WO2018070250A1 - Film - Google Patents

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Publication number
WO2018070250A1
WO2018070250A1 PCT/JP2017/035049 JP2017035049W WO2018070250A1 WO 2018070250 A1 WO2018070250 A1 WO 2018070250A1 JP 2017035049 W JP2017035049 W JP 2017035049W WO 2018070250 A1 WO2018070250 A1 WO 2018070250A1
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WIPO (PCT)
Prior art keywords
film
organic particles
resin
layer
base film
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PCT/JP2017/035049
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English (en)
Japanese (ja)
Inventor
蓑毛克弘
新崎盛昭
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2017553433A priority Critical patent/JP6965750B2/ja
Publication of WO2018070250A1 publication Critical patent/WO2018070250A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules

Definitions

  • the present invention relates to a film excellent in shear deformability, slipperiness and appearance, which are characteristics of the texture.
  • Patent Document 1 discloses a moisture permeable film having improved tactile sensation by mixing and stretching an olefin resin with barium sulfate having an average particle size of 2 ⁇ m or more.
  • Patent Document 2 discloses a film whose surface is coated with particles.
  • the present invention provides a film that improves the drawbacks of the prior art and has the mechanical properties necessary for use as a film and is excellent in the shear deformation, slipperiness, and appearance that are the characteristics of the texture. Let it be an issue.
  • the present invention has the following configuration. (1) It has organic particles on at least one outermost surface of the base film, and the ratio of the average particle diameter ( ⁇ m) of the organic particles to the average thickness ( ⁇ m) of the base film (average of base film) (Thickness / average particle diameter of organic particles) is 0.5 or more and 3.0 or less, and shear strength in the KES method is 0.1 gf / (cm ⁇ deg) or more and 6.0 gf / (cm ⁇ deg) or less. A film characterized by that. (2) In the surface having organic particles, when the area of the entire film is 100%, the ratio of the area occupied by the organic particles is 20% or more and less than 100%, the film.
  • the base film has a laminated structure of at least a layer in contact with the organic particles (A layer) and a layer (B layer) located on the opposite side of the organic particles with the A layer interposed therebetween.
  • the film according to any one of (1) to (7).
  • (9) When the total resin component in the A layer is 100% by mass so that the absolute value of the solubility parameter difference becomes the smallest, 1 out of 5% by mass or more of the resin contained in the A layer
  • one resin (resin A) is selected and the total resin component of the organic particles is 100% by mass
  • one resin (resin B) is selected from the resins contained in the organic particles at 5% by mass or more.
  • the film according to (8), wherein an absolute value of a difference in solubility parameter between the resin A and the resin B is 0.10 (MPa) 0.5 or less.
  • the present invention it is possible to provide a film having mechanical properties necessary for use as a film and excellent in shear deformation, slipperiness, and appearance, which are the characteristics of the texture.
  • the film of the present invention has organic particles on at least one outermost surface of the substrate film, and the ratio of the average particle diameter ( ⁇ m) of the organic particles to the average thickness ( ⁇ m) of the substrate film (substrate)
  • the average thickness of the film / the average particle diameter of the organic particles is 0.5 or more and 3.0 or less, and the shear strength in the KES method is 0.1 gf / (cm ⁇ deg) or more and 6.0 gf / (cm ⁇ deg). It is characterized by the following.
  • FIGS. 1A and 1B are schematic cross-sectional views showing an example of the film of the present invention.
  • reference numeral 1 indicates organic particles
  • reference numeral 2 indicates a base film.
  • Half or more of the organic particles on the surface of the base film may protrude from the surface (FIG. 1 (A)), or less than half of the organic particles may protrude (FIG. 1 (B)).
  • the organic particles may be present individually as shown in FIGS. 1A and 1B, or a plurality of particles may be aggregated or aggregated (FIG. 1C).
  • organic particles may be arranged on the surface of the base film in a plane with almost no gap (FIG. 2A), or a plurality of particles may overlap in the thickness direction of the film (FIG. 2). (B)).
  • the thickness direction means a direction perpendicular to the film surface.
  • the base film in the present invention preferably contains a thermoplastic elastomer from the viewpoint of shear deformability.
  • the thermoplastic elastomer refers to a high molecular weight body having rubber elasticity at 25 ° C.
  • the thermoplastic elastomer may be either a crystalline thermoplastic elastomer or an amorphous thermoplastic elastomer, or a mixture of both, as long as the effects of the present invention are not impaired.
  • the thermoplastic elastomer having crystallinity is a crystal melting peak when heated in a hot air oven at 100 ° C. for 24 hours and then heated from 25 ° C. to 250 ° C. at a heating rate of 20 ° C./min.
  • the amorphous thermoplastic elastomer refers to a thermoplastic elastomer in which no crystal melting peak is observed under the same conditions.
  • thermoplastic elastomer having crystallinity in the base film is not particularly limited as long as the effects of the present invention are not impaired.
  • a polyester-based elastomer, a polyolefin-based elastomer, and a polyamide-based elastomer are used alone or in combination. Can do.
  • polyester-based elastomer examples include a block copolymer of an aromatic polyester and an aliphatic polyester, and a block copolymer of an aromatic polyester and an aliphatic polyether. From the viewpoint, it is preferable to use a block copolymer of an aromatic polyester and an aliphatic polyether.
  • polyester-based elastomer examples include “Hytrel” (registered trademark) G3548 and HTR8206 grade manufactured by Toray DuPont.
  • polyamide-based elastomer examples include a block copolymer of aliphatic polyamide and aliphatic polyester, and a block copolymer of aliphatic polyamide and aliphatic polyether. From the viewpoint of imparting, it is preferable to use a block copolymer of an aliphatic polyamide and an aliphatic polyether.
  • polyamide-based elastomer examples include “PEBAX” (registered trademark) MV1074, MV1041, MV3000, and MH1657 grades manufactured by Arkema.
  • the content of the thermoplastic elastomer having crystallinity in the base film is not particularly limited as long as the effects of the present invention are not impaired, but from the viewpoint of film formation stability, the entire resin in the base film is 100% by mass. Is preferably 10% by mass or more and 100% by mass or less, more preferably 10% by mass or more and 95% by mass or less, and further preferably 20% by mass or more and 90% by mass or less.
  • the content of the thermoplastic elastomer having crystallinity is calculated by adding all thermoplastic elastomers having crystallinity.
  • amorphous thermoplastic elastomer examples include polyurethane elastomers, styrene elastomers, acrylic elastomers, etc. Among them, polyurethane elastomers are used particularly from the viewpoint of shear deformation. It is preferable.
  • polyurethane elastomer examples include a block copolymer of a hard segment phase comprising a short-chain glycol and diisocyanate and a soft segment phase comprising a polyether, and a block copolymer comprising the hard segment phase and a soft segment phase comprising a polyester.
  • a polymer etc. are mentioned, it is preferable that it is a block co-polymer which has a soft segment phase which consists of polyether from a viewpoint of moisture permeability provision.
  • amorphous polyurethane-based elastomer examples include OP85A10 grade and ET885FG grade of “Elastollan” (registered trademark) manufactured by BASF Japan.
  • the base film may contain resin with high compatibility with an organic particle from the viewpoint of the adhesiveness of the base film mentioned later and an organic particle.
  • the organic particles and the high compatibility resin has a solubility parameter (MPa 0.5) is in the range of solubility parameters ⁇ 0.10 of a resin contained most in the organic particles (MPa 0.5) Resin Say.
  • the solubility parameter (MPa 0.5 ) of any resin in which the solubility parameter (MPa 0.5 ) is most contained in the organic particles is present in the base film.
  • the base film is considered to contain a resin highly compatible with organic particles.
  • the type of resin highly compatible with organic particles is not particularly limited as long as the effects of the present invention are not impaired, and as the above-described crystalline thermoplastic elastomer or amorphous thermoplastic elastomer, “organic particles and The use of a resin that satisfies the conditions of “highly compatible resin” can also be used when the above-mentioned crystalline thermoplastic elastomer or amorphous thermoplastic elastomer is not “resin highly compatible with organic particles”. It is also possible to add another resin.
  • the solubility parameter is a parameter calculated on the basis of the cohesive energy density and molar molecular weight of each atomic group constituting the resin. Specifically, Hideki Yamamoto, “SP Value Basics / Applications and Calculation Methods” ) Calculated based on Fedor's estimation method described in Information Technology Issue (2005), paragraphs 66-67). In the case where the resin structure is unclear and cannot be calculated by the above method, an experimental method (“Polymer Handbook Fourth Edition (Polymer Handbook Fourth)” is used. Edition) ”by J. Brand, published by Wiley, 1998), and the value can be substituted.
  • Solubility parameter of polymer consisting of repeating unit A and repeating unit B (solubility parameter of repeating unit A) ⁇ (molar fraction of repeating unit A) + (solubility parameter of repeating unit B) ⁇ (molar fraction of repeating unit B) Rate) ...
  • the base film contains a resin that is highly compatible with the organic particles, thereby improving the adhesion between the organic particles and the base film in the method of fixing the organic particles described later to the outermost surface of the base film by a thermal history. It becomes easy.
  • the content of the amorphous thermoplastic elastomer in the base film of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but from the viewpoint of shear deformability, moisture permeability, and film formation stability, the present invention.
  • the total resin in the base film is 100% by mass, it is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and more preferably 15% by mass or more. More preferably, it is 40 mass% or less.
  • the content of amorphous thermoplastic elastomer is calculated by adding all amorphous thermoplastic elastomers together. And
  • the thickness of the base film of the present invention is not particularly limited as long as the effects of the present invention are not impaired.
  • the thickness of a base film here can be measured as follows, for example. First, an ultrathin section was sampled at ⁇ 100 ° C. using a microtome so that the machine direction-thickness direction cross section (hereinafter, referred to as film cross section) of the sample piece was the observation surface, and a scanning electron microscope was used. Take a picture of the film cross section at a magnification of 500 times. Using the photograph of the obtained cross section, the thickness of the portion where no organic particles are present on the outermost surface of the film is measured by the length measuring function of the microscope.
  • microtome for example, a rotary microtome manufactured by Japan Microtome Research Institute Co., Ltd. can be used, and as the scanning electron microscope, for example, S-3400N manufactured by Hitachi, Ltd. can be used. Hereinafter, it is the same about the measuring method using these.
  • the thickness of the base film By setting the thickness of the base film to 3 ⁇ m or more, the stiffness of the film becomes stronger, the handleability is improved, and the roll winding shape and unwinding property are also improved.
  • the thickness of the base film By setting the thickness of the base film to 200 ⁇ m or less, particularly in the inflation film forming method, bubbles are stabilized by their own weight. From such points, the thickness of the base film is more preferably 5 ⁇ m or more and 150 ⁇ m or less, and further preferably 6 ⁇ m or more and 40 ⁇ m or less.
  • the film of the present invention has organic particles on at least one outermost surface of the base film from the viewpoint of imparting a touch like cloth to the film.
  • the organic particles in the present invention are not particularly limited as long as the effects of the present invention are not impaired.
  • Organic particles containing as a main component are used.
  • the organic particle which has polyolefin resin and acrylic resin as a main component from a viewpoint of the slipperiness of the film obtained.
  • the main component of the polyolefin-based resin means that 50% by mass or more of the polyolefin-based resin is included when the entire resin component constituting the organic particles is 100% by mass.
  • main component can be similarly interpreted.
  • the shape of the organic particles is not particularly limited as long as the effects of the present invention are not impaired.
  • a spherical shape, an ellipsoidal shape, a polyhedral shape, and a shape obtained by making these three-dimensional bodies porous are used. Can do.
  • the shape of the organic particles is preferably spherical.
  • Whether or not the shape of the organic particles is spherical is determined by the following procedure. First, the surface having organic particles on the outermost surface of the film is observed from a direction perpendicular to the film surface with a laser microscope by magnifying the magnification of the objective lens to 150 times, and the organic particles located on the outermost layer are centered in the observation field. 100 are extracted in ascending order. For each extracted organic particle, the area and perimeter of the two-dimensional projection shape are measured, and the circularity is calculated by the following equation 1. When the average value of the obtained circularity is 0.3 or more and 1.0 or less, it is determined that the shape of the organic particles is spherical.
  • circularity 4 ⁇ ⁇ (area of 2D projection shape) / (peripheral length of 2D projection shape) 2
  • the circularity is more preferably 0.4 or more and 1.0 or less, and further preferably 0.5 or more and 1.0 or less.
  • the method for making the shape of the organic particles spherical is not particularly limited as long as the effect of the present invention is not impaired, for example, a method of using a resin obtained by suspension polymerization or emulsion polymerization as organic particles, Examples include a method of increasing the weight average molecular weight of the resin in the organic particles to reduce the deformation of the organic particles due to the heat history in the production process.
  • the average particle size of the organic particles in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but from the viewpoint of adhesion between the base film and the organic particles, it is preferably 1 ⁇ m or more and 200 ⁇ m or less, and 3 ⁇ m or more and 150 ⁇ m. More preferably, it is more preferably 5 ⁇ m or more and 100 ⁇ m or less.
  • the average particle diameter of the organic particles can be measured by the following method. First, using a microtome, the film is cut in a direction perpendicular to the film surface at a knife inclination angle of 3 °. The obtained cross section is observed with a scanning electron microscope, and a square or rectangle is drawn so as to completely surround one organic particle and have the smallest area. Uses the average value of the lengths of the long side and the short side as the particle diameter of the organic particles. The same measurement is performed on 100 organic particles, and the average value of the obtained values is defined as the average particle size of the organic particles.
  • the film of the present invention has a weight average molecular weight of 500,000 or more from the viewpoint of suppressing deformation of the particles due to the thermal history when taking a manufacturing process in which the base film and the organic particles are pressure-bonded by the thermal history as described later. It is preferable that By reducing the deformation of the particles within the range of the weight average molecular weight, it becomes easy to reduce the contact area between the finger and the film when the film is touched with the finger, and the touch of the film is improved.
  • the weight average molecular weight of the organic particles is more preferably 1,000,000 or more, and even more preferably 1,500,000 or more. From the above viewpoint, the higher the weight average molecular weight of the organic particles, the more preferably the upper limit is not particularly limited, but 10 million is sufficient from a practical viewpoint.
  • the weight average molecular weight of the resin is defined as the weight average molecular weight of the organic particles.
  • the weight average molecular weight of the organic particles is determined by multiplying the weight average molecular weight of each resin by the content ratio (mass ratio).
  • the weight average molecular weight of the resin can be measured by a gel permeation chromatography (GPC) method, and detailed conditions will be described later.
  • polyolefin resins that can be used for organic particles include “Mipelon” (registered trademark), “Hi-Z Million” (registered trademark) manufactured by Mitsui Chemicals, Inc., and “Sunfine” (registered trademark) manufactured by Asahi Kasei Chemicals Corporation. Trademark), “Flowsen” (registered trademark) manufactured by Sumitomo Seika Co., Ltd., and the like.
  • acrylic resin that can be used for the organic particles include “Gantz Pearl” (registered trademark) manufactured by Aika Kogyo Co., Ltd. and “Matsumoto Microsphere” (registered trademark) M manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Series etc. are mentioned.
  • the ratio of the average particle size ( ⁇ m) of the organic particles to the average thickness ( ⁇ m) of the substrate film is 0.5 or more and 3 It is important that the value is 0.0 or less.
  • the “average thickness of the base film / average particle diameter of the organic particles” is 0.5 or more, the average particle diameter of the organic particles does not become too large, and the organic particles do not easily fall out of the film, and slippery. And the feeling of touch is less likely to be impaired.
  • “average thickness of base film / average particle diameter of organic particles” is 3.0 or less, the thickness of the base film does not become too large, and the shear deformability of the film is improved. From this point, “average thickness of base film / average particle diameter of organic particles” is more preferably 0.6 or more and 2.5 or less, and further preferably 0.7 or more and 2.0 or less.
  • the film of the present invention preferably has a ratio of the area occupied by organic particles of 20% or more and less than 100% when the area of the whole film is 100% on the surface having organic particles.
  • the area of the whole film is 100% and the proportion of the area occupied by the organic particles is 20% or more, the appearance and slipperiness of the film are improved.
  • the ratio of the area occupied by the organic particles is 100%, a layer made of the same component as the organic particles is formed on the surface of the base film.
  • the organic particles used for improving the slipperiness are harder than the base film, so if the ratio of the area occupied by the organic particles is 100%, the shear strength described later becomes excessively large, and the film itself is soft. May be damaged.
  • the ratio of the area occupied by the organic particles when the area of the entire film is 100% is more preferably 20% or more and 90% or less, and 30% or more. 90% or less is more preferable, and 40% or more and 85% or less is particularly preferable.
  • the ratio of the area of the organic particles in the entire film can be obtained, for example, as follows. First, the surface of the film having organic particles is observed with a scanning electron microscope at 200 times magnification, and the number of organic particles on the film surface is counted. Next, the product of the number of organic particles on the film surface and the average particle diameter of the organic particles described above is obtained, and this is defined as the area of the organic particles. Furthermore, the area of the observation image is defined as the area of the entire film, and the ratio of the area of organic particles in the entire film is calculated.
  • the film of the present invention preferably has a peel strength between the base film and the organic particles of 30 gf / 25 mm or more from the viewpoint of maintaining the slipperiness by suppressing the falling off of the outermost organic particles.
  • the peel strength refers to an average value of a flat portion of a peel curve obtained in a peel test described later.
  • the peel strength between the base film and the organic particles is more preferably 40 gf / 25 mm or more, and further preferably 45 gf / 25 mm or more.
  • the upper limit of the adhesion force of the organic particles is preferably as high as possible, but 300 gf / 25 mm is sufficient from a practical viewpoint.
  • the method for setting the peel strength between the base film and the organic particles to 30 gf / 25 mm or more, or the above preferable range is not particularly limited as long as the effects of the present invention are not impaired.
  • the peel strength between the base film and the organic particles can be increased by increasing the heat history applied to the particles, or by adding a component having high compatibility with the organic particles to the base film.
  • shear strength measured according to the KES method is 0.1 gf / (cm ⁇ deg) or more and 6.0 gf / (cm ⁇ deg) or less from the viewpoint of bringing the shear deformability closer to the cloth. It is.
  • Shear deformation refers to a deformation pattern that is most easily received by a cloth composed of warp and weft crossing. The fact that a two-dimensional cloth can easily cover a three-dimensional curved surface greatly depends on this shear deformation, and the greater the shear deformation, that is, the smaller the shear strength, the easier it is to fit a curved surface like a human body, A feeling of wearing will be good. That is, when a film having a shear strength of 0.1 gf / (cm ⁇ deg) or more and 6.0 gf / (cm ⁇ deg) or less is used for an application that may be worn on a human body such as a sanitary material. This is preferable.
  • the shear strength measured according to the KES method refers to the shear hardness calculated from the shear stress in the machine direction and the width direction measured according to the Kawabata Evaluation System method.
  • the machine direction refers to the direction in which the film proceeds during film production
  • the width direction refers to the direction that is parallel to the film transport surface and orthogonal to the machine direction (hereinafter the same). More specifically, the shear stress in the machine direction and the width direction at points where the shear deformation is ⁇ 2.5 °, ⁇ 0.5 °, 0.5 °, and 2.5 ° is measured by the KES method.
  • the shear stress at each point may be referred to as HG ⁇ 2.5 , HG ⁇ 0.5 , HG 0.5 , and HG 2.5 respectively).
  • the conditions for measurement of the shear stress are room temperature 23 ° C., relative humidity 65%, forced load 10 gf, shear shear rate 0.417 mm / sec, and sample shear deformation range ⁇ 8 ° to 8 °.
  • the shear hardness measured according to the KES method may be simply referred to as shear hardness.
  • the shear hardness is more preferably 0.1 gf / (cm ⁇ deg) or more and 3.5 gf / (cm ⁇ deg) or less, and more preferably 0.1 gf / (cm ⁇ deg) or more and 2.0 gf / ( cm ⁇ deg) or less, more preferably 0.1 gf / (cm ⁇ deg) or more and 1.5 gf / (cm ⁇ deg) or less.
  • the method for setting the shear hardness of the film of the present invention to 0.1 gf / (cm ⁇ deg) or more and 6.0 gf / (cm ⁇ deg) or less, or the preferable range described above is particularly effective as long as the effects of the present invention are not impaired.
  • the shear hardness can be reduced by increasing the content of the thermoplastic elastomer in the base film, reducing the thickness of the film, embossing described later, and the like.
  • the film of the present invention preferably has a coefficient of friction of 0.05 or more and 0.80 or less, measured according to the KES method, on the surface having organic particles, from the viewpoint of the slipperiness and productivity of the film.
  • the friction coefficient measured according to the KES method is 0.05 or more
  • the productivity of the film is improved.
  • the slipperiness of a film improves that the friction coefficient measured according to KES method is 0.80 or less.
  • the friction coefficient measured according to the KES method on the surface having organic particles is more preferably 0.05 or more and 0.35 or less, and further preferably 0.05 or more and 0.15 or less.
  • the friction coefficient measured according to the KES method is as follows: sample size is 10 cm (machine direction) ⁇ 10 cm (width direction), load is 25 gf, slider (standard friction element (fingerprint type)) Friction coefficient measured by the KES method at a speed of 1 mm / sec, a room temperature of 23 ° C., and a relative humidity of 65%.
  • the friction coefficient measured according to the KES method may be simply referred to as a friction coefficient.
  • the method for setting the coefficient of friction of the film of the present invention to 0.05 gf / (cm ⁇ deg) or more and 0.80 gf / (cm ⁇ deg) or less, or the above preferable range is particularly effective as long as the effect of the present invention is not impaired.
  • the coefficient of friction can be lowered by increasing the ratio of the area occupied by the organic particles to the total area of the film, or by bringing the shape of the organic particles closer to a spherical shape.
  • the film of the present invention preferably has a cushioning property from the viewpoint of a comfortable tactile film.
  • the cushioning property herein is an index representing bulkiness and flexibility, and can be expressed as a measure of a work amount (compression work amount) when the film is compressed.
  • the compression work can be measured according to the KES method. Specifically, the film was compressed between a steel plate having a circular plane with an area of 2 cm 2 under an atmosphere of a room temperature of 23 ° C. and a relative humidity of 65% under the conditions of a compression speed of 20 ⁇ m / sec and a maximum compression load of 10 gf / cm 2 . It can be measured by the KES method.
  • the compression work measured according to the KES method is simply referred to as compression work.
  • the film of the present invention preferably has a compression work of 0.02 gf ⁇ cm / cm 2 or more, more preferably 0.04 gf ⁇ cm / cm 2 or more, and 0.06 gf ⁇ cm 2. / Cm 2 or more is more preferable. If the compression work of the film is less than 0.02 gf ⁇ cm / cm 2 , the cushioning properties and the touch may be lowered. On the other hand, if the amount of compression work is too high, the handleability of the film and the post-processing suitability when post-processing such as printing and bonding may be deteriorated. From these viewpoints, the upper limit of the compression work is preferably 0.5 gf ⁇ cm / cm 2 .
  • the method for adjusting the compression work of the film of the present invention to 0.02 gf ⁇ cm / cm 2 or more, or the above preferable range is not particularly limited as long as the effects of the present invention are not impaired. Examples thereof include a method for adjusting the particle diameter, a method for imparting an uneven shape by embossing described later, and the like. Specifically, the compression work can be increased by increasing the average particle diameter of the organic particles, increasing the height of the concavo-convex portions, or the like.
  • the moisture permeability of the film 500g / (m 2 ⁇ day ) or more 5,000g / (m 2 ⁇ day) is preferably not more than.
  • a film can be used suitably for the use as which moisture permeability, such as a sanitary material, is requested
  • the moisture permeability of the film is more preferably 1,500 g / (m 2 ⁇ day) or more, and 2,000 g / (m 2 ⁇ day) or more.
  • the upper limit of the moisture permeability of the film is about 5,000 g / (m 2 ⁇ day) from the viewpoint of application to sanitary materials.
  • the water vapor transmission rate of a film here means the water vapor transmission rate measured by the method prescribed
  • the moisture permeability of the film can be improved by using a polyester elastomer having excellent moisture permeability as the resin constituting the base film.
  • the base film of the present invention may have a single-layer structure or a laminated structure as long as the effects of the present invention are not impaired, but is a characteristic of the entire film while reducing the dropping of the outermost organic particles from the base film.
  • it is preferably a laminated structure.
  • the layer in direct contact with the organic particles contains a resin component excellent in compatibility with the organic particles, and the other layers are suitable for setting the above-mentioned shear hardness and moisture permeability within a preferable range. By setting it as a composition, it becomes easy to obtain a film excellent in moisture permeability, shear hardness, and organic particle adhesion.
  • the base film has a laminated structure of at least a layer in contact with the organic particles (A layer) and a layer (B layer) located on the opposite side of the organic particles with the A layer interposed therebetween.
  • “consisting of a laminated structure of at least a layer in contact with organic particles (A layer) and a layer (B layer) located on the opposite side of the organic particles across the A layer” means “A layer and B layer” Is in contact with the organic particles on the surface of the A layer.
  • Examples include a base film having a three-layer structure.
  • the A layer and the B layer in the film of the present invention preferably contain a thermoplastic elastomer from the viewpoint of shear deformability.
  • the thermoplastic elastomer is not particularly limited as long as the effects of the present invention are not impaired, and may be either a crystalline thermoplastic elastomer or an amorphous thermoplastic elastomer, or a mixture of both. Good.
  • thermoplastic elastomer in the A layer it is preferable to use a polyester elastomer, a polyolefin elastomer, an acrylic elastomer, or the like alone or in combination from the viewpoint of facilitating adhesion with the organic particles.
  • thermoplastic elastomer in the B layer it is preferable to use a polyester elastomer from the viewpoint of moisture permeability of the obtained film.
  • a layer may contain the component enumerated as a component which comprises organic particle other than a thermoplastic elastomer.
  • a component which comprises organic particle other than a thermoplastic elastomer when the total resin component of the organic particles is 100% by mass, the component contained in the organic particles at 5% by mass or more, or a component having a chemical structure close to 100% by mass makes the total resin component of the A layer 100
  • the content is 5% by mass, the absolute value of the difference between the solubility parameters of the resin A and the resin B is reduced by being contained in the layer A by 5% by mass or more.
  • the absolute value of the difference between the solubility parameters of the resin A and the resin B is 0.10 (MPa) 0.5 or less, the adhesion between the layer A and the organic particles becomes strong, and the organic particles are caused by the load or contact with the film surface. Therefore, it becomes easy to give the film a touch like cloth.
  • the absolute value of the difference between the solubility parameters of the resin A and the resin B is more preferably 0.05 (MPa) 0.5 or less, and further preferably 0.01 (MPa) 0.5 or less.
  • the absolute value of the difference between the solubility parameters of the resin A and the resin B is preferably as small as possible in order to reduce the falling off of the organic particles, and therefore the lower limit can be set to 0 (MPa) 0.5 .
  • the method of setting the absolute value of the difference between the solubility parameters of the resin A and the resin B to 0.10 (MPa) 0.5 or less is not particularly limited as long as the effect of the present invention is not impaired. Examples thereof include a method in which the resin A and the resin B contained in the organic particles have the same components or their chemical structures as close as possible. For example, when the resin A and the resin B are the same component, the difference in the solubility parameter is 0 (MPa) 0.5 .
  • the A layer contains 5% by mass or more and 100% by mass or less of the resin A when the entire resin component in the A layer is 100% by mass. Is preferred. If the amount of the resin A in the A layer is less than 5% by mass when the total resin component in the A layer is 100% by mass, even if the absolute value of the difference in solubility parameter with the resin B described later is small, A Since the ratio of the resin A occupying the outermost surface of the layer is too small, sufficient adhesion may not be obtained between the A layer and the organic particles.
  • the content of the resin A in the A layer when the entire resin component in the A layer is 100% by mass is 10% by mass or more and 100% by mass or less. Is more preferable, and it is 15 to 100 mass%.
  • the organic particles of the present invention contain 50% by mass or more and 100% by mass or less of the resin B when the total resin component in the organic particles is 100% by mass. It is preferable.
  • the content of the resin B in the organic particles is 50% by mass or more when the total resin component in the organic particles is 100% by mass, the adhesion between the A layer and the organic particles can be improved.
  • the amount of the resin B in the organic particles is 90% by mass or more and 100% by mass or less when the entire resin component of the organic particles is 100% by mass. It is more preferable.
  • the resin A when there are a plurality of combinations satisfying the conditions of the resin A and the resin A, a resin having the largest content (% by mass) in the A layer is selected as the resin A.
  • a combination shall be adopted.
  • the resin A when there are a plurality of resins having the same content (% by mass) in the A layer, the resin A can be arbitrarily selected from the candidate resins.
  • the film of this invention may contain components other than the component mentioned above in the range which does not impair the effect of this invention.
  • fillers, antioxidants, UV stabilizers, anti-coloring agents, matting agents, antibacterial agents, deodorants, weathering agents, antioxidants, ion exchange agents, tackifiers, coloring pigments, dyes, etc. May be included.
  • the film of the present invention preferably has an uneven structure by embossing from the viewpoint of bringing the feel and softness of the film closer to cloth.
  • embossing since the bulkiness of a film can be adjusted, it becomes easy to make compression work into the said preferable range. Further, since the degree of spatial freedom can be adjusted depending on the degree of the concavo-convex structure, it is easy to set the shearing hardness within the preferred range.
  • the shape of the surface of the embossing roll used for the embossing is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the desired amount of compression work or shearing strength. For example, by increasing the height of the convex portion on the surface of the embossing roll, the compression work can be increased and the shearing strength can be decreased.
  • melt kneading for producing the composition by melt-kneading each component
  • the method is preferred.
  • the melt kneading method is not particularly limited, and a known mixer such as a kneader, roll mill, Banbury mixer, single screw or twin screw extruder can be used. Among these, from the viewpoint of productivity, it is preferable to use a single screw or twin screw extruder.
  • a non-oriented film can be produced by a known film production method such as an inflation method, a tubular method, or a T-die cast method.
  • the obtained non-oriented film is preferably uniaxially or biaxially stretched, and further considering the economy and productivity, it is uniaxially stretched only in the machine direction. More preferably. Uniaxial stretching in the machine direction can be performed by a known stretching apparatus such as a roll type longitudinal stretching apparatus or a stenter.
  • the draw ratio at this time is preferably 1.1 times or more and more preferably 1.5 times or more and 8.0 times or less from the viewpoints of improvement in mechanical properties, weight reduction, moisture permeability improvement, economy, and productivity. preferable.
  • the film of the present invention can be obtained by spraying organic particles on the surface of the base film and heat laminating.
  • Thickness of base film A sample piece is cut out from the center portion in the width direction of the film, and a cross section in the machine direction-thickness direction of the sample piece (hereinafter sometimes referred to as a film cross section) is observed using an ultramicrotome. Ultrathin sections were collected at ⁇ 100 ° C. Using a scanning electron microscope (S-3400N, manufactured by Hitachi High-Technologies Corporation), take a photograph of the film cross section at a magnification of 500 times. The thickness was measured. The measurement was performed 10 times while changing the observation location, and the average value of the obtained values was defined as the thickness ( ⁇ m) of the base film.
  • S-3400N scanning electron microscope
  • the average value of the obtained particle diameter values was defined as the average particle diameter ( ⁇ m) of the organic particles.
  • 100 organic particles to be measured were selected in order from the center of the observation image.
  • the number of particles included in the observation image of the microscope is less than 100, all the particles included in the observation image are to be measured, and further from the central portion until the total reaches 100 from the observation image in another part. The selection was made in order of proximity.
  • Shear stress may be HG ⁇ 2.5 , HG ⁇ 0.5 , HG 0.5 , and HG 2.5 , respectively.
  • the following formula 2 is used to determine the shear strength in the positive direction (G (+)).
  • the following formula 3 is used to determine the negative shear strength. Shear hardness (G ( ⁇ )) was calculated.
  • Shear stress measurement and calculation of G (+) and G (-) were performed 3 times in both machine direction and width direction (6 times in total), and the average value of all G (+) and G (-) values The value obtained by rounding off the third decimal place was defined as the shear hardness (G) (gf / (cm ⁇ deg)) of the film.
  • the film was measured in accordance with the method defined in JIS Z0208 (1976) with a constant temperature and humidity device set to a moisture permeability of 25 ° C. and a relative humidity of 90%. The measurement was performed three times, and the average value of the obtained values was taken as the moisture permeability of the film (g / (m 2 ⁇ day)). The moisture permeability of the film was measured from the surface having organic particles.
  • Shape of organic particles A surface of the film having organic particles is observed with a laser microscope VK-9700 manufactured by Keyence Co., Ltd. at an objective lens magnification of 150 times. Collected. Subsequently, the image was stored in the png file format, and then analyzed with image analysis software ImageJ (version: 1.44p) developed by the National Institutes of Health. Image analysis was performed according to the following procedure. First, the obtained color image was divided into three types of luminance of red, blue and green by ImageJ. Next, an image having red luminance was subjected to automatic processing by ImageJ using the binarization function of Otsu, so that the organic particle portion was red and the other portions were white.
  • ImageJ version: 1.44p
  • the red and white image thus obtained was subjected to automatic particle analysis processing using ImageJ, and the circularity of the red particle portion was determined.
  • the exclude on edges function was used, and particles in contact with the edge of the image were excluded from the analysis target.
  • each setting parameter at the time of performing particle analysis was as follows. Size: 1-40,000 ⁇ m 2 circularity: 0-1 show: outlines The circularity of 100 organic particles is measured by the above method, and the average value thereof is defined as the circularity of the organic particles. When the circularity value is 0.3 or more and 1.0 or less, the organic particles are spherical. Judged that there was.
  • the observation image when the number of particles included in the observation image is 100 or more, 100 particles are selected in order from the center, and when the number of particles included in the observation image is less than 100, the observation image in another part is selected. Thus, the organic particles were selected in order from the center until the total reached 100 particles.
  • the cellophane tape was peeled off under the following conditions using the same apparatus, and the average value of the peel force observed in the region of displacement 10 cm to 20 cm after the start of the test was determined in the peel curve obtained at that time. The same measurement was performed 5 times at different measurement locations, and the average value obtained was defined as the peel strength (gf / 25 mm) of the organic particles. Peel angle: 180 ° Peeling speed: 100 mm / min Peeling direction: Machine direction (10) For resins whose solubility parameters and compatibility level structure between the base film and organic particles are known, Hideki Yamamoto “SP Value Basics / Applications and Calculation Methods” The solubility parameter was calculated based on the Fedor's estimation method described in (issues of Information Technology Co., Ltd.
  • the absolute value of the difference between the solubility parameters of each resin constituting the base film and the resin constituting the organic particles is calculated from the solubility parameter of each resin obtained, and the resin constituting the base film having the minimum value Was the resin having the highest compatibility with the organic particles.
  • the resin which comprises a base film was 1 type, this resin was made into resin with the highest compatibility with an organic particle.
  • the absolute value of the difference in solubility parameter between the resin having the highest compatibility with the organic particles and the resin constituting the organic particles was determined, and the compatibility level between the base film and the organic particles was evaluated according to the following criteria. A.
  • the absolute value of the difference in solubility parameter between the resin having the highest compatibility with the organic particles and the resin constituting the organic particles was 0.10 (MPa 0.5 ) or less.
  • the absolute value of the difference in solubility parameter between the resin having the highest compatibility with the organic particles and the resin constituting the organic particles was greater than 0.10 (MPa 0.5 ).
  • Weight average molecular weight of organic particles The weight average molecular weight of the resin constituting the organic particles was measured by gel permeation chromatography (GPC) method under the following conditions. When the constituent component of the organic particles was a single resin, each measured value was defined as the weight average molecular weight of the organic particles. When the constituent component of the organic particles is a plurality of resins, the value obtained by multiplying each measured value by the content ratio (mass ratio) was taken as the weight average molecular weight of the organic particles.
  • GPC gel permeation chromatography
  • Measuring device PL-20 manufactured by Polymer Laboratories Column: “Shodex” (registered trademark) UT806M manufactured by Showa Denko KK Column temperature: 145 ° C Solvent (mobile phase): o-dichlorobenzene Solvent flow rate: 1.0 mL / min Sample preparation: 5 mL of measurement solvent is added to 10 mg of sample, and heated and stirred at 140 to 150 ° C. for about 20 minutes. Injection amount: 0.200 mL Detector: Differential refractive index detector RI Standard sample: Monodispersed polystyrene (12) Compression work of film (12) Film was cut to a size of 12 cm square and used as a sample and attached to a test bench.
  • the attached sample was compressed between steel plates having a circular plane with an area of 2 cm 2 in an atmosphere of room temperature 23 ° C. and relative humidity 65%.
  • the film was compressed under the conditions of a speed of 20 ⁇ m / sec and a maximum compression load of 10 gf / cm 2 , and the compression work (gf ⁇ cm / cm 2 ) of the film was measured.
  • the measurement was performed 3 times (6 times in total) on both the inner and outer surfaces of the film, and the value obtained by rounding off the third decimal place of the average value of all the data was taken as the compression work of the film.
  • Tactile sensation of the surface having organic particles of the film was evaluated by the following criteria for 24 people.
  • A was the most excellent, and it was judged that if there was an evaluation of D or higher, it could withstand practicality.
  • polyester elastomer (trade name: “Hytrel” (registered trademark) G3548, manufactured by Toray DuPont Co., Ltd.) Before use, the polyester elastomer was dried at 90 ° C. for 5 hours in a rotary vacuum dryer. It is a crystalline thermoplastic elastomer.
  • A2 Polyolefin-based elastomer (trade name: “ACRlift” (registered trademark) WH303, manufactured by Sumitomo Chemical Co., Ltd.) A crystalline thermoplastic elastomer.
  • A3 Low-density polyethylene (trade name: “Sumikasen” (registered trademark) F200, manufactured by Sumitomo Chemical Co., Ltd.)
  • A4) Acrylic elastomer (trade name: “Clarity” (registered trademark) LA4285, manufactured by Kuraray Co., Ltd.) An amorphous elastomer.
  • the pellets of this composition were vacuum-dried at a temperature of 80 ° C. for 5 hours using a rotary drum type vacuum dryer.
  • the pellets of the vacuum-dried composition were supplied to a single screw extruder with a screw diameter of 60 mm at a cylinder temperature of 190 ° C. by an inflation method, and with an annular die having a diameter of 250 mm, a lip clearance of 1.0 mm, and a temperature set to 175 ° C.
  • the product was extruded upward in a bubble shape at a blow ratio of 2.0, air-cooled by a cooling ring, taken up while being folded by a nip roll above the die, and wound into a roll.
  • a substrate film having a thickness shown in Table 1 was obtained by adjusting the take-up speed.
  • the obtained base film was cut into a size of 20 cm ⁇ 20 cm, and the mass described in Table 1 was sprinkled on the organic particles described in Table 1 from above the cut base film using a 150-mesh sieve. After that, the base film was pulled up vertically to drop excess organic particles.
  • a film having organic particles on the surface was obtained by heat laminating a base film sprinkled with resin particles with a thermal laminator (manufactured by MCK Corporation, MRK-600) under the following conditions.
  • the physical properties and evaluation results of the obtained film are shown in Table 1.
  • ⁇ Thermal lamination conditions> Roll temperature: 150 degrees
  • a film having organic particles on the surface was obtained by the method described in Example 1 except that the raw material resin, organic particles, and additives of the base film were changed to the amounts shown in Table 1.
  • Example 10 and Comparative Example 5 a 50-mesh sieve was used.
  • Tables 1 to 3 show the physical properties and evaluation results of the obtained films.
  • Example 2 A base film having the thickness shown in Table 1 was obtained in the same manner as in Example 1. Apply the following resin layer coating solution on one side of the obtained base film using a bar coater so that the coating thickness is about 5 ⁇ m, and dry at 80 degrees to laminate the coating layer. Got. Table 3 shows the physical properties and evaluation results of the obtained film.
  • HALS HYBRID registered trademark
  • Example 16 The film obtained in Example 1 was set in an electric heating embossing machine “HTEM-300” manufactured by Yuri Roll Co., and a surface having organic particles between a nonwoven fabric pattern embossing roll having an arithmetic average roughness of 50 ⁇ m and a rubber roll; The opposite side was the nonwoven fabric pattern embossing roll side, and the roll temperature was 120 ° C. (both upper and lower stages), the nip pressure (linear pressure) was 50 kg / cm, and the roll rotation speed was 5.0 m / min. Table 2 shows the physical properties and evaluation results of the obtained film.
  • Example 17 A film was obtained in the same manner as in Example 16 except that a roll having an arithmetic average roughness of 80 ⁇ m was used as the nonwoven fabric pattern embossing roll. Table 2 shows the physical properties and evaluation results of the obtained film.
  • Each raw material for layer A and layer B is supplied to a twin screw extruder with a vacuum vent with a screw diameter of 44 mm and a cylinder temperature of 190 ° C. so as to achieve the blending ratio shown in Table 2, and then homogenized. And then pelletized to obtain a composition.
  • the pellet of this composition was vacuum-dried at 90 degreeC for 5 hours using the rotary drum type vacuum dryer, and the composition for A layer and B layer was obtained. Subsequently, these compositions were supplied to independent single screw extruders having a cylinder temperature of 200 ° C.
  • Example 20 The film obtained in Example 18 was embossed by the same method as in Example 16. Table 2 shows the physical properties and evaluation results of the obtained film.
  • Example 21 The film obtained in Example 18 was embossed by the same method as in Example 17. Table 2 shows the physical properties and evaluation results of the obtained film.
  • the raw material resin (mass%) of the base film was calculated based on the total resin component in the base film as 100 mass%.
  • the additive (mass part) computed the whole resin component in a base film as 100 mass parts.
  • the film of the present invention is used for applications that require shear deformability and slipperiness, specifically medical and hygiene materials such as bed sheets, pillow covers, back sheets for absorbent articles such as sanitary napkins and paper diapers, and for rainy weather.
  • Clothing materials such as clothing, gloves, garbage bags and compost bags, packaging materials such as food bags such as vegetables and fruits, bags for various industrial products, building materials such as buildings, houses, decorative boards, railway vehicles, ships, aircraft, etc. It can be preferably used for interior materials, building materials, etc. in a transport aircraft.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un film qui est doté de propriétés mécaniques nécessaires destiné à être utilisé en tant que film et qui présente un très bel aspect, une aptitude au glissement et une déformabilité en cisaillement excellentes, qui sont des caractéristiques relatives à la texture. Un film, selon la présente invention, est caractérisé en ce que : des particules organiques sont comprises sur au moins une des surfaces les plus extérieures d'un film de matériau de base ; le rapport (épaisseur moyenne du film de matériau de base/diamètre moyen de particule des particules organiques) entre le diamètre moyen des particules (µm) des particules organiques et l'épaisseur moyenne (µm) du film de matériau de base se situant entre 0,5 et 3,0 ; et la dureté en cisaillement telle que mesurée par un procédé KES se situant entre 0,1 et 6,0 gf/(cm·deg).
PCT/JP2017/035049 2016-10-12 2017-09-27 Film WO2018070250A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7439651B2 (ja) 2019-06-04 2024-02-28 東レ株式会社 積層フィルム

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07278441A (ja) * 1994-04-06 1995-10-24 Idemitsu Petrochem Co Ltd 絹フィブロイン超微粉末含有熱可塑性樹脂組成物、フィルム又はシート及びこれを用いた積層体
JPH08323931A (ja) * 1995-05-30 1996-12-10 Sekisui Chem Co Ltd 積層シート及びその製造方法
JP2008207393A (ja) * 2007-02-23 2008-09-11 Three M Innovative Properties Co 防水シート及びその製造方法
WO2012133824A1 (fr) * 2011-03-30 2012-10-04 ユニ・チャーム株式会社 Adjuvant de rétention d'eau, et matériau absorbant, absorbant et objet absorbant le comprenant
WO2016152670A1 (fr) * 2015-03-25 2016-09-29 東レ株式会社 Film présentant d'excellentes propriétés de sensation au toucher et de déformabilité en cisaillement

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07278441A (ja) * 1994-04-06 1995-10-24 Idemitsu Petrochem Co Ltd 絹フィブロイン超微粉末含有熱可塑性樹脂組成物、フィルム又はシート及びこれを用いた積層体
JPH08323931A (ja) * 1995-05-30 1996-12-10 Sekisui Chem Co Ltd 積層シート及びその製造方法
JP2008207393A (ja) * 2007-02-23 2008-09-11 Three M Innovative Properties Co 防水シート及びその製造方法
WO2012133824A1 (fr) * 2011-03-30 2012-10-04 ユニ・チャーム株式会社 Adjuvant de rétention d'eau, et matériau absorbant, absorbant et objet absorbant le comprenant
WO2016152670A1 (fr) * 2015-03-25 2016-09-29 東レ株式会社 Film présentant d'excellentes propriétés de sensation au toucher et de déformabilité en cisaillement

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7439651B2 (ja) 2019-06-04 2024-02-28 東レ株式会社 積層フィルム

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