WO2021172345A1 - Rouleau de film poreux étiré - Google Patents

Rouleau de film poreux étiré Download PDF

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Publication number
WO2021172345A1
WO2021172345A1 PCT/JP2021/006830 JP2021006830W WO2021172345A1 WO 2021172345 A1 WO2021172345 A1 WO 2021172345A1 JP 2021006830 W JP2021006830 W JP 2021006830W WO 2021172345 A1 WO2021172345 A1 WO 2021172345A1
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WO
WIPO (PCT)
Prior art keywords
porous film
stretched porous
basis weight
film roll
mass
Prior art date
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PCT/JP2021/006830
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English (en)
Japanese (ja)
Inventor
隆敏 牟田
祐里 桑名
滋充 間野
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三菱ケミカル株式会社
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Priority to JP2022503643A priority Critical patent/JPWO2021172345A1/ja
Publication of WO2021172345A1 publication Critical patent/WO2021172345A1/fr

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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
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene

Definitions

  • the present invention relates to a stretched porous film roll that is suitably used for manufacturing sanitary materials, clothes, and other members and materials that are required to have breathability and moisture permeability (hereinafter, may be referred to as "use members"). More specifically, the present invention relates to a stretched porous film roll that solves problems caused by widening and lengthening of a stretched porous film for improving productivity when applied to these applications.
  • thermoplastic resin such as a polyolefin resin and an inorganic filler
  • voids microporous
  • a stretched porous film made of a resin composition containing a polyolefin-based resin and an inorganic filler has high air permeability and moisture permeability because the microporous film inside forms communication holes, but is liquid. It is used as a moisture-permeable waterproof film that suppresses the permeation of plastic.
  • the stretched porous film is, for example, breathable in sanitary materials such as disposable diapers and sanitary products for women, clothing such as work clothes, jumpers, jackets, medical clothing, and chemical protective clothing, masks, covers, drapes, sheets, and wraps. It is widely used in applications that require moisture permeability and waterproofness.
  • the stretched porous film is often used as a composite member with other materials.
  • sanitary materials such as disposable diapers and sanitary napkins for women are manufactured by feeding out a non-woven fabric and a stretched porous film from a non-woven fabric roll and a stretched porous film roll, and continuously bonding the two with a hot melt type adhesive or the like. After that, a liquid absorbing layer, rubber, or the like is laminated on the same production line, and then continuously cut to efficiently produce the product.
  • a liquid absorbing layer, rubber, or the like is laminated on the same production line, and then continuously cut to efficiently produce the product.
  • the length of the stretched porous film wound around the stretched porous film roll is short, it is necessary to frequently replace the roll and splice the film with the previously unwound film, resulting in high productivity. Significantly inhibited.
  • Basis weight is the mass of the film per unit area. Since the stretched porous film has voids inside, the uniformity of the porous structure can be confirmed by confirming the fluctuation of the basis weight of the film.
  • the ventilation characteristics and moisture permeability characteristics may fluctuate depending on the position in the width direction, which may impair the product quality. Further, in the manufacturing of application members such as printing, secondary processing such as slits, and bonding with other members, it may cause meandering, misalignment, and synchronization deviation during transportation. Therefore, it is important to suppress fluctuations in basis weight in the width direction of the stretched porous film roll in order to achieve widening and lengthening of the roll.
  • Patent Documents 1 and 2 an attempt to solve curvature and slack
  • Patent Document 3 an attempt to improve the flatness of a film
  • Patent Document 4 An attempt to suppress wrinkles
  • Patent Document 6 an attempt to improve the uniformity of various physical properties such as air permeability and porosity
  • Patent Document 7 an attempt to improve dimensional stability.
  • Japanese Unexamined Patent Publication No. 2016-0271139 JP 2011-140633 Japanese Unexamined Patent Publication No. 2014-177524 Japanese Unexamined Patent Publication No. 2013-216868 Japanese Unexamined Patent Publication No. 2013-067783 Japanese Unexamined Patent Publication No. 2010-24260 Japanese Unexamined Patent Publication No. 2010-100845
  • Patent Documents 1 to 7 discloses the technical idea regarding the suppression of defects and the fluctuation of the basis weight, which are important issues in widening and lengthening the film roll.
  • An object of the present invention is to have excellent breathability, moisture permeability, strength, and heat resistance, and to suppress thermal deterioration during molding, defects caused by the heat deterioration, and fluctuation of the basis weight in the width direction of the stretched porous film roll.
  • An object of the present invention is to provide a stretched porous film roll which is effective for widening and lengthening a film.
  • the present inventor has succeeded in obtaining a stretched porous film roll capable of solving the above-mentioned problems of the prior art, and has completed the present invention.
  • the gist of the present invention is the following [1] to [19].
  • Stretched porous film made of a resin composition (Z) containing 25% by mass to 54% by mass of a thermoplastic resin and 46% by mass to 75% by mass of an inorganic filler (A) is wound around a core.
  • a stretched porous film roll which is a film roll and has an oxidation induction time of 50 minutes or more of the stretched porous film measured at a measurement temperature of 200 ° C. using a differential scanning calorimeter (DSC).
  • the mass (g) of the film at each of the 5 to 50 cut-out parts is measured with an electronic balance, and the value obtained by multiplying the value by 20 is taken as the basis weight (g / m 2 ) of each part.
  • the coefficient of variation of the basis weight in the width direction is calculated by dividing the basis weight of each part obtained by this basis weight measurement by the standard deviation calculated for the entire population by the average basis weight.
  • thermoplastic resin is a polyolefin resin
  • a stretched porous film composed of a resin composition (Z) containing an inorganic filler (A), a plant-derived polyolefin resin (B), a petroleum-derived polyethylene-based resin (C), and a petroleum-derived polypropylene-based resin (D).
  • a stretched porous film roll having an oxidation induction time of 50 minutes or more of the stretched porous film measured at a measurement temperature of 200 ° C. using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the mass (g) of the film at each of the 5 to 50 cut-out parts is measured with an electronic balance, and the value obtained by multiplying the value by 20 is taken as the basis weight (g / m 2 ) of each part.
  • the coefficient of variation of the basis weight in the width direction is calculated by dividing the basis weight of each part obtained by this basis weight measurement by the standard deviation calculated for the entire population by the average basis weight.
  • a stretched porous film composed of a resin composition (Z) containing 25% by mass to 54% by mass of a thermoplastic resin and 46% by mass to 75% by mass of an inorganic filler (A) is wound around a core.
  • the stretched porous film is divided into 5 to 50 at equal intervals with a width of 20 to 60 mm with respect to the width direction of the stretched porous film roll (the end of the roll is cut off when a fraction is generated), and the stretched porous film is subjected to the longitudinal direction (MD). Cut into a rectangle of 2,500 mm, lateral direction (TD): 20 mm.
  • the mass (g) of the film at each of the 5 to 50 cut-out parts is measured with an electronic balance, and the value obtained by multiplying the value by 20 is taken as the basis weight (g / m 2 ) of each part.
  • the coefficient of variation of the basis weight in the width direction is calculated by dividing the basis weight of each part obtained by this basis weight measurement by the standard deviation calculated for the entire population by the average basis weight.
  • a stretched porous film roll composed of a resin composition (Z) containing an inorganic filler (A) and a plant-derived polyolefin resin (B) is wound around a core, and is a differential scanning calorimeter.
  • a stretched porous film roll in which a stretched porous film composed of a resin composition (Z) containing an inorganic filler (A) and a thermoplastic resin is wound around a core, and is measured in the following basis weight and in the width direction.
  • the stretched porous film is divided into 5 to 50 at equal intervals with a width of 20 to 60 mm with respect to the width direction of the stretched porous film roll (the end of the roll is cut off when a fraction is generated), and the stretched porous film is subjected to the longitudinal direction (MD). Cut into a rectangle of 2,500 mm, lateral direction (TD): 20 mm.
  • the mass (g) of the film at each of the 5 to 50 cut-out parts is measured with an electronic balance, and the value obtained by multiplying the value by 20 is taken as the basis weight (g / m 2 ) of each part.
  • the coefficient of variation of the basis weight in the width direction is calculated by dividing the basis weight of each part obtained by this basis weight measurement by the standard deviation calculated for the entire population by the average basis weight.
  • thermoplastic resin contains a plant-derived polyolefin resin (B).
  • the present invention has excellent breathability, moisture permeability, strength, and heat resistance, and also causes thermal deterioration during molding and defects caused by the defects and defects in secondary processing such as printing of a stretched porous film roll. It is possible to provide a stretched porous film roll that suppresses the film and is effective in increasing the width and length of the film.
  • the stretched porous film roll of the present invention can be suitably used for improving the productivity of application members that are required to have breathability and moisture permeability.
  • the stretched porous film roll of the present invention (hereinafter, may be referred to as “the film roll of the present invention”) as an example of the embodiment of the present invention will be described.
  • the scope of the present invention is not limited to the embodiments described below.
  • the stretched porous film is a porous film stretched at least in the uniaxial direction.
  • the stretched porous film roll of the present invention refers to a stretched porous film wound around a core.
  • it refers to a stretched porous film having a length of 500 m or more and 20,000 m or less and a width of 100 mm or more and 2,500 mm or less wound around a core.
  • the length of the stretched porous film is 500 m or more, particularly 1,000 m or more, it is possible to improve the productivity in various applications by increasing the length.
  • the length of the stretched porous film is 20,000 m or less
  • the weight and diameter of the film roll can be suppressed, and the film roll can be easily transported and installed in the manufacturing apparatus of the application member.
  • the width of the stretched porous film is 100 mm or more, particularly 140 mm or more, it is possible to improve productivity in various applications by increasing the width and prevent unwinding of the film roll.
  • the width of the stretched porous film is 2,500 mm or less, the weight and width of the film roll can be suppressed, and the film roll can be easily transported and installed in the manufacturing apparatus of the application member.
  • the "main component” means a component that occupies the largest mass ratio in the constituent composition, and the content thereof is preferably 45% by mass or more, more preferably 50% by mass or more, 55. More preferably by mass% or more.
  • X to Y (X, Y are arbitrary numbers) is described, it means “X or more and Y or less”, and “preferably larger than X” and “preferably smaller than Y”. It is meant to be included.
  • Resin composition (Z) The stretched porous film constituting the film roll of the present invention (hereinafter, may be referred to as “stretched porous film of the present invention”) contains 25% by mass of a thermoplastic resin in 100% by mass of the resin composition (Z). It is composed of a resin composition (Z) containing ⁇ 54% by mass and an inorganic filler (A) in an amount of 46% by mass to 75% by mass (hereinafter, may be referred to as “resin composition (Z) of the present invention”). is important.
  • the resin composition (Z) of the present invention when the inorganic filler (A) exceeds 75% by mass, it becomes difficult to melt-form the stretched porous film.
  • the inorganic filler (A) when the inorganic filler (A) is less than 46% by mass, the air permeability and moisture permeability of the stretched porous film become insufficient.
  • the stretched porous film of the present invention made of the resin composition (Z) of the present invention has an oxidation induction time of 50 minutes or more measured at a measurement temperature of 200 ° C. using a differential scanning calorimeter (DSC). is important.
  • the oxidation induction time of the stretched porous film measured at the measurement temperature of 200 ° C. is 50 minutes or more, the number of defects contained in one stretched porous film roll having a length and width can be reduced, and the stretched porous film can be reduced. It is possible to reduce the deviation of the roll product specifications and improve the production yield.
  • Reducing the number of defects is also effective in increasing the length and width of the stretched porous film roll.
  • These defects are mainly caused by defects called fisheyes that occur during extrusion molding and burnt lumps that occur due to heat. According to the study by the present inventor, it was found that there is a correlation between the frequency of occurrence of these defects and the oxidation induction time of the stretched porous film. In order to reduce the number of defects, it is important in the present invention that the oxidation induction time of the stretched porous film measured at the measurement temperature of 200 ° C. is 50 minutes or more.
  • the oxidation induction time is measured as follows using a differential scanning calorimeter (DSC). Approximately 5 mg of the stretched porous film is rapidly heated to 200 ° C. at a heating rate of 20 ° C./min in nitrogen gas, stabilized at a measurement atmosphere of 200 ° C., and then the measurement atmosphere is switched to the atmosphere to maintain the state. At this time, the time from when the measurement atmosphere is switched to the atmosphere until the oxidative exothermic peak rises is calculated as the oxidative induction time.
  • DSC differential scanning calorimeter
  • the oxidation induction time of the stretched porous film of the present invention measured at a measurement temperature of 200 ° C. may be 50 minutes or more, preferably 60 minutes or more, more preferably 70 minutes or more, still more preferably 90 minutes or more. be.
  • Inorganic filler (A) examples of the inorganic filler (A) contained in the resin composition (Z) of the present invention include fine particles such as calcium carbonate, calcium sulfate, barium carbonate, barium sulfate, titanium oxide, talc, clay, kaolinite, and montmorillonite. Examples include fine particles of minerals. Of these, calcium carbonate and barium sulfate are preferably used because of their advantages such as the development of microporousness, high versatility, low price, and abundance of brands.
  • the average particle size of the inorganic filler (A) is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 5 ⁇ m, and even more preferably 0.5 to 3 ⁇ m.
  • the average particle size is 0.1 ⁇ m or more, poor dispersion and secondary aggregation of the inorganic filler (A) are suppressed, and the inorganic filler (Z) can be uniformly dispersed in the resin composition (Z), which is preferable.
  • the average particle size is 10 ⁇ m or less, it is possible to suppress the generation of large voids when the film is thinned, and it is possible to secure sufficient strength and water resistance of the film.
  • the inorganic filler is coated with a surface treatment agent such as fatty acid or fatty acid ester in advance to make the surface compatible with the resin in order to improve the dispersibility and miscibility with the resin.
  • a surface treatment agent such as fatty acid or fatty acid ester
  • Such a surface treatment may also be applied to the inorganic filler (A) used in the present invention.
  • the inorganic filler (A) only one of the above-mentioned inorganic fillers may be used, or two or more kinds having different materials, average particle diameters, presence / absence of surface treatment, etc. may be mixed and used.
  • the inorganic filler (A) is composed of two or more types, the mass ratio in the resin composition (Z) is calculated with the total as the mass of the inorganic filler (A).
  • thermoplastic resin examples include polyolefin-based resin, polystyrene-based resin, acrylic-based resin, polyvinyl chloride-based resin, polyvinylidene chloride-based resin, and chlorinated polyethylene-based resin.
  • Polyester resin polycarbonate resin, polyamide resin, ethylene / vinyl alcohol copolymer, ethylene / vinyl acetate copolymer, polymethylpentene resin, polyvinyl alcohol resin, cyclic olefin resin, polylactic acid resin , Polybutylene succinate resin, polyacrylonitrile resin, polyethylene oxide resin, cellulose resin, polyimide resin, polyurethane resin, polyphenylene sulfide resin, polyphenylene ether resin, polyvinyl acetal resin, polybutadiene resin, polybutene Based resin, polyamideimide resin, polyamide bismaleimide resin, polyarylate resin, polyetherimide resin, polyether ether ketone resin, polyether ketone resin, polyether sulfone resin, polyketone resin, polysulfone type Examples thereof include resins, aramid resins, fluororesins, and polyacetal resins.
  • polyolefin resins ethylene / vinyl alcohol resins, polymethylpentene resins, polylactic acid resins, polyketone resins, fluorine resins, polyacetal resins and the like are preferable from the viewpoint of heat resistance.
  • Polyolefin-based resins are particularly preferable from the viewpoints of flexibility, heat resistance, formation of communication holes, environmental hygiene, odor, and the like.
  • thermoplastic resins may be of one type or two or more types.
  • the total is the mass of the thermoplastic resin, and the mass ratio of the thermoplastic resin in the resin composition (Z) is calculated.
  • a polyolefin-based resin is a resin containing an olefin monomer as a main monomer component.
  • the main monomer component refers to a monomer component that occupies 50% by mass or more and 100% by mass or less in the resin.
  • the olefin monomer include ⁇ -olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene, diene, isoprene, butylene and butadiene, and these alone. It may be a polymer, or it may be a multidimensional copolymer obtained by copolymerizing two or more kinds.
  • vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, glycidyl (meth) acrylate, vinyl alcohol, ethylene glycol, maleic anhydride, styrene, and cyclic olefin may be copolymerized.
  • ethylene homopolymer branched low-density polyethylene, propylene homopolymer, ethylene / ⁇ -olefin copolymer, propylene / ⁇ -olefin copolymer (other than propylene) , Ethylene / vinyl acetate copolymer, styrene / ethylene / propylene copolymer, styrene / ethylene / butylene copolymer are preferable.
  • thermoplastic resin when the thermoplastic resin is a polyolefin-based resin, it may be one type or two or more types as long as it is a resin containing an olefin monomer as a main monomer component.
  • the polyolefin-based resin is composed of two or more types, the total is the mass of the polyolefin-based resin.
  • the resin composition (Z) of the present invention preferably contains a plant-derived polyolefin resin (B).
  • a plant-derived polyolefin resin (B) By including the plant-derived polyolefin resin (B) in the resin composition (Z), the oxidation induction time of the stretched porous film made of the resin composition (Z) can be improved. The reason for this has not been clarified at this time, but it is considered that the plant-derived polyolefin resin (B) is less likely to be oxidized than the petroleum-derived polyolefin resin.
  • the resin composition (Z) of the present invention contains the plant-derived polyolefin resin (B)
  • the melt tension of the resin composition (Z) increases, and the tension is easily applied uniformly in the film width direction. Therefore, it is preferable that the variation of the basis weight in the width direction of the stretched porous film roll can be reduced and the coefficient of variation of the basis weight in the width direction of the stretched porous film can be reduced.
  • the resin composition (Z) of the present invention preferably contains a petroleum-derived polyethylene-based resin (C) together with a plant-derived polyolefin-based resin (B).
  • a petroleum-derived polyethylene-based resin (C) together with a plant-derived polyolefin-based resin (B) in the resin composition (Z), physical properties suitable for a moisture-permeable waterproof film can be obtained.
  • the resin composition (Z) of the present invention preferably contains a petroleum-derived polypropylene-based resin (D) together with a plant-derived polyolefin-based resin (B). Since the resin composition (Z) contains the petroleum-derived polypropylene-based resin (D) together with the plant-derived polyolefin-based resin (B), the stretched porous film is unwound from the film roll of the present invention to provide a non-woven fabric or the like. In the process of bonding with the member, the heat resistance to the heat laminate and the hot melt type adhesive can be improved.
  • the plant-derived polyolefin resin (B) is a resin containing a plant-derived olefin monomer as a main monomer component.
  • the main monomer component refers to a monomer component that occupies 50% by mass or more and 100% by mass or less in the resin.
  • Examples of the plant-derived olefin monomer include ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene obtained from alcohols produced by fermentation of plant-derived biomass such as sugar cane and corn. , 1-octene and the like, and examples thereof include diene, isoprene, butylene and butadiene.
  • the plant-derived polyolefin resin (B) may be a homopolymer of these or a multipolymer in which two or more kinds are copolymerized.
  • the plant-derived polyolefin resin (B) may be copolymerized with the same petroleum-derived monomer component as long as it is a resin containing a plant-derived olefin monomer as a main monomer component.
  • it may be a polyethylene-based resin having both a plant-derived ethylene component and a petroleum-derived ethylene component, and the plant-derived ethylene component accounts for 50% by mass or more in the resin.
  • the plant-derived polyolefin resin (B) contains vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, glycidyl (meth) acrylate, vinyl alcohol, ethylene glycol, and maleic anhydride in addition to these plant-derived olefin monomers.
  • Acrylic acid, styrene, and cyclic olefin may be copolymerized.
  • ethylene copolymers containing plant-derived ethylene as a main monomer component branched low-density polyethylene, and ethylene / ⁇ -olefins. Copolymers are preferred.
  • the ratio of the plant-derived olefin monomer to the plant-derived polyolefin resin (B) the degree of biomass plastic specified by ISO16620 or ASTM D6866 is used. Specifically, it can be calculated by measuring the concentration of radioactive carbon (14 C) in the plant-derived polyolefin resin (B).
  • the plant-derived polyolefin resin (B) may be of one type or two or more types as long as it is a resin containing a plant-derived olefin monomer as a main monomer component.
  • the plant-derived polyolefin resin (B) is composed of two or more types, the total is the mass of the plant-derived polyolefin resin (B).
  • At least one type of the plant-derived polyolefin resin (B) is branched low-density polyethylene containing a plant-derived ethylene monomer as a main monomer component.
  • the melt tension of the resin composition (Z) increases and the molding processability is improved. It is preferable because it improves.
  • the melting tension of the resin composition (Z) increases, tension is uniformly applied in the film width direction in the stretching step of the molten resin that occurs while the molten film discharged from the mouthpiece is cooled and solidified, and the film is not stretched.
  • the thickness distribution in the width direction of the film is made uniform, and the stretching stress is uniformly applied in the width direction of the film even in the stretching step of the unstretched film, so that the appearance and the porous structure of the stretched porous film tend to be made uniform.
  • the coefficient of variation of the basis weight in the width direction of the stretched porous film roll can be reduced, which is preferable.
  • the density of the plant-derived polyolefin resin (B) is preferably 0.850 g / cm 3 or more and 0.940 g / cm 3 or less.
  • the stretched porous film has breathability, moisture permeability, dimensional stability, liquid leakage resistance, and concealment. It is preferable because it is possible to satisfy the properties, appearance and the like, and the thermal stability at the time of extrusion molding can be improved.
  • the density is the density measured by the pycnometer method (JIS K7112: 1999 B method). Further, the density of the resin, which will be described later, is also a value when measured in the same manner.
  • the plant-derived polyolefin resin (B) preferably has a melting point of 100 ° C. to 170 ° C., more preferably 105 ° C. to 165 ° C.
  • the melting point of the plant-derived polyolefin resin (B) is 100 ° C. to 170 ° C., it tends to be possible to impart dimensional stability and heat resistance to the stretched porous film, which is preferable. Further, it is not necessary to raise the melting temperature excessively at the time of molding the stretched porous film, which is preferable from the viewpoint of suppressing thermal deterioration and improving moldability.
  • the melting point use a differential scanning calorimeter (DSC) to raise the temperature of about 10 mg of resin from -40 ° C to 200 ° C at a heating rate of 10 ° C / min, hold it at 200 ° C for 1 minute, and then cool it at a cooling rate of 10 ° C / min. It is the crystal melting peak temperature (Tm) (° C.) obtained from the thermogram measured when the temperature was lowered to ⁇ 40 ° C. and again raised to 200 ° C. at a heating rate of 10 ° C./min.
  • Tm crystal melting peak temperature
  • the melting point of the resin which will be described later, is also a value when measured in the same manner.
  • the plant-derived polyolefin resin (B) preferably has a melt flow rate (MFR) of 0.1 to 20 g / 10 minutes, more preferably 0.5 to 10 g / 10 minutes. It is preferable that the MFR is 0.1 g / 10 minutes or more because the moldability of the stretched porous film can be sufficiently maintained. It is preferable that the MFR is 20 g / 10 minutes or less because the strength of the stretched porous film can be sufficiently maintained.
  • MFR melt flow rate
  • MFR is a value measured in accordance with JIS K7210-1: 2014.
  • the measurement conditions are 190 ° C. and a load of 2.16 kg.
  • the plant-derived polyolefin resin (B) is a resin containing a plant-derived propylene monomer as a main monomer component
  • the measurement conditions are 230 ° C. and a load of 2.16 kg.
  • the petroleum-derived polyethylene-based resin (C) is a resin containing petroleum-derived ethylene as a main monomer component.
  • the main monomer component refers to a monomer component that occupies 50% by mass or more and 100% by mass or less in the resin.
  • the petroleum-derived polyethylene-based resin (C) may be a petroleum-derived ethylene homopolymer, or may be a copolymer containing petroleum-derived ethylene as a main monomer component and containing other monomers.
  • copolymers examples include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1.
  • -Ethylene / ⁇ -olefin copolymer such as octene copolymer, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, ethylene / (Meta) glycidyl acrylate, ethylene / vinyl alcohol copolymer, ethylene / ethylene glycol copolymer, ethylene / maleic anhydride copolymer, ethylene / styrene copolymer, ethylene / diene copolymer, ethylene / cyclic olefin Examples include copolymers.
  • the petroleum-derived polyethylene-based resin (C) may be a multi-dimensional copolymer containing two or more kinds of monomer components other than ethylene, such as an ethylene / propylene / 1-butene copolymer.
  • the petroleum-derived polyethylene-based resin (C) may be an ethylene homopolymer containing petroleum-derived ethylene as a main monomer component and containing plant-derived ethylene.
  • the petroleum-derived polyethylene resin (C) is preferably an ethylene homopolymer or an ethylene / ⁇ -olefin copolymer.
  • the petroleum-derived polyethylene-based resin (C) may be of one type or two or more types as long as it is a resin containing petroleum-derived ethylene as a main monomer component.
  • the petroleum-derived polyethylene-based resin (C) is composed of two or more types, the total is the mass of the petroleum-derived polyethylene-based resin (C).
  • the density of the petroleum-derived polyethylene-based resin (C) is preferably 0.850 g / cm 3 or more and 0.970 g / cm 3 or less.
  • the stretched porous film has breathability, moisture permeability, dimensional stability, liquid leakage resistance, and concealment. It is possible to make the sex and appearance more satisfying.
  • the density of the petroleum-derived polyethylene resin (C), more preferably at most 0.880 g / cm 3 or more 0.970g / cm 3, 0.910g / cm 3 or more 0.965 g / cm 3 that less is Is particularly preferable.
  • the petroleum-derived polyethylene resin (C) may be linear or branched.
  • the method for producing the petroleum-derived polyethylene-based resin (C) is not particularly limited, and a known polymerization method using a known catalyst for olefin polymerization, for example, a multisite catalyst typified by a Ziegler-Natta type catalyst, or metallocene. Examples thereof include a polymerization method using a single-site catalyst typified by a system catalyst.
  • the petroleum-derived polyethylene resin (C) preferably has a melting point of 110 ° C. to 135 ° C., more preferably 110 ° C. to 130 ° C.
  • the melting point of the petroleum-derived polyethylene resin (C) is 110 ° C. to 135 ° C.
  • the dimensional stability of the stretched porous film can be improved, which is preferable.
  • the melting point can be measured using the DSC described above.
  • the petroleum-derived polyethylene-based resin (C) preferably has a melt flow rate (MFR) of 0.1 g / 10 minutes to 20 g / 10 minutes, and preferably 0.5 g / 10 minutes to 10 g / 10 minutes. More preferred. It is preferable that the MFR is 0.1 g / 10 minutes or more because the moldability of the stretched porous film can be sufficiently maintained. It is preferable that the MFR is 20 g / 10 minutes or less because the strength of the stretched porous film can be sufficiently maintained.
  • MFR melt flow rate
  • MFR is a value measured in accordance with JIS K7210-1: 2014, and the measurement conditions are 190 ° C. and 2.16 kg load.
  • the petroleum-derived polypropylene-based resin (D) is a resin containing petroleum-derived propylene as a main monomer component.
  • the main monomer component refers to a monomer component that occupies 50% by mass or more and 100% by mass or less in the resin.
  • the petroleum-derived polypropylene-based resin (D) may be a petroleum-derived propylene homopolymer, or may be a copolymer containing petroleum-derived propylene as a main monomer component and containing other monomers. It may be a propylene homopolymer containing petroleum-derived propylene as a main monomer component and containing plant-derived propylene.
  • the density of the petroleum-derived polypropylene-based resin (D) is not particularly limited, but is preferably 0.880 g / cm 3 or more and 0.920 g / cm 3 or less.
  • the melting point of the petroleum-derived polypropylene resin (D) is preferably 140 ° C to 170 ° C.
  • the melting point of the petroleum-derived polypropylene-based resin (D) is 140 ° C. or higher, the heat resistance to a heat laminate or a hot melt type adhesive can be improved, which is preferable.
  • the melting point is 170 ° C. or lower, it is not necessary to raise the melting temperature excessively at the time of molding the stretched porous film, which is preferable from the viewpoint of suppressing thermal deterioration and improving moldability.
  • the melting point can be measured using the DSC described above.
  • the MFR of the petroleum-derived polypropylene resin (D) is preferably 10 g / 10 minutes to 50 g / 10 minutes.
  • the MFR of the petroleum-derived polypropylene-based resin (D) is 10 g / 10 minutes or more, the petroleum-derived polypropylene-based resin (D) is uniformly dispersed in the resin composition (Z), and in the film roll of the present invention, the petroleum-derived polypropylene-based resin (D) is uniformly dispersed. It is preferable because it becomes easy to uniformly impart heat resistance at any of the width direction and the length direction of the film.
  • the MFR of the petroleum-derived polypropylene-based resin (D) is 50 g / 10 minutes or less, it becomes easy to suppress thermal deterioration in the molding of the stretched porous film.
  • the MFR of the petroleum-derived polypropylene resin (D) is a value measured in accordance with JIS K7210-1: 2014, and the measurement conditions are 230 ° C. and a 2.16 kg load.
  • the resin composition (Z) of the present invention contains an inorganic filler (A), a plant-derived polyolefin resin (B), a petroleum-derived polyethylene resin (C), and a petroleum-derived resin. It is preferable that the polypropylene resin (D) is contained.
  • inorganic filler (A) "plant-derived polyolefin resin (B)”, “petroleum-derived polyethylene-based resin (C)”, and “petroleum-derived polypropylene-based resin (D)" are simply referred to as “(A)”. , "(B)", “(C)”, “(D)” may be described.)
  • the resin composition (Z) of the present invention contains an inorganic filler (A), a plant-derived polyolefin resin (B), a petroleum-derived polyethylene-based resin (C), and a petroleum-derived polypropylene-based resin (D)
  • the mixed composition ratio of the inorganic filler (A) In the mixed composition ratio of the inorganic filler (A), the plant-derived polyolefin resin (B), the petroleum-derived polyethylene-based resin (C), and the petroleum-derived polypropylene-based resin (D), the mixed composition ratio of the inorganic filler (A).
  • the melt-forming of the stretched porous film becomes easy, the continuous stretched porous film tends to be easily collected, and the film roll tends to be easily obtained.
  • the mixed composition ratio of the inorganic filler (A) is at least the lower limit of the above-mentioned preferable range, the air permeability and moisture permeability of the stretched porous film tend to be sufficient.
  • the mixed composition ratio of the plant-derived polyolefin resin (B) is within the above-mentioned preferable range, thermal deterioration during film molding is suppressed, and a stretched porous film roll with few defects can be collected. Further, the melt tension of the resin composition (Z) is increased, and the tension can be uniformly applied in the width direction of the film. The coefficient of variation of the quantity can be reduced.
  • the mixed composition ratio of the petroleum-derived polyethylene-based resin (C) is equal to or higher than the lower limit in the above-mentioned preferable range, the raw material cost is suppressed, the film-forming property and physical properties of the stretched porous film are good, and the film quality according to the application member is good. It tends to be easier to adjust.
  • the mixed composition ratio of the petroleum-derived polyethylene-based resin (C) is equal to or less than the upper limit in the above-mentioned preferable range, thermal deterioration is unlikely to occur during film formation of the stretched porous film, and defects in the obtained film roll tend to be suppressed. preferable.
  • it is preferable that the variation of the basis weight in the width direction of the stretched porous film roll is easily suppressed and the coefficient of variation of the basis weight in the width direction tends to be small.
  • the mixed composition ratio of the petroleum-derived polypropylene-based resin (D) is equal to or higher than the lower limit in the above-mentioned preferable range, the heat resistance when the stretched porous film roll is bonded to other members is likely to be sufficient.
  • the mixed composition ratio of the petroleum-derived polypropylene-based resin (D) is not more than the upper limit in the above-mentioned preferable range, the obtained film is less likely to be hardened, and the usability as a moisture-permeable waterproof film requiring flexibility is less likely to be impaired. ..
  • the resin composition (Z) of the present invention preferably further contains the plasticizer (E) in an amount of 0.1% by mass to 8.0% by mass. If the plasticizer (E) is contained in an amount of 0.1% by mass or more, the resin composition (Z) can be imparted with flexibility. When the content of the plasticizer (E) is 8.0% by mass or less, the bleed-out of the plasticizer (E) can be suppressed, blocking when the stretched porous film is wound into a roll, and printing. It becomes easier to suppress printing defects at the time.
  • plasticizer (E) examples include an ester-based plasticizer having the following polar structure.
  • Monovalent carboxylic acid ester-based plasticizers Monovalent carboxylic acids such as butanoic acid, isobutanoic acid, hexane acid, 2-ethylhexanoic acid, heptanoic acid, octyl acid, 2-ethylhexanoic acid, lauric acid, and ethylene Compounds obtained by condensation reaction with polyhydric alcohols such as glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and glycerin Specific compounds include triethylene glycol di2-ethylhexanoate and triethylene.
  • Glycoldiisobutanoate triethylene glycol-hexanoate, triethylene glycol di2-ethylbutanoate, triethylene glycol dilaurate, ethylene glycol di2-ethylhexanoate, diethylene glycol di2-ethylhexanoate, tetraethylene glycol di 2-Ethylene Hexanoate, Tetraethylene Glycol Diheptanoate, PEG # 400 Di2-Ethyl Hexanoate, Triethylene Glycol Mono 2-Ethyl Hexanoate, Glycerin Tri 2-Ethyl Hexanoate, Pentaerythritol Tetrasle Examples thereof include Alate, Dipentaerythritol Hexaoctanoate, Diglycerin Tetrastearate, and Diglycerin Distearate.
  • Polyvalent carboxylic acid ester-based plasticizers Adipic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and other polyvalent carboxylic acids, and methanol, ethanol, butanol, hexanol, 2 -Compounds obtained by condensation reaction with monovalent alcohols having 1 to 12 carbon atoms such as ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, butoxyethanol, butoxyethoxyethanol, and benzyl alcohol.
  • Hydroxycarboxylic acid ester-based plasticizers monovalent alcohol esters of hydroxycarboxylic acids; methyl ricinolate, ethyl ricinolate, butyl ricinolate, methyl 6-hydroxyhexanoate, ethyl 6-hydroxyhexanoate, butyl 6-hydroxyhexanoate, Polyhydric alcohol ester of hydroxycarboxylic acid; ethylene glycol di (6-hydroxyhexanoic acid) ester, diethylene glycol di (6-hydroxyhexanoic acid) ester, triethylene glycol di (6-hydroxyhexanoic acid) ester, 3-methyl-1 , 5-Pentanediol di (6-hydroxyhexanoic acid) ester, 3-Methyl-1,5-Pentanedioldi (2-hydroxybutyric acid) ester, 3-Methyl-1,5-Pentanedioldi (3-hydroxybutyric acid) ) Ester, 3-methyl-1,5-pentan
  • Castor oil Normal castor oil, refined castor oil, hardened castor oil and dehydrated castor oil.
  • Examples of the cured castor oil include cured castor oil containing triglyceride composed of 12-hydroxyoctadecanoic acid and glycerin as a main component.
  • the resin composition (Z) of the present invention contains other resin raw materials, recycled resins generated from trimming loss of ears, etc., compatibilizers, processing aids, and melt viscosity. Improvement agents, antioxidants, antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, UV absorbers, neutralizers, nucleating agents, cross-linking agents, lubricants, anti-blocking agents, slip agents, anti-fog agents. It may contain agents, antibacterial agents, deodorants, flame retardants, antistatic agents, colorants, pigments and the like.
  • the amount of the antioxidant contained in the resin composition (Z) is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and 0.1% by mass or less. Is even more preferable.
  • the resin composition (Z) is a plant. It is preferable to contain the derived polyolefin resin (B).
  • the antioxidant used in the present invention known antioxidants can be used.
  • the average basis weight of the stretched porous film roll of the present invention is preferably 10 g / m 2 to 50 g / m 2 , and more preferably 12 g / m 2 to 40 g / m 2 .
  • the average basis weight is 10 g / m 2 or more, it is easy to sufficiently secure mechanical strength such as tensile strength and tear strength.
  • the average basis weight is 50 g / m 2 or less, it is easy to obtain a sufficient feeling of light weight.
  • the average basis weight is obtained as follows.
  • the stretched porous film is subjected to the longitudinal direction (MD) at a portion where the width is 20 to 60 mm and is divided into 5 to 50 at equal intervals (the end of the roll is cut off if a fraction is generated) with respect to the width direction of the stretched porous film roll. Cut into a rectangle of 2,500 mm, lateral direction (TD): 20 mm, measure the mass (g) of the film at each of the 5 to 50 cut out parts with an electronic balance, and multiply the value by 20 for each value.
  • the basis weight of each part is defined as (g / m 2 ), and the total basis weight of each part is divided by the number of parts in the width direction cut out to obtain the average basis weight.
  • the basis weight of the stretched porous film roll can be measured at an arbitrary winding length position of the film roll, and each part is cut out at an arbitrary winding length position of the film roll at equal intervals in the width direction.
  • the basis weight may be measured.
  • the basis weight of the stretched porous film roll determines the cutout position of each member to be measured within the range of 0 (m) to 10 (m) when the winding end position of the film roll is 0 (m).
  • Each member may be cut out and measured. More specifically, the cut-out position of each part to be measured is determined as the position of 1 (m) of the film roll, and the width is set at the winding length position of 1 (m) to 3.5 (m) of the film roll.
  • Each part (rectangle of vertical direction (MD): 2,500 mm, horizontal direction (TD): 20 mm) may be cut out and measured at equal intervals in the direction.
  • the coefficient of variation of the basis weight in the width direction of the stretched porous film roll can be calculated by dividing the standard deviation calculated for the entire population by dividing the basis weight of each part obtained by the above-mentioned basis weight measurement by the average basis weight. can.
  • the coefficient of variation of the basis weight in the width direction of the stretched porous film roll of the present invention is preferably 0.050 or less, more preferably 0.048 or less, still more preferably 0.046 or less.
  • the coefficient of variation of the basis weight in the width direction of the stretched porous film roll is 0.050 or less, the difference in winding diameter of the stretched porous film roll in the width direction becomes small, and the stretched porous film roll is miswound or unwound. Wrinkles are less likely to occur. Since these effects become more remarkable when the winding length of the stretched porous film roll is long, the coefficient of variation of the basis weight in the width direction of the stretched porous film roll of the present invention is preferably 0.050 or less.
  • the coefficient of variation of the basis weight in the width direction of the stretched porous film roll is calculated from the measurement of the basis weight at the position of an arbitrary winding length of the film roll described above. For example, even if the coefficient of variation of the basis weight in the width direction of the position of a part of the film roll is not in the preferable range, the coefficient of variation of the basis weight in the width direction of any other winding length position is preferable. It may be in the range. That is, even if the coefficient of variation of the basis weight in the width direction of the winding length position of a part of the stretched porous film roll does not fall within the above preferable range, the coefficient of variation of the basis weight in the width direction of the other winding length position remains. Within the above-mentioned preferable range, the difference in winding diameter of the stretched porous film roll in the width direction becomes small, and the effect that winding deviation of the stretched porous film roll and wrinkles at the time of feeding are less likely to occur is achieved.
  • the difference between the maximum value and the minimum value of the basis weight in the width direction of the stretched porous film roll obtained by the above-mentioned basis weight measurement is preferably 3.0 g / m 2 or less, and is preferably 2.8 g. / more preferably m is 2 or less, and more preferably 2.6 g / m 2 or less.
  • the difference between the maximum value and the minimum value of the basis weight in the width direction of the stretched porous film roll is 3.0 g / m 2 or less, the difference in the winding diameter of the roll in the width direction of the stretched porous film roll becomes small, and the stretched porous film roll is stretched. Miswinding of the perforated film roll and wrinkles during feeding are less likely to occur.
  • the difference between the maximum value and the minimum value of the basis weight in the width direction in the stretched porous film roll of the present invention is 3.0 g. It is preferably / m 2 or less.
  • the average air permeability of the stretched porous film roll of the present invention is preferably 1 second / 100 mL to 5000 seconds / 100 mL, more preferably 10 seconds / 100 mL to 4000 seconds / 100 mL, and 100 seconds / 100 mL to 3000. More preferably, it is s / 100 mL.
  • the average air permeability is 1 second / 100 mL or more, it is easy to sufficiently secure water resistance and liquid permeability resistance.
  • An average air permeability of 5000 seconds / 100 mL or less suggests that it has sufficient communication holes.
  • the air permeability is the number of seconds that 100 mL of air, which is measured according to the method specified in JISP8117: 2009 (Garley test machine method), passes through the film. It can be measured using an air permeability measuring machine EGO1-55 type).
  • the stretched porous film roll of the present invention is divided into 10 in the width direction, the air permeability of the film sample is measured at each width direction position, and the arithmetic mean value of the 10-point measurement value is average transparency. Take the temper.
  • the winding length position of the stretched porous film roll in the air permeability measurement can be measured at any winding length position.
  • the moisture permeability stretched porous film roll of the present invention is 1000g / (m 2 ⁇ 24hrs) ⁇ 15000g / (m 2 ⁇ 24hrs), more preferably 1500g / (m 2 ⁇ 24hrs) ⁇ 12000g / (m a 2 ⁇ 24hrs).
  • Moisture permeability is 15000g / (m 2 ⁇ 24hrs) or less, suggesting that it has a sufficient water resistance.
  • Moisture permeability is 1000g / (m 2 ⁇ 24hrs) above suggest that the pores has sufficient communicability.
  • Moisture vapor transmission rate indicates water vapor transmission rate (WVTR).
  • WVTR water vapor transmission rate
  • JIS Z0208: 1976; 20.0 g of distilled water was placed in a measuring cup (inner diameter 60 mm, inner diameter area 28.27 ⁇ 10 -4 m 2 ) of the moisture permeability test method (cup method) of the moisture-proof packaging material. After that, it was covered with a stretched porous film obtained by feeding it from a stretched porous film roll, sealed with wax, and exposed to a constant temperature and humidity environment at a temperature of 40 ° C. and a relative humidity of 60% for 24 hours to reduce the amount of distilled water reduction ⁇ w (unit: g).
  • the sample is randomly measured at two points, and the arithmetic mean value is taken as the moisture permeability.
  • the tensile breaking strength in the stretching direction of the stretched porous film roll of the present invention is preferably 7N / 25mm or more, more preferably 9N / 25mm or more.
  • the upper limit of the tensile breaking strength is not particularly limited, but is preferably 35 N / 25 mm or less in consideration of stretchability.
  • the stretched porous film roll of the present invention is a uniaxially stretched film roll
  • the tensile breaking strength in the non-stretching direction is preferably 1 N / 25 mm or more, more preferably 1.5 N / 25 mm or more.
  • the tensile breaking strength in the non-stretching direction is 1 N / 25 mm or more, it is possible to prevent tearing from occurring when used in an application member.
  • the tensile breaking strength in the stretching direction is in accordance with JIS K7127: 1999, and a sample cut out in a stretching direction of 100 mm ⁇ a stretching direction of 25 mm is prepared using a stretched porous film obtained by feeding out from a stretched porous film roll.
  • This is the tensile breaking strength when broken using a triple tensile tester under the conditions of a tensile speed of 200 m / min and a chuck distance of 50 mm in an environment of 23 ° C. and a relative humidity of 50%.
  • the arithmetic mean value of the tensile breaking strength calculated by performing three measurements is taken as the tensile breaking strength.
  • the tensile breaking strength in the non-stretching direction is the tensile breaking strength calculated by the same method except that the sample is cut out in the non-stretching direction 100 mm ⁇ the stretching direction 25 mm.
  • the tensile elongation at break in the stretching direction of the stretched porous film roll of the present invention is preferably 40% to 400%, more preferably 80% to 300%.
  • a sanitary product such as a moisture-permeable waterproof back sheet such as a sanitary treatment product
  • the film When the tensile elongation at break is 400% or less, the film has appropriate rigidity and tensile strength and has excellent mechanical properties, and the elongation and strain of the film during printing, slitting, and winding are small, and excellent mechanical suitability in a production line can be obtained. Be done.
  • the stretched porous film roll of the present invention is a uniaxially stretched film roll
  • the tensile elongation at break in the non-stretching direction is preferably 100% or more, more preferably 150% or more, still more preferably 200% or more.
  • the tensile elongation at break in the non-stretching direction is 100% or more, it is possible to prevent tearing from occurring when used in an application member.
  • the stretched porous film roll of the present invention is a uniaxially stretched film roll
  • a sample cut out in a stretching direction of 100 mm ⁇ a direction perpendicular to the stretching direction of 25 mm was prepared using a stretched porous film obtained by feeding out from a stretched porous film roll in accordance with JIS K7127: 1999.
  • the arithmetic mean value of the tensile elongation at break calculated by measuring three times is defined as the elongation at break.
  • the tensile elongation at break in the non-stretching direction is the tensile elongation at break calculated by the same method except that the sample is cut out in the non-stretching direction 100 mm ⁇ the stretching direction 25 mm.
  • the total light transmittance of the stretched porous film roll of the present invention is preferably 18% to 60%. Since the total light transmittance is 18% or more, when the stretched porous film roll of the present invention is used for hygiene products such as a moisture-permeable waterproof back sheet such as a disposable diaper, even if an indicator drug for urinating is applied. It will be easier to recognize. When the total light transmittance is 60% or less, the film is white and can be imparted with concealment.
  • the total light transmittance was measured at 5 points at random from the stretched porous film obtained by feeding out from the stretched porous film roll using a haze meter conforming to JIS K7361-1: 1997, and the arithmetic mean value was obtained. ..
  • the heat-resistant temperature for breaking the film in the stretched porous film roll of the present invention is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, and even more preferably 160 ° C. or higher.
  • the stretched porous film roll of the present invention is sufficiently applied to the stretched porous film without breaking due to heat from a hot melt adhesive or the like when adhering and laminating the stretched porous film roll with other members. It can be judged that the heat resistance is imparted.
  • the rupture heat resistant temperature is obtained as follows. A film sample (100 mm x 100 mm) obtained by feeding out from a stretched porous film roll is sandwiched between two stainless steel plates (100 mm x 100 mm x 2 mm (thickness)) whose center is punched into a circle of ⁇ 50 mm, and the four sides are clipped. After fixing and heating the inside of the tank in a convection oven at a heat resistant temperature, for example, 160 ° C. for 2 minutes, the sample of the circular punched part of the stainless steel plate melts and is not perforated. Visually judge. Those having no tears or holes are evaluated as having a heat resistance of the film rupture heat resistance temperature, for example, 160 ° C. or higher.
  • the number of defects in the stretched porous film roll of the present invention is preferably 0.020 pieces / m 2 or less, more preferably 0.018 pieces / m 2 or less, and even more preferably 0.015 pieces / m 2 or less.
  • the number of defects is determined by detecting the number of defects per film roll by feeding out a stretched porous film roll and holding the stretched porous film in a support roll and passing it through a defect detector, and using the detected value as the value of the stretched porous film. It is obtained by counting the number of defects per area calculated from the width and length. The film that has passed through the defect detector is wound up on another core.
  • the method for producing a stretched porous film roll of the present invention is not particularly limited, and can be produced by a conventionally known method. It is important that the stretched porous film roll of the present invention is stretched at least in the uniaxial direction.
  • “Film” has the meaning of including thick sheets to thin films.
  • the film may be flat or tubular, but the flat shape is preferable from the viewpoint of productivity (several pieces can be taken as a product in the width direction of the raw sheet) and printing on the inner surface is possible. ..
  • the resin composition (Z) of the present invention is melted using an extruder, extruded into a film from a die, and cooled and solidified by a cooling roll, air cooling, or water cooling.
  • An example is a method of obtaining a film roll by stretching the film (unstretched film) to be obtained in at least one axial direction and then winding it around a core.
  • the resin composition (Z) of the present invention As a method for obtaining the unstretched film, it is preferable to mix the resin composition (Z) of the present invention and then melt-knead it. Specifically, after mixing for an appropriate time with a mixer such as a tumbler mixer, a mixing roll, a Banbury mixer, a ribbon blender, or a super mixer, an extruder such as a different-direction twin-screw extruder or a same-direction twin-screw extruder is used. Use to promote uniform dispersion distribution of the composition.
  • the obtained resin composition (Z) can be formed into a film by connecting a base such as a T die or a round die to the tip of an extruder.
  • the pellet of the obtained resin composition (Z) is simply pelleted. It can also be introduced into a shaft extruder or the like, and a base such as a T die or a round die can be connected to the tip of the extruder to form a film.
  • a film forming method such as inflation molding, tubular molding, or T-die molding is preferable.
  • the extrusion temperature is preferably about 180 to 260 ° C, more preferably 190 to 250 ° C. Controlling the dispersed state of the material by optimizing the extrusion temperature and the state of shearing is also effective in adjusting the various physical and mechanical properties of the above-mentioned film to desired values.
  • the stretched porous film roll of the present invention can be produced by stretching the unstretched film.
  • the resin is melted using an extruder, extruded from a T die or a round die, cooled and solidified by a cooling roll, rolled in the vertical direction (film flow direction, MD), or in the horizontal direction (film flow direction). It is stretched in at least uniaxial direction by tenter stretching in the direction perpendicular to TD). Further, it may be stretched in the vertical direction and then in the horizontal direction, or may be stretched in the horizontal direction and then in the vertical direction. Further, it may be stretched twice or more in the same direction. Further, it may be stretched in the vertical direction, then stretched in the horizontal direction, and further stretched in the vertical direction.
  • the simultaneous biaxial stretching machine may simultaneously stretch in the vertical direction and the horizontal direction.
  • the tubular unstretched film may be radially stretched by internal pressure by tubular molding.
  • the ears of the folded tube-shaped stretched porous film are cut and wound into two pieces. May be good.
  • the ears of the folded unstretched film may be cut, separated into two unstretched films, stretched respectively, and wound up.
  • the stretched porous film roll of the present invention is preferably produced by inflation molding or tubular molding.
  • the stretched porous film roll of the present invention is made porous by stretching the unstretched film at least in the uniaxial direction.
  • the molten resin composition (Z) spreads radially and is cooled and solidified, so that the anisotropy of the unstretched film can be reduced. Therefore, since the anisotropy of the unstretched film is small, the stretching stress is likely to be uniformly applied in the width direction of the film during stretching, and the uniformity of the basis weight in the width direction of the obtained stretched porous film roll can be improved. ..
  • the stretched porous film roll of the present invention is preferably produced by inflation molding or tubular molding. Further, since the anisotropy of the unstretched film is small, it is easy to be uniformly stretched in the flow direction of the film during stretching, and even when printing is performed on the stretched porous film of the present invention, it is uniformly stretched in the flow direction of the film roll. It is easy to print, and especially when pitch printing is performed, the print pitch length at the roll length position is easy to stabilize. Therefore, the stretched porous film roll of the present invention is preferably produced by inflation molding or tubular molding.
  • the stretching temperature is preferably 0 ° C. to 90 ° C., more preferably 20 ° C. to 70 ° C.
  • the total draw ratio is preferably 1.5 to 6.0 times, more preferably 2.0 to 5.0 times. By setting the draw ratio to 1.5 times or more in total, there is a tendency that a stretched porous film that is uniformly stretched and has an excellent appearance can be obtained. By setting the draw ratio to 6.0 times or less in total, there is a tendency that the breakage of the film can be suppressed.
  • heat treatment or relaxation treatment can be performed at a temperature of 50 ° C. or higher and 120 ° C. or lower, if necessary, for the purpose of improving various physical properties.
  • heat treatment can be performed by bringing the stretched film into contact with a heated roll (annealing roll) between the stretching step and the winding step.
  • the relaxation treatment can be performed by making the speed of the next contacting roll slower than the annealing roll speed while heating with the annealing roll.
  • heat treatment or relaxation treatment it is preferable to perform heat treatment or relaxation treatment at a temperature of 50 ° C. or higher and 120 ° C. or lower. These heat treatments and relaxation treatments may be carried out in a plurality of times.
  • the stretched porous film roll of the present invention can be subjected to surface treatment such as slitting, corona treatment, printing, adhesive coating, coating, and thin film deposition, and surface treatment, if necessary.
  • the stretched porous film roll of the present invention is a stretched porous film roll in which defects are suppressed, it is effective to print on the stretched porous film roll of the present invention. Further, the stretched porous film roll of the present invention is preferably pitch-printed.
  • Pitch printing is different from endless printing in which a continuous printing pattern (design) is printed in the length direction of the stretched porous film wound on the stretched porous film roll.
  • Pitch printing is a printing method in which independent printing patterns (designs) are periodically printed in the length direction (MD direction) of the stretched porous film. Since a continuous printing pattern (design) is printed on the endless printed film, which film length is obtained when the film is cut to a certain length with respect to the length direction of the film unwound from the roll. The same applies to the position.
  • the pitch-printed film roll independent printing patterns (designs) are printed periodically with respect to the length position of the film, so that the pitch printing is printed at a specific length position of the film. If there is a discrepancy between the pattern and the pitch of the pitch-printed pattern printed at a different length position, the printed pattern (design) will be the cut film when it is cut to a certain length with respect to the length direction of the film. A deviation occurs from a specific position of the above, and it becomes difficult to obtain a similar cutting film.
  • the pitch of pitch printing indicates the periodic length (printing pitch length) of the printed independent printed pattern (design) with respect to the length direction (MD direction) of the film.
  • the film roll of the present invention suppresses defects in the stretched porous film, stable pitch printing can be performed in the length direction (MD direction) of the stretched porous film. That is, another form of the present invention is a stretched porous film roll in which a stretched porous film is pitch-printed.
  • the pitch-printed stretched porous film is continuously bonded to other members and then punched to be used as a sanitary material such as a diaper. It becomes a use member such as.
  • the stretched porous film roll subjected to pitch printing is required to have a small difference in printing pitch length with respect to the roll length position.
  • n ⁇ L / 10 ( m) The print pitch length (dn) at the length position of (n is an integer of 1 ⁇ n ⁇ 9) is 98 (%) ⁇ (n) with respect to the average value (dave) of the print pitch length at the length position.
  • dn / dave ⁇ 100 (%) ⁇ 102 (%) is preferable, 99 (%) ⁇ (dn / dave) ⁇ 100 (%) ⁇ 101 (%) is more preferable, and 99.5. Most preferably, (%) ⁇ (dn / dave) ⁇ 100 (%) ⁇ 100.5 (%).
  • the core for winding the stretched porous film is usually cylindrical, and the material thereof is not particularly limited, and the core is made of paper, plastic, a combination thereof, or a cushioning material such as polyethylene foam. It may be evenly attached to the surface.
  • the size of the core is not particularly limited, but is usually 80 to 200 mm in outer diameter, 70 to 160 mm in inner diameter, and 5 to 20 mm in wall thickness, and the width (length) is about 1 to 20 mm larger than the width of the stretched porous film. Is preferable.
  • a method of winding the stretched porous film of the present invention around such a core there is a method of winding the stretched porous film around the core by applying tension with a winding motor.
  • the stretched porous film wound on the stretched porous film roll of the present invention is formed in a large number of fine particles penetrating the front and back surfaces and has excellent air permeability. Therefore, sanitary goods such as paper diapers and sanitary goods for women; clothes such as work clothes, jumpers, jackets, medical clothes, chemical protective clothing; and also breathable and breathable such as masks, covers, drapes, sheets and wraps. Can be suitably used for the required applications. That is, another form of the present invention is a stretched porous film roll in which the stretched porous film unwound from the stretched porous film roll of the present invention is applied to a use member to which a non-woven fabric is bonded.
  • Basis weight of stretched porous film roll (average basis weight, difference between maximum and minimum values of basis weight)
  • the winding end position of the stretched porous film rolls obtained in Examples and Comparative Examples is 0 (m)
  • the winding length positions are 1 (m) to 3.5 (m) at equal intervals with a width of 55 mm.
  • the basis weight of the portion in the width direction was measured according to the above-mentioned method. Further, the average was taken by the number of parts in the width direction, and the difference between the average basis weight of the stretched porous film roll and the maximum value and the minimum value of the basis weight of the parts in the width direction was obtained.
  • the air permeability of the stretched porous film roll was calculated according to the above method.
  • the air permeability measuring device the Oken type air permeability measuring machine EGO1-55 manufactured by Asahi Seiko Co., Ltd. was used.
  • the number of defects per film roll is determined by feeding out the stretched porous film rolls obtained in Examples and Comparative Examples and passing the film through a defect detector while holding the film on the support roll. Detected. The number of defects per area was calculated from the area of the detected value calculated from the width and length of the drawn drawn porous film.
  • the raw materials used in each example and comparative example are as follows.
  • C ⁇ Petroleum-derived polyethylene resin
  • C-1 -Linear low-density polyethylene "Novatec LL UF230” manufactured by Japan Polyethylene Corporation (density 0.921 g / cm 3 , MFR 1.0 g / 10 minutes, melting point 121 ° C.).
  • C-1 -Linear low-density polyethylene "Novatec LL UF961” manufactured by Japan Polyethylene Corporation (density 0.935 g / cm 3 , MFR 5.0 g / 10 minutes, melting point 127 ° C).
  • C-2 -Linear low-density polyethylene
  • D-1 ⁇ Petroleum-derived polypropylene resin (D)> -Polypropylene "Novatec PP SA03" manufactured by Japan Polypropylene Corporation (density 0.900 g / cm 3 , MFR 30 g / 10 minutes, melting point 165 ° C.). Hereinafter, it is abbreviated as "D-1".
  • Example 1 After weighing each raw material at the composition ratio shown in Table 1, it is put into a Henschel mixer, mixed and dispersed for 5 minutes, and melt-kneaded at a set temperature of 200 ° C. using a twin-screw extruder in the same direction. , Compound pellets were obtained using a strand die connected to the tip of a twin-screw extruder in the same direction. After that, the obtained compound pellets were introduced into a single-screw extruder set at 200 ° C., inflation molding was performed, and the tube-shaped film was folded and rolled to 2.75 times MD at a roll set at 60 ° C. It was stretched.
  • both ends of the tubular film are slit, the film is divided into two sheets, and then the cores (outer diameter 100.6 mm, inner diameter 76.5 mm) are respectively.
  • a cylindrical core made of paper having a width of 1010 mm), and a stretched porous film having a length of 11,000 m and a width of 1,000 mm was wound to obtain a stretched porous film roll.
  • Various evaluations were performed on the obtained stretched porous film roll. The results are summarized in Table 2.
  • Example 2 A stretched porous film roll was obtained by the same method as in Example 1 except that the raw materials were changed to the composition ratios shown in Table 1. Various evaluations were performed on the obtained stretched porous film roll. The results are summarized in Table 2.
  • Example 3 The stretched porous film was fed out from the stretched porous film roll obtained in the same manner as in Example 1, pitch printing was performed at a printing speed of 200 m / min using a center drum type 6-color flexographic printing machine, and the core (outside) was again used. It was wound around a paper cylindrical core having a diameter of 100.6 mm, an inner diameter of 76.5 mm, and a width of 1010 mm. Further, the wound pitch-printed stretched porous film roll is slit by a slitting machine and wound again on a core (a paper cylindrical core having an outer diameter of 100.6 mm, an inner diameter of 76.5 mm, and a width of 204 mm).
  • a pitch-printed stretched porous film roll having a length of 10,000 m and a width of 200 mm was collected.
  • printing was performed using a printing plate having a design pitch length of 353 mm (periodic intervals of patterns applied to the printing plate).
  • Example 4 The stretched porous film was fed out from the stretched porous film roll obtained in the same manner as in Example 2, pitch printing was performed at a printing speed of 200 m / min using a center drum type 6-color flexographic printing machine, and the core (outside) was again used. It was wound around a paper cylindrical core having a diameter of 100.6 mm, an inner diameter of 76.5 mm, and a width of 1010 mm. Further, the wound pitch-printed stretched porous film roll is slit by a slitting machine and wound again on a core (a paper cylindrical core having an outer diameter of 100.6 mm, an inner diameter of 76.5 mm, and a width of 204 mm).
  • a pitch-printed stretched porous film roll having a length of 10,000 m and a width of 200 mm was collected.
  • printing was performed using a printing plate having a design pitch length of 353 mm (periodic intervals of patterns applied to the printing plate).
  • 1,000 m was unwound from the end of winding (0 m) of the pitch-printed stretched porous film roll, and the print pitch length (d1) at the length position of 1,000 m. was measured with a tape measure.
  • the print pitch length (d2) at the length position of 2,000 m was measured with a tape measure after feeding 1,000 m.
  • the stretched porous film of the stretched porous film rolls obtained in Examples 1, 2 and Comparative Example 1 is excellent in air permeability and moisture permeability, and has suitable tensile breaking strength, total light transmittance, and heat resistance. It was a film to have. It was also confirmed that the stretched porous films of the stretched porous film rolls obtained in Examples 1 and 2 had improved tensile elongation at break in the non-stretching direction as compared with Comparative Example 1.
  • Example 1 and Example 2 When the number of defects of the film rolls obtained in Example 1 and Example 2 and Comparative Example 1 was calculated, the number of defects in Example 1 and Example 2 was less than half that of Comparative Example 1. It turned out. When the defects detected in Comparative Example 1 were confirmed, it was found that most of the defects were caused by fish eyes and heat-deteriorated substances. From this, the oxidation induction time of the stretched porous film rolls of Examples 1 and 2 was 50 minutes or more, and the deterioration was suppressed during the molding of the stretched porous film. It is considered that the stretched porous film roll of Example 2 had few defects.
  • the stretched porous film of the stretched porous film rolls obtained in Examples 1 and 2 has a coefficient of variation of basis weight of 0.050 or less in the width direction, the surface of the film roll has less unevenness and the end face of the film roll. No winding deviation was seen.
  • the stretched porous film roll obtained in Comparative Example 1 unevenness was observed on the surface of the film roll, and some winding misalignment occurred on the end face of the film roll. This is because the coefficient of variation of the basis weight in the width direction of the stretched porous film of the stretched porous film roll of Comparative Example 1 exceeded 0.050, so that the uniformity in the width direction of the stretched porous film could not be maintained, and the stretched porous film could not be maintained. It is probable that the surface of the film roll was uneven and misaligned in the process of winding the film.
  • the present invention has been described in relation to the most practical and preferable embodiments at present, but the present invention is not limited to the embodiments disclosed in the present specification. It can be appropriately changed within the scope of the claims and the gist of the invention that can be read from the entire specification, or within the range not contrary to the idea, and the stretched porous film roll accompanied by such a change is also included in the technical scope of the present invention. Must be understood as a thing.
  • the stretched porous film roll of the present invention has excellent breathability, moisture permeability, strength, and heat resistance, suppresses thermal deterioration and defects caused by it during molding, and is effective for lengthening the film. Since it is a film roll, sanitary goods such as paper diapers and sanitary goods for women; clothes such as work clothes, jumpers, jackets, medical clothes, chemical protective clothes; and ventilation of masks, covers, drapes, sheets, wraps, etc. It can be suitably used for applications that require properties and moisture permeability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un rouleau de film poreux étiré dans lequel un film poreux étiré qui constitué d'une composition de résine (Z) contenant ２５ à ５４% en masse d'une résine thermoplastique et ４６ à ７５% en masse d'une charge inorganique (A), est enroulé sur un mandrin, et qui est tel que le temps d'induction d'oxydation de ce film poreux étiré mesuré à une température de mesure de 200°C par analyse calorimétrique différentielle (ACD), est supérieur ou égal à 50 minutes. Plus précisément, l'invention fournit un rouleau de film poreux étiré qui tout en présentant d'excellentes propriétés de perméabilité à l'air, de perméabilité à l'humidité, de solidité et de résistance à la chaleur, inhibe la dégradation thermique et les défauts dus à celle-ci lors d'une opération de moulage, et se révèle efficace en termes d'élargissement et d'allongement de film.
PCT/JP2021/006830 2020-02-27 2021-02-24 Rouleau de film poreux étiré WO2021172345A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074731A1 (fr) * 2021-10-29 2023-05-04 株式会社トクヤマ Film poreux étiré et procédé de production associé

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019039973A (ja) * 2017-08-23 2019-03-14 コニカミノルタ株式会社 ヘッドマウントディスプレイ
WO2019098283A1 (fr) * 2017-11-16 2019-05-23 三菱ケミカル株式会社 Film poreux orienté
JP2019119827A (ja) * 2018-01-10 2019-07-22 興人フィルム＆ケミカルズ株式会社 通気性フィルム
JP2019142992A (ja) * 2018-02-16 2019-08-29 三菱ケミカル株式会社 延伸多孔フィルム
JP2019155939A (ja) * 2018-03-07 2019-09-19 アイシン・エィ・ダブリュ株式会社 空調補助システム、空調補助プログラム
WO2019208592A1 (fr) * 2018-04-27 2019-10-31 国立大学法人静岡大学 Système de positionnement par satellite

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019039973A (ja) * 2017-08-23 2019-03-14 コニカミノルタ株式会社 ヘッドマウントディスプレイ
WO2019098283A1 (fr) * 2017-11-16 2019-05-23 三菱ケミカル株式会社 Film poreux orienté
JP2019119827A (ja) * 2018-01-10 2019-07-22 興人フィルム＆ケミカルズ株式会社 通気性フィルム
JP2019142992A (ja) * 2018-02-16 2019-08-29 三菱ケミカル株式会社 延伸多孔フィルム
JP2019155939A (ja) * 2018-03-07 2019-09-19 アイシン・エィ・ダブリュ株式会社 空調補助システム、空調補助プログラム
WO2019208592A1 (fr) * 2018-04-27 2019-10-31 国立大学法人静岡大学 Système de positionnement par satellite

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074731A1 (fr) * 2021-10-29 2023-05-04 株式会社トクヤマ Film poreux étiré et procédé de production associé

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