WO2015115289A1 - Film poreux, feuille à l'épreuve de l'eau perméable à l'humidité, complexe, et vêtement de protection - Google Patents

Film poreux, feuille à l'épreuve de l'eau perméable à l'humidité, complexe, et vêtement de protection Download PDF

Info

Publication number
WO2015115289A1
WO2015115289A1 PCT/JP2015/051619 JP2015051619W WO2015115289A1 WO 2015115289 A1 WO2015115289 A1 WO 2015115289A1 JP 2015051619 W JP2015051619 W JP 2015051619W WO 2015115289 A1 WO2015115289 A1 WO 2015115289A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
stretching
porous film
temperature
width direction
Prior art date
Application number
PCT/JP2015/051619
Other languages
English (en)
Japanese (ja)
Inventor
生駒啓
藤本聡一
大倉正寿
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2015523732A priority Critical patent/JPWO2015115289A1/ja
Publication of WO2015115289A1 publication Critical patent/WO2015115289A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing

Definitions

  • the present invention relates to a porous film having excellent water pressure resistance and moisture permeability, high elongation, and excellent laminating properties with a nonwoven fabric. Further, by using the porous film, the present invention relates to a moisture permeable waterproof sheet, a composite, and protective clothing that are excellent in water pressure resistance and moisture permeability, have high elongation, reduce stuffiness when worn, and have excellent clothing comfort. .
  • a material obtained by coating or bonding a water-repellent resin to a fabric is often used because it is excellent in water resistance and processability.
  • conventional materials are inferior in moisture permeability or air permeability, moisture is trapped inside the protective clothing in a hot and humid working environment, causing discomfort, and when used as a waterproof sheet, There was a problem that mold and the like occurred.
  • Patent Document 1 a laminated cloth in which a porous resin film is laminated on a fiber material cloth has been proposed.
  • Patent Documents 5, 6, and 7 a moisture permeable film that does not use inorganic particles such as calcium carbonate or organic particles has been proposed (for example, Patent Documents 5, 6, and 7).
  • JP 2001-38839 A JP-A-6-316022 JP 2003-145697 A JP-A-8-53561 JP 2006-28495 A JP 2001-342272 A Japanese Patent Laid-Open No. 9-3226
  • Patent Document 1 as a laminated fabric, a technique in which a porous resin film is formed by applying and drying a coating material in which silica or zeolite or the like is added to a polyurethane resin as an adsorbent in an amount of 10% by weight or more is dried.
  • a coating material in which silica or zeolite or the like is added to a polyurethane resin as an adsorbent in an amount of 10% by weight or more is dried.
  • the object of the present invention is to solve the above-mentioned problems. In other words, it is excellent in water pressure and moisture permeability, high in elongation, excellent in laminating properties with non-woven fabric, reduced in stuffiness when worn, and suitable for protective clothing base materials with excellent clothing comfort. It is to provide an adhesive film and a moisture permeable waterproof sheet, a composite, and protective clothing using the same. Furthermore, another object is to provide a moisture permeable waterproof sheet and protective clothing with very little incineration residue when no longer needed.
  • an object of the present invention is to provide a porous film having excellent water pressure resistance and moisture permeability, high elongation, excellent laminating property with a non-woven fabric, hardly torn, and excellent process passability.
  • Another object of the present invention is to provide a moisture-permeable waterproof sheet, a composite, and protective clothing using the porous film, which has excellent water pressure resistance, high elongation, reduces the feeling of stuffiness when worn, and is excellent in clothing comfort.
  • Another object of the present invention is to provide a moisture-permeable waterproof sheet and protective clothing that have very little residue (ash) when incinerated when no longer needed.
  • the moisture permeability is 250 g / m 2 ⁇ h or more
  • the sum of the tensile elongation in the longitudinal direction and the width direction of the film is 100 to 500%
  • the water pressure resistance is 4,500 mmH 2 O or more.
  • it can be achieved by a porous film having an ash content (JIS L 1013) after incineration at a temperature of 850 ° C. of 0.5% by mass or less.
  • the porous film of the present invention is excellent in water pressure resistance, reduces the feeling of stuffiness when worn, and is suitable for a base material of a protective garment excellent in clothes comfort and a moisture-permeable waterproof sheet using the same, Complexes and protective clothing can be provided.
  • the present invention can provide a porous film excellent in water pressure resistance and moisture permeability. Since the breaking elongation is high, it is possible to provide a porous film excellent in laminate processability (that is, process passability) with a nonwoven fabric. Further, by using the porous film, it is possible to provide a moisture permeable waterproof sheet, a composite, and protective clothing that are excellent in water pressure resistance, reduce the feeling of stuffiness when worn, and have excellent clothing comfort. Furthermore, it is possible to provide a moisture-permeable waterproof sheet and protective clothing that have very little ash after incineration when it is no longer needed.
  • the porous film of the present invention is a film having many fine through-holes penetrating both surfaces of the film and having air permeability.
  • the resin constituting the porous film may be any of polyolefin resin, polycarbonate, polyamide, polyimide, polyamideimide, aromatic polyamide, fluorine resin, etc., but heat resistance, moldability, production cost reduction, chemical resistance, A polyolefin resin is desirable from the viewpoint of oxidation resistance and reduction resistance. Therefore, the porous film of the present invention preferably contains a polyolefin resin.
  • Examples of the monomer component constituting the polyolefin resin include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-hexene and 4-methyl.
  • These homopolymers and at least two or more types of copolymers selected from the above monomer components examples include, but are not limited to, blends of copolymers and copolymers.
  • vinyl alcohol, maleic anhydride or the like may be copolymerized or graft polymerized, but is not limited thereto.
  • polyethylene using ethylene as a monomer component and / or polypropylene using propylene as a monomer component is preferable.
  • Propylene is particularly preferable from the viewpoint of heat resistance, air permeability, porosity, and the like.
  • Polypropylene using as a monomer component is preferable, and the main component is preferable.
  • the porous film of the present invention contains a polyolefin resin, and the polyolefin resin is polypropylene.
  • the “main component” means that the proportion of a specific component in all components is 50% by mass. % Or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and most preferably 95% by mass or more.
  • an upper limit is not specifically limited, 100 mass% becomes a substantial upper limit.
  • the wet method means that a polyolefin resin is used as a matrix resin, an extractable to be extracted after sheeting is added, and the mixed resin composition is made into a sheet, and then the additive is used using a good solvent of the extractable. This is a method in which voids are generated in the matrix resin by extracting only.
  • the dry method is, for example: By adopting low temperature extrusion and high draft ratio at the time of melt extrusion, the lamella structure in the film before stretching is controlled, and this is uniaxially stretched after heat treatment to generate cleavage at the lamella interface, and voids are created.
  • Forming method (so-called lamellar stretching method); A method of forming voids by adding a large amount of incompatible resin as particles to polypropylene, which is an inorganic particle or matrix resin, forming a sheet and stretching it to cause cleavage at the interface between the particle and the polypropylene resin (particle method) , Phase separation method); and a method of forming voids in the film by utilizing the crystal density difference and crystal transition between ⁇ -type crystal ( ⁇ crystal) and ⁇ -type crystal ( ⁇ crystal), which are polymorphs of polypropylene (So-called ⁇ crystal method)
  • ⁇ crystal method a method of forming voids in the film by utilizing the crystal density difference and crystal transition between ⁇ -type crystal ( ⁇ crystal) and ⁇ -type crystal ( ⁇ crystal), which are polymorphs of polypropylene
  • the ⁇ crystal forming ability of the porous film is preferably 40% or more. If the ⁇ -crystal forming ability is less than 40%, the amount of ⁇ -crystals is small at the time of film production, so the number of voids formed in the film is reduced by utilizing the transition to ⁇ -crystal, and as a result, only a film with low permeability is obtained. It may not be possible.
  • the upper limit of the ⁇ -crystal forming ability is not particularly limited, but it exceeds 99.9% by adding a large amount of the ⁇ -crystal nucleating agent described later or the stereoregulation of the polypropylene resin to be used. The industrial practical value is low, for example, the film forming stability is lowered. Industrially, the ⁇ -crystal forming ability is preferably 65 to 99.9%, particularly preferably 70 to 95%.
  • a polypropylene resin with a high isotactic index is used, or a ⁇ crystal is selectively formed by adding it to a polypropylene resin called a ⁇ crystal nucleating agent.
  • the crystallization nucleating agent to be used is preferably used as an additive.
  • ⁇ crystal nucleating agents include alkali or alkaline earth metal salts of carboxylic acids such as calcium 1,2-hydroxystearate and magnesium succinate, and N, N′-dicyclohexyl-2,6-naphthalenedicarboxyamide.
  • Amide compounds such as 3,9-bis [4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, benzenesulfonic acid
  • aromatic sulfonic acid compounds such as sodium and sodium naphthalene sulfonate, imide carboxylic acid derivatives, phthalocyanine pigments, and quinacridone pigments.
  • amides disclosed in JP-A-5-310665 are preferred.
  • ⁇ crystal nucleating agent is preferably 0.05 to 0.5% by mass, more preferably 0.1 to 0.3% by mass, based on the polypropylene composition. If it is less than 0.05% by mass, formation of ⁇ crystals becomes insufficient, and the air permeability of the porous film may be lowered. If it exceeds 0.5% by mass, coarse voids are formed, and physical property changes during application of organic solvents and drying may increase.
  • a polypropylene composition is a composition containing all the materials which comprise porous films, such as a beta crystal nucleating agent and antioxidant, in addition to a polypropylene resin.
  • the polypropylene resin constituting the porous film of the present invention preferably has a melt flow rate (hereinafter referred to as MFR, measurement conditions are 230 ° C., 2.16 kg) in the range of 2 to 30 g / 10 min. It is preferable that it is an isotactic polypropylene resin.
  • MFR melt flow rate
  • measurement conditions are 230 ° C., 2.16 kg
  • MFR isotactic polypropylene resin.
  • the MFR is less than 2 g / 10 minutes, the melt viscosity of the resin becomes high and high-precision filtration becomes difficult, and the quality of the film may be lowered.
  • the MFR exceeds 30 g / 10 min, the molecular weight becomes too low, so that the film is easily broken during stretching, and the productivity may be lowered. More preferably, the MFR is 3 to 20 g / 10 minutes.
  • the isotactic index is preferably 90 to 99.9%, more preferably 95 to 99%. If the isotactic index is less than 90%, the crystallinity of the resin is low, and it may be difficult to achieve high air permeability.
  • a polypropylene resin in the present invention not only a homopolypropylene resin can be used, but also from the viewpoint of stability in the film-forming process, film-forming properties, and uniformity of physical properties, an ethylene component or butene is added to polypropylene.
  • a resin obtained by copolymerizing an ⁇ -olefin component such as hexene or octene in an amount of 5% by mass or less, more preferably 2.5% by mass or less can be used.
  • the form of introduction of the comonomer (copolymerization component) into polypropylene may be either random copolymerization or block copolymerization.
  • polypropylene high MFR polypropylene
  • MFR polypropylene
  • the upper limit of MFR is preferably 5000 g / 10 min or less. If the MFR exceeds 5000 g / 10 min, it may be difficult to make it uniform with the above-mentioned isotactic polypropylene.
  • high MFR polypropylene (especially isotactic polypropylene) having an MFR of 70 g / 10 min or more has not been used in the field of films because it has poor stretchability and causes a decrease in elongation.
  • the high MFR polypropylene is contained in an amount of 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably 0.7 to 5% by mass.
  • the high MFR polypropylene added in a small amount increases the molecular chain end concentration at the crystal interface and promotes pore formation at the crystal interface in the longitudinal stretching, that is, it acts as a pore opening aid, resulting in uniform pore opening. While having water pressure resistance and elongation, it can have moisture permeability and can achieve conflicting properties.
  • an antioxidant In the polypropylene resin that forms the porous film of the present invention, an antioxidant, a heat stabilizer, a light stabilizer, a neutralizer, an antistatic agent and a lubricant composed of organic particles, as long as the effects of the present invention are not impaired. Furthermore, you may contain various additives, such as an antiblocking agent, a filler, and an incompatible polymer. In particular, it is preferable to add an antioxidant for the purpose of suppressing the oxidative deterioration due to the heat history of the polypropylene resin, but when the polypropylene composition is 100% by mass, the antioxidant addition amount is 2% by mass or less. More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less.
  • the inorganic filler is preferably not added because it remains as ash after incineration.
  • the porous film of the present invention has a moisture permeability of 250 g / m 2 ⁇ h or more.
  • the moisture permeability is less than 250 g / m 2 ⁇ h, when the porous film of the present invention is worn as protective clothing, the feeling of stuffiness may be felt strongly, and the clothing comfort may be low.
  • the moisture permeability is preferably high, but the upper limit is practically 2,000 g / m 2 ⁇ h.
  • the moisture permeability is preferably 250 to 2,000 g / m 2 ⁇ h, more preferably 300 to 2,000 g / m 2 ⁇ h, and further preferably 350 to 2,000 g / m 2 ⁇ h. preferable.
  • the moisture permeability is adjusted by adjusting the amount of ⁇ -crystal nucleating agent added in the raw material, the amount of high MFR polypropylene added in the raw material, adjusting the stretching ratio and temperature in the longitudinal direction, re-stretching, and re-stretching. It can be controlled by adjusting the stretching temperature and the magnification.
  • the addition amount of the ⁇ crystal nucleating agent in the raw material is further increased within the range of 0.05 to 0.5% by mass
  • the temperature of the cast drum is increased within the range of 105 to 130 ° C.
  • Increase the moisture permeability by increasing the amount of high MFR polypropylene in the range of 0.1 to 20% by mass or lowering the longitudinal stretching temperature in the range of 90 to 140 ° C.
  • the moisture permeability can be increased by increasing the draw ratio in the longitudinal direction within a range of 3 to 7 times.
  • the film stretched in the longitudinal direction and the width direction is re-stretched in the longitudinal direction, and the re-stretching stretching temperature is lowered within the range of 130 to 170 ° C., or the re-stretching stretching ratio is 1.02.
  • Moisture permeability can be increased by stretching at a high magnification within a range of up to 2.0 times.
  • the sum of the tensile elongation in the longitudinal direction and the width direction of the film is 100 to 500%.
  • the porous film breaks during the operation, and the water pressure resistance decreases.
  • the process passability may be inferior in the process of bonding to a nonwoven fabric.
  • the process passability in processing such as stretching of the film when tension is applied in the processing step may be inferior.
  • the sum of the tensile elongation in the longitudinal direction and the width direction of the film is preferably 100 to 400%. 130 to 400% is more preferable, and 150 to 400% is more preferable.
  • the sum of the tensile elongation in the longitudinal and width directions of the film is to adjust the temperature of the cast drum, the stretching ratio and temperature and stretching speed in the longitudinal direction, the stretching speed and magnification in the width direction, and the temperature and time in the heat treatment process. In particular, it can be easily controlled by the redrawing temperature and the magnification in the longitudinal direction.
  • the sum of the tensile elongation in the longitudinal direction and the width direction of the film is, for example, higher in the temperature of the cast drum in the range of 105 to 130 ° C. or more in the range of 90 to 140 ° C. in the longitudinal direction.
  • the stretching ratio in the longitudinal direction is in the range of 3 to 7 times, and the moisture permeability value is lowered to such a degree as to satisfy the above-mentioned preferable numerical range, or the stretching speed in the longitudinal direction is set to 200.
  • the draw ratio in the width direction is in the range of 4 to 15 times, and the water pressure resistance value is lowered to a value that satisfies a suitable numerical range described later, or the draw speed in the width direction is set to 500 to 10, Accelerating within the range of 000% / min, increasing the heat treatment temperature in the heat treatment step before the relaxation treatment, and heat treatment temperature in the heat treatment step after the relaxation treatment within the range of 140 to 170 ° C, or relaxing treatment
  • the heat treatment time in the previous heat treatment step and the heat treatment time in the heat treatment step after the relaxation treatment are made longer in the range of 0.1 to 10 seconds, or the draw ratio of redrawing is 1.02 to 2.0.
  • the sum of the tensile elongation in the longitudinal direction and the width direction of the film can be increased.
  • the sum of the tensile elongation in the longitudinal direction and the width direction of the film can be increased.
  • the porous film of the present invention has a water pressure resistance of 4,500 mmH 2 O or more. If the water pressure resistance is less than 4,500mmH 2 O, when used as protective clothing, water may permeate when it is in strong rain and wind, with elbows, knees, or sitting down. If so, water may soak in and mold may form inside.
  • the upper limit of the water pressure resistance is preferably 25,000 mmH 2 O from the viewpoint of moisture permeability. From the viewpoint of workability and workability on site, the water pressure resistance is preferably 5,000 to 25,000 mmH 2 O, and more preferably 8,000 to 25,000 mmH 2 O.
  • the water pressure resistance is adjusted by adjusting the temperature of the cast drum, the stretching ratio and temperature and stretching speed in the longitudinal direction, the stretching speed and magnification in the width direction, the temperature and time in the heat treatment process, and the relaxation rate in the relaxation process. It can be controlled by stretching, adjusting the redrawing temperature and magnification, and adjusting the temperature of the heat treatment after redrawing.
  • the water pressure can be increased by increasing the temperature of the cast drum within the range of 105 to 130 ° C., or by increasing the stretching temperature in the longitudinal direction within the range of 90 to 140 ° C.
  • the stretching ratio is increased within the range of 3 to 7 times, the longitudinal stretching speed is increased within the range of 200,000 to 1,000,000% / min, or the stretching speed in the width direction is increased.
  • the heat treatment in the heat treatment step is set to a higher temperature within the range of 140 to 170 ° C., or the heat treatment time in the heat treatment step before the relaxation treatment or the heat treatment time in the heat treatment step after the relaxation treatment is 0.1 to 10 seconds.
  • Ri Within a longer range Ri, it is possible to increase the water pressure by a higher relaxation rate in the relaxation process in the range of 5 to 35%.
  • the stretching temperature at the time of re-stretching in the longitudinal direction and / or the width direction is set to a high temperature such that the film does not melt within the range of 130 to 170 ° C., or the stretching ratio of re-stretching is 1.02 to 2.0 times.
  • the water pressure resistance can be increased by stretching at a high magnification within the range, or by increasing the temperature of the heat treatment after re-stretching within a range of 145 to 175 ° C. so that the film does not melt.
  • the amount of ⁇ crystal nucleating agent added in the raw material is adjusted.
  • adjusting the addition amount of the ⁇ crystal nucleating agent in the raw material adjusting the temperature of the cast drum, adjusting the stretching ratio, temperature and stretching speed in the longitudinal direction.
  • the balance of characteristics is insufficient by adjusting only the process conditions such as adjusting the magnification in the width direction, adjusting the temperature and time in the heat treatment step, and adjusting the relaxation rate in the relaxation treatment step. .
  • the stretching speed in the width direction is within the range described below
  • re-stretching and the re-stretching temperature and magnification are within the range described below.
  • the content of the high MFR polypropylene is preferably 0.1 to 20% by mass.
  • the porous film of the present invention has an ash content (JIS L1013) after incineration at a temperature of 850 ° C. of 0.5% by mass or less. If the ash content after incineration at a temperature of 850 ° C. is more than 0.5% by mass, ash content is generated by incineration for disposable use. In the case of protective clothing, ash content may be further processed for safety and health. .
  • the lower limit of the ash content after incineration at a temperature of 850 ° C. is ideally 0%, but is substantially about 0.01%. In order to reduce the ash content after incineration at a temperature of 850 ° C. to 0.5% by mass or less, it can be achieved by making the raw material porous by a method in which inorganic particles are not added.
  • the porous film of the present invention preferably has a tensile elongation ratio in the (longitudinal direction / width direction) of 0.6 to 1.5.
  • the tensile elongation ratio in the (longitudinal direction / width direction) of the film means the ratio of the tensile elongation in the film longitudinal direction to the tensile elongation in the film width direction (that is, tensile elongation / longitudinal / (Tensile elongation in the width direction).
  • the ratio of the tensile elongation in the longitudinal direction to the tensile elongation in the width direction of the film is 0.6 to 1.5. It is preferable that When the ratio of the tensile elongation in the longitudinal direction to the tensile elongation in the width direction of the film is less than 0.6 or greater than 1.5, when the porous film is used as a base material for protective clothing, the porous film is anisotropic.
  • the ratio is more preferably 0.6 to 1.4, and even more preferably 0.7 to 1.3.
  • the basis weight of the porous film of the present invention is preferably 5 g / m 2 or more.
  • the basis weight is less than 5 g / m 2 , the elongation of the film, for example, the tensile elongation is low, and in the case of a protective garment based on the porous film of the present invention, the porous film breaks during work, The water pressure resistance is lowered, water leakage occurs, or the process passability in the process of bonding the porous film of the present invention to a nonwoven fabric may be inferior.
  • the upper limit of the basis weight is actually 40 g / m 2 .
  • Basis weight, from the viewpoint of tensile elongation and wear preferably 5 ⁇ 30g / m 2, more preferably 5 ⁇ 20g / m 2, more preferably 8 ⁇ 15g / m 2.
  • a moisture-permeable waterproof sheet using the above-mentioned porous film.
  • complex of fiber layers, such as this moisture-permeable waterproof sheet and a nonwoven fabric can also be comprised.
  • a preferable composite is a composite of the moisture permeable waterproof sheet and the nonwoven fabric.
  • the basis weight of the composite of the present invention is preferably 100 g / m 2 or less, more preferably 50 g / m 2 or less, and further preferably 45 g / m 2 or less.
  • the basis weight is larger than 50 g / m 2 , the clothing becomes heavy and the comfort of clothing may be reduced. In particular, when the basis weight is larger than 100 g / m 2 , the tendency becomes more remarkable.
  • the lower limit of the basis weight is preferably 25 g / m 2 or more from the viewpoint of the strength of the composite.
  • the porous film of the present invention preferably has a film thickness of 5 ⁇ m or more. If the thickness is less than 5 ⁇ m, the film may break during processing or use.
  • the film thickness is more preferably 10 ⁇ m or more, and even more preferably 10 to 50 ⁇ m.
  • the method for producing the porous film of the present invention will be described based on a specific example.
  • the manufacturing method of the porous film of this invention is not limited to this.
  • Extruders used in melt blending may be either single-screw extruders or twin-screw extruders, but they can be mixed at high shear, and the mixing ratio is easily controlled to be uniform, raw material uniformity, resin deterioration suppression, and production. It is preferable to carry out with a twin screw extruder from a viewpoint of property. Moreover, in order to control a dispersion state, you may melt-knead in multiple times with a twin-screw extruder.
  • polypropylene resin 96.5 parts by mass of homopolypropylene resin with MFR 4 g / 10 min, 3 parts by mass of high MFR polypropylene resin with MFR 1,000 g / 10 min, and N, N′-dicyclohexyl-2,6-naphthalene as ⁇ crystal nucleating agent
  • the raw material is supplied from the measuring hopper to the twin screw extruder so that 0.3 parts by mass of dicarboxamide and 0.2 parts by mass of the antioxidant are mixed at this ratio, and then melt-kneaded and discharged from the die in a strand shape. Then, it is cooled and solidified in a 25 ° C. water tank, and cut into chips to prepare a polypropylene raw material (propylene composition).
  • the melting temperature is preferably 280 to 310 ° C.
  • the film forming method of the porous film of the present invention will be described, but the following film forming method can also be applied when a raw material other than the above-mentioned polypropylene raw material is used.
  • the cast drum preferably has a surface temperature of 105 to 130 ° C. from the viewpoint of controlling the ⁇ crystal fraction of the cast film to be high.
  • the end portion is sprayed with spot air to be brought into close contact with the drum.
  • the obtained cast film is biaxially oriented to form pores in the film.
  • a biaxial orientation method the film is stretched in the longitudinal direction of the film and then stretched in the width direction, or the sequential biaxial stretching method in which the film is stretched in the width direction and then stretched in the longitudinal direction.
  • the simultaneous biaxial stretching method can be used, but it is preferable to adopt the sequential biaxial stretching method from the viewpoint of moisture permeability, elongation, and water pressure resistance, and in particular, stretching in the longitudinal direction and then stretching in the width direction. It is preferable.
  • the stretching temperature in the longitudinal direction is preferably 90 to 140 ° C. If the stretching temperature in the longitudinal direction is less than 90 ° C., the film may break, the elongation may decrease, or the water pressure resistance may decrease. If the stretching temperature in the longitudinal direction exceeds 140 ° C., moisture permeability may be reduced.
  • the stretching temperature in the longitudinal direction is more preferably 110 to 135 ° C, particularly preferably 125 to 130 ° C.
  • the stretching ratio in the longitudinal direction is preferably 3 to 7 times.
  • the draw ratio in the longitudinal direction is less than 3, the moisture permeability may be lowered.
  • the higher the stretching ratio in the longitudinal direction the better the moisture permeability.
  • stretching more than 7 times may cause the film to break, the elongation to decrease, or the water pressure resistance to decrease.
  • the draw ratio in the longitudinal direction is more preferably 4 to 7 times.
  • the stretching speed in the longitudinal direction at this time is preferably 200,000% / min or more, more preferably 250,000% / min or more, and further 300,000% / min or more. preferable.
  • the pore structure after biaxial stretching forms a network in the three-dimensional direction, making it easy to achieve both moisture permeability, water pressure resistance, and elongation.
  • the upper limit of the stretching speed is 1,000,000% / min from the viewpoint of film breakage (productivity) and moisture permeability during stretching in the longitudinal direction.
  • the stretching temperature in the width direction is preferably 130 to 155 ° C.
  • the film may break, the elongation may decrease, or the water pressure resistance may decrease.
  • the stretching temperature in the width direction exceeds 155 ° C.
  • moisture permeability may decrease.
  • the stretching temperature in the width direction is more preferably 140 to 155 ° C. from the viewpoint of achieving both moisture permeability, elongation, and water pressure resistance.
  • the draw ratio in the width direction is preferably 4 to 15 times. If the draw ratio in the width direction is less than 4, moisture permeability may be reduced.
  • the draw ratio in the width direction is preferably high, but if it exceeds 15 times, the film may be broken and productivity may be lowered or moisture permeability may be lowered.
  • the stretching ratio in the width direction is more preferably 4 to 12 times, still more preferably 6 to 12 times, and particularly preferably 8 to 11 times.
  • the stretching speed in the width direction at this time is generally 500 to 10,000% / min. From the viewpoint of achieving both moisture permeability, water pressure resistance and elongation, 1,500 to 7,000. % / Min is preferable, and 2,000 to 5,000% / min is more preferable.
  • rate of a longitudinal direction and the width direction is computable with the following formula
  • Stretching speed [% / min] stretching ratio [%] / (stretching section length [m] / speed passing through stretching section [m / min])
  • stretching area of a longitudinal direction can be calculated with the following formula
  • Speed passing through stretching section (Roll peripheral speed before stretching + Roll peripheral speed after stretching) / 2
  • the speed of passing through the stretching section in the width direction is the speed of the tenter type stretching machine when passing through the stretching section in the width direction.
  • the “longitudinal draw ratio ⁇ width draw ratio” (a value obtained by multiplying the draw ratio in the longitudinal direction by the draw ratio in the width direction) is preferably 20 to 90 times, more preferably 30 to 90 times. .
  • the pre-relaxation heat treatment refers to performing heat treatment with the width after stretching in the width direction.
  • Relaxation treatment refers to heat treatment while relaxing the film by narrowing the width of the tenter.
  • the heat treatment after relaxation treatment refers to performing heat treatment with the width after the relaxation treatment.
  • the heat treatment step before the relaxation treatment, the relaxation treatment step, and the heat treatment step after the relaxation treatment may be collectively referred to as “heat treatment step”.
  • the heat treatment temperature before relaxation is preferably 140 to 170 ° C. If the heat treatment temperature before relaxation is less than 140 ° C., the elongation may be lowered or the water pressure resistance may be lowered. If the heat treatment temperature before relaxation exceeds 170 ° C., the porous film surface melts and moisture permeability decreases, or the porous film shrinks in the width direction and breaks, which may reduce productivity. is there.
  • the heat treatment temperature before relaxation is more preferably 150 to 168 ° C. from the viewpoint of achieving both moisture permeability, elongation, and water pressure resistance.
  • the heat treatment time before relaxation is preferably 0.1 seconds or more and 10 seconds or less, more preferably 3 seconds or more and 8 seconds or less, from the viewpoint of achieving both elongation, water pressure resistance and productivity.
  • the relaxation rate is preferably 5 to 35%. If the relaxation rate is less than 5%, the elongation may decrease, the water pressure resistance may decrease, or the thermal contraction rate in the width direction in the width direction may increase. If the relaxation rate exceeds 35%, the moisture permeability may decrease or the physical property unevenness may increase. From the viewpoint of coexistence of moisture permeability, elongation, and water pressure resistance, it is more preferably 5 to 15%.
  • the relaxation rate can be calculated by [(width of porous film before relaxation ⁇ width of porous film after relaxation) / (width of porous film before relaxation)].
  • the relaxation temperature (heat treatment temperature) is preferably 155 to 170 ° C.
  • the relaxation temperature is lower than 155 ° C.
  • the contraction stress for relaxation is lowered, and the above-described high relaxation rate may not be achieved, the elongation may be decreased, and the water pressure resistance may be decreased.
  • the relaxation temperature exceeds 170 ° C., the polymer around the pores melts due to the high temperature, and the moisture permeability may decrease.
  • the relaxation temperature is more preferably 160 to 168 ° C. from the viewpoints of moisture permeability, elongation, and water pressure resistance.
  • the relaxation rate is preferably 100 to 1,000% / min.
  • the relaxation rate is less than 100% / min, it is necessary to slow down the film forming rate or lengthen the tenter length, which may be inferior in productivity.
  • the relaxation speed exceeds 1,000% / min, the speed at which the film contracts is slower than the speed at which the rail width of the tenter shrinks, the film flutters in the tenter and tears, the unevenness in the width direction increases, It may cause deterioration of sex.
  • the relaxation rate is more preferably 150 to 500% / min.
  • the heat treatment temperature after relaxation is preferably 155 to 170 ° C.
  • the heat treatment temperature after relaxation is less than 155 ° C., the contraction stress for relaxation becomes low, and the above-described high relaxation rate may not be achieved, the elongation may decrease, and the water pressure resistance may decrease.
  • the heat treatment temperature after relaxation exceeds 170 ° C., the polymer around the pores melts due to the high temperature, and the moisture permeability may decrease.
  • the heat treatment temperature after relaxation is more preferably 160 to 168 ° C. from the viewpoints of moisture permeability, elongation, and water pressure resistance.
  • the heat treatment time after relaxation is preferably 0.1 second or more and 10 seconds or less, more preferably 3 seconds or more and 8 seconds or less from the viewpoint of achieving both elongation, water pressure resistance and productivity.
  • the film after initial stretching (the film after being stretched once each in the longitudinal direction and the width direction) may be subsequently stretched (re-stretched) again.
  • Re-stretching may be performed either before or after the heat treatment step.
  • the heat treatment process before redrawing can be omitted.
  • a re-stretching method re-stretching in the longitudinal direction or re-stretching in the width direction can be used.
  • a method of re-stretching in the width direction after re-stretching in the longitudinal direction, a method of re-stretching in the longitudinal direction after re-stretching in the width direction, and the like can also be used.
  • a simultaneous biaxial stretching method in which the longitudinal direction and the width direction of the film are stretched almost simultaneously can also be used.
  • the film after initial stretching (the film after being stretched once each in the longitudinal direction and the width direction) is controlled to a temperature at which it can be re-stretched in the longitudinal direction.
  • a temperature control method a method using a temperature-controlled rotating roll, a method using a hot air oven, or the like can be adopted.
  • the re-stretching temperature in the longitudinal direction is preferably 130 ° C. or higher, and more preferably 140 ° C. or higher, from the viewpoint of film properties and uniformity.
  • the stretching stress increases, so the number of film breaks may increase.
  • the re-stretching temperature in the longitudinal direction is too high, the polymer around the pores may melt at a high temperature and the water vapor transmission rate may be lowered, so 170 ° C. is the upper limit.
  • the redrawing ratio in the longitudinal direction is preferably 1.02 to 2.0 times, more preferably 1.1 to 1.7 times, and still more preferably 1.1 to 1.4 times. If the redrawing ratio in the longitudinal direction is less than 1.02, the redrawing effect may not be exhibited.
  • the re-stretch ratio in the longitudinal direction exceeds 2.0 times, the normal temperature shrinkage in the longitudinal direction of the film increases, and when the porous film is wound as a roll, the tightening becomes stronger and the flatness is lowered. There is a case.
  • the film When re-stretching in the longitudinal direction, following re-stretching, the film may be introduced by holding the film end by a tenter-type stretching machine and re-stretching in the width direction, or in the width direction. Heat treatment may be performed by passing through a tenter type stretching machine without re-stretching.
  • the re-stretching temperature in the width direction is preferably from 130 to 170 ° C., more preferably from 140 to 170 ° C., and still more preferably from 150 to 165 ° C. from the viewpoint of film characteristics and uniformity. If the re-stretching temperature in the width direction is less than 140 ° C., the stretching stress increases, so the number of film breaks may increase. If the re-stretching temperature in the width direction is higher than 170 ° C., the polymer around the pores may melt and the moisture permeability may be lowered.
  • the redrawing ratio in the width direction is preferably 1.02 to 2.0 times, more preferably 1.05 to 1.5 times, and still more preferably 1.05 to 1.3 times.
  • the re-stretch ratio in the width direction is less than 1.0, it means contraction in the width direction and is not usually referred to as stretching.
  • the re-stretch ratio in the width direction exceeds 2.0 times, the normal temperature shrinkage amount in the width direction of the film becomes large, and when the porous film is wound as a roll, the tightening becomes strong and the flatness is increased. May decrease.
  • the heat treatment temperature is preferably 145 to 175 ° C.
  • the heat treatment temperature is lower than 145 ° C.
  • the elongation may decrease or the water pressure resistance may decrease.
  • the heat treatment temperature exceeds 175 ° C.
  • the porous film surface melts and moisture permeability decreases, and the porous film shrinks in the width direction and breaks, which may reduce productivity.
  • the heat treatment temperature is more preferably 155 to 170 ° C. from the viewpoint of achieving both moisture permeability, elongation, and water pressure resistance.
  • the heat treatment time is preferably from 0.1 seconds to 10 seconds.
  • a wound porous film can be obtained with a winder after re-stretching and roll heat treatment.
  • the porous film of the present invention is excellent in moisture permeability, elongation and water pressure resistance, it can be suitably used as a moisture permeable waterproof sheet, for protective clothing, packaging materials for warmers, diapers, sanitary products, adhesive bandages, oil It can also be suitably used for adsorption sheets, civil engineering and building materials, and medical applications. Moreover, the porous film of this invention and a moisture-permeable waterproof sheet using the same are excellent in the process passage property in a process. In addition, since the composite of the moisture permeable waterproof sheet and the nonwoven fabric of the present invention is excellent in low basis weight and moisture permeability, it can be suitably used as a base material for protective clothing and protective clothing.
  • the base material and the protective clothing of the protective clothing of the present invention are not heavy when worn, and are excellent in the comfort of clothing to reduce the stuffiness in the clothing, and excellent in water pressure resistance. Therefore, the base material and protective clothing of the protective clothing of the present invention can be suitably used not only for chemical protective clothing but also for medical use.
  • ⁇ -crystal forming ability 5 mg of a porous film was sampled in an aluminum pan and measured using a differential scanning calorimeter (Seiko Denshi Kogyo RDC220).
  • the temperature is raised from room temperature to 260 ° C. at 10 ° C./min (first run) in a nitrogen atmosphere, held for 10 minutes, and then cooled to 40 ° C. at 10 ° C./min.
  • the melting peak observed when the temperature is raised again (second run) at 10 ° C / min after holding for 5 minutes is the melting peak of 145 ° C to 157 ° C.
  • the melting of the ⁇ crystal is the melting peak of the ⁇ crystal
  • the melting peak of the ⁇ crystal is taken as the melting peak of the base
  • ⁇ crystal forming ability (%) [ ⁇ H ⁇ / ( ⁇ H ⁇ + ⁇ H ⁇ )] ⁇ 100
  • the ⁇ crystal fraction in the state of the sample can be calculated by calculating the abundance ratio of the ⁇ crystal in the same manner from the melting peak observed in the first run.
  • the measurement was performed by stacking two test pieces. However, even when two test pieces are stacked and measured, it is not necessary to divide the measured value by 2, and the obtained measured value is used as it is.
  • Ash content after incineration (JIS L 1013) Based on JIS L 1013: 2010 8.25, the ash content after incineration of the porous film or composite at 850 ° C. was measured.
  • MFR Melt flow rate
  • Weight per unit A porous film or composite was cut into a square of 100 mm in the longitudinal direction and 100 mm in the width direction to obtain a sample. Using an analytical electronic balance (HR-202i manufactured by A & D Co., Ltd.), the mass was measured in an atmosphere at a room temperature of 23 ° C. and a relative humidity of 65%. The measurement was performed three times, the average value was defined as the mass W of the film or composite, and the basis weight was calculated using the following equation.
  • HR-202i manufactured by A & D Co., Ltd.
  • the subject In the constant temperature and humidity chamber set to 35 ° C and 50% Rh assuming the outdoor temperature in summer, the subject wore a dress made from one shirt and one work pants. The subject attached a thermo-hygrometer near the center of the chest from the top of the shirt and measured the humidity in the clothes after entering the room. This was performed on three subjects. The case where the average humidity of three people after 30 minutes was 60% Rh or less was evaluated as Good, and the case where the average humidity difference was higher than 60% Rh was evaluated as Bad.
  • the obtained polypropylene composition (I) is supplied to a uniaxial melt extruder, melt extruded at 220 ° C., foreign matter is removed with a 60 ⁇ m cut sintered filter, and the surface temperature is adjusted to 116 ° C. with a T-die.
  • a cast film was obtained by discharging onto a controlled cast drum. Next, preheating was performed using a ceramic roll heated to 122 ° C., and the film was stretched 5 times in the longitudinal direction of the film at a stretching temperature of 122 ° C. and a stretching speed of 380,000% / min. Next, the end portion was introduced into a tenter type stretching machine with a clip, preheated at 150 ° C. for 3 seconds, then stretched 9.0 times at 150 ° C., and stretched in the width direction at a stretching rate of 3,300% / min.
  • heat treatment was performed at 150 ° C. for 3 seconds while maintaining the distance between the clips after stretching (distance between the clips in the film width direction), and further relaxation treatment was performed at 164 ° C. with a relaxation rate of 10%.
  • Heat treatment was performed at 164 ° C. for 5 seconds while keeping the distance.
  • preheating is performed using a ceramic roll heated to 155 ° C., the film is re-stretched 1.2 times in the longitudinal direction of the film at a re-stretching temperature of 155 ° C., and then the ceramic roll heated to 150 ° C. is used.
  • Heat treatment was performed for 5 seconds, and the porous film was wound around the core with a winder to a thickness of 500 m to obtain a porous film having a thickness of 20 ⁇ m.
  • Example 2 In the stretching process of Example 1, preheating was performed using a ceramic roll heated to 125 ° C., and the film was stretched 5 times in the longitudinal direction of the film at a stretching temperature of 125 ° C. and a stretching speed of 390,000% / min. Next, it was introduced into a tenter type stretching machine by gripping the end with a clip, preheated at 150 ° C. for 3 seconds, then stretched 9.0 times at 150 ° C., and stretched at a stretching speed of 4,000% / min. A porous film having a thickness of 20 ⁇ m was obtained under the same conditions as in 1.
  • a porous film having a thickness of 20 ⁇ m was obtained from the obtained polypropylene composition (II) under the same conditions as in Example 1.
  • Example 4 The porous film obtained in Example 1 was introduced into a tenter type stretching machine by gripping the end with a clip, preheated at 160 ° C. for 3 seconds, stretched 1.2 times in the width direction at 160 ° C., and porous with a winder The porous film was wound around the core by 500 m to obtain a porous film having a thickness of 19 ⁇ m.
  • Example 5 The porous film obtained in Example 1 was introduced into a tenter-type stretching machine by gripping the end with a clip, preheated at 160 ° C. for 3 seconds, stretched 1.2 times in the width direction at 160 ° C., and then While maintaining the distance between the clips after stretching, heat treatment was performed at 165 ° C. for 3 seconds, and the porous film was wound around the core with a winder by 500 m to obtain a porous film having a thickness of 18 ⁇ m.
  • Example 6 A cast film was obtained using the resin raw material (polypropylene composition (I) described in Example 1 under the casting conditions described in Example 1. The film was then preheated using a ceramic roll heated to 130 ° C. In the longitudinal direction, the film was stretched 4.5 times at a stretching temperature of 130 ° C. at a stretching speed of 360,000% / min. After preheating at 3 ° C. for 3 seconds, the film was stretched 5.0 times at 150 ° C. at a stretching speed of 3,600% / min.
  • heat treatment was performed at 150 ° C. for 3 seconds while maintaining the distance between the clips after stretching, and further relaxation treatment was performed at 164 ° C. with a relaxation rate of 15%, and the distance between the clips after relaxation was maintained at 164 ° C. Heat treatment was performed for 5 seconds. Subsequently, preheating is performed using a ceramic roll heated to 155 ° C., and the film is re-stretched 1.1 times in the longitudinal direction of the film at a re-stretching temperature of 155 ° C., and then the ceramic roll heated to 150 ° C. is used.
  • Heat treated for 5 seconds introduced into a tenter-type stretching machine by gripping the end with a clip, preheated at 160 ° C for 3 seconds, stretched 1.1 times at 160 ° C, and then the distance between the clips after stretching While being maintained at 165 ° C., heat treatment was performed at 165 ° C. for 3 seconds to obtain a porous film having a thickness of 20 ⁇ m.
  • Comparative Example 1 40 parts by mass of high-density polyethylene powder (“Hi-Zex” 340M, manufactured by Mitsui Chemicals, Inc.), 30 parts by mass of polyethylene wax (“High Wax” 110P, manufactured by Mitsui Chemicals, Inc.), and calcium carbonate (trade name: A composition in which 30 parts by weight of “Star Piggot” 15A, manufactured by Shiraishi Calcium Co., Ltd., average particle size of 0.15 ⁇ m) was supplied to a twin-screw extruder, melted and mixed at 200 ° C., and then passed through the T die die. The film was extruded into a sheet shape, closely contacted on a cast drum having a surface temperature of 30 ° C., and 20 ° C.
  • Example 2 It was produced according to the conditions described in Example 1 of JP-A-2006-28495.
  • a resin composition of the polypropylene film a polypropylene having a melting temperature of 165 ° C. (manufactured by Sumitomo Chemical Co., Ltd., WF836 DG-3, MFR: 7 g / 10 min) and 50 wt% of a polypropylene containing a ⁇ crystal nucleating agent manufactured by SUNOCO Bepol ”(type: B022-SP) 50% by weight is added and mixed, fed to a twin screw extruder, melted and mixed at 300 ° C., extruded into a gut shape, cooled through a 10 ° C.
  • the ⁇ crystal nucleating agent-added polypropylene is supplied to an extruder heated to 300 ° C., melted, extruded into a sheet through a T die die, and placed on a cast drum heated to a surface temperature of 125 ° C.
  • the cast film was produced by intimately adhering and blowing hot air at 120 ° C. from the non-drum surface side.
  • the porous film was wound around the core by 500 m with a winder to obtain a porous film having a thickness of 20 ⁇ m.
  • the raw material is fed to the twin screw extruder, melt kneaded at 302 ° C., discharged from the die into strands, cooled and solidified in a 25 ° C. water bath, cut into chips, and the polypropylene composition (III) is obtained. Obtained.
  • the obtained polypropylene composition (III) is supplied to a uniaxial melt extruder, melt extruded at 220 ° C., foreign matter is removed with a 60 ⁇ m cut sintered filter, and the surface temperature is adjusted to 116 ° C. with a T-die.
  • a cast film was obtained by discharging onto a controlled cast drum. Next, preheating was performed using a ceramic roll heated to 122 ° C., and the film was stretched 5 times in the longitudinal direction of the film at a stretching speed of 150,000% / min. Next, the end portion was introduced into a tenter type stretching machine by holding it with a clip, preheated at 155 ° C. for 3 seconds, stretched 9.0 times at 150 ° C., and stretched at a stretching rate of 3,300% / min.
  • heat treatment was performed at 150 ° C. for 3 seconds while maintaining the distance between the clips after stretching, and further relaxation treatment was performed at 164 ° C. with a relaxation rate of 15%, and the distance between the clips after relaxation was maintained at 164 ° C. Heat treatment was performed for 5 seconds.
  • porous film was wound around the core by a winder for 500 m to obtain a porous film having a thickness of 20 ⁇ m.
  • the polypropylene composition (I) was supplied to a single screw melt extruder, melt extruded at 220 ° C., foreign matter was removed with a 60 ⁇ m cut sintered filter, and the surface temperature was controlled to 116 ° C. with a T-die.
  • the film was discharged onto a drum to obtain a cast film.
  • preheating was performed using a ceramic roll heated to 135 ° C., and the film was stretched 4 times in the longitudinal direction of the film at a stretching speed of 450,000% / min.
  • the end portion was introduced into a tenter type stretching machine by holding it with a clip, preheated at 155 ° C. for 3 seconds, stretched 9.0 times at 155 ° C., and stretched at a stretching rate of 3,300% / min.
  • heat treatment was performed at 150 ° C. for 3 seconds while maintaining the distance between the clips after stretching, and further relaxation treatment was performed at 164 ° C. with a relaxation rate of 20%, and the distance between the clips after relaxation was maintained at 164 ° C. Heat treatment was performed for 5 seconds.
  • porous film was wound around the core by a winder for 500 m to obtain a porous film having a thickness of 20 ⁇ m.
  • the polypropylene composition (I) was supplied to a single screw melt extruder, melt extruded at 220 ° C., foreign matter was removed with a 60 ⁇ m cut sintered filter, and the surface temperature was controlled to 116 ° C. with a T-die.
  • the film was discharged onto a drum to obtain a cast film.
  • preheating was performed using a ceramic roll heated to 125 ° C., and the film was stretched 5 times in the longitudinal direction of the film under conditions of a stretching temperature of 125 ° C. and a stretching speed of 400,000% / min.
  • the end portion was introduced into a tenter-type stretching machine by holding it with a clip, preheated at 155 ° C. for 3 seconds, stretched 9.0 times at 155 ° C., and stretched at a stretching speed of 8,500% / min.
  • heat treatment was performed at 150 ° C. for 3 seconds while maintaining the distance between the clips after stretching, and further relaxation treatment was performed at 164 ° C. with a relaxation rate of 10%, and the distance between the clips after relaxation was maintained at 164 ° C. Heat treatment was performed for 5 seconds.
  • porous film was wound around the core by a winder for 500 m to obtain a porous film having a thickness of 20 ⁇ m.
  • porous films of Examples satisfying the requirements of the present invention were excellent in moisture permeability, water pressure resistance, and elongation.
  • the porous films of the examples were able to be suitably used as moisture permeable waterproof sheets and protective clothing with reduced ash content after incineration by reducing the stuffiness in the clothes when worn.
  • the porous film of the comparative example had insufficient moisture permeability, elongation, water pressure resistance, and ash content after incineration. Therefore, it was insufficient as a moisture-permeable waterproof sheet and protective clothing.
  • Spunbond 1 / porous film of Example 1 / spunbond 1 in a three-layer structure was performed at a temperature of 2 ° C. and a roll pressure of 2 MPa to obtain a composite having a bonding area of 10%.
  • the network pattern hot press roll has a mesh pattern height of 3 mm that does not touch the porous film and the spunbond of which the roll surface other than the bonded part forms a composite so as to exhibit moisture permeability even after the bonding process. A roll was used.
  • Reference Example 201 A composite having an adhesion area of 10% was obtained in the same manner as in Reference Example 101 except that the porous film obtained in Comparative Example 1 was used as the porous film.
  • the composite of Reference Example 101 using the porous film of Example 1 that satisfies the requirements of the present invention was excellent in moisture permeability and water pressure resistance. Further, Reference Example 101 was not heavy and had little ash after incineration. On the other hand, the composite of Reference Example 201 using the porous film of Comparative Example 1 was insufficient in moisture permeability and water pressure resistance. In addition, Reference Example 201 was heavy and a large amount of ash remained after incineration.

Abstract

L'objet de l'invention est de pourvoir à un film poreux qui convient à titre de matériau de base pour un vêtement de protection ayant une excellente résistance à la pression d'eau et un certain confort de port par réduction de l'échauffement interne du vêtement porté, ainsi qu'à une feuille à l'épreuve de l'eau perméable à l'humidité et à un vêtement de protection utilisant ledit film poreux. Cet objet est atteint par un film poreux caractérisé par une perméabilité à l'humidité de 250 g/m2∙h ou plus, une somme des degrés d'allongement en traction dans le sens de la longueur et dans le sens de la largeur du film de 100 à 500 %, une résistance à la pression d'eau de 4500 mm H2O ou plus, et une teneur en cendres après incinération à une température de 850°C (JIS L 1013) de 0,5 % en poids ou moins.
PCT/JP2015/051619 2014-01-28 2015-01-22 Film poreux, feuille à l'épreuve de l'eau perméable à l'humidité, complexe, et vêtement de protection WO2015115289A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015523732A JPWO2015115289A1 (ja) 2014-01-28 2015-01-22 多孔性フィルム、透湿防水シート、複合体および防護服

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014013050 2014-01-28
JP2014-013050 2014-01-28

Publications (1)

Publication Number Publication Date
WO2015115289A1 true WO2015115289A1 (fr) 2015-08-06

Family

ID=53756865

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/051619 WO2015115289A1 (fr) 2014-01-28 2015-01-22 Film poreux, feuille à l'épreuve de l'eau perméable à l'humidité, complexe, et vêtement de protection

Country Status (2)

Country Link
JP (1) JPWO2015115289A1 (fr)
WO (1) WO2015115289A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016102202A (ja) * 2014-11-12 2016-06-02 東レ株式会社 多孔性フィルム、透湿防水シート、複合体および防護服
JP2018144490A (ja) * 2017-03-02 2018-09-20 三菱ケミカル株式会社 積層フィルム、画像表示装置用積層体及び画像表示装置
JP2019506318A (ja) * 2015-12-21 2019-03-07 スリーエム イノベイティブ プロパティズ カンパニー 延伸した熱可塑性層を有する積層体を製造する方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH093225A (ja) * 1995-06-19 1997-01-07 Kao Corp 多孔性シート及びそれを用いた吸収性物品
JPH093226A (ja) * 1995-06-19 1997-01-07 Kao Corp 多孔性シート及びそれを用いた吸収性物品
JPH093224A (ja) * 1995-06-19 1997-01-07 Kao Corp 多孔性シート及びそれを用いた吸収性物品
JP2000169608A (ja) * 1998-12-04 2000-06-20 New Japan Chem Co Ltd 吸収性物品
JP2006028495A (ja) * 2004-06-18 2006-02-02 Toray Ind Inc 微多孔ポリプロピレンフィルムおよびそれを用いてなる透湿防水布。

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH093225A (ja) * 1995-06-19 1997-01-07 Kao Corp 多孔性シート及びそれを用いた吸収性物品
JPH093226A (ja) * 1995-06-19 1997-01-07 Kao Corp 多孔性シート及びそれを用いた吸収性物品
JPH093224A (ja) * 1995-06-19 1997-01-07 Kao Corp 多孔性シート及びそれを用いた吸収性物品
JP2000169608A (ja) * 1998-12-04 2000-06-20 New Japan Chem Co Ltd 吸収性物品
JP2006028495A (ja) * 2004-06-18 2006-02-02 Toray Ind Inc 微多孔ポリプロピレンフィルムおよびそれを用いてなる透湿防水布。

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016102202A (ja) * 2014-11-12 2016-06-02 東レ株式会社 多孔性フィルム、透湿防水シート、複合体および防護服
JP2019506318A (ja) * 2015-12-21 2019-03-07 スリーエム イノベイティブ プロパティズ カンパニー 延伸した熱可塑性層を有する積層体を製造する方法
US11020949B2 (en) 2015-12-21 2021-06-01 3M Innovative Properties Company Method of making a laminate with a stretched thermoplastic layer
JP2018144490A (ja) * 2017-03-02 2018-09-20 三菱ケミカル株式会社 積層フィルム、画像表示装置用積層体及び画像表示装置
JP7283033B2 (ja) 2017-03-02 2023-05-30 三菱ケミカル株式会社 積層フィルム、画像表示装置用積層体及び画像表示装置

Also Published As

Publication number Publication date
JPWO2015115289A1 (ja) 2017-03-23

Similar Documents

Publication Publication Date Title
RU2674199C1 (ru) Пористая пленка, водонепроницаемый и влагопроницаемый материал, а также использующие их медицинская одежда и защитная одежда
JP6497082B2 (ja) 多孔性積層体
KR101249180B1 (ko) 다공성 폴리프로필렌 필름
KR101305264B1 (ko) 폴리올레핀 다층 미세 다공막의 제조 방법
JP5087906B2 (ja) 微多孔ポリプロピレンフィルムおよびその製造方法
JP2016508535A (ja) 超高分子量ポリエチレン由来の多孔質物品の製造方法
JP2002522610A (ja) 耐破壊性ポリオレフィン膜
JP6641953B2 (ja) 透湿性積層体
JPWO2017175878A1 (ja) 延伸多孔性フィルム及びその製造方法
US10790492B2 (en) Microporous polyolefin membrane, separator for battery, and production processes therefor
WO2015115289A1 (fr) Film poreux, feuille à l'épreuve de l'eau perméable à l'humidité, complexe, et vêtement de protection
KR20220034247A (ko) 공중합체 멤브레인, 섬유, 제품 및 방법
JP6337422B2 (ja) 複合フィルム
WO2014103713A1 (fr) Film de polyéthylène poreux et son procédé de production, et séparateur pour dispositif de stockage l'utilisant
JP2016089009A (ja) 透湿性フィルムおよび透湿性フィルム積層体
JP2003217554A (ja) 電池セパレーター用ポリオレフィン微多孔膜
JP5705605B2 (ja) ポリプロピレン系樹脂多孔シート及びポリプロピレン系樹脂多孔シートの製造方法
TWI730999B (zh) 積層聚烯烴微多孔膜、電池用隔膜及其製造方法以及積層聚烯烴微多孔膜捲繞體之製造方法
JP2016102203A (ja) 多孔性フィルム、および透湿防水シート
JP2016102201A (ja) 多孔性フィルム
JP2016102202A (ja) 多孔性フィルム、透湿防水シート、複合体および防護服
JP2015163464A (ja) 透湿防水シート
JP2006037095A (ja) 油吸収性微多孔質ポリプロピレンシート
KR20140048147A (ko) 다공성 폴리프로필렌 필름 및 그의 제조 방법
JP2022532673A (ja) 多層構造

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2015523732

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15743641

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15743641

Country of ref document: EP

Kind code of ref document: A1