Classifications

• • 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

Definitions

• the present invention relates to a stretched porous film having excellent feel such as flexibility and texture, suppressing generation of unpleasant sound generated when rubbing the film, and excellent also in air permeability, moisture permeability and strength. More specifically, sanitary products such as disposable diapers and feminine hygiene products; clothing such as work clothes, jumpers, jackets, medical clothes, chemical protective clothing, etc .; other masks, covers, drapes, sheets, wraps, breathable, etc.
• An excellent stretched porous film having a feeling of use that can be suitably used for applications requiring
• thermoplastic resin such as polyolefin resin and an inorganic filler
• interfacial peeling is generated between the thermoplastic resin and the inorganic filler, and a large number of voids (microporous)
• a porous film formed is known.
• a stretched porous film made of a resin composition containing a polyolefin resin and an inorganic filler has a fine internal pore forming a communicating hole, so that it can transmit liquid while having high air permeability and moisture permeability.
• the porous film used in these applications is often used directly for touching the human skin, it is desirable that the film has an unpleasant sound or feel such as squeakyness and sizzling when it is worn. It becomes a factor that disturbs the feeling. Therefore, the porous film is required to have a good texture and flexibility and a good touch, and to suppress unpleasant noise.
• an inorganic filler is contained with respect to 100 parts by weight of a total amount of ethylene / ⁇ -olefin copolymer 65 to 90% by weight and thermoplastic elastomer 35 to 10% by weight.
• a moisture-permeable film is disclosed which contains 50 to 400 parts by weight of an inorganic filler with respect to 100 parts by weight of the component.
• an inorganic filler 50 to 300 parts by mass of an inorganic filler and 1 to 30 parts by mass of a plasticizer are included with respect to 100 parts by mass of a total of 30 to 70 parts by mass of a polyethylene resin and 70 to 30 parts by mass of an olefin elastomer.
• Resin component containing 100 to 40 parts by mass of a hydrophobic film (Patent Document 3), 40 to 90 parts by mass of polyethylene resin, 5 to 30 parts by mass of propylene homopolymer, and 5 to 30 parts by mass of propylene / ethylene copolymer elastomer
• a moisture-permeable film containing 100 to 200 parts by mass of an inorganic filler and 1 to 20 parts by mass of a plasticizer (Patent Document 4), a moisture-permeable film containing a polyethylene resin composition, an inorganic filler, and a styrene elastomer 5)
• Patent Document 4 a moisture-permeable film containing a polyethylene resin composition, an inorganic filler, and a styrene elastomer 5
• 30 to 85 parts by mass of linear low density polyethylene 5 to 20 parts by mass of high pressure polymerization low density polyethylene, metallocene
• a moisture-permeable film comprising a resin component
• Patent Document 7 a resin composition containing a thermoplastic resin, a film containing 80% or less of porosity and containing 1 to 70% by mass of a filler
• Patent Document 8 a thermoplastic resin, an organic filler, and an inorganic filler
• Patent Document 8 A porous film having a porosity of 10 to 80% is disclosed.
• Patent Documents 1 and 2 an ethylene / ⁇ -olefin copolymer having a melting point of 60 to 100 ° C. and a crystalline low density polyethylene containing 12% by weight or more of an ⁇ -olefin comonomer having 4 to 8 carbon atoms are used. Since the film is a main component, it has a high degree of flexibility, but may melt under high temperature conditions generated in the step of bonding other members, etc., resulting in insufficient dimensional stability, heat resistance and the like.
• Patent Documents 3 to 6 in compositions containing a polyethylene resin and an inorganic filler, an olefin elastomer, a propylene / ethylene copolymer elastomer, a styrene elastomer, a metallocene ethylene / ⁇ -olefin copolymer, etc.
• an olefin elastomer a propylene / ethylene copolymer elastomer
• a styrene elastomer a metallocene ethylene / ⁇ -olefin copolymer, etc.
• Patent Documents 3 to 6 do not refer to technical design guidelines for suppressing unpleasant noise.
• Patent Document 7 a filler is contained in a biodegradable resin typified by a polylactic acid-based resin, and attempts have been made to achieve both water resistance and degradability, and the porosity is 80% or less Although it is described that the water resistance of the film is suppressed by doing so, no mention is made as to suppression of unpleasant noise. Further, Patent Document 8 also describes that lowering the moisture permeability, the film strength, the heat retention effect, and the dustproof effect is suppressed by setting the porosity to 10 to 80%, but similarly, the unpleasant noise There is no mention of the suppression of
• the present invention has been made in view of the above problems, and has an excellent tactile sensation such as flexibility and texture, as well as suppressing the generation of unpleasant noise generated when the film is rubbed, and excellent also in air permeability, moisture permeability and strength. It is an object of the present invention to provide a stretched porous film.
• the present inventors succeeded in obtaining a stretched porous film capable of solving the problems of the above-mentioned prior art, and came to complete the present invention. That is, the object of the present invention is achieved by the following stretched porous film (hereinafter, also referred to as "the stretched porous film of the present invention").
• an object of the present invention is a stretched porous film comprising a thermoplastic resin and a resin composition (Z) containing an inorganic filler (A), which is calculated from the dynamic viscoelasticity measurement of the resin composition (Z) Ratio of storage elastic modulus (E ′) to loss elastic modulus (E ′ ′), which is equal to or greater than 0.100 at ⁇ 20 ° C., and a porosity of 25 It is solved by a stretched porous film (the first embodiment of the present invention) which is% -80%.
• Another object of the present invention is a stretched porous film comprising a thermoplastic resin and a resin composition (Z) containing an inorganic filler (A), which is calculated from the dynamic viscoelasticity measurement of the resin composition (Z).
• a stretched porous film having excellent feel such as softness and texture, suppressing generation of unpleasant sound generated when rubbing the film, and being excellent also in air permeability, moisture permeability and strength.
• it can, it can be suitably used for applications requiring breathability and moisture permeability.
• the stretched porous film 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 a uniaxial direction.
• main component refers to a component that occupies the largest mass ratio in the composition, and is preferably 45 mass% or more, more preferably 50 mass% or more, 55 mass% The above is more preferable.
• X to Y X and Y are arbitrary numbers
• Stretched porous film 1-1 Stretched porous film (first embodiment of the present invention)
• the stretched porous film of the first embodiment of the present invention is a stretched porous film comprising a thermoplastic resin and a resin composition (Z) containing an inorganic filler (A), and the dynamic of the resin composition (Z)
• the stretched porous film of the first embodiment of the present invention comprises 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).
• the stretched porous film of the first embodiment of the present invention is a resin composition 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).
• the upper limit of tan ⁇ of the resin composition (Z) constituting the stretched porous film is not particularly limited, but is preferably 1.000 or less at -20 ° C. from the viewpoint of heat resistance and dimensional stability. .
• the film is excellent in touch such as flexibility and texture.
• the tan ⁇ is preferably 0.100 or more at -20 ° C to -10 ° C, more preferably 0.100 or more at -20 ° C to 0 ° C, and 0.100 at -20 ° C to 10 ° C.
• the above is more preferable, the range of -0.100 or more at -20 ° C to 20 ° C is even more preferable, and the range of 0.100 or more at -30 ° C to 30 ° C is most preferable.
• the temperature range in which tan ⁇ calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of the first embodiment of the present invention is 0.100 or more is broadened In addition, unpleasant noises of various frequencies can be suppressed.
• the porosity of the stretched porous film of the first embodiment of the present invention is 25% to 80%.
• the porosity is more preferably 30% to 80%, and still more preferably 35% to 80%.
• the porosity is 25% or more, as described later, the energy loss opportunity of sound propagating in the pores of the stretched porous film increases, and unpleasant noise can be sufficiently suppressed.
• the porosity is 80% or less, it is possible to secure a film strength that can be practically used, and further, the waterproofness is sufficient, and it becomes difficult to cause the leakage of the liquid material in contact.
• the stretched porous film of the first embodiment of the present invention is a film having a void communicated with the inside of the resin composition (Z).
• the sound is formed by vibrating the resin composition (Z) forming the solid portion as a film and propagating inside the film It shows two ways of transmission with the sound that propagates through the air gap that has communicated. Therefore, to suppress the sound, it is necessary to consider the suppression of the sound that propagates by vibrating the resin composition (Z), and the suppression of the sound that propagates through the open space.
• the damping of the sound by the vibration source or medium is effective for the suppression of the sound propagating by vibrating the resin composition (Z).
• a viscoelastic body such as a resin
• tan ⁇ which is the ratio of the storage elastic modulus (E ′) to the loss elastic modulus (E ′ ′)
• the peak value of tan ⁇ of the resin composition (Z) constituting the stretched porous film be larger.
• the peak position of tan ⁇ of the resin composition (Z) constituting the stretched porous film of the first embodiment of the present invention is related to the attenuation at the temperature at which the sound is generated, and from the viewpoint of the temperature-time conversion law. It also relates to the attenuation to the frequency. Therefore, it is preferable that the peak width of tan ⁇ be wider in order to absorb or not generate unpleasant sounds having various frequencies.
• the porosity of the porous film suppresses the propagation of sound.
• the first embodiment of the present invention relates to the ratio of the storage elastic modulus (E ′) to the loss elastic modulus (E ′ ′) calculated from the dynamic viscoelasticity measurement of the resin composition (Z).
• the stretched porous film of the first embodiment of the present invention preferably has a crystal melting enthalpy ( ⁇ Hm) of 10 J / g to 45 J / g.
• the crystal melting enthalpy ( ⁇ Hm) is more preferably 12 J / g to 43 J / g, still more preferably 14 J / g to 41 J / g, and further preferably 16 J / g to 39 J / g. More preferable.
• the crystal melting enthalpy ( ⁇ Hm) is 10 J / g or more, the heat resistance and the dimensional stability of the stretched porous film can be secured.
• the crystal melting enthalpy ( ⁇ Hm) is 45 J / g or less, generation of unpleasant noise described later can be suppressed.
• the thermoplastic resin As a method of suppressing the unpleasant sound generated when rubbing the stretched porous film, it is considered effective to suppress the generation of the sound from the sound source as well as suppressing the above-mentioned propagation sound.
• the thermoplastic resin Focusing on the thermoplastic resin contained in the resin composition (Z) constituting the stretched film of the first embodiment of the present invention, the thermoplastic resin is a viscoelastic body having both elastic properties and viscous properties. is there. That is, by reducing the proportion of elastic properties of the thermoplastic resin, when an external force of rubbing the film is applied, the elastic component that repels to the external force and vibrates is reduced, and the generation of sound is suppressed.
• the elastic property of the macro viewpoint is the storage elastic modulus (E ') calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of the first embodiment of the present invention described above.
• the elastic property of the micro viewpoint is a crystalline component of the resin described later.
• Thermoplastic resins are classified into amorphous resins and crystalline resins in terms of crystals.
• Amorphous resin is a thermoplastic resin in which the molecular chain can not be folded regularly and has no crystal part because the molecular chain has a relatively bulky structure.
• a crystalline resin is a thermoplastic resin in which molecular chains are regularly folded and has a high-density crystal part inside.
• it is a crystalline resin, there is no crystalline resin in which 100% of the molecular chains are crystallized, and both an amorphous part in which the molecular chains are randomly arranged and a crystalline part in which the molecular chains are regularly folded Have.
• the amorphous part of the crystalline resin is capable of micro-brown movement in a temperature range above the glass transition temperature (Tg), and is in a state of high mobility.
• Tg glass transition temperature
• Tm melting point
• the crystal melting enthalpy ( ⁇ Hm) is an index of the crystal component ratio in the stretched porous film of the first embodiment of the present invention, and is preferably 10 J / g to 45 J / g.
• the storage elastic modulus (E ′) calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film is preferably 8.0 ⁇ 10 8 Pa or less at 20 ° C. More preferably, it is 7.0 ⁇ 10 8 Pa or less, still more preferably 6.0 ⁇ 10 8 Pa or less.
• the storage elastic modulus (E ′) is 8.0 ⁇ 10 8 Pa or less at 20 ° C.
• the stretched porous film is excellent in touch such as texture and flexibility.
• the lower limit is not particularly limited, but from the viewpoint of handling of the stretched porous film, 1.0 ⁇ 10 7 Pa or more is preferable at 20 ° C.
• the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of the first embodiment of the present invention is carried out using a strip-like sample piece cut out with a width of 4 mm and a length of 35 mm at a measurement frequency of 10 Hz. From a measured strain of 0.1%, a distance between chucks of 25 mm, and a measured temperature of -100 ° C., measurement is performed while raising the temperature at a temperature rising rate of 3 ° C./min. At this time, the storage elastic modulus (E ′), loss elastic modulus (E ′ ′), and storage elastic modulus (E ′) and loss elastic modulus (E ′) at each temperature are obtained from the temperature dependence profile of dynamic viscoelasticity obtained.
• the thickness of the sample piece is measured in advance, and the cross-sectional area of the sample piece is calculated by inputting the thickness of the sample piece and the value of the width of the sample piece into the measuring device. It is calculated.
• the stretched porous film of the first embodiment of the present invention since the pores are generated in the resin composition (Z), when the porous body is measured as it is, the calculated storage elastic modulus (E ′), loss, Errors easily occur in the elastic modulus (E ′ ′) and tan ⁇ .
• the resin composition Z Dynamic viscoelasticity measurement is preferably performed on strip-shaped sample pieces cut out in the longitudinal direction (MD): 4 mm and the transverse direction (TD): 35 mm using the unstretched film of.
• MD longitudinal direction
• TD transverse direction
• a press sample is prepared, and a strip-like sample piece is cut out from the press sample to perform dynamic viscoelasticity measurement.
• any measurement method can be adopted.
• a stretched porous film is cut into a size of 50 mm in the longitudinal direction (MD) and 50 mm in the transverse direction (TD), and the specific gravity (W1) of the stretched porous film is measured.
• the specific gravity (W0) of the resin composition (Z) constituting the stretched porous film of the first embodiment of the present invention is measured.
• the unstretched film of the stretched porous film of the first embodiment of the present invention is 50 mm in the longitudinal direction (MD) and 50 mm in the transverse direction (TD).
• the specific gravity can be measured by cutting out to the size of.
• the stretched porous film of the first embodiment of the present invention is heated to the melting point or more to melt the stretched porous film and eliminate the pores, and then a press sample is prepared.
• the specific gravity can be measured by cutting out the pressed sample into a size of 50 mm in the longitudinal direction (MD) and 50 mm in the transverse direction (TD).
• the crystal melting enthalpy ( ⁇ Hm) of the stretched porous film of the first embodiment of the present invention is a differential scanning calorimeter (DSC) of the stretched porous film of the first embodiment of the present invention from -40 ° C to a high temperature
• the temperature is raised to the holding temperature at a heating rate of 10 ° C./min, held for 1 minute, then lowered from a high temperature holding temperature to -40 ° C. at a cooling rate of 10 ° C./min, held for 1 minute, and further -40 ° C. to the above
• the crystal melting enthalpy ( ⁇ Hm) is calculated from the crystal melting peak area when the temperature is raised again to a high temperature holding temperature at a heating rate of 10 ° C./min.
• the high temperature holding temperature can be arbitrarily selected in the range of Tm + 20 ° C. or more and Tm + 150 ° C. or less with respect to the crystal melting peak temperature (Tm) of the thermoplastic resin to be used.
• the crystal melting enthalpy ( ⁇ Hm) defined in the first embodiment of the present invention is the reheating process even in the case of cold crystallization as seen in semicrystalline resins in the above reheating process.
• the ⁇ Hm calculated from the crystal melting peak generated in That is, the enthalpy of crystallization ( ⁇ Hc) calculated from the exothermic peak area in cold crystallization occurring in the reheating process is not subtracted from ⁇ Hm obtained in the reheating process.
• the stretched porous film of the first embodiment of the present invention is laminated with another layer, if DSC measurement is performed on the laminate as it is, ⁇ Hm derived from the stretched porous film may be estimated to be low. Therefore, when the stretched porous film of the first embodiment of the present invention is a laminate, the stretched porous film of the first embodiment of the present invention can be peeled off, and the ⁇ Hm can be measured for this porous layer. When peeling is difficult, ⁇ Hm of the stretched porous film of the first embodiment of the present invention in the entire laminate is calculated by DSC measurement, and the lamination ratio of the porous layer in the entire laminate is calculated. From the equation, ⁇ Hm defined in the first embodiment of the present invention can be calculated.
• the calculation of the lamination ratio is not particularly limited, it is preferably calculated by cross-sectional observation with an optical microscope, an electron microscope or the like.
• ⁇ Hm (J / g) defined in the first embodiment of the present invention ⁇ Hm (J / g) of the stretched porous film in the whole laminate / lamination ratio (%) / 100 (% of the porous layer in the whole laminate) )
• the crystal melting peak temperature (Tm) in the stretched porous film of the first embodiment of the present invention is preferably 70 ° C. or more, more preferably 80 ° C. or more, and 90 ° C. or more More preferable.
• the number of crystal melting peaks may be one, or two or more.
• one crystal melting peak temperature (Tm) is preferably 70 ° C. or more.
• the crystal melting enthalpy ( ⁇ Hm) is the sum of the crystal melting enthalpies ( ⁇ Hm) calculated from the two or more crystal melting peaks.
• the crystal melting start temperature is 30% of the crystal melting peak temperature (Tm) It melts little by little from temperatures lower than ° C and often shows a broad peak. Therefore, by raising the differential scanning calorimetry (DSC) temperature from -40.degree. C., the baseline can be clarified and the crystal melting enthalpy (.DELTA.Hm) can be calculated more accurately.
• DSC differential scanning calorimetry
• the basis weight of the stretched porous film of the first embodiment of the present invention is preferably 10 g / m 2 to 50 g / m 2 , more preferably 15 g / m 2 to 40 g / m 2 .
• the basis weight is 10 g / m 2 or more, mechanical strength such as tensile strength and tear strength can be easily secured sufficiently.
• the basis weight is 50 g / m 2 or less, it is easy to obtain a feeling of sufficient lightness.
• a mass (g) of a sample (longitudinal direction (MD): 250 mm, lateral direction (TD): 200 mm) is measured with an electronic balance, and a value obtained by multiplying the value by 20 is taken as basis weight.
• the air permeability of the stretched porous film according to the first embodiment 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. It is more preferable that the ratio is from / 100 mL to 3000 seconds / 100 mL.
• the air permeability is 1 second / 100 mL or more, it is easy to ensure sufficient water resistance and liquid permeation resistance.
• the air permeability of 5000 seconds / 100 mL or less suggests that it has sufficient communication holes.
• the air permeability is the number of seconds in which 100 mL of air passes through the paper, which is measured according to the method defined in JIS P8117: 2009 (Gurley testing machine method).
• the air permeability measuring device It can be measured using a manufacturing laboratory type air permeability measuring machine EGO1-55). In the present invention, samples are randomly measured at 10 points, and their arithmetic mean value is taken as air permeability.
• the moisture permeability of the stretched porous film according to the first embodiment of the present invention is preferably 1000 g / (m 2 ⁇ 24 h) to 15000 g / (m 2 ⁇ 24 h), and more preferably 1500 g / (m 2 ⁇ 24 h) to 12000 g / (M 2 ⁇ 24 h).
• the moisture permeability of 15000 g / (m 2 ⁇ 24 h) or less suggests that it has water resistance.
• the holes have sufficient communication because the moisture permeability is 1000 g / (m 2 ⁇ 24 h) or more.
• the moisture permeability conforms to the conditions of JIS Z 0208 (The moisture permeability test method of moisture-proof packaging material (cup method)).
• the moisture permeability test method of moisture-proof packaging material (cup method) The moisture permeability test method of moisture-proof packaging material (cup method)).
• the tensile breaking strength at break is 7 N / 25 mm or more, mechanical strength and flexibility sufficient for practical use can be secured.
• the upper limit is not particularly limited, but in view of stretchability, it is preferably 35 N / 25 mm or less.
• the tensile breaking strength in the stretching direction is a sample cut out in the stretching direction 100 mm ⁇ the stretching direction 25 mm in accordance with JIS K7127, and the tensile speed is 200 m under an environment of 23 ° C. and 50% relative humidity. It is a tensile breaking strength at the time of breaking using a triple tension tester under the condition of 50 min. In the present invention, an arithmetic mean value of tensile strength at break calculated by performing measurement three times is used.
• the tensile breaking elongation in the stretching direction in the stretched porous film of the first embodiment of the present invention is preferably 40% to 400%, and more preferably 100% to 300%.
• a hygienic product such as a moisture-permeable back sheet such as a menstrual treatment product with a tensile elongation at break of 40% or more
• the touch is good and the excellent feel is excellent Is obtained.
• the tensile elongation at break when the tensile elongation at break is 400% or less, it has appropriate rigidity and tensile strength, is excellent in mechanical properties, and has low elongation and distortion of film during printing, slitting, and winding processing, and excellent mechanical suitability in a production line Is obtained.
• the tensile elongation at break in the stretching direction is prepared according to JIS K7127 by preparing a sample cut out in a stretching direction of 100 mm ⁇ 25 mm perpendicular to the stretching direction, under an environment of 23 ° C. and a relative humidity of 50%.
• the heat shrinkage rate in the stretching direction when the stretched porous film of the first embodiment of the present invention is heated at 60 ° C. for 1 hour is preferably less than 5.0%, and more preferably less than 4.0%. preferable.
• the heat shrinkage rate in the stretching direction when heated at 60 ° C. for 1 hour is less than 5.0%, blocking and winding tightness when the roll-shaped sample of the stretched porous film is stored over time are preferable.
• the thermal contraction rate is left standing and heated for 1 hour in a convection oven in which the temperature in the tank is set to 60 ° C., for which the sample cut out in the stretching direction of 200 mm ⁇ 10 mm perpendicular to the stretching direction is set.
• the length L (mm) in the stretching direction is measured, which is a value calculated by the formula “(200-L) / 200 ⁇ 100 (%)”.
• the measurement is made three times to obtain the arithmetic mean value of the thermal contraction rate calculated.
• the total light transmittance of the stretched porous film of the first embodiment of the present invention is preferably 18% to 60%.
• the stretched porous film of the first embodiment of the present invention for sanitary goods such as back sheets for moisture-permeable waterproofs such as disposable diapers by having a total light transmittance of 18% or more, an indicator drug which indicates that urination has occurred Even if it applies, it can recognize.
• the film is white and rich in hiding power because the total light transmittance is 60% or less.
• the total light transmittance is obtained by randomly measuring five points using a haze meter in accordance with JIS K7361 and calculating its arithmetic mean value.
• the stretched porous film of the second embodiment of the present invention comprises 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).
• the stretched porous film of the second embodiment of the present invention more preferably is a resin composition 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).
• the upper limit of tan ⁇ of the resin composition (Z) constituting the stretched porous film is not particularly limited, but is preferably 1.000 or less at -20 ° C. from the viewpoint of dimensional stability.
• the film is excellent in touch such as flexibility and texture.
• the tan ⁇ is preferably 0.100 or more at -20 ° C to -10 ° C, more preferably 0.100 or more at -20 ° C to 0 ° C, and 0.100 at -30 ° C to 0 ° C. It is more preferable that the above is more preferably 0.100 or more at -30 ° C to 10 ° C, still more preferably 0.100 or more at -30 ° C to 20 ° C. Most preferably, it is 0.100 or more in ° C.
• the temperature range in which tan ⁇ calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of the second embodiment of the present invention is 0.100 or more is broadened.
• unpleasant noises of various frequencies can be suppressed.
• the porosity of the stretched porous film of the second embodiment of the present invention is preferably 15% to 80%.
• the porosity is more preferably 20% to 80%, and still more preferably 25% to 80%.
• the porosity is 15% or more, as described later, the energy loss opportunity of sound propagating in the pores of the stretched porous film increases, and unpleasant noise can be sufficiently suppressed.
• the porosity is 80% or less, it is possible to secure a film strength that can be practically used, and further, the waterproofness is sufficient, and it becomes difficult to cause the leakage of the liquid material in contact.
• the stretched porous film of the second embodiment of the present invention is a film having a void communicated with the inside of the resin composition (Z).
• the sound is formed by vibrating the resin composition (Z) forming the solid portion as a film and propagating inside the film It shows two ways of transmission with the sound that propagates through the air gap that has communicated. Therefore, to suppress the sound, it is necessary to consider the suppression of the sound that propagates by vibrating the resin composition (Z), and the suppression of the sound that propagates through the open space.
• the stretched porous film of the second embodiment of the present invention it is considered that damping of the vibration source of sound or the medium is effective for suppressing the sound which propagates by vibrating the resin composition (Z).
• a viscoelastic body such as a resin
• tan ⁇ which is the ratio of the storage elastic modulus (E ′) to the loss elastic modulus (E ′ ′)
• the peak value of tan ⁇ of the resin composition (Z) constituting the stretched porous film be larger.
• the peak position of tan ⁇ of the resin composition (Z) constituting the stretched porous film of the second embodiment of the present invention relates to the attenuation at the temperature at which the sound is generated, and from the viewpoint of the temperature-time conversion law. It also relates to the attenuation to the frequency. Therefore, it is preferable that the peak width of tan ⁇ be wider in order to absorb or not generate unpleasant sounds having various frequencies.
• the porosity of the porous film is also considered to contribute to the suppression of the propagating sound.
• the porosity of the stretched porous film is 15% or more in order to increase the energy loss opportunity of sound propagating in the pores of the film.
• the stretched porous film of the second embodiment of the present invention has a crystal melting peak (Pm1) at 140 ° C. to 200 ° C.
• the crystal melting peak (Pm1) is preferably at 150 ° C. to 190 ° C., and more preferably at 160 ° C. to 180 ° C. Having a crystal melting peak (Pm1) at 140 ° C. or higher makes it possible to impart sufficient heat resistance when bonding and laminating the stretched porous film with other members, which is important. Further, by having the crystal melting peak (Pm1) at 200 ° C. or less, there is no need to extremely increase the extrusion temperature in forming a stretched porous film, and therefore it is difficult to generate resin degradation products and the like, productivity is improved.
• the thermoplastic resin having a melting point of 140 ° C. to 200 ° C. is contained in the resin composition (Z) constituting the stretched porous film of the second embodiment of the present invention. Can be adjusted to have the crystal melting peak (Pm1) in the above range.
• the crystal melting enthalpy ( ⁇ Hm1) calculated from the crystal melting peak (Pm1) is preferably 1 J / g to 10 J / g.
• the crystal melting enthalpy ( ⁇ Hm1) is more preferably 1 J / g to 8 J / g, and still more preferably 2 J / g to 6 J / g.
• the crystal melting enthalpy ( ⁇ Hm1) is 1 J / g or more, it is preferable because it has a sufficient crystal component to impart heat resistance to the stretched porous film.
• the crystal melting enthalpy ((DELTA) Hm1) is 10 J / g or less.
• the crystal melting enthalpy ( ⁇ Hm1) can be reduced by adjusting the mixing ratio of the thermoplastic resin having a melting point of 140 ° C. to 200 ° C. It can adjust to the said range.
• the stretched porous film of the second embodiment of the present invention preferably further has a crystal melting peak (Pm2) at 30 ° C to 130 ° C.
• the crystal melting enthalpy ( ⁇ Hm2) calculated from the crystal melting peak (Pm2) is preferably 10 J / g to 45 J / g.
• the crystal melting enthalpy ( ⁇ Hm2) is more preferably 12 J / g to 43 J / g, and still more preferably 14 J / g to 41 J / g.
• the crystal melting enthalpy ( ⁇ Hm2) is 10 J / g or more, the heat resistance and the dimensional stability of the stretched porous film can be secured.
• the resin composition (Z) constituting the stretched porous film of the second embodiment of the present invention contains a thermoplastic resin having a melting point of 30 ° C to 130 ° C, By adjusting the mixing ratio, the crystal melting peak (Pm2) and the crystal melting enthalpy ( ⁇ Hm2) can be adjusted to the above ranges.
• thermoplastic resin contained in the resin composition (Z) constituting the stretched porous film of the second embodiment of the present invention is a viscoelastic body having both elastic properties and viscous properties. It is.
• the elastic property of the macro viewpoint is the storage elastic modulus (E ') calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of the second embodiment of the present invention described above.
• the elastic property of the micro viewpoint is a crystalline component of the resin described later.
• the storage elastic modulus (E) calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of the second embodiment of the present invention (E) ') Is preferably 8.0 ⁇ 10 8 Pa or less at 20 ° C. More preferably, it is 7.0 ⁇ 10 8 Pa or less, still more preferably 6.0 ⁇ 10 8 Pa or less.
• the storage elastic modulus (E ′) is 8.0 ⁇ 10 8 Pa or less at 20 ° C.
• the stretched porous film is excellent in touch such as texture and flexibility, and suppresses generation of unpleasant noise. It is preferable because The lower limit is not particularly limited, but from the viewpoint of handling of the stretched porous film, 1.0 ⁇ 10 7 Pa or more is preferable at 20 ° C.
• the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film according to the second embodiment of the present invention is performed on a strip-like sample piece cut out with a width of 4 mm and a length of 35 mm at a measurement frequency of 10 Hz. From a measured strain of 0.1%, a distance between chucks of 25 mm, and a measured temperature of -100 ° C., measurement is performed while raising the temperature at a temperature rising rate of 3 ° C./min. At this time, the storage elastic modulus (E ′), loss elastic modulus (E ′ ′), and storage elastic modulus (E ′) and loss elastic modulus (E ′) at each temperature are obtained from the temperature dependence profile of dynamic viscoelasticity obtained.
• the thickness of the sample piece is measured in advance, and the cross-sectional area of the sample piece is calculated by inputting the thickness of the sample piece and the value of the width of the sample piece into the measuring device. It is calculated.
• the stretched porous film of the second embodiment of the present invention since the pores are generated in the resin composition (Z), when the porous body is measured as it is, the calculated storage elastic modulus (E ′), loss, Errors easily occur in the elastic modulus (E ′ ′) and tan ⁇ .
• a resin composition Z It is preferable to perform a dynamic viscoelasticity measurement about the strip-like sample piece cut out by MD: 4 mm and TD: 35 mm using the unstretched film of 2.).
• a press sample is prepared, and a strip-like sample piece is cut out from the press sample to perform dynamic viscoelasticity measurement.
• any measurement method can be adopted.
• Thermoplastic resins are classified into amorphous resins and crystalline resins in terms of crystals.
• Amorphous resin is a thermoplastic resin in which the molecular chain can not be folded regularly and has no crystal part because the molecular chain has a relatively bulky structure.
• a crystalline resin is a thermoplastic resin in which molecular chains are regularly folded and has a high-density crystal part inside.
• crystalline resin there is no crystalline resin in which 100% of the molecular chains are crystallized, and both an amorphous part in which the molecular chains are randomly arranged and a crystalline part in which the molecular chains are regularly folded Have.
• the amorphous part of the crystalline resin is capable of micro-brown movement in a temperature range above the glass transition temperature, and is in a state of high mobility.
• molecular chains are confined as crystals in a temperature range of not less than the glass transition temperature and not more than the melting point, and it becomes a part having a very high elastic modulus.
• the crystal melting enthalpy is an index of the crystal component ratio in the stretched porous film of the second embodiment of the present invention, and the crystal melting enthalpy ( ⁇ Hm1) is preferably 1 J / g to 10 J / g.
• the crystal melting enthalpy ( ⁇ Hm2) is preferably 10 J / g to 45 J / g.
• the crystalline melting peak (Pm) and the peak temperature (Tm) of the stretched porous film of the second embodiment of the present invention are the differential scanning calorimeter (DSC), and the stretched of the second embodiment of the present invention
• DSC differential scanning calorimeter
• the porous film is heated from -40 ° C to a high temperature holding temperature at a heating rate of 10 ° C / min, held for 1 minute, then lowered from a high temperature holding temperature to -40 ° C at a cooling rate of 10 ° C / min, held for 1 minute Crystal melting peak (Pm) which appears when the temperature is raised again from ⁇ 40 ° C. to the above-mentioned high temperature holding temperature at a heating rate of 10 ° C./min, and the temperature (Tm) showing the peak.
• the crystal melting enthalpy ( ⁇ Hm) is calculated from the peak area of the crystal melting peak (Pm) that appears when the temperature is raised again.
• the high temperature holding temperature can be arbitrarily selected in the range of Tm + 20 ° C. or more and Tm + 150 ° C. or less with respect to the highest crystal melting peak temperature (Tm) of the thermoplastic resin to be used.
• the crystal melting enthalpy ( ⁇ Hm) occurs in the reheating process, even in the case of cold crystallization as seen in a semicrystalline resin in the reheating process.
• the ⁇ Hm calculated from the crystal melting peak is applied. That is, the crystallization enthalpy ( ⁇ Hc) calculated from the exothermic peak area in cold crystallization occurring in the reheating process is not subtracted from ⁇ Hm obtained in the reheating process.
• the stretched porous film of the second embodiment of the present invention when the DSC measurement is performed on the laminate as it is, ⁇ Hm derived from the stretched porous film may be estimated to be low. Therefore, when the stretched porous film of the second embodiment of the present invention is a laminate, the stretched porous film of the second embodiment of the present invention can be peeled off, and ⁇ Hm can be measured for this porous layer. When peeling is difficult, while calculating ⁇ Hm of the stretched porous film of the second embodiment of the present invention in the entire laminate by DSC measurement, the lamination ratio of the porous layer in the entire laminate is calculated, and the following From the calculation formula, ⁇ Hm in the second embodiment of the present invention can be calculated.
• ⁇ Hm (J / g) ⁇ Hm (J / g) of the stretched porous film in the whole laminate / lamination ratio (%) / 100 (%) of the porous layer in the whole laminate
• the crystal melting peak (Pm1) in the stretched porous film of the second embodiment of the present invention has at 140 ° C. to 200 ° C.
• at least one crystal melting peak at 140 ° C. to 200 ° C. may be two or more.
• the crystal melting enthalpy ( ⁇ Hm1) is the sum of crystal melting enthalpies calculated from two or more crystal melting peaks.
• the crystal melting peak (Pm2) is also preferably at least one crystal melting peak at 30 ° C. to 130 ° C., but may be two or more.
• the crystal melting enthalpy ( ⁇ Hm 2) is a total value of crystal melting enthalpies calculated from two or more crystal melting peaks.
• the crystal melting start temperature is more than 30 from the crystal melting peak temperature (Tm) It melts little by little from temperatures lower than ° C and often shows a broad peak. Therefore, by raising the differential scanning calorimetry (DSC) temperature from -40.degree. C., the baseline can be clarified and the crystal melting enthalpy (.DELTA.Hm) can be calculated more accurately.
• DSC differential scanning calorimetry
• the second embodiment of the present invention relates to the ratio of the storage elastic modulus (E ′) to the loss elastic modulus (E ′ ′) calculated from the dynamic viscoelasticity measurement of the resin composition (Z).
• a sound absorption coefficient to suppress unpleasant noise generated when the film rubs, as well as excellent in touch such as flexibility and texture by setting the temperature at which certain tan ⁇ and crystal melting peak (Pm1) occur to a suitable range while improving the (vibration attenuation rate), the heat resistance required for the stretched porous film can be compatible.
• the porosity of the stretched porous film according to the second embodiment of the present invention is as follows: the stretched porous film is cut into a size of 50 mm in the longitudinal direction (MD) and 50 mm in the transverse direction (TD); Measure W1). Next, the specific gravity (W0) of the resin composition (Z) constituting the stretched porous film of the second embodiment of the present invention is measured. In the measurement of the specific gravity (W0) of the resin composition (Z), the unstretched film of the stretched porous film of the second embodiment of the present invention is a longitudinal direction (MD): 50 mm, a transverse direction (TD): 50 mm The specific gravity can be measured by cutting out to the size of.
• the stretched porous film of the second embodiment of the present invention is heated to a temperature higher than the melting point to melt the stretched porous film and eliminate pores, and then prepare a press sample.
• the specific gravity can be measured by cutting out the pressed sample into a size of 50 mm in the longitudinal direction (MD) and 50 mm in the transverse direction (TD).
• the basis weight of the stretched porous film of the second embodiment of the present invention is preferably 10 g / m 2 to 50 g / m 2 , more preferably 12 g / m 2 to 40 g / m 2 .
• the basis weight is 10 g / m 2 or more, mechanical strength such as tensile strength and tear strength can be easily secured sufficiently.
• the basis weight is 50 g / m 2 or less, it is easy to obtain a feeling of sufficient lightness.
• a mass (g) of a sample (longitudinal direction (MD): 250 mm, lateral direction (TD): 200 mm) is measured with an electronic balance, and a value obtained by multiplying the value by 20 is taken as basis weight.
• the air permeability of the stretched porous film of the second embodiment 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. It is more preferable that the ratio is from / 100 mL to 3000 seconds / 100 mL.
• the air permeability is 1 second / 100 mL or more, it is easy to ensure sufficient water resistance and liquid permeation resistance.
• the air permeability of 5000 seconds / 100 mL or less suggests that it has sufficient communication holes.
• the air permeability is the number of seconds in which 100 mL of air passes through the paper, which is measured according to the method defined in JIS P8117: 2009 (Gurley testing machine method).
• the air permeability measuring device It can be measured using a manufacturing laboratory type air permeability measuring machine EGO1-55). In the present invention, samples are randomly measured at 10 points, and their arithmetic mean value is taken as air permeability.
• the moisture permeability of the stretched porous film according to the second embodiment of the present invention is preferably 1000 g / (m 2 ⁇ 24 h) to 15000 g / (m 2 ⁇ 24 h), more preferably 1500 g / (m 2 ⁇ 24 h) to 1 2000 g / (M 2 ⁇ 24 h).
• the moisture permeability of 15000 g / (m 2 ⁇ 24 h) or less suggests that it has water resistance.
• the holes have sufficient communication because the moisture permeability is 1000 g / (m 2 ⁇ 24 h) or more.
• the moisture permeability conforms to the conditions of JIS Z 0208 (The moisture permeability test method of moisture-proof packaging material (cup method)).
• the moisture permeability test method of moisture-proof packaging material (cup method) The moisture permeability test method of moisture-proof packaging material (cup method)).
• the tensile breaking strength at break is 7 N / 25 mm or more, mechanical strength and flexibility sufficient for practical use can be secured.
• the upper limit is not particularly limited, but in view of stretchability, it is preferably 35 N / 25 mm or less.
• the tensile breaking strength in the stretching direction is a sample cut out in the stretching direction 100 mm ⁇ the stretching direction 25 mm in accordance with JIS K7127, and the tensile speed is 200 m under an environment of 23 ° C. and 50% relative humidity. It is a tensile breaking strength at the time of breaking using a triple tension tester under the condition of 50 min. In the present invention, an arithmetic mean value of tensile strength at break calculated by performing measurement three times is used.
• the tensile breaking elongation in the stretching direction in the stretched porous film of the second embodiment of the present invention is preferably 40% to 400%, and more preferably 80% to 300%.
• the stretched porous film of the second embodiment of the present invention as a tensile diaper with a tensile elongation at break of 40% or more for sanitary goods such as disposable diapers and back sheets for moisture-permeable waterproofs such as sanitary products, the touch is good. You get an excellent feeling of comfort.
• the tensile elongation at break when the tensile elongation at break is 400% or less, it has appropriate rigidity and tensile strength, is excellent in mechanical properties, and has low elongation and distortion of film during printing, slitting, and winding processing, and excellent mechanical suitability in a production line Is obtained.
• the tensile elongation at break in the stretching direction is prepared according to JIS K7127 by preparing a sample cut out in a stretching direction of 100 mm ⁇ 25 mm perpendicular to the stretching direction, under an environment of 23 ° C. and a relative humidity of 50%.
• the total light transmittance of the stretched porous film of the second embodiment of the present invention is preferably 18% to 60%.
• An indicator medicine which indicates that urination has occurred when the stretched porous film of the second embodiment of the present invention is used for sanitary goods such as back sheets for moisture-permeable waterproofs such as paper diapers by having a total light transmittance of 18% or more Even if it applies, it can recognize.
• the film is white and rich in hiding power because the total light transmittance is 60% or less.
• the total light transmittance is obtained by randomly measuring five points using a haze meter in accordance with JIS K7361 and calculating its arithmetic mean value.
• 120 degreeC or more is preferable, as for the film-breaking heat resistance temperature in the stretched porous film of the 2nd Embodiment of this invention, 140 degreeC or more is more preferable, and 160 degreeC or more is still more preferable.
• the film does not break by heat such as a hot melt adhesive. It can be judged that the heat resistance necessary for the stretched porous film is imparted.
• the heat resistance temperature of the film is held by holding a sample (100 mm ⁇ 100 mm) with two stainless steel plates (100 mm ⁇ 100 mm ⁇ 2 mm (thickness)) obtained by punching the center into a 5050 mm circle and fixing the four sides with clips. After standing for 2 minutes in a convection oven with a temperature of 120 ° C in the bath and heating, the sample of the circular punching point of the stainless steel sheet melts, and the appearance of holes is visually judged, and tears and holes The one with no opening is made to have a rupture heat resistance temperature of 120 ° C. or more. In addition, the temperature in the tank is changed to 140 ° C. and 160 ° C., and when the same evaluation is performed, those having no tear or hole opening are made to have a rupture heat resistance temperature of 140 ° C. or more and 160 ° C. or more.
• oriented porous film of the present invention refers to the above-mentioned “oriented porous film of the first embodiment of the present invention” and “oriented porous film of the second embodiment of the present invention”.
• Resin composition (Z) constituting stretched porous film It is important that the stretched porous film of the present invention comprises 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).
• Inorganic filler (A) examples include fine particles and minerals of calcium carbonate, calcium sulfate, barium carbonate, barium sulfate, titanium oxide, talc, clay, kaolinite, montmorillonite etc. Calcium carbonate and barium sulfate can be suitably used because of advantages such as expression, high versatility, low price, and abundant brand name.
• the average particle diameter of the inorganic filler (A) is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 5 ⁇ m, and still more preferably 0.5 to 3 ⁇ m. If the average particle size is 0.1 ⁇ m or more, dispersion failure and secondary aggregation of the inorganic filler (A) are suppressed, and the resin can be uniformly dispersed in the resin composition (Z), which is preferable. On the other hand, when the average particle diameter is 10 ⁇ m or less, generation of large voids can be suppressed at the time of film thinning, and sufficient strength and water resistance can be secured for the film.
• the inorganic filler (A) to be treated it is preferable to previously coat the inorganic filler with a fatty acid, fatty acid ester or the like to make the surface of the inorganic filler conformable to the resin.
• a surface-treated inorganic filler can be used.
• thermoplastic resin polyolefin resin, polystyrene resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, chlorinated polyethylene resin, polyester resin, polycarbonate resin, polyamide resin 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 resin Fat, polyamide imide resin, polyamide bis maleimide resin, poly arylate resin, polyether imide resin, polyether ether ketone resin, polyether ketone resin, polyether sulfone resin, poly
• thermoplastic resin a polyolefin resin is preferable as the thermoplastic resin from the viewpoints of flexibility, heat resistance, formation of communicating holes, environmental hygiene, odor and the like.
• the thermoplastic resin may be of one type or of two or more types. When the said thermoplastic resin is comprised by 2 or more types, the sum total turns into a mass of the said thermoplastic resin, and the mass ratio of the said thermoplastic resin in resin composition (Z) is calculated.
• the polyolefin 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 mole or more and 100% by mole or less in the resin.
• olefin monomers include ethylene, propylene, ⁇ -olefins such as 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene, dienes, isoprenes, butylenes, butadienes and the like. Or a multicomponent copolymer obtained by copolymerizing two or more of them.
• vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, glycidyl (meth) acrylic acid, vinyl alcohol, ethylene glycol, maleic anhydride, styrene, diene, cyclic olefin may be copolymerized.
• ethylene homopolymer, branched low density polyethylene, ethylene / ⁇ -olefin copolymer, ethylene / vinyl acetate copolymer, styrene / ethylene / propylene copolymer, styrene from the viewpoint of imparting flexibility and texture / Ethylene / butylene copolymer is preferred.
• thermoplastic resin is a polyolefin 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 said polyolefin resin is comprised by 2 or more types, the sum total becomes the mass of the said polyolefin resin.
• the density of the polyolefin resin is preferably 0.850 g / cm 3 or more and 0.940 g / cm 3 or less.
• polyethylene resin (B) having a density of 0.910 g / cm 3 or more and 0.940 g / cm 3 or less, and a density of 0.850 g / cm 3 or more and 0.910 g / cm 3 or less
• soft polyolefin resin (C) of
• the polyethylene resin (B) is a resin having a density of 0.910 g / cm 3 or more and 0.940 g / cm 3 or less and ethylene as a main monomer component.
• the main monomer component refers to a monomer component that occupies 50% by mole or more and 100% by mole or less in the resin. Therefore, the polyethylene-based resin (B) may be an ethylene homopolymer, or may be a copolymer containing ethylene as a main monomer component and containing other monomers.
• copolymer examples include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1.
• Ethylene / ⁇ -olefin copolymers such as -octene copolymer, and also ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, Ethylene / glycidyl (meth) acrylate, ethylene / vinyl alcohol copolymer, ethylene / ethylene glycol copolymer, ethylene / maleic anhydride copolymer, ethylene / styrene copolymer, ethylene / diene copolymer, ethylene / ethylene copolymer A cyclic olefin copolymer etc. are mentioned.
• a multicomponent copolymer containing two or more of the above-mentioned monomer components such as an ethylene / propylene / 1-butene copolymer, may be used.
• ethylene homopolymers and ethylene / ⁇ -olefin copolymers are preferable from the viewpoint of heat shrinkage resistance and dimensional stability.
• the polyethylene resin (B) may have a density of 0.910 g / cm 3 or more and 0.940 g / cm 3 or less, and may be one type as long as it is a resin containing ethylene as a main monomer component. It may be two or more types. When the said polyethylene-type resin (B) is comprised by 2 or more types, the sum total becomes the mass of the said polyethylene-type resin (B). Permeability, moisture permeability, heat shrinkage resistance, dimensional stability, liquid leakage resistance of the stretched porous film by containing the polyethylene resin (B) having a density of 0.910 g / cm 3 or more and 0.940 g / cm 3 or less , Concealment, appearance, etc. can be satisfied.
• the density of the polyethylene resin (B) is more preferably at most 0.910 g / cm 3 or more 0.937 g / cm 3, not more than 0.910 g / cm 3 or more 0.935 g / cm 3, especially preferable.
• the density is a density measured by the pycnometer method (JIS K7112 B method). Moreover, it is a value when it measures similarly about the density of resin mentioned later.
• the polyethylene resin (B) may be linear or branched.
• the method for producing the polyethylene-based resin (B) is not particularly limited, and a known polymerization method using a known olefin polymerization catalyst, for example, a multisite catalyst represented by a Ziegler-Natta type catalyst, a metallocene-based catalyst The polymerization method etc. which used the single site catalyst represented by these are mentioned.
• At least one kind of the polyethylene resin (B) is branched low density polyethylene.
• the melt tension of the resin composition (Z) is increased, and the molding processability is preferably improved.
• tan ⁇ E ′ ′ / E ′
• the melting point of the polyethylene resin (B) is preferably 110 to 135 ° C., and more preferably 110 to 130 ° C. If the melting point of the polyethylene-based resin (B) is 110 to 135 ° C., it is preferable because the heat shrinkage resistance and the dimensional stability of the stretched porous film can be improved.
• the melting point is about 10 mg of resin heated to -40 ° C. to 200 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC), and maintained at 200 ° C. for 1 minute, then a cooling rate 10
• DSC differential scanning calorimeter
• the melt flow rate (MFR) of the polyethylene resin (B) is preferably 0.1 to 20 g / 10 minutes, and more preferably 0.5 to 10 g / 10 minutes.
• MFR is a value measured based on JISK7219, and the measurement conditions are 190 ° C and 2.16 kg load.
• the soft polyolefin resin (C) is a resin having a density of 0.850 g / cm 3 or more and less than 0.910 g / cm 3 and containing an olefin monomer as a main monomer component.
• the main monomer component refers to a monomer component that occupies 50% by mole or more and 100% by mole or less in the resin.
• olefin monomers include ethylene, propylene, ⁇ -olefins such as 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene, dienes, isoprenes, butylenes, butadienes and the like.
• a multicomponent copolymer obtained by copolymerizing two or more of them may be copolymerized.
• vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, glycidyl (meth) acrylic acid, vinyl alcohol, ethylene glycol, maleic anhydride, styrene, diene, cyclic olefin may be copolymerized.
• ethylene homopolymer branched low density polyethylene, ethylene / ⁇ -olefin copolymer, ethylene / vinyl acetate copolymer, styrene / ethylene / propylene copolymer, styrene from the viewpoint of imparting flexibility and texture / Ethylene / butylene copolymer is preferred.
• the soft polyolefin resin (C) has a density of not less than 0.850 g / cm 3 and not more than 0.910 g / cm 3 , and even if it is a resin having an olefin monomer as a main monomer component, It may be two or more types. When the said soft polyolefin resin (C) is comprised by 2 or more types, the sum total becomes the mass of the said soft polyolefin resin (C).
• the soft polyolefin resin (C) having a density of 0.850 g / cm 3 or more and less than 0.910 g / cm 3 , the flexibility and the texture of the stretched porous film can be improved, and the touch satisfaction can be improved.
• the density of the flexible polyolefin resin (C) is preferably less than 0.855 g / cm 3 or more 0.910 g / cm 3, less than 0.860 g / cm 3 or more 0.910 g / cm 3 Is more preferred.
• the soft polyolefin resin (C) preferably has a melt flow rate (MFR) of 0.1 to 20 g / 10 min, and more preferably 0.5 to 10 g / 10 min.
• MFR melt flow rate
• the peak of is preferably in the range of -50 to 50.degree.
• the peak of tan ⁇ of the soft polyolefin resin (C) is in the range of ⁇ 50 to 50 ° C., this is preferable because it contributes to suppression of unpleasant noise such as rattle and snail.
• the peak value of is preferably 0.100 or more, more preferably 0.200 or more, and still more preferably 0.300 or more.
• the peak value of tan ⁇ of the soft polyolefin resin (C) is 0.100 or more, this is preferable because it contributes to the suppression of unpleasant noise such as rattle and gowagowa.
• the thermoplastic resin is a polyolefin resin
• the polyolefin resin is a polyethylene resin (B) having a density of 0.910 g / cm 3 or more and 0.940 g / cm 3 or less, and a density of 0.850 g / cm
• soft polyolefin resin (C) 3 or more and less than 0.910 g / cm 3 respectively, mixed composition of the inorganic filler (A), the polyethylene resin (B), and the soft polyolefin resin (C)
• the mixed composition ratio of the inorganic filler (A) is at least the lower limit in the above-mentioned preferable range In some cases, the formation of the pores accompanied by the stretching is sufficient to easily form the communicating holes, and it is easy to develop sufficient air permeability and moisture permeability characteristics. Moreover, when the mixing composition ratio of the said inorganic filler (A) is below the upper limit in the above-mentioned preferable range, shaping
• the mixed composition ratio of the polyethylene resin (B) is not less than the lower limit in the above-mentioned preferable range, and the mixed composition ratio of the soft polyolefin resin (C) is not more than the upper limit in the above-mentioned preferable range It becomes a film excellent in heat shrinkage resistance and dimensional stability. Furthermore, when the mixed composition ratio of the polyethylene resin (B) is not more than the upper limit in the above-mentioned preferable range, and the mixed composition ratio of the soft polyolefin resin (C) is not less than the lower limit in the above-mentioned preferable range And a soft touch such as softness and texture can be obtained, and it is easy to suppress unpleasant noise generated when the film is rubbed.
• polyethylene resin (B) having a density of 0.910 g / cm 3 or more and 0.940 g / cm 3 or less, and a density of 0.850 g / cm 3 or more and 0.910 g / cm 3 You may have the polypropylene resin (D) mentioned later other than the soft polyolefin resin (C) of less than.
• Polypropylene resin (D) is preferably a density less than 0.890 g / cm 3 or more 0.910 g / cm 3.
• the melting point is preferably 140 ° C to 170 ° C.
• the MFR is preferably 10 to 50 g / 10 min.
• MFR of a polypropylene resin (D) is a value measured based on the conditions M of JISK7210, and the measurement conditions are 230 degreeC and a 2.16-kg load.
• the thermoplastic resin is a polyolefin resin
• the polyolefin resin is a polyethylene resin (B) having a density of 0.910 g / cm 3 or more and 0.940 g / cm 3 or less, a density of 0.850 g / cm 3 or more
• the soft polyolefin resin (C) and the polypropylene resin (D) each having less than 0.910 g / cm 3 are contained
• the polyethylene resin (B), the soft polyolefin resin (C), and the polypropylene resin (D) (B) / (C) / (D) 1% by mass to 25% by mass / 50% by mass to 98% by mass / 1% by mass to 25% by mass (wherein (B) and (C)
• the mixed composition ratio of the polypropylene-based resin (D) is at least the lower limit in the above-mentioned preferable range When it is, it becomes easy to express sufficient heat resistance to an extending
• the mixed composition ratio of the polypropylene resin (D) is not more than the upper limit in the above preferable range
• the mixed composition ratio of the polyethylene resin (B) is not more than the upper limit in the above preferable range
• the mixed composition ratio of the soft polyolefin resin (C) is equal to or more than the lower limit in the above-mentioned preferable range, a good touch feeling such as softness and texture can be obtained, and unpleasant noise generated when the film rubs can be easily suppressed.
• the stretched porous film of the present invention preferably contains the plasticizer (E) in an amount of 0.1% by mass to 8.0% by mass in the resin composition (Z).
• the plasticizer (E) is contained at 0.1% by mass or more, the value of tan ⁇ of the resin composition (Z) is increased, and the peak width of tan ⁇ of the resin composition (Z) is further broadened.
• the crystal melting enthalpy ( ⁇ Hm) of the stretched porous film can be reduced.
• the plasticizer (E) is 8.0% by mass or less, bleeding out of the plasticizer can be suppressed, and blocking when the stretched porous film is wound in a roll, and printing failure at the time of printing Can be suppressed.
• ester plasticizers As a plasticizer (E), the following ester plasticizers are mentioned. Those having a polar structure, for example, monovalent carboxylic acid ester plasticizers (butanoic acid, isobutanoic acid, hexanoic acid, 2-ethylhexanoic acid, hyptanic acid, octylic acid, 2-ethylhexanoic acid, lauric acid etc. And the compounds obtained by the condensation reaction of monohydric carboxylic acids of the formula (I) with polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol and glycerin etc.
• monovalent carboxylic acid ester plasticizers butanoic acid, isobutanoic acid, hexanoic acid, 2-ethylhexanoic acid, hyptanic acid, octylic acid, 2-ethylhexanoic acid, la
• Castor oils include conventional castor oil, refined castor oil, hydrogenated castor oil and dehydrated castor oil.
• the hydrogenated castor oil may, for example, be a hydrogenated castor oil mainly composed of triglyceride composed of 12-hydroxyoctadecanoic acid and glycerin.
• compatibilizer In addition to the above-mentioned raw materials, other resin raw materials, recycled resins generated from trimming loss of ears, etc. according to the purpose of use, compatibilizer, processing aid, melt viscosity improver, antioxidant, anti-aging agent , Heat stabilizer, light stabilizer, weather resistant stabilizer, UV absorber, neutralizer, nucleating agent, crosslinking agent, lubricant, anti-blocking agent, slip agent, anti-fogging agent, antibacterial agent, deodorant, hard You may add suitably a flame retardant, an antistatic agent, a coloring agent, a pigment, etc. to the resin composition (Z) which comprises the oriented porous film of this invention.
• the method for producing a stretched porous film of the present invention is not particularly limited, and it can be produced by a conventionally known method, but it is important to be stretched in at least uniaxial direction.
• film is meant to encompass from thick sheets to thin films.
• the film may be planar or tubular, but is preferably planar from the viewpoint of productivity (can be taken as a product in the width direction of the original sheet) and printing on the inner surface. .
• the film can be exemplified by a method of obtaining a film by stretching the film in at least one uniaxial direction and winding the film with a winder.
• the composition (Z) which comprises the stretched porous film of this invention it is preferable to carry out melt-kneading.
• a mixer such as tumbler mixer, mixing roll, Banbury mixer, ribbon blender, super mixer, etc.
• an extruder such as a counter-direction twin-screw extruder, co-direction twin-screw extruder, etc.
• the obtained resin composition can be molded into a film by connecting a die such as a T-die or a round die to the tip of an extruder.
• a die such as a T-die or a round die may be connected to the tip of the extruder to form a film.
• film forming methods such as inflation molding, tubular molding, T-die molding and the like are preferable.
• the extrusion temperature is preferably about 180 to 260 ° C., more preferably 190 to 250 ° C. It is also effective to control the dispersion state of the material by optimizing the extrusion temperature and the shear state, to bring various physical properties and mechanical properties of the film described below to desired values.
• the stretched porous film 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, roll stretching in the longitudinal direction (film flow direction, MD), transverse direction (film flow direction) In at least one direction, such as by tenter stretching in the direction perpendicular to T.D.
• MD longitudinal direction
• the film may be stretched in the lateral direction and further stretched in the longitudinal direction. Further, the film may be simultaneously stretched in the longitudinal direction and the lateral direction by the simultaneous biaxial stretching machine.
• a tubular non-stretched film may be radially stretched by internal pressure by tubular molding.
• the ear of the folded tube-like stretched porous film is cut, divided into two pieces, and wound respectively.
• the folded unstretched film may be cut and divided into two unstretched films, which may then be stretched and wound respectively.
• the stretching temperature is preferably 0 ° C to 90 ° C, and more preferably 20 ° C to 70 ° C.
• the total stretching ratio is preferably 1.5 to 6.0 times in total, more preferably 2.0 to 5.0 times. By making the draw ratio 1.5 times or more in total, a stretched porous film can be obtained which is uniformly stretched and has an excellent appearance. On the other hand, by setting the draw ratio to a total of 6.0 times or less, breakage of the film can be suppressed.
• heat treatment or relaxation treatment can be performed at a temperature of 50 ° C. or more and 120 ° C. or less after stretching for the purpose of reducing the heat shrinkage rate, improving the physical properties, and the like.
• 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.
• a relaxation process can be performed by making the speed of the roll which contacts next time slower than an annealing roll speed, heating with an annealing roll.
• these heat processing and relaxation processing can also be performed in another process, after extending
• heat treatment or relaxation treatment If the temperature of the heat treatment or relaxation treatment is too low, the shrinkage of the film is difficult to reduce, and if the temperature is too high, the film may be wound around the roll or the formed micropores may be clogged. Therefore, it is preferable to perform heat treatment or relaxation treatment at a temperature of 50 ° C. or more and 120 ° C. or less. These heat treatments and relaxation treatments may be divided into multiple steps.
• the stretched porous film of the present invention can be subjected to surface treatment such as slit, corona treatment, printing, application of an adhesive, coating, vapor deposition and the like, if necessary.
• the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
• the measured value shown to the Example and evaluation were performed as follows.
• the flow direction of the film is described as the "longitudinal" direction (or MD)
• the perpendicular direction is referred to as the "lateral” direction (or TD).
• the air permeability of the stretched porous film was calculated according to the method described above.
• an Oken type air permeability measuring machine EGO1-55 manufactured by Asahi Seiko Co., Ltd. was used.
• the crystal melting enthalpy ( ⁇ Hm) of the stretched porous film was calculated from the crystal melting peak (Pm) in the temperature rising process and the peak area of the crystal melting peak (Pm) in the reheating process.
• the presence or absence of a crystal melting peak (Pm1) was confirmed at 140 ° C. to 200 ° C. at this time. Further, peak temperature (Tm1) and crystal melting enthalpy ( ⁇ Hm1) were calculated from the above (Pm1). Similarly, the presence or absence of a crystal melting peak (Pm2) was confirmed at 30 ° C. to 130 ° C. Further, the peak temperature (Tm2) and the crystal melting enthalpy ( ⁇ Hm2) were calculated from the above (Pm2).
• the TD end portions of the laminated stretched porous film were sandwiched, and the distance between the held TD end portions was adjusted to 100 mm. Furthermore, after adjusting the distance between the stretched porous film held thereby and the microphone (sound collecting portion) of the ordinary sound level meter to be 100 mm, the MD and TD in the direction perpendicular to the held stretched porous film (thickness direction The film was rubbed by vibrating the clamped end three times back and forth in 1 second, and the time average sound level (LAeq) in 10 seconds of measurement time was measured and evaluated according to the following judgment criteria.
• LAeq time average sound level
• time average sound level (LAeq) in 10 seconds of measurement time in the state which does not vibrate a film (non-operating state) was 26 dB.
• (14-2) Examples 105 to 108 and Comparative Examples 103 to 104 In view of the evaluations described in (1) to (7) and (9) to (12) above, comprehensive evaluation was performed on the basis of the following criteria.
• B A film that has excellent feel such as flexibility and texture and is excellent in air permeability and moisture permeability, but is a film that feels the generation of unpleasant noise.
• Film that combines B A film suitable for applications requiring breathability and moisture permeability, which has excellent tactile sensation such as flexibility and texture and suppresses the generation of unpleasant noise generated when rubbing the film, but heat resistance is insufficient It is.
• C A film excellent in air permeability and moisture permeability, but it is a film which does not feel a sense of flexibility or texture and feels the generation of an unpleasant sound.
• D A film having insufficient physical properties required for a stretched porous film such as air permeability and moisture permeability.
• Raw materials used in each example and comparative example are as follows.
• A-1 Heavy calcium carbonate
• B linear low density polyethylene
• Novatec LL UF230 linear low density polyethylene
• E ⁇ Plasticizer (E)> -Kaif Trading Co., Ltd., hardened castor oil "HCO-P3".
• E-1 hardened castor oil
• E-2 -A liquid polyester plasticizer
• E-2 antioxidant
• Irganox B225 antioxidant
• F-1 antioxidant
• Example 101 Each raw material is weighed according to the composition ratio shown in Table 1, then charged in a Henschel mixer, mixed and dispersed for 5 minutes, and melt-kneaded at a set temperature of 200 ° C. using a co-directional twin-screw extruder The resin composition was extruded with a T-die connected to the tip of a co-directional twin-screw extruder, pulled out with a casting roll set at 50 ° C., and cooled and solidified to obtain an unstretched film. Dynamic viscoelasticity measurement was performed on the obtained unstretched film.
• the obtained unstretched film is (S)-(T)
• (T)-(U) draw ratio 130% (draw ratio: 2.3 times) was multiplied to give a total draw of 5.3 times in MD.
• the stretched porous film was obtained by performing heat treatment and relaxation treatment with a roll (V) set to 90 ° C.
• Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 1.
• Example 102 In the same manner as in Example 101, an unstretched film was collected. Thereafter, between the roll (S) set to 60 ° C., the roll (T) set to 60 ° C., and the roll (U) set to 60 ° C., the obtained unstretched film is (S)-(T) A draw ratio of 100% (stretching ratio: 2.0 times) and (T)-(U) draw ratio 100% (stretching ratio: 2.0 times) were applied to make a total of 4.0 times stretching in MD. Subsequently, the stretched porous film was obtained by performing heat treatment and relaxation treatment with a roll (V) set to 90 ° C. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 1.
• Example 103 In the same manner as in Example 101, an unstretched film was collected. Thereafter, between the roll (S) set to 60 ° C., the roll (T) set to 60 ° C., and the roll (U) set to 60 ° C., the obtained unstretched film is (S)-(T) ) Draw ratio 70% (stretching ratio 1.7 times), (T)-(U) draw ratio 70% (stretching ratio 1.7 times), and the film was stretched in total by 2.9 times in MD. Subsequently, the stretched porous film was obtained by performing heat treatment and relaxation treatment with a roll (V) set to 90 ° C. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 1.
• Example 104 Each raw material is weighed according to the composition ratio shown in Table 1, then charged in a Henschel mixer, mixed and dispersed for 5 minutes, and melt-kneaded at a set temperature of 200 ° C. using a co-directional twin-screw extruder The resin composition was extruded with a T-die connected to the tip of a co-directional twin-screw extruder, pulled out with a casting roll set at 50 ° C., and cooled and solidified to obtain an unstretched film. Dynamic viscoelasticity measurement was performed on the obtained unstretched film.
• the obtained unstretched film is (S)-(T)
• a draw ratio of 100% (stretching ratio: 2.0 times) and (T)-(U) draw ratio 100% (stretching ratio: 2.0 times) were applied to make a total of 4.0 times stretching in MD.
• the stretched porous film was obtained by performing heat treatment and relaxation treatment with a roll (V) set to 90 ° C.
• Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 1.
• Comparative Example 102 Each raw material is weighed according to the composition ratio shown in Table 1, then charged in a Henschel mixer, mixed and dispersed for 5 minutes, and melt-kneaded at a set temperature of 200 ° C. using a co-directional twin-screw extruder The resin composition was extruded with a T-die connected to the tip of a co-directional twin-screw extruder, pulled out with a casting roll set at 50 ° C., and cooled and solidified to obtain an unstretched film. Dynamic viscoelasticity measurement was performed on the obtained unstretched film.
• the obtained unstretched film is (S)-(T)
• (T)-(U) draw ratio 130% (draw ratio: 2.3 times) was multiplied to give a total draw of 5.3 times in MD.
• the stretched porous film was obtained by performing heat treatment and relaxation treatment with a roll (V) set to 90 ° C.
• Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 1.
• the stretched porous films obtained in Examples 101 to 104 were films having excellent air permeability and moisture permeability, and also having suitable tensile strength at break, tensile elongation at break, heat shrinkage, and total light transmittance. . In addition, even when the stretched porous films obtained in Examples 101 to 104 were rubbed together, no unpleasant sound was felt. The results show that the tan ⁇ calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of the present invention and the porosity of the stretched porous film satisfy the range specified in the present invention.
• tan ⁇ calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of Examples 101 to 104 is 0.100 or more at ⁇ 20 ° C., It is considered that the sound propagating by vibrating the resin composition (Z) is attenuated and contributes to the suppression of the unpleasant sound.
• the porosity of the stretched porous films of Examples 101 to 104 is in the range of 25% to 80%, the sound propagating through the communicated voids is the sound of the voids and the wall surface of the resin composition (Z). It is thought that the number of energy losses that occur during a collision increases and contributes to the suppression of unpleasant noise.
• the film obtained in Comparative Example 101 is a film using the resin composition (Z) satisfying the above-mentioned definition of tan ⁇ defined in the present invention as in Examples 101 to 103, but Comparative Example The stretched porous film obtained in 101 deviates from the porosity defined in the present invention. Therefore, although the film obtained in Comparative Example 101 is excellent in touch such as flexibility and texture, it was insufficient for suppression of unpleasant noise. Moreover, although the film obtained in Comparative Example 102 satisfies the porosity defined by the present invention, tan ⁇ at ⁇ 20 ° C. is less than 0.100, which is insufficient for suppression of unpleasant noise. The That is, it is important that both the above-mentioned tan ⁇ and the porosity satisfy the range defined by the present invention in order to achieve both the excellent feel and the suppression of the unpleasant noise generated when the film is rubbed. I understand.
• Example 105 Each raw material is weighed according to the composition ratio shown in Table 2, then charged in a Henschel mixer, mixed and dispersed for 5 minutes, and melt-kneaded at a set temperature of 200 ° C. using a co-directional twin-screw extruder The resin composition was extruded with a T-die connected to the tip of a co-directional twin-screw extruder, pulled out with a casting roll set at 50 ° C., and cooled to solidify to obtain an unstretched film with a thickness of 30 ⁇ m. Dynamic viscoelasticity measurement was performed on the obtained unstretched film.
• the obtained unstretched film is (S)-(T)
• a draw ratio of 100% (stretching ratio: 2.0 times) and (T)-(U) draw ratio 100% (stretching ratio: 2.0 times) were applied to make a total of 4.0 times stretching in MD.
• the stretched porous film was obtained by performing heat treatment and relaxation treatment with a roll (V) set to 90 ° C.
• Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 2.
• Example 106 An unstretched film with a thickness of 30 ⁇ m was collected by the same method as in Example 105 except that the raw materials were changed to the composition ratios shown in Table 2. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 105 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 2.
• Example 107 An unstretched film with a thickness of 30 ⁇ m was collected by the same method as in Example 105 except that the raw materials were changed to the composition ratios shown in Table 2. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 105 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 2.
• Example 108 An unstretched film with a thickness of 50 ⁇ m was collected by the same method as in Example 105 except that the raw materials were changed to the composition ratios shown in Table 2. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 105 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 2.
• Comparative Example 103 An unstretched film with a thickness of 50 ⁇ m was collected by the same method as in Example 105 except that the raw materials were changed to the composition ratios shown in Table 2. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 105 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 2.
• Comparative Example 104 An unstretched film with a thickness of 50 ⁇ m was collected by the same method as in Example 105 except that the raw materials were changed to the composition ratios shown in Table 2. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 105 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 2.
• the stretched porous films obtained in Examples 105 to 108 were films excellent in air permeability and moisture permeability as well as having suitable tensile strength at break, tensile elongation at break and total light transmittance.
• the time average sound level (LAeq) when the stretched porous films obtained in Examples 105 to 108 were rubbed together showed a low value, and no unpleasant sound was felt.
• tan ⁇ calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of the present invention and the range in which the porosity of the stretched porous film is defined in the present invention, And, it is considered that the crystal melting enthalpy ( ⁇ Hm) of the stretched porous film is 10 g / J to 45 g / J.
• tan ⁇ calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of Examples 105 to 108 is 0.100 or more at ⁇ 20 ° C., It is considered that the sound propagating by vibrating the resin composition (Z) is attenuated and contributes to the suppression of the unpleasant sound.
• the crystal melting enthalpy ( ⁇ Hm) of the stretched porous films of Examples 1 to 4 is in the range of 10 J / g to 45 J / g, there are few crystal components that repel and vibrate when an external force is applied. It is thought that the sound to be on the other hand, the films obtained in Comparative Examples 103 and 104 do not satisfy the preferable range of tan ⁇ specified in the present invention or the crystal melting enthalpy ( ⁇ Hm), so they are insufficient for suppressing unpleasant noise, and the time average Sound level (LAeq) showed a high value.
• the crystal melting enthalpy ( ⁇ Hm) of the stretched porous film is preferably in the range of 10 g / J to 45 g / J.
• Example 201 Each raw material is weighed according to the composition ratio shown in Table 3, then charged in a Henschel mixer, mixed and dispersed for 5 minutes, and melt-kneaded at a set temperature of 200 ° C. using a co-directional twin-screw extruder The resin composition was extruded with a T-die connected to the tip of a co-directional twin-screw extruder, pulled out with a casting roll set at 50 ° C., and cooled to solidify to obtain an unstretched film with a thickness of 35 ⁇ m. Dynamic viscoelasticity measurement was performed on the obtained unstretched film.
• the obtained unstretched film is (S)-(T)
• a draw ratio of 100% (stretching ratio: 2.0 times) and (T)-(U) draw ratio 100% (stretching ratio: 2.0 times) were applied to make a total of 4.0 times stretching in MD.
• the stretched porous film was obtained by performing heat treatment and relaxation treatment with a roll (V) set to 90 ° C.
• Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 3.
• Embodiment 202 An unstretched film with a thickness of 35 ⁇ m was collected by the same method as in Example 201 except that the raw materials were changed to the composition ratios shown in Table 3. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 201 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 3.
• Embodiment 203 An unstretched film with a thickness of 35 ⁇ m was collected by the same method as in Example 201 except that the raw materials were changed to the composition ratios shown in Table 3. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 201 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 3.
• Embodiment 204 An unstretched film with a thickness of 35 ⁇ m was collected by the same method as in Example 201 except that the raw materials were changed to the composition ratios shown in Table 3. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 201 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 3.
• Embodiment 205 An unstretched film with a thickness of 35 ⁇ m was collected by the same method as in Example 201 except that the raw materials were changed to the composition ratios shown in Table 3. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 201 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 3.
• Comparative Example 201 An unstretched film with a thickness of 50 ⁇ m was collected by the same method as in Example 201 except that the raw materials were changed to the composition ratios shown in Table 3. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 201 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 3.
• Comparative Example 202 An unstretched film with a thickness of 50 ⁇ m was collected by the same method as in Example 201 except that the raw materials were changed to the composition ratios shown in Table 3. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 201 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 3.
• Comparative Example 203 An unstretched film with a thickness of 30 ⁇ m was collected by the same method as in Example 201 except that the raw materials were changed to the composition ratios shown in Table 3. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 201 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 3.
• Comparative Example 204 An unstretched film with a thickness of 35 ⁇ m was collected by the same method as in Example 201 except that the raw materials were changed to the composition ratios shown in Table 3. Dynamic viscoelasticity measurement was performed on the obtained unstretched film. Thereafter, the obtained unstretched film is stretched, heat-treated and relaxed in the same manner as in Example 201 to obtain a stretched porous film. Various evaluations were performed on the obtained stretched porous film. The results are summarized in Table 3.
• the stretched porous films obtained in Examples 201 to 205 were films excellent in air permeability and moisture permeability as well as having suitable tensile strength at break, tensile elongation at break, and total light transmittance.
• the time average sound level (LAeq) when the stretched porous films obtained in Examples 201 to 205 were rubbed together showed a low value, and no unpleasant sound was felt.
• the film rupture heat resistance test the film did not rupture at 120 ° C., 140 ° C., and even at 160 ° C.
• tan ⁇ calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of the present invention and the appearance temperature of the crystal melting peak satisfy the range specified by the present invention It is thought that it is for.
• tan ⁇ calculated from the dynamic viscoelasticity measurement of the resin composition (Z) constituting the stretched porous film of Examples 201 to 205 is 0.100 or more at ⁇ 20 ° C., It is considered that the sound propagating by vibrating the resin composition (Z) is attenuated and contributes to the suppression of the unpleasant sound.
• the stretched porous films obtained in Examples 201 to 205 have crystal melting peaks at 140 ° C. to 200 ° C., they were shown to have high heat resistance.
• the films obtained in Comparative Examples 201 and 202 do not satisfy tan ⁇ prescribed by the present invention, they are insufficient for suppressing unpleasant noise, and the time average sound level (LAeq) shows a high value.
• the film obtained in Comparative Example 203 is a film that is soft and suppresses unpleasant noise because it does not have a crystal melting peak in the range of 140 ° C. to 200 ° C., but the heat resistance required for the stretched porous film is It turns out that it is somewhat inadequate.
• Comparative Example 204 is a film containing an ⁇ -olefin copolymer having a density of less than 0.850 g / cm 3 , but because the film does not satisfy tan ⁇ specified by the present invention, it is insufficient for suppressing unpleasant noise.
• Met That is, in order to achieve both the heat resistance required for the stretched porous film and the suppression of the unpleasant noise generated when the film rubs, both the above-mentioned tan ⁇ and the temperature at which the crystal melting peak appears are the present invention. It is understood that it is important to satisfy the specified range.
• the stretched porous film of the present invention has an excellent tactile sensation such as flexibility and texture, and also suppresses the generation of unpleasant sound generated when the film is rubbed, and is also excellent in air permeability, moisture permeability and strength. Therefore, sanitary products such as disposable diapers and feminine hygiene products using stretched porous film; clothing such as work clothes, jumpers, jackets, medical clothes, chemical protective clothes, etc. Furthermore, masks, covers, drapes, sheets, wraps Etc. It can utilize suitably for the use by which air permeability, moisture permeability, etc. are calculated

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