 hour in a convection oven set at a bath temperature of 60 ° C. Thereafter, the length L (mm) in the machine flow direction (MD) was measured. Randomly select and measure three locations on the moisture-permeable film, obtain the respective heat shrinkage rate by the formula “(L-200) / 200 ⁇ 100 (%)”, and calculate the arithmetic average value of the heat-permeable film. It was set as the shrinkage rate.
  • filter paper ““FILTER PAPER No. 2 (trade name)”, manufactured by Advantech Co., Ltd.
  • a moisture-permeable film cut into a 100 mm ⁇ 100 mm square and a commercial kitchen paper cut into a 70 mm ⁇ 70 mm square are layered, and the test solution is gently placed with a dropper on the center of the commercial kitchen paper. 0.0 mL was added dropwise.
  • a resin plate (diameter: 60 mm, thickness: 5 mm) was layered on a commercially available kitchen paper, and a 2 kg weight was placed thereon and left for 30 minutes.
  • the area of the filter paper colored in red due to the bleeding of the test liquid was measured, and the ratio of the area in the entire pressurized filter paper was calculated. The value was defined as the oozing area.
  • the evaluation criteria are as follows. A: Exudation area is less than 10% B: Exudation area is 10% or more and less than 20% C: Exudation area is 20% or more and less than 30% D: Exudation area is 30% or more
  • Example 1 and Example 2 are excellent in air permeability and moisture permeability, but also have a small heat shrinkage rate and good results of the liquid leakage test. Furthermore, since the MD tensile modulus is 50 MPa or less, the flexibility is sufficient. On the other hand, although Comparative Example 1 is satisfactory in terms of air permeability and moisture permeability, the MD tensile elastic modulus is 80 MPa or more and the flexibility is not sufficient. Since the comparative example 2 uses the liquid plasticizer, the result of the liquid leak test is not sufficient, and the moisture permeability and the heat shrinkage rate are slightly inferior.
  • Example 1 and Example 2 are excellent in the concealability (total light transmittance), breathability and moisture permeability of the moisture permeable film, but also have good liquid leakage test results. Furthermore, the flexibility and the heat shrinkage ratio are sufficiently suitable for practical use, and are excellent overall. Further, in Example 2, it was considered that the concealability and moisture permeability were improved because the stretching whitening was promoted by dividing the stretching in the MD direction into two. From the above results, it was found that without adding a white pigment, it is possible to produce a moisture permeable film that is highly concealed and excellent in moisture permeability but hardly leaks. On the other hand, in Comparative Example 1, although flexibility is satisfied, the concealability, air permeability, moisture permeability, and heat shrinkage rate are poor.
  • the moisture-permeable film obtained by the present invention is a moisture-permeable film that is excellent in flexibility, breathability and moisture permeability, has a good appearance, has good concealment properties, and is resistant to heat shrinkage and liquid leakage, it is a disposable diaper and sanitary treatment article. It can be suitably used as a moisture permeable and waterproof back sheet for sanitary products such as

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
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Abstract

L'invention concerne un film perméable à l'humidité ayant une perméabilité à l'air de 50 à 5000 s/100 ml et comprenant une composition de résine qui contient : un constituant résine contenant (A) 30 à 85 parties en masse d'un polyéthylène basse densité à chaîne droite ayant une masse volumique de 0,910 à 0,940 g/cm3, (B) 5 à 20 parties en masse d'un polyéthylène basse densité polymérisé à haute pression et ayant une masse volumique de 0,910 à 0,930 g/cm3 et (C) 10 à 50 parties en masse d'un copolymère d'éthylène-α-oléfine formé à l'aide d'un métallocène et ayant une masse volumique supérieure ou égale à 0,875 g/cm3 et inférieure à 0,910 g/cm3 ; 100 à 200 parties en masse de (D) une charge inorganique pour 100 parties en masse du constituant résine ; et 1 à 20 parties en masse de (E) un plastifiant pour 100 parties en masse du constituant résine. Ainsi, il est possible de produire un film perméable à l'humidité qui, tout en ayant d'excellentes souplesse, respirabilité et perméabilité à l'humidité, a une résistance au retrait thermique et une résistance au passage de liquide satisfaisantes. En outre, il est possible de produire un film perméable à l'humidité qui a un excellent aspect, qui a des propriétés de protection amplement suffisantes et qui en outre, tout en ayant une excellente perméabilité à l'humidité, n'est pas enclin au passage de liquide.
PCT/JP2015/066261 2014-06-04 2015-06-04 Film perméable à l'humidité WO2015186808A1 (fr)

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JP2014116259 2014-06-04
JP2014116263 2014-06-04
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018083926A (ja) * 2016-11-25 2018-05-31 株式会社Ｔｂｍ 樹脂成形体の製造方法
EP3647345A1 (fr) * 2018-11-05 2020-05-06 Windmöller & Hölscher KG Film thermoplastique respirable à retrait réduit
JP2020152424A (ja) * 2019-03-22 2020-09-24 三菱ケミカル株式会社 ヒートシール用フィルムおよび収納袋
US11584111B2 (en) 2018-11-05 2023-02-21 Windmoeller & Hoelscher Kg Breathable thermoplastic film with reduced shrinkage

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JPH01185337A (ja) * 1988-01-18 1989-07-24 Sumitomo Chem Co Ltd 通気性フィルム
JPH0925372A (ja) * 1995-07-12 1997-01-28 Maruzen Petrochem Co Ltd 透湿性フィルム
JP2001261868A (ja) * 2000-01-12 2001-09-26 Mitsui Chemicals Inc 多孔性フィルム及びその製造方法
JP2008179757A (ja) * 2006-12-28 2008-08-07 Nippon Polyethylene Kk 通気性フィルム

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JPH01185337A (ja) * 1988-01-18 1989-07-24 Sumitomo Chem Co Ltd 通気性フィルム
JPH0925372A (ja) * 1995-07-12 1997-01-28 Maruzen Petrochem Co Ltd 透湿性フィルム
JP2001261868A (ja) * 2000-01-12 2001-09-26 Mitsui Chemicals Inc 多孔性フィルム及びその製造方法
JP2008179757A (ja) * 2006-12-28 2008-08-07 Nippon Polyethylene Kk 通気性フィルム

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Title
ASAHI KASEI AMIDASU KABUSHIKI KAISHA, PLASTICS' HENSHUBU, PLASTIC DATA BOOK, 1 December 1999 (1999-12-01), pages 326, 344 *
KAZUO MATSUURA ET AL., POLYETHYLENE GIJUTSU TOKUHON, 1 July 2001 (2001-07-01), pages 163 - 166 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018083926A (ja) * 2016-11-25 2018-05-31 株式会社Ｔｂｍ 樹脂成形体の製造方法
WO2018096834A1 (fr) * 2016-11-25 2018-05-31 株式会社Ｔｂｍ Procédé de production d'objet en résine moulé
EP3647345A1 (fr) * 2018-11-05 2020-05-06 Windmöller & Hölscher KG Film thermoplastique respirable à retrait réduit
US11584111B2 (en) 2018-11-05 2023-02-21 Windmoeller & Hoelscher Kg Breathable thermoplastic film with reduced shrinkage
JP2020152424A (ja) * 2019-03-22 2020-09-24 三菱ケミカル株式会社 ヒートシール用フィルムおよび収納袋

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