WO2018070250A1 - Film - Google Patents
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- 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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- Prior art keywords
- film
- organic particles
- resin
- layer
- base film
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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
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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
- 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.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Provided is a film that is provided with mechanical properties necessary for use as a film and that has excellent appearance, slidability, and shear deformability, which are characteristics pertaining to texture. A film according to the present invention is characterized in that: organic particles are included on at least one of the outermost surfaces of a base material film; the ratio (average thickness of base material film / average particle diameter of organic particles) of the average particle diameter (µm) of the organic particles to the average thickness (µm) of the base material film is 0.5-3.0; and the shear hardness as measured by a KES method is 0.1-6.0 gf/(cm·deg).
Description
本発明は、風合いの特徴であるせん断変形性、すべり性、および外観に優れたフィルムに関するものである。
The present invention relates to a film excellent in shear deformability, slipperiness and appearance, which are characteristics of the texture.
近年、フィルムとして用いるために必要な機械特性を備えた上で、さらに別の機能を有する単体のフィルムが要求されている。例えば、医療・衛生材料の分野では、フィルムとして用いるために必要な機械特性を備え、かつ風合いの特徴であるせん断変形性、すべり性、および外観に優れるフィルムが望まれている。
In recent years, there has been a demand for a single film having other functions in addition to mechanical properties necessary for use as a film. For example, in the field of medical and hygiene materials, 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, is desired.
これまでにフィルムの触感を改善するため、種々の開発がなされている。例えば、特許文献1には、オレフィン樹脂に平均粒径2μm以上の硫酸バリウムを混合して延伸することにより、触感が改善された透湿フィルムが開示されている。また、特許文献2には、表面が粒子で被覆されたフィルムが開示されている。
[To date, various developments have been made to improve the feel of the film. For example, 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 μm or more. Patent Document 2 discloses a film whose surface is coated with particles.
しかしながら、特許文献1の技術では、オレフィン樹脂を用いているため風合いの特徴であるせん断変形性は優れるが、硫酸バリウムが樹脂に埋包されているためフィルムに光沢があり、フィルムの外観が劣るという課題があった。また、特許文献2に記載の技術により得られるフィルムは、表面が粒子で覆われているため、風合いの特徴であるすべり性には優れるが、製造工程で剛質なフィルムを用いる必要があり、十分なせん断変形性が得られない。また、粒子の溶剤分散液をコートする方法を用いているため、最終的に得られるフィルムに微量の溶剤が残留しており、フィルムを医療・衛生材料の分野では用いることが困難であるという課題もあった。
However, in the technique of Patent Document 1, since an olefin resin is used, the shear deformability which is a feature of the texture is excellent, but since the barium sulfate is embedded in the resin, the film is glossy and the appearance of the film is inferior. There was a problem. Moreover, since the film obtained by the technique described in Patent Document 2 is covered with particles, the film is excellent in slipperiness, which is a feature of the texture, but it is necessary to use a rigid film in the manufacturing process. Sufficient shear deformability cannot be obtained. In addition, since a method of coating a solvent dispersion of particles is used, a trace amount of solvent remains in the finally obtained film, and it is difficult to use the film in the field of medical / hygiene materials. There was also.
本発明はかかる従来技術の欠点を改良し、フィルムとして用いるために必要な機械特性を備え、かつ風合いの特徴であるせん断変形性、すべり性、および外観に優れたフィルムを提供することを、その課題とする。
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.
上記課題を解決するため、本発明は、下記の構成からなる。
(1) 基材フィルムの少なくとも一方の最表面に有機粒子を有し、前記有機粒子の平均粒径(μm)と、前記基材フィルムの平均厚み(μm)との比(基材フィルムの平均厚み/有機粒子の平均粒径)が0.5以上3.0以下であり、かつKES法におけるせん断かたさが0.1gf/(cm・deg)以上6.0gf/(cm・deg)以下であることを特徴とする、フィルム。
(2) 有機粒子を有する面において、フィルム全体の面積を100%としたときに、有機粒子の占める面積の割合が20%以上100%未満であることを特徴とする、(1)に記載のフィルム。
(3) 有機粒子を有する面において、KES法に従い測定される摩擦係数が0.05以上0.80以下であることを特徴とする、(1)または(2)に記載のフィルム。
(4) フィルムの透湿度が、500g/(m2・day)以上5,000g/(m2・day)以下であることを特徴とする(1)~(3)のいずれかに記載のフィルム。
(5) 前記有機粒子の形状が球形状であることを特徴とする、(1)~(4)のいずれかに記載のフィルム。
(6) 前記基材フィルムと前記有機粒子との剥離強度が30gf/25mm以上であることを特徴とする(1)~(5)のいずれかに記載のフィルム。
(7) 前記基材フィルムが、熱可塑性エラストマーを含むことを特徴とする、(1)~(6)のいずれかに記載のフィルム。
(8) 前記基材フィルムが、少なくとも、前記有機粒子と接する層(A層)と、A層を挟んで前記有機粒子と反対側に位置する層(B層)の積層構成からなることを特徴とする、(1)~(7)のいずれかに記載のフィルム。
(9) 溶解度パラメータの差の絶対値が最も小さくなるように、前記A層中の樹脂成分全体を100質量%としたときに、前記A層中に5質量%以上含まれる樹脂の中から1つの樹脂(樹脂A)を選択し、前記有機粒子の樹脂成分全体を100質量%としたときに、前記有機粒子中に5質量%以上含まれる樹脂の中から1つの樹脂(樹脂B)を選択した際に、前記樹脂Aと前記樹脂Bの溶解度パラメータの差の絶対値が0.10(MPa)0.5以下であることを特徴とする、(8)に記載のフィルム。 In order to solve the above problems, 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 (μm) of the organic particles to the average thickness (μm) 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.
(3) The film according to (1) or (2), wherein the coefficient of friction measured according to the KES method is 0.05 to 0.80 on the surface having organic particles.
(4) water vapor permeability of the film, according to any of 500g / (m 2 · day) or more 5,000 g /, characterized in that it is (m 2 · day) or less (1) to (3) Film .
(5) The film according to any one of (1) to (4), wherein the organic particles have a spherical shape.
(6) The film according to any one of (1) to (5), wherein a peel strength between the base film and the organic particles is 30 gf / 25 mm or more.
(7) The film according to any one of (1) to (6), wherein the base film contains a thermoplastic elastomer.
(8) 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 When 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.
(1) 基材フィルムの少なくとも一方の最表面に有機粒子を有し、前記有機粒子の平均粒径(μm)と、前記基材フィルムの平均厚み(μm)との比(基材フィルムの平均厚み/有機粒子の平均粒径)が0.5以上3.0以下であり、かつKES法におけるせん断かたさが0.1gf/(cm・deg)以上6.0gf/(cm・deg)以下であることを特徴とする、フィルム。
(2) 有機粒子を有する面において、フィルム全体の面積を100%としたときに、有機粒子の占める面積の割合が20%以上100%未満であることを特徴とする、(1)に記載のフィルム。
(3) 有機粒子を有する面において、KES法に従い測定される摩擦係数が0.05以上0.80以下であることを特徴とする、(1)または(2)に記載のフィルム。
(4) フィルムの透湿度が、500g/(m2・day)以上5,000g/(m2・day)以下であることを特徴とする(1)~(3)のいずれかに記載のフィルム。
(5) 前記有機粒子の形状が球形状であることを特徴とする、(1)~(4)のいずれかに記載のフィルム。
(6) 前記基材フィルムと前記有機粒子との剥離強度が30gf/25mm以上であることを特徴とする(1)~(5)のいずれかに記載のフィルム。
(7) 前記基材フィルムが、熱可塑性エラストマーを含むことを特徴とする、(1)~(6)のいずれかに記載のフィルム。
(8) 前記基材フィルムが、少なくとも、前記有機粒子と接する層(A層)と、A層を挟んで前記有機粒子と反対側に位置する層(B層)の積層構成からなることを特徴とする、(1)~(7)のいずれかに記載のフィルム。
(9) 溶解度パラメータの差の絶対値が最も小さくなるように、前記A層中の樹脂成分全体を100質量%としたときに、前記A層中に5質量%以上含まれる樹脂の中から1つの樹脂(樹脂A)を選択し、前記有機粒子の樹脂成分全体を100質量%としたときに、前記有機粒子中に5質量%以上含まれる樹脂の中から1つの樹脂(樹脂B)を選択した際に、前記樹脂Aと前記樹脂Bの溶解度パラメータの差の絶対値が0.10(MPa)0.5以下であることを特徴とする、(8)に記載のフィルム。 In order to solve the above problems, 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 (μm) of the organic particles to the average thickness (μm) 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.
(3) The film according to (1) or (2), wherein the coefficient of friction measured according to the KES method is 0.05 to 0.80 on the surface having organic particles.
(4) water vapor permeability of the film, according to any of 500g / (
(5) The film according to any one of (1) to (4), wherein the organic particles have a spherical shape.
(6) The film according to any one of (1) to (5), wherein a peel strength between the base film and the organic particles is 30 gf / 25 mm or more.
(7) The film according to any one of (1) to (6), wherein the base film contains a thermoplastic elastomer.
(8) 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 When 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.
本発明により、フィルムとして用いるために必要な機械特性を備え、かつ風合いの特徴であるせん断変形性、すべり性、および外観に優れたフィルムを提供することができる。
According to 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.
本発明のフィルムは、基材フィルムの少なくとも一方の最表面に有機粒子を有し、前記有機粒子の平均粒径(μm)と、前記基材フィルムの平均厚み(μm)との比(基材フィルムの平均厚み/有機粒子の平均粒径)が0.5以上3.0以下であり、かつKES法におけるせん断かたさが0.1gf/(cm・deg)以上6.0gf/(cm・deg)以下であることを特徴とする。
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 (μm) of the organic particles to the average thickness (μm) 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.
以下に、本発明を実施するための望ましい形態について説明するが、本発明はこれに限定されるものではない。
Hereinafter, desirable modes for carrying out the present invention will be described, but the present invention is not limited to these.
図1、2は、本発明のフィルムの一例を示す模式断面図である。図1、2において、符号1が有機粒子、符号2が基材フィルムを示している。基材フィルム表面における有機粒子は、その半分以上が表面に突出していてもよいし(図1(A))、その半分未満が突出していてもよい(図1(B))。有機粒子は、図1(A)や図1(B)に示すように個別に存在しても、複数個の粒子が集合あるいは凝集した状態でもよい(図1(C))。また、基材フィルム表面に平面的にほぼ隙間なく有機粒子が配列されていても(図2(A))、フィルムの厚み方向に複数個の粒子が重なった状態であってもよい(図2(B))。ここで厚み方向とは、フィルム面に垂直な方向をいう。
1 and 2 are schematic cross-sectional views showing an example of the film of the present invention. 1 and 2, reference numeral 1 indicates organic particles, and 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). In addition, 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)). Here, the thickness direction means a direction perpendicular to the film surface.
(基材フィルム)
本発明における基材フィルムは、せん断変形性の観点から、熱可塑性エラストマーを含むことが好ましい。ここで熱可塑性エラストマーとは、25℃でゴム弾性を有する高分子量体をいう。 (Base film)
The base film in the present invention preferably contains a thermoplastic elastomer from the viewpoint of shear deformability. Here, the thermoplastic elastomer refers to a high molecular weight body having rubber elasticity at 25 ° C.
本発明における基材フィルムは、せん断変形性の観点から、熱可塑性エラストマーを含むことが好ましい。ここで熱可塑性エラストマーとは、25℃でゴム弾性を有する高分子量体をいう。 (Base film)
The base film in the present invention preferably contains a thermoplastic elastomer from the viewpoint of shear deformability. Here, the thermoplastic elastomer refers to a high molecular weight body having rubber elasticity at 25 ° C.
熱可塑性エラストマーとしては、本発明の効果を損なわない限り、結晶性を有する熱可塑性エラストマー、非晶性の熱可塑性エラストマーのいずれであってもよく、また、両者を混合してもよい。ここで、結晶性を有する熱可塑性エラストマーとは、100℃の熱風オーブン中で24時間加熱させた後に、25℃から昇温速度20℃/分で250℃まで昇温した際に、結晶融解ピークが観測される熱可塑性エラストマーをいう。一方、非晶性の熱可塑性エラストマーとは、同様の条件で結晶融解ピークが観測されない熱可塑性エラストマーをいう。
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. Here, 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. Refers to a thermoplastic elastomer in which is observed. On the other hand, the amorphous thermoplastic elastomer refers to a thermoplastic elastomer in which no crystal melting peak is observed under the same conditions.
基材フィルムにおける結晶性を有する熱可塑性エラストマーとしては、本発明の効果を損なわない限り特に制限されず、例えば、ポリエステル系エラストマー、ポリオレフィン系エラストマー、およびポリアミド系エラストマーなどを単独でまたは組み合わせて用いることができる。中でも、せん断変形性、製膜安定性、および耐熱性等の観点から、ポリエステル系エラストマー、ポリアミド系エラストマーを単独でまたは2種類以上を組み合わせて用いることが好ましい。
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. For example, a polyester-based elastomer, a polyolefin-based elastomer, and a polyamide-based elastomer are used alone or in combination. Can do. Among these, from the viewpoint of shear deformability, film-forming stability, heat resistance, and the like, it is preferable to use a polyester elastomer or a polyamide elastomer alone or in combination of two or more.
前記ポリエステル系エラストマーとしては、例えば、芳香族ポリエステルと脂肪族ポリエステルとのブロック共重合体、芳香族ポリエステルと脂肪族ポリエーテルとのブロック共重合体等が挙げられるが、フィルムに透湿性を付与する観点から、芳香族ポリエステルと脂肪族ポリエーテルとのブロック共重合体を用いることが好ましい。
Examples of the polyester-based elastomer 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.
基材フィルムに用いることができるポリエステル系エラストマーとしては、例えば、東レ・デュポン(株)製の“ハイトレル”(登録商標)のG3548やHTR8206グレード等が挙げられる。
Examples of the polyester-based elastomer that can be used for the base film include “Hytrel” (registered trademark) G3548 and HTR8206 grade manufactured by Toray DuPont.
また、前記ポリアミド系エラストマーとしては、例えば、脂肪族ポリアミドと脂肪族ポリエステルとのブロック共重合体、脂肪族ポリアミドと脂肪族ポリエーテルとのブロック共重合体等が挙げられるが、フィルムに透湿性を付与する観点から、脂肪族ポリアミドと脂肪族ポリエーテルとのブロック共重合体を用いることが好ましい。
Examples of the polyamide-based elastomer 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.
基材フィルムに用いることができるポリアミド系エラストマーとしては、例えば、アルケマ社製の“PEBAX”(登録商標)のMV1074、MV1041、MV3000、MH1657グレード等が挙げられる。
Examples of the polyamide-based elastomer that can be used for the base film include “PEBAX” (registered trademark) MV1074, MV1041, MV3000, and MH1657 grades manufactured by Arkema.
基材フィルム中の結晶性を有する熱可塑性エラストマーの含有量は、本発明の効果を損なわない限り特に限定されないが、製膜安定性の観点から、基材フィルム中の樹脂全体を100質量%としたときに、10質量%以上100質量%以下であることが好ましく、10質量%以上95質量%以下であることがより好ましく、20質量%以上90質量%以下であることがさらに好ましい。なお、基材フィルム中の結晶性を有する熱可塑性エラストマーが複数種である場合においては、結晶性を有する熱可塑性エラストマーの含有量は全ての結晶性を有する熱可塑性エラストマーを合算して算出するものとする。
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. In addition, when there are multiple types of thermoplastic elastomers having crystallinity in the base film, the content of the thermoplastic elastomer having crystallinity is calculated by adding all thermoplastic elastomers having crystallinity. And
基材フィルムに用いることができる非晶性の熱可塑性エラストマーとしては、ポリウレタン系エラストマー、スチレン系エラストマー、アクリル系エラストマー等が挙げられるが、その中でも特にせん断変形性の観点から、ポリウレタン系エラストマーを用いることが好ましい。
Examples of the amorphous thermoplastic elastomer that can be used for the base film include polyurethane elastomers, styrene elastomers, acrylic elastomers, etc. Among them, polyurethane elastomers are used particularly from the viewpoint of shear deformation. It is preferable.
前記ポリウレタン系エラストマーとしては、例えば、短鎖グリコールとジイソシアネートによりなるハードセグメント相とポリエーテルよりなるソフトセグメント相とのブロック共重合体や、同ハードセグメント相とポリエステルよりなるソフトセグメント相とのブロック共重合体等が挙げられるが、透湿性付与の観点から、ポリエーテルよりなるソフトセグメント相を有するブロック共同重合体であることが好ましい。
Examples of the polyurethane elastomer 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. Although 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.
基材フィルムに用いることができる非晶性のポリウレタン系エラストマーとしては、例えば、BASFジャパン(株)製“エラストラン”(登録商標)のOP85A10グレードやET885FGグレード等が挙げられる。
Examples of the amorphous polyurethane-based elastomer that can be used for the base film include OP85A10 grade and ET885FG grade of “Elastollan” (registered trademark) manufactured by BASF Japan.
また、基材フィルムは、後述する基材フィルムと有機粒子との密着性の観点から、有機粒子と相溶性が高い樹脂を含んでいてもよい。ここで有機粒子と相溶性が高い樹脂とは、溶解度パラメータ(MPa0.5)が、有機粒子中に最も多く含まれる樹脂の溶解度パラメータ±0.10(MPa0.5)の範囲である樹脂をいう。
Moreover, 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. Here, 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.
なお、有機粒子中に最も多く含まれる樹脂が2種類以上ある場合は、基材フィルム中に、溶解度パラメータ(MPa0.5)が有機粒子中に最も多く含まれるいずれかの樹脂の溶解度パラメータ(MPa0.5)±0.10MPa0.5の範囲である樹脂を含むのであれば、基材フィルムは有機粒子と相溶性が高い樹脂を含むものとみなす。
In addition, when there are two or more kinds of resins most often contained in the organic particles, 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. As long as it contains a resin in the range of 0.5 MPa) 0.5 0.10 MPa, the base film is considered to contain a resin highly compatible with organic particles.
また、有機粒子と相溶性が高い樹脂の種類は、本発明の効果を損なわない限り特に制限されず、前述の結晶性の熱可塑性エラストマーや、非晶性の熱可塑性エラストマーとして、「有機粒子と相溶性が高い樹脂」の条件に該当するものを使用することも、前述の結晶性の熱可塑性エラストマーや、非晶性の熱可塑性エラストマーが「有機粒子と相溶性が高い樹脂」でない場合に、別の樹脂を加えることも可能である。
In addition, 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.
溶解度パラメータとは、樹脂を構成する各原子団の凝集エネルギー密度とモル分子量を基に計算されるパラメータであり、具体的には、山本秀樹著「SP値 基礎・応用と計算方法」((株)情報機構発行(2005年)第66~67項)に記載のFedorの推算法に基づき計算されるものである。なお、樹脂の構造が不明瞭であり前記方法により計算できない場合においては、溶解度パラメータが既知である溶媒に対して溶解するか否かの判定による実験法(「ポリマーハンドブック 第4版(Polymer Handbook Fourth Edition)」 ジェー・ブランド(J.Brand)著、ワイリー(Wiley)社 1998年発行)によりSP値を算出し、その値を代用することができる。なお、Fedorの推算法は、通常は高分子重合体を構成する繰り返し単位が単一の場合に、その単位に対して計算した値を高分子重合体の溶解度パラメータとしているが、繰り返し単位が2成分以上存在する場合(例えば、繰り返し単位Aと繰り返し単位Bが存在する場合)は、以下の式(1)ように計算することができる。
繰り返し単位Aと繰り返し単位Bからなる重合体の溶解度パラメータ
=(繰り返し単位Aの溶解度パラメータ)×(繰り返し単位Aのモル分率)+(繰り返し単位Bの溶解度パラメータ)×(繰り返し単位Bのモル分率)・・・式(1)
基材フィルムが有機粒子と相溶性が高い樹脂を含むことにより、後述する有機粒子を熱履歴により基材フィルムの最表面に固定する方法において、有機粒子と基材フィルムとの密着性を向上しやすくなる。 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. In the Fedor's estimation method, when there is usually a single repeating unit constituting the polymer, the value calculated for that unit is used as the solubility parameter of the polymer. When more than the component exists (for example, when the repeating unit A and the repeating unit B exist), it can be calculated as the following formula (1).
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) ... Formula (1)
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.
繰り返し単位Aと繰り返し単位Bからなる重合体の溶解度パラメータ
=(繰り返し単位Aの溶解度パラメータ)×(繰り返し単位Aのモル分率)+(繰り返し単位Bの溶解度パラメータ)×(繰り返し単位Bのモル分率)・・・式(1)
基材フィルムが有機粒子と相溶性が高い樹脂を含むことにより、後述する有機粒子を熱履歴により基材フィルムの最表面に固定する方法において、有機粒子と基材フィルムとの密着性を向上しやすくなる。 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. In the Fedor's estimation method, when there is usually a single repeating unit constituting the polymer, the value calculated for that unit is used as the solubility parameter of the polymer. When more than the component exists (for example, when the repeating unit A and the repeating unit B exist), it can be calculated as the following formula (1).
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) ... Formula (1)
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.
本発明の基材フィルムにおける非晶性の熱可塑性エラストマーの含有量は、本発明の効果を損なわない限り特に限定されないが、せん断変形性、透湿性、および製膜安定性の観点から、本発明の基材フィルム中の樹脂全体を100質量%としたときに、5質量%以上50質量%以下であることが好ましく、10質量%以上45質量%以下であることがより好ましく、15質量%以上40質量%以下であることがさらに好ましい。なお、基材フィルム中の非晶性の熱可塑性エラストマーが複数種である場合においては、非晶性の熱可塑性エラストマーの含有量は全ての非晶性の熱可塑性エラストマーを合算して算出するものとする。
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. When 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. When there are multiple types of amorphous thermoplastic elastomers in the base film, the content of amorphous thermoplastic elastomer is calculated by adding all amorphous thermoplastic elastomers together. And
本発明の基材フィルムの厚みは、本発明の効果を損なわない限り特に制限はないが、取り扱い性と生産性の観点から、3μm以上200μm以下であることが好ましい。ここでいう基材フィルムの厚みは、例えば、以下のようにして測定することができる。まず、ミクロトームを用いてサンプル片の機械方向-厚み方向断面(以下、フィルム断面ということがある。)を観察面とするように-100℃で超薄切片を採取し、走査型電子顕微鏡を用いて倍率500倍でフィルム断面の写真を撮影する。得られた断面の写真を用いて、顕微鏡の測長機能によりフィルムの最表面に有機粒子がない部分の厚みを測定する。なお、ミクロトームとしては、例えば日本ミクロトーム研究所(株)製ロータリー式ミクロトーム等を、走査型電子顕微鏡としては、例えば(株)日立製作所製S-3400N等を使用することができる。以下、これらを使用する測定方法について同様である。
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. As the 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.
基材フィルムの厚みを3μm以上とすることで、フィルムのコシが強くなり、取り扱い性が向上し、また、ロール巻姿や巻出し性も良好となる。基材フィルムの厚みを200μm以下とすることで、特にインフレーション製膜法においては、自重によりバブルが安定化する。このような点から、基材フィルムの厚みは、5μm以上150μm以下であることがより好ましく、6μm以上40μm以下であることがさらに好ましい。
By setting the thickness of the base film to 3 μm or more, the stiffness of the film becomes stronger, the handleability is improved, and the roll winding shape and unwinding property are also improved. By setting the thickness of the base film to 200 μm 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 μm or more and 150 μm or less, and further preferably 6 μm or more and 40 μm or less.
(有機粒子)
本発明のフィルムは、フィルムに布のような触感を付与する観点から、基材フィルムの少なくとも一方の最表面に有機粒子を有することが重要である。このような態様とすることにより、フィルムを指で触れたときの両者の接触面積が小さくなるため、両者間の摩擦が軽減され、すべり性が向上する。本発明における有機粒子は、本発明の効果を損なわない限り特に限定されるものではなく、例えば、アクリル系樹脂、シリコーン系樹脂、ナイロン系樹脂、スチレン系樹脂、ポリオレフィン系樹脂、ウレタン系樹脂粒子等を主成分とする有機粒子が用いられる。中でも、得られるフィルムのすべり性の観点から、ポリオレフィン系樹脂やアクリル系樹脂を主成分とする有機粒子を用いることが好ましい。ここでポリオレフィン系樹脂を主成分とするとは、有機粒子を構成する樹脂成分全体を100質量%としたときに、ポリオレフィン系樹脂を50質量%以上含むことをいう。以下、「主成分とする」については同様に解釈することができる。 (Organic particles)
It is important that 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. By setting it as such an aspect, since the contact area of both when a film is touched with a finger | toe becomes small, the friction between both is reduced and slipperiness improves. The organic particles in the present invention are not particularly limited as long as the effects of the present invention are not impaired. For example, acrylic resins, silicone resins, nylon resins, styrene resins, polyolefin resins, urethane resin particles, etc. Organic particles containing as a main component are used. Especially, it is preferable to use the organic particle which has polyolefin resin and acrylic resin as a main component from a viewpoint of the slipperiness of the film obtained. Here, 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. Hereinafter, “main component” can be similarly interpreted.
本発明のフィルムは、フィルムに布のような触感を付与する観点から、基材フィルムの少なくとも一方の最表面に有機粒子を有することが重要である。このような態様とすることにより、フィルムを指で触れたときの両者の接触面積が小さくなるため、両者間の摩擦が軽減され、すべり性が向上する。本発明における有機粒子は、本発明の効果を損なわない限り特に限定されるものではなく、例えば、アクリル系樹脂、シリコーン系樹脂、ナイロン系樹脂、スチレン系樹脂、ポリオレフィン系樹脂、ウレタン系樹脂粒子等を主成分とする有機粒子が用いられる。中でも、得られるフィルムのすべり性の観点から、ポリオレフィン系樹脂やアクリル系樹脂を主成分とする有機粒子を用いることが好ましい。ここでポリオレフィン系樹脂を主成分とするとは、有機粒子を構成する樹脂成分全体を100質量%としたときに、ポリオレフィン系樹脂を50質量%以上含むことをいう。以下、「主成分とする」については同様に解釈することができる。 (Organic particles)
It is important that 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. By setting it as such an aspect, since the contact area of both when a film is touched with a finger | toe becomes small, the friction between both is reduced and slipperiness improves. The organic particles in the present invention are not particularly limited as long as the effects of the present invention are not impaired. For example, acrylic resins, silicone resins, nylon resins, styrene resins, polyolefin resins, urethane resin particles, etc. Organic particles containing as a main component are used. Especially, it is preferable to use the organic particle which has polyolefin resin and acrylic resin as a main component from a viewpoint of the slipperiness of the film obtained. Here, 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. Hereinafter, “main component” can be similarly interpreted.
また、有機粒子の形状は、本発明の効果を損なわない限り特に限定されるものではなく、例えば、球形状、楕円体形状、多面体形状、およびこれらの立体を多孔質化した形状等とすることができる。但し、フィルムのすべり性の観点から、有機粒子の形状が球形状であることが好ましい。
Further, the shape of the organic particles is not particularly limited as long as the effects of the present invention are not impaired. For example, a spherical shape, an ellipsoidal shape, a polyhedral shape, and a shape obtained by making these three-dimensional bodies porous are used. Can do. However, from the viewpoint of the slipperiness of the film, the shape of the organic particles is preferably spherical.
有機粒子の形状が球形状であるか否かは、以下の手順により判別するものとする。まず、フィルムの最表面に有機粒子を有する面を、フィルム面と垂直な方向からレーザー顕微鏡で対物レンズの倍率を150倍に拡大して観察し、最表層に位置する有機粒子を観察視野の中心から近い順に100個抽出する。抽出した各有機粒子について、2次元投影形状の面積および周囲長を測定し、以下の式1により円形度を算出する。得られた円形度の平均値が0.3以上1.0以下である場合、有機粒子の形状が球形状であると判断する。なお、円形度の最大値は1.0であり、円形度が1.0であることは、測定対象の形状が真円であることと同義である。
式1:円形度=4π×(2次元投影形状の面積)/(2次元投影形状の周囲長)2
有機粒子の形状は、円形度が大きく真球に近い(2次元投影形状が真円に近い)ほど、フィルムに触れたときの有機粒子の引っかかりを軽減することができ、摩擦係数を低く抑えやすくなる。このような観点から、上記円形度は0.4以上1.0以下であることがより好ましく、0.5以上1.0以下であることがさらに好ましい。 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 thefollowing 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. In addition, the maximum value of circularity is 1.0, and circularity being 1.0 is synonymous with the shape of a measuring object being a perfect circle.
Formula 1: Circularity = 4π × (area of 2D projection shape) / (peripheral length of 2D projection shape) 2
As the shape of the organic particles is larger and closer to a perfect sphere (the two-dimensional projection shape is closer to a perfect circle), the organic particles can be less caught when touching the film, and the friction coefficient can be kept low. Become. From such a viewpoint, 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.
式1:円形度=4π×(2次元投影形状の面積)/(2次元投影形状の周囲長)2
有機粒子の形状は、円形度が大きく真球に近い(2次元投影形状が真円に近い)ほど、フィルムに触れたときの有機粒子の引っかかりを軽減することができ、摩擦係数を低く抑えやすくなる。このような観点から、上記円形度は0.4以上1.0以下であることがより好ましく、0.5以上1.0以下であることがさらに好ましい。 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
Formula 1: Circularity = 4π × (area of 2D projection shape) / (peripheral length of 2D projection shape) 2
As the shape of the organic particles is larger and closer to a perfect sphere (the two-dimensional projection shape is closer to a perfect circle), the organic particles can be less caught when touching the film, and the friction coefficient can be kept low. Become. From such a viewpoint, 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.
有機粒子の形状を球形状とするための方法は、本発明の効果を損なわない限り特に限定されず、例えば、懸濁重合法や乳化重合法により得られた樹脂を有機粒子として用いる方法や、有機粒子中の樹脂の重量平均分子量を大きくして、製造工程での熱履歴による有機粒子の変形を軽減する方法等が挙げられる。
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.
本発明における有機粒子の平均粒径は、本発明の効果を損なわない限り特に制限されないが、基材フィルムと有機粒子と密着性の観点から、1μm以上200μm以下であることが好ましく、3μm以上150μm以下であることがより好ましく、5μm以上100μm以下であることがさらに好ましい。
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 μm or more and 200 μm or less, and 3 μm or more and 150 μm. More preferably, it is more preferably 5 μm or more and 100 μm or less.
なお、有機粒子の平均粒径は以下の方法で測定することができる。まず、ミクロトームを用いてナイフ傾斜角度3°でフィルム面に垂直な方向にフィルムを切断する。得られた断面を走査型電子顕微鏡で観察し、1個の有機粒子を完全に囲みかつ面積が最も小さくなるように正方形または長方形を描いて、正方形の場合は1辺の長さ、長方形の場合は長辺と短辺の長さの平均値を該有機粒子の粒子径とする。同様の測定を100個の有機粒子について行い、得られた値の平均値を有機粒子の平均粒径とする。
In addition, 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.
本発明のフィルムは、後述するように基材フィルムと有機粒子を熱履歴により圧着させる製造工程をとる場合、熱履歴による粒子の変形を抑制する観点から、有機粒子の重量平均分子量が50万以上であることが好ましい。重量平均分子量をかかる範囲として粒子の変形を軽減することにより、フィルムを指で触った際における指とフィルムの接触面積を低減しやすくなり、フィルムの触感が向上する。熱履歴による粒子の変形を抑制する観点から、有機粒子の重量平均分子量は、100万以上であることがより好ましく、さらに好ましくは150万以上である。上記観点からは、有機粒子の重量平均分子量は高ければ高いほど好ましく上限は特に制限されないが、実用的な観点から1,000万あれば十分である。
As described later, 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. From the viewpoint of suppressing particle deformation due to thermal history, 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.
なお、有機粒子の構成成分が単一の樹脂である場合、該樹脂の重量平均分子量を有機粒子の重量平均分子量とする。有機粒子の構成成分が複数の樹脂である場合は、各樹脂の重量平均分子量に含有比率(質量比)を掛け合わせて合計した値を有機粒子の重量平均分子量とする。樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法で測定することができ、詳細な条件は後述する。
In addition, when the constituent component of the organic particles is a single resin, the weight average molecular weight of the resin is 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 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.
有機粒子に用いることができるポリオレフィン系樹脂としては、例えば、三井化学(株)製“ミペロン”(登録商標)、“ハイゼックスミリオン”(登録商標)、旭化成ケミカルズ(株)製“サンファイン”(登録商標)、住友精化(株)製“フローセン”(登録商標)等が挙げられる。また、有機粒子に用いることができるアクリル系樹脂としては、例えば、アイカ工業(株)製“ガンツパール”(登録商標)、松本油脂製薬(株)製“マツモトマイクロスフェアー”(登録商標)Mシリーズ等が挙げられる。
Examples of 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. Examples of the 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.
本発明のフィルムは、有機粒子の平均粒径(μm)と、基材フィルムの平均厚み(μm)との比(基材フィルムの平均厚み/有機粒子の平均粒径)が0.5以上3.0以下であることが重要である。「基材フィルムの平均厚み/有機粒子の平均粒径」が0.5以上であることにより、有機粒子の平均粒径が大きくなり過ぎず、フィルムから有機粒子の脱落が起こり難くなり、すべり性や触感が損なわれにくくなる。一方、「基材フィルムの平均厚み/有機粒子の平均粒径」が3.0以下であることにより、基材フィルムの厚みが大きくなり過ぎず、フィルムのせん断変形性が向上する。このような点から、「基材フィルムの平均厚み/有機粒子の平均粒径」は0.6以上2.5以下であればより好ましく、0.7以上2.0以下であればさらに好ましい。
In the film of the present invention, the ratio of the average particle size (μm) of the organic particles to the average thickness (μm) of the substrate film (average thickness of the substrate film / average particle size of the organic particles) is 0.5 or more and 3 It is important that the value is 0.0 or less. When 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. On the other hand, when “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.
本発明のフィルムは、有機粒子を有する面において、フィルム全体の面積を100%としたときに、有機粒子の占める面積の割合が20%以上100%未満であることが好ましい。フィルム全体の面積を100%としたときに、有機粒子の占める面積の割合が20%以上であれば、フィルムの外観およびすべり性が向上する。一方、有機粒子の占める面積の割合が100%である場合は、基材フィルムの表面に有機粒子と同一成分よりなる層が形成されている状態となる。通常、すべり性向上のために用いられる有機粒子は基材フィルムよりも硬いため、有機粒子の占める面積の割合が100%であると、後述するせん断かたさが過度に大きくなり、フィルム自体の柔らかさが損なわれることがある。このようにフィルムのすべり性と柔軟性を両立する観点から、フィルム全体の面積を100%としたときの、有機粒子の占める面積の割合は、20%以上90%以下がより好ましく、30%以上90%以下がさらに好ましく、40%以上85%以下が特に好ましい。
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. When 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. On the other hand, when 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. Usually, 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. Thus, from the viewpoint of achieving both slipperiness and flexibility of the film, 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.
フィルム全体に占める有機粒子の面積の割合は、例えば、以下のようにして求めることができる。まず、フィルムの有機粒子を有する面を走査型電子顕微鏡で200倍に拡大して観察し、フィルム表面の有機粒子の個数を数える。次いで、フィルム表面における有機粒子の個数と前述した有機粒子の平均粒径との積を求め、これを有機粒子の面積とする。さらに、観察画像の面積をフィルム全体の面積とし、フィルム全体に占める有機粒子の面積の割合を算出する。
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.
(有機粒子の密着性)
本発明のフィルムは、最表面の有機粒子の脱落を抑制してすべり性を持続する観点から、基材フィルムと有機粒子との剥離強度が30gf/25mm以上であることが好ましい。ここでいう、剥離強度とは後述する剥離試験において得られる剥離曲線の平坦部分の平均値を指す。剥離強度をかかる範囲とすることで、基材フィルムと有機粒子との密着性が強固になるため有機粒子の脱落が抑えられ、フィルムのすべり性がより持続する。 (Adhesion of organic particles)
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. Here, the peel strength refers to an average value of a flat portion of a peel curve obtained in a peel test described later. By setting the peel strength within such a range, the adhesion between the base film and the organic particles becomes strong, so that the organic particles are prevented from falling off, and the slipperiness of the film is further maintained.
本発明のフィルムは、最表面の有機粒子の脱落を抑制してすべり性を持続する観点から、基材フィルムと有機粒子との剥離強度が30gf/25mm以上であることが好ましい。ここでいう、剥離強度とは後述する剥離試験において得られる剥離曲線の平坦部分の平均値を指す。剥離強度をかかる範囲とすることで、基材フィルムと有機粒子との密着性が強固になるため有機粒子の脱落が抑えられ、フィルムのすべり性がより持続する。 (Adhesion of organic particles)
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. Here, the peel strength refers to an average value of a flat portion of a peel curve obtained in a peel test described later. By setting the peel strength within such a range, the adhesion between the base film and the organic particles becomes strong, so that the organic particles are prevented from falling off, and the slipperiness of the film is further maintained.
有機粒子の脱落を抑制する観点から、基材フィルムと有機粒子との剥離強度は、40gf/25mm以上がより好ましく、45gf/25mm以上がさらに好ましい。有機粒子の密着力の上限値は高ければ高いほどよいが、実用的な観点から300gf/25mmあれば十分である。
From the viewpoint of suppressing the falling off of the organic particles, 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.
基材フィルムと有機粒子との剥離強度を30gf/25mm以上、または上記の好ましい範囲とするための方法は、本発明の効果を損なわない限り特に限定されないが、例えば、後述する製造工程での有機粒子にかかる熱履歴を大きくすることや、基材フィルムに有機粒子と相溶性の高い成分を含有させること等により、基材フィルムと有機粒子との剥離強度を上げることができる。
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.
(せん断かたさ)
本発明のフィルムは、せん断変形性を布に近づける観点から、KES法に従い測定されるせん断かたさが0.1gf/(cm・deg)以上6.0gf/(cm・deg)以下であることが重要である。 (Shear hardness)
In the film of the present invention, it is important that the 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.
本発明のフィルムは、せん断変形性を布に近づける観点から、KES法に従い測定されるせん断かたさが0.1gf/(cm・deg)以上6.0gf/(cm・deg)以下であることが重要である。 (Shear hardness)
In the film of the present invention, it is important that the 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.
せん断変形とは、経糸と緯糸とが交差することにより構成されている布が最も容易に受ける変形様式をいう。2次元の布が3次元の曲面を容易にカバーすることができるのはこのせん断変形に大きく依存し、せん断変形が大きい、つまり、せん断かたさが小さい方が人体のような曲面によりフィットし易く、着用感がよいものとなる。つまり、せん断かたさが0.1gf/(cm・deg)以上6.0gf/(cm・deg)以下であるフィルムは、例えば衛生材等の人体に着用する可能性のある用途に使用される際に好ましいものとなる。
“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.
KES法に従い測定されるせん断かたさとは、Kawabata Evaluation System法に従い測定される機械方向および幅方向のせん断応力より算出するせん断かたさをいう。ここで、機械方向とはフィルム製造時にフィルムが進行する方向を指し、幅方向とはフィルムの搬送面に平行であり、機械方向と直交する方向を指す(以下同じ)。より具体的には、せん断変形が-2.5°、-0.5°、0.5°、および2.5°である点における、機械方向および幅方向のせん断応力をKES法により測定し(以下、各点におけるせん断応力をそれぞれHG-2.5、HG-0.5、HG0.5、HG2.5ということがある)、機械方向および幅方向について、式2を用いて正方向のせん断かたさ(G(+))を、式3用いて負方向のせん断かたさ(G(-))を算出し、機械方向および幅方向のG(+)およびG(-)を平均して得られるせん断かたさをいう。なお、せん断応力の測定時の条件は、室温23℃、相対湿度65%、強制荷重10gf、せん断ずり速度0.417mm/sec、および試料のせん断変形範囲-8°~8°である。なお、以後、KES法に従い測定されるせん断かたさのことを、単にせん断かたさと記すことがある。
式2:G(+)=(HG2.5-HG0.5)/(2.5°-0.5°)
式3:G(-)=(HG-2.5-HG-0.5)/(-2.5°-(-0.5°))
上記観点から、せん断かたさは、0.1gf/(cm・deg)以上3.5gf/(cm・deg)以下であることがより好ましく、0.1gf/(cm・deg)以上2.0gf/(cm・deg)以下であることがさらに好ましく、0.1gf/(cm・deg)以上1.5gf/(cm・deg)以下であることが特に好ましい。 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. Here, the machine direction refers to the direction in which the film proceeds during film production, and 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. (Hereinafter, 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). Calculate the shear strength in the direction (G (+)) using Equation 3 to calculate the shear strength in the negative direction (G (−)), and average G (+) and G (−) in the machine direction and width direction. The shear strength obtained. 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 °. Hereinafter, the shear hardness measured according to the KES method may be simply referred to as shear hardness.
Formula 2: G (+) = (HG 2.5 -HG 0.5 ) / (2.5 ° -0.5 °)
Formula 3: G (−) = (HG −2.5 −HG −0.5 ) / (− 2.5 ° − (− 0.5 °))
From the above viewpoint, 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.
式2:G(+)=(HG2.5-HG0.5)/(2.5°-0.5°)
式3:G(-)=(HG-2.5-HG-0.5)/(-2.5°-(-0.5°))
上記観点から、せん断かたさは、0.1gf/(cm・deg)以上3.5gf/(cm・deg)以下であることがより好ましく、0.1gf/(cm・deg)以上2.0gf/(cm・deg)以下であることがさらに好ましく、0.1gf/(cm・deg)以上1.5gf/(cm・deg)以下であることが特に好ましい。 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. Here, the machine direction refers to the direction in which the film proceeds during film production, and 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. (Hereinafter, 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). Calculate the shear strength in the direction (G (+)) using Equation 3 to calculate the shear strength in the negative direction (G (−)), and average G (+) and G (−) in the machine direction and width direction. The shear strength obtained. 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 °. Hereinafter, the shear hardness measured according to the KES method may be simply referred to as shear hardness.
Formula 2: G (+) = (HG 2.5 -HG 0.5 ) / (2.5 ° -0.5 °)
Formula 3: G (−) = (HG −2.5 −HG −0.5 ) / (− 2.5 ° − (− 0.5 °))
From the above viewpoint, 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.
本発明のフィルムのせん断かたさを0.1gf/(cm・deg)以上6.0gf/(cm・deg)以下、または上記の好ましい範囲とするための方法は、本発明の効果を損なわない限り特に限定されないが、例えば、基材フィルムにおける熱可塑性エラストマーの含有量を増やすこと、フィルムの厚みを薄くすること、後述するエンボス加工を施すこと等によりせん断かたさを低くすることができる。
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. Although it is not limited, for example, 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.
(摩擦係数)
本発明のフィルムは、フィルムのすべり性、および生産性の観点から、有機粒子を有する面において、KES法に従い測定される摩擦係数が0.05以上0.80以下であることが好ましい。KES法に従い測定される摩擦係数が0.05以上であると、フィルムの生産性が向上する。また、KES法に従い測定される摩擦係数が0.80以下であると、フィルムのすべり性が向上する。有機粒子を有する面におけるKES法に従い測定される摩擦係数は、上記観点から、0.05以上0.35以下がより好ましく、0.05以上0.15以下がさらに好ましい。 (Coefficient of friction)
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. When the friction coefficient measured according to the KES method is 0.05 or more, the productivity of the film is improved. Moreover, the slipperiness of a film improves that the friction coefficient measured according to KES method is 0.80 or less. From the above viewpoint, 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.
本発明のフィルムは、フィルムのすべり性、および生産性の観点から、有機粒子を有する面において、KES法に従い測定される摩擦係数が0.05以上0.80以下であることが好ましい。KES法に従い測定される摩擦係数が0.05以上であると、フィルムの生産性が向上する。また、KES法に従い測定される摩擦係数が0.80以下であると、フィルムのすべり性が向上する。有機粒子を有する面におけるKES法に従い測定される摩擦係数は、上記観点から、0.05以上0.35以下がより好ましく、0.05以上0.15以下がさらに好ましい。 (Coefficient of friction)
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. When the friction coefficient measured according to the KES method is 0.05 or more, the productivity of the film is improved. Moreover, the slipperiness of a film improves that the friction coefficient measured according to KES method is 0.80 or less. From the above viewpoint, 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.
KES法に従い測定される摩擦係数とは、具体的には、試料の大きさを10cm(機械方向)×10cm(幅方向)、荷重を25gf、滑り子(標準摩擦子(指紋タイプ))の移動速度を1mm/sec、室温を23℃、相対湿度を65%としてKES法により測定する摩擦係数をいう。なお、以後、KES法に従い測定される摩擦係数のことを、単に摩擦係数ということがある。
Specifically, 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%. Hereinafter, the friction coefficient measured according to the KES method may be simply referred to as a friction coefficient.
本発明のフィルムの摩擦係数を0.05gf/(cm・deg)以上0.80gf/(cm・deg)以下、または上記の好ましい範囲とするための方法は、本発明の効果を損なわない限り特に限定されないが、例えば、フィルム全体の面積に対する有機粒子の占める面積の割合を大きくすることや、有機粒子の形状をより球形状に近づけること等により、摩擦係数を低くすることができる。
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. Although not limited, for example, 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.
(圧縮仕事量)
本発明のフィルムは、心地良い触感のフィルムとする観点から、クッション性を有することが好ましい。ここでいうクッション性とは、嵩高性と柔軟性を表す指標であり、フィルムを圧縮したときの仕事量(圧縮仕事量)を尺度として表現することができる。圧縮仕事量は、KES法に従い測定することができる。具体的には、室温23℃、相対湿度65%の雰囲気下でフィルムを面積2cm2の円形平面を持つ鋼板間で圧縮速度20μm/sec、圧縮最大荷重10gf/cm2の条件で圧縮して、KES法により測定することができる。以後、KES法に従い測定した圧縮仕事量のことを、単に圧縮仕事量と記す。 (Compression work)
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 μm / sec and a maximum compression load of 10 gf / cm 2 . It can be measured by the KES method. Hereinafter, the compression work measured according to the KES method is simply referred to as compression work.
本発明のフィルムは、心地良い触感のフィルムとする観点から、クッション性を有することが好ましい。ここでいうクッション性とは、嵩高性と柔軟性を表す指標であり、フィルムを圧縮したときの仕事量(圧縮仕事量)を尺度として表現することができる。圧縮仕事量は、KES法に従い測定することができる。具体的には、室温23℃、相対湿度65%の雰囲気下でフィルムを面積2cm2の円形平面を持つ鋼板間で圧縮速度20μm/sec、圧縮最大荷重10gf/cm2の条件で圧縮して、KES法により測定することができる。以後、KES法に従い測定した圧縮仕事量のことを、単に圧縮仕事量と記す。 (Compression work)
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 μm / sec and a maximum compression load of 10 gf / cm 2 . It can be measured by the KES method. Hereinafter, the compression work measured according to the KES method is simply referred to as compression work.
本発明のフィルムは、上記観点から、圧縮仕事量が0.02gf・cm/cm2以上であることが好ましく、0.04gf・cm/cm2以上であることがより好ましく、0.06gf・cm/cm2以上であることがさらに好ましい。フィルムの圧縮仕事量が0.02gf・cm/cm2未満であれば、そのクッション性や触感が低下することがある。一方、圧縮仕事量が高すぎると、フィルムの取り扱い性や、印刷や貼り合わせなどの後加工を施す際の後加工適性が低下することがある。これらの観点から、圧縮仕事量の上限は0.5gf・cm/cm2であることが好ましい。
From the above viewpoint, 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 .
本発明のフィルムの圧縮仕事量を0.02gf・cm/cm2以上、または上記の好ましい範囲とするための方法は、本発明の効果を損なわない限り特に限定されないが、例えば、有機粒子の平均粒径を調整する方法、後述するエンボス加工により凹凸形状を付与する方法等が挙げられる。具体的には、有機粒子の平均粒径を大きくすることや、凹凸部の高さを高くすること等により、圧縮仕事量を大きくすることができる。
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.
(フィルムの透湿度)
本発明においては、フィルムの透湿度が、500g/(m2・day)以上5,000g/(m2・day)以下であることが好ましい。このような態様とすることにより、フィルムは衛生材などの透湿性が要求される用途に好適に用いることができるものとなる。衛生材などの透湿性が要求される用途に好適に用いる観点から、フィルムの透湿度は、1,500g/(m2・day)以上であることがより好ましく、2,000g/(m2・day)以上であることがより好ましい。また、フィルムの透湿度の上限は、衛生材に適用するとの観点からすると、5,000g/(m2・day)程度あれば十分である。 (Water permeability of film)
In the present invention, the moisture permeability of the film, 500g / (m 2 · day ) or more 5,000g / (m 2 · day) is preferably not more than. By setting it as such an aspect, a film can be used suitably for the use as which moisture permeability, such as a sanitary material, is requested | required. From the viewpoint of being suitably used for applications requiring moisture permeability such as sanitary materials, 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. Further, 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.
本発明においては、フィルムの透湿度が、500g/(m2・day)以上5,000g/(m2・day)以下であることが好ましい。このような態様とすることにより、フィルムは衛生材などの透湿性が要求される用途に好適に用いることができるものとなる。衛生材などの透湿性が要求される用途に好適に用いる観点から、フィルムの透湿度は、1,500g/(m2・day)以上であることがより好ましく、2,000g/(m2・day)以上であることがより好ましい。また、フィルムの透湿度の上限は、衛生材に適用するとの観点からすると、5,000g/(m2・day)程度あれば十分である。 (Water permeability of film)
In the present invention, the moisture permeability of the film, 500g / (m 2 · day ) or more 5,000g / (
なお、ここでフィルムの透湿度とは、25℃、90%RHに設定した恒温恒湿装置にて、JIS Z0208(1976)に規定された方法により測定する透湿度をいう。
In addition, the water vapor transmission rate of a film here means the water vapor transmission rate measured by the method prescribed | regulated to JIS Z0208 (1976) with the constant temperature and humidity apparatus set to 25 degreeC and 90% RH.
フィルムの透湿度を500g/(m2・day)以上5,000g/(m2・day)以下または上記の好ましい範囲とする方法は、本発明の効果を損なわない限り特に制限されず、例えば、基材フィルムを構成する樹脂として、透湿性に優れたポリエステル系エラストマーを用いることによりフィルムの透湿度を向上させることができる。
How to the moisture permeability of the film and 500g / (m 2 · day) or more 5,000g / (m 2 · day) or less or the above preferred ranges is not particularly limited as long as it does not impair the effects of the present invention, for example, 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.
(基材フィルムの層構成)
本発明の基材フィルムは、本発明の効果を損なわない限り、単層構成でも積層構成でもよいが、最表面の有機粒子の基材フィルムからの脱落を軽減しつつ、フィルム全体の特性であるせん断かたさや、透湿度を前記の好ましい範囲とする観点から、積層構成であることが好ましい。より具体的には、有機粒子と直接接する層は、有機粒子との相溶性に優れた樹脂成分を含有するとともに、その他の層は前記のせん断かたさや透湿度を好ましい範囲とするのに適した組成とすることにより、透湿度、せん断かたさ、および有機粒子の密着性に優れたフィルムを得やすくなる。 (Layer structure of 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. From the viewpoint of making the shear hardness and moisture permeability within the above preferred ranges, it is preferably a laminated structure. More specifically, 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.
本発明の基材フィルムは、本発明の効果を損なわない限り、単層構成でも積層構成でもよいが、最表面の有機粒子の基材フィルムからの脱落を軽減しつつ、フィルム全体の特性であるせん断かたさや、透湿度を前記の好ましい範囲とする観点から、積層構成であることが好ましい。より具体的には、有機粒子と直接接する層は、有機粒子との相溶性に優れた樹脂成分を含有するとともに、その他の層は前記のせん断かたさや透湿度を好ましい範囲とするのに適した組成とすることにより、透湿度、せん断かたさ、および有機粒子の密着性に優れたフィルムを得やすくなる。 (Layer structure of 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. From the viewpoint of making the shear hardness and moisture permeability within the above preferred ranges, it is preferably a laminated structure. More specifically, 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.
上記観点から、基材フィルムが、少なくとも、有機粒子と接する層(A層)と、A層を挟んで前記有機粒子と反対側に位置する層(B層)の積層構成からなることが好ましい。ここで、「少なくとも、有機粒子と接する層(A層)と、A層を挟んで前記有機粒子と反対側に位置する層(B層)の積層構成からなる」とは、A層とB層が接しており、かつA層表面に有機粒子が付着している状態をいう。このような態様の基材フィルムとしては、例えば、A層/B層の2種2層構成の基材フィルムや、A層/B層/C層(A層及びB層と異なる層)の3種3層構成の基材フィルムが挙げられる。
From the above viewpoint, it is preferable that 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. Here, “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. As a base film of such an aspect, for example, a base film having two types and two layers of A layer / B layer and A layer / B layer / C layer (a layer different from the A layer and the B layer) 3 Examples include a base film having a three-layer structure.
本発明のフィルムにおけるA層及びB層は、せん断変形性の観点から、熱可塑性エラストマーを含むことが好ましい。熱可塑性エラストマーとしては、本発明の効果を損なわない限り特に制限されず、結晶性を有する熱可塑性エラストマー、非晶性の熱可塑性エラストマーのいずれであってもよく、また、両者を混合してもよい。
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.
A層における熱可塑性エラストマーとしては、有機粒子との密着を容易にする観点から、ポリエステル系エラストマー、ポリオレフィン系エラストマー、およびアクリル系エラストマーなどを単独でまたは組み合わせて用いることが好ましい。B層における熱可塑性エラストマーとしては、得られるフィルムの透湿性の観点から、ポリエステル系エラストマーを用いることが好ましい。
As the 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. As the 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層および有機粒子中の樹脂成分の溶解度パラメータ、樹脂A、および樹脂B)
本発明のフィルムは前述のA層及びB層を有する場合、溶解度パラメータの差の絶対値が最も小さくなるように、A層中の樹脂成分全体を100質量%としたときに、A層中に5質量%以上含まれる樹脂の中から1つの樹脂(樹脂A)を選択し、有機粒子の樹脂成分全体を100質量%としたときに、有機粒子中に5質量%以上含まれる樹脂の中から1つの樹脂(樹脂B)を選択した際に、樹脂Aと樹脂Bの溶解度パラメータの差の絶対値が0.10(MPa)0.5以下であることが好ましい。 (Solubility parameter of resin component in layer A and organic particles, resin A and resin B)
When the film of the present invention has the aforementioned A layer and B layer, when the total resin component in the A layer is 100% by mass so that the absolute value of the difference in solubility parameter is minimized, When one resin (resin A) is selected from among resins contained in an amount of 5% by mass or more and the entire resin component of the organic particles is 100% by mass, the resin contained in the organic particles is contained in an amount of 5% by mass or more. When one resin (resin B) is selected, the absolute value of the difference in solubility parameter between resin A and resin B is preferably 0.10 (MPa) 0.5 or less.
本発明のフィルムは前述のA層及びB層を有する場合、溶解度パラメータの差の絶対値が最も小さくなるように、A層中の樹脂成分全体を100質量%としたときに、A層中に5質量%以上含まれる樹脂の中から1つの樹脂(樹脂A)を選択し、有機粒子の樹脂成分全体を100質量%としたときに、有機粒子中に5質量%以上含まれる樹脂の中から1つの樹脂(樹脂B)を選択した際に、樹脂Aと樹脂Bの溶解度パラメータの差の絶対値が0.10(MPa)0.5以下であることが好ましい。 (Solubility parameter of resin component in layer A and organic particles, resin A and resin B)
When the film of the present invention has the aforementioned A layer and B layer, when the total resin component in the A layer is 100% by mass so that the absolute value of the difference in solubility parameter is minimized, When one resin (resin A) is selected from among resins contained in an amount of 5% by mass or more and the entire resin component of the organic particles is 100% by mass, the resin contained in the organic particles is contained in an amount of 5% by mass or more. When one resin (resin B) is selected, the absolute value of the difference in solubility parameter between resin A and resin B is preferably 0.10 (MPa) 0.5 or less.
A層は、熱可塑性エラストマーの他、有機粒子を構成する成分として列挙した成分を含んでいてもよい。これらの成分のうち、有機粒子の樹脂成分全体を100質量%としたときに、有機粒子中に5質量%以上含まれる成分や、それに化学構造の近い成分が、A層の樹脂成分全体を100質量%としたときに、A層中に5質量%以上含まれることにより、樹脂Aと樹脂Bの溶解度パラメータの差の絶対値が小さくなる。樹脂Aと樹脂Bの溶解度パラメータの差の絶対値が0.10(MPa)0.5以下であると、A層と有機粒子の密着力が強固となり、フィルム表面への負荷や接触により有機粒子の脱落が軽減されるため、フィルムに布のような触感を付与することが容易となる。
A layer may contain the component enumerated as a component which comprises organic particle other than a thermoplastic elastomer. Among these components, 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 When 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. If 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.
安定してフィルムに布のような触感を付与する点では、A層と有機粒子の密着力は高ければ高いほど好ましい。そのため、樹脂Aと樹脂Bの溶解度パラメータの差の絶対値は0.05(MPa)0.5以下であることがより好ましく、0.01(MPa)0.5以下であることがさらに好ましい。なお、樹脂Aと樹脂Bの溶解度パラメータの差の絶対値は、有機粒子の脱落を軽減するには小さければ小さいほど好ましいため、その下限値は0(MPa)0.5とすることができる。
The higher the adhesion between the A layer and the organic particles, the more preferable it is to stably give the film a tactile feel like a cloth. Therefore, 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 .
樹脂Aと樹脂Bの溶解度パラメータの差の絶対値を0.10(MPa)0.5以下とする方法としては、本発明の効果を損なわない限り特に制限されないが、例えば、A層に含まれる樹脂Aと有機粒子に含まれる樹脂Bを同一成分、若しくはそれらの化学構造をできるだけ近いものとする方法が挙げられる。例えば、樹脂Aと樹脂Bを同一成分とすることにより、溶解パラメータの差は0(MPa)0.5となる。
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 .
本発明のフィルムは、A層と有機粒子の密着力の観点から、A層中の樹脂成分全体を100質量%としたときに、A層が樹脂Aを5質量%以上100質量%以下含むことが好ましい。A層中の樹脂成分全体を100質量%としたときのA層における樹脂Aの量が5質量%より少ないと、後述する樹脂Bとの溶解度パラメータの差の絶対値が小さかったとしても、A層最表面に占める樹脂Aの割合が小さすぎるため、A層と有機粒子の間に十分な密着力が得られないことがある。A層と有機粒子の密着力を向上させる観点から、A層中の樹脂成分全体を100質量%としたときのA層における樹脂Aの含有量は、10質量%以上100質量%以下であることが好ましく、さらに好ましくは15%質量以上100質量%以下である。
In the film of the present invention, from the viewpoint of adhesion between the A layer and the organic particles, 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. From the viewpoint of improving the adhesion 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%.
本発明の有機粒子は、A層と有機粒子の密着力の観点から、有機粒子中の樹脂成分全体を100質量%としたときに、有機粒子が樹脂Bを50質量%以上100質量%以下含むことが好ましい。有機粒子中の樹脂成分全体を100質量%としたときの、有機粒子における樹脂Bの含有量を50質量%以上とすることにより、A層と有機粒子との密着力を向上させることができる。A層と有機粒子の密着力を向上させる観点からは、有機粒子中の樹脂Bの量は、有機粒子の樹脂成分全体を100質量%としたときに、90質量%以上100質量%以下であることがより好ましい。
From the viewpoint of adhesion between the A layer and the organic particles, 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. By setting the content of the resin B in the organic particles to 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. From the viewpoint of improving the adhesion between the A layer and the organic particles, 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.
なお、本発明において前記の樹脂Aおよび樹脂Aの条件を満たす組み合わせが複数存在する場合は、候補となる樹脂のうち、A層に占める含有量(質量%)が最も大きいものを樹脂Aとする組み合わせを採用するものとする。なお、A層に占める含有量(質量%)が等しい樹脂が複数存在する場合は、候補となる樹脂から任意に樹脂Aを選択することができる。
In the present invention, 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. In addition, 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.
(添加剤)
本発明のフィルムは、本発明の効果を損なわない範囲で前述した成分以外の成分を含有してもよい。例えば、充填剤、酸化防止剤、紫外線安定化剤、着色防止剤、艶消し剤、抗菌剤、消臭剤、耐候剤、抗酸化剤、イオン交換剤、粘着性付与剤、着色顔料、染料などを含めてもよい。 (Additive)
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. For example, 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.
本発明のフィルムは、本発明の効果を損なわない範囲で前述した成分以外の成分を含有してもよい。例えば、充填剤、酸化防止剤、紫外線安定化剤、着色防止剤、艶消し剤、抗菌剤、消臭剤、耐候剤、抗酸化剤、イオン交換剤、粘着性付与剤、着色顔料、染料などを含めてもよい。 (Additive)
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. For example, 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.
(エンボス加工)
本発明のフィルムは、フィルムの触感と柔らかさを布に近づける観点から、エンボス加工を施すことにより、凹凸構造を付与することも好ましい。このような態様とすることにより、フィルムの嵩高さを調節することができるため、圧縮仕事量を前記の好ましい範囲とすることが容易となる。また、凹凸構造の程度により空間自由度を調節することができるため、せん断かたさを前記の好ましい範囲とすることも容易となる。エンボス加工に用いるエンボスロールの表面の形状は、本発明の効果を損なわない限り特に制限されず、目的とする圧縮仕事量やせん断かたさの大きさ等に応じて適宜選択することができる。例えば、エンボスロールの表面の凸部の高さを大きくすることで、圧縮仕事量を大きく、せん断かたさを小さくすることができる。 (Embossing)
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. By setting it as such an aspect, 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.
本発明のフィルムは、フィルムの触感と柔らかさを布に近づける観点から、エンボス加工を施すことにより、凹凸構造を付与することも好ましい。このような態様とすることにより、フィルムの嵩高さを調節することができるため、圧縮仕事量を前記の好ましい範囲とすることが容易となる。また、凹凸構造の程度により空間自由度を調節することができるため、せん断かたさを前記の好ましい範囲とすることも容易となる。エンボス加工に用いるエンボスロールの表面の形状は、本発明の効果を損なわない限り特に制限されず、目的とする圧縮仕事量やせん断かたさの大きさ等に応じて適宜選択することができる。例えば、エンボスロールの表面の凸部の高さを大きくすることで、圧縮仕事量を大きく、せん断かたさを小さくすることができる。 (Embossing)
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. By setting it as such an aspect, 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.
(フィルムの製造方法)
次に、基材フィルムが単層構成である場合を例に挙げて、本発明のフィルムを製造する方法について具体的に説明する。但し、本発明のフィルムの製造方法はこれに限定されるものではない。 (Film production method)
Next, the case where the substrate film has a single layer structure is taken as an example, and the method for producing the film of the present invention will be specifically described. However, the manufacturing method of the film of this invention is not limited to this.
次に、基材フィルムが単層構成である場合を例に挙げて、本発明のフィルムを製造する方法について具体的に説明する。但し、本発明のフィルムの製造方法はこれに限定されるものではない。 (Film production method)
Next, the case where the substrate film has a single layer structure is taken as an example, and the method for producing the film of the present invention will be specifically described. However, the manufacturing method of the film of this invention is not limited to this.
本発明のフィルムにおける基材フィルムを得るために用いる組成物、つまり、熱可塑性エラストマー、添加剤などを含有する組成物を得るにあたっては、各成分を溶融混練することにより組成物を製造する溶融混練法が好ましい。溶融混練方法については、特に制限はなく、ニーダー、ロールミル、バンバリーミキサー、単軸または二軸押出機などの公知の混合機を用いることができる。中でも生産性の観点から、単軸または二軸押出機の使用が好ましい。
In obtaining a composition used for obtaining a base film in the film of the present invention, that is, a composition containing a thermoplastic elastomer, an additive, etc., 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.
次に、上記した方法により得られた組成物を用いて、インフレーション法、チューブラー法、Tダイキャスト法などの公知のフィルム製造法により、無配向フィルムを製造することができる。
Next, using the composition obtained by the above-described method, 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.
さらに、機械特性向上、軽量化、および透湿性向上の観点から、得られた無配向フィルムを一軸または二軸延伸することが好ましく、さらに経済性や生産性も考慮すると、機械方向のみに一軸延伸することがより好ましい。機械方向への一軸延伸は、ロール式の縦延伸装置やステンターなど公知の延伸装置により行うことができる。また、このときの延伸倍率は、機械特性向上、軽量化、透湿性向上、経済性、および生産性の観点から、1.1倍以上が好ましく、1.5倍以上8.0倍以下がより好ましい。
Furthermore, from the viewpoint of improving mechanical properties, reducing weight, and improving moisture permeability, 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. In addition, 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.
基材フィルムを製膜した後に、有機粒子を基材フィルムの表面に吹きつけ、熱ラミネートすることにより本発明のフィルムを得ることができる。
After forming the base film, the film of the present invention can be obtained by spraying organic particles on the surface of the base film and heat laminating.
以下に実施例を示して本発明をさらに具体的に説明するが、本発明はこれにより何ら制限を受けるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
[測定および評価方法]
実施例中に示す測定や評価は次に示すような条件で行った。 [Measurement and evaluation method]
Measurements and evaluations shown in the examples were performed under the following conditions.
実施例中に示す測定や評価は次に示すような条件で行った。 [Measurement and evaluation method]
Measurements and evaluations shown in the examples were performed under the following conditions.
(1)基材フィルムの厚み
フィルムの幅方向のセンター部からサンプル片を切り出し、ウルトラミクロトームを用いて該サンプル片の機械方向-厚み方向断面(以下、フィルム断面ということがある。)を観察面とするように-100℃で超薄切片を採取した。走査型電子顕微鏡((株)日立ハイテクノロジーズ製 S-3400N)を用いて倍率500倍でフィルム断面の写真を撮影し、顕微鏡の測長機能を用いてフィルムの最表面に有機粒子がない部分の厚みを測定した。測定は、観察箇所を変えて10回行い、得られた値の平均値を基材フィルムの厚み(μm)とした。 (1) 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 (μm) of the base film.
フィルムの幅方向のセンター部からサンプル片を切り出し、ウルトラミクロトームを用いて該サンプル片の機械方向-厚み方向断面(以下、フィルム断面ということがある。)を観察面とするように-100℃で超薄切片を採取した。走査型電子顕微鏡((株)日立ハイテクノロジーズ製 S-3400N)を用いて倍率500倍でフィルム断面の写真を撮影し、顕微鏡の測長機能を用いてフィルムの最表面に有機粒子がない部分の厚みを測定した。測定は、観察箇所を変えて10回行い、得られた値の平均値を基材フィルムの厚み(μm)とした。 (1) 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 (μm) of the base film.
(2)有機粒子の平均粒径
まず、ウルトラミクロトームを用いてナイフ傾斜角度(厚み方向とナイフ面のなす角度)3°でフィルムを切断し、得られた断面を走査型電子顕微鏡((株)日立ハイテクノロジーズ製 S-3400N)により倍率500倍で拡大観察し、顕微鏡の測長機能により1個の有機粒子を完全に囲みかつ面積が最も小さくなるように正方形または長方形を描いて、正方形の場合は1辺の長さ、長方形の場合は長辺と短辺の長さの平均値を該有機粒子の粒子径とした。同様の測定を100個の有機粒子について行い、得られた粒子径の値の平均値を有機粒子の平均粒子径(μm)とした。このとき、測定対象の有機粒子は、観察画像の中心部から近い順に100個選定するものとした。なお、顕微鏡の観察画像に含まれる粒子が100個未満の場合は、その観察画像に含まれる粒子は全て測定対象とし、さらに別の部位における観察画像より、合計が100個に達するまで中心部から近い順に選定するものとした。 (2) Average particle size of organic particles First, an ultramicrotome was used to cut the film at an angle of knife inclination (angle between the thickness direction and the knife surface) of 3 °, and the resulting cross section was scanned using an electron microscope (Corporation). In the case of a square, a magnified image is magnified 500 times with Hitachi High-Technologies S-3400N), and a square or rectangle is drawn so that one organic particle is completely enclosed and the area is minimized by the length measurement function of the microscope. Is the length of one side, and in the case of a rectangle, the average value of the length of the long side and the short side is taken as the particle diameter of the organic particles. The same measurement was performed on 100 organic particles, and the average value of the obtained particle diameter values was defined as the average particle diameter (μm) of the organic particles. At this time, 100 organic particles to be measured were selected in order from the center of the observation image. In addition, when 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.
まず、ウルトラミクロトームを用いてナイフ傾斜角度(厚み方向とナイフ面のなす角度)3°でフィルムを切断し、得られた断面を走査型電子顕微鏡((株)日立ハイテクノロジーズ製 S-3400N)により倍率500倍で拡大観察し、顕微鏡の測長機能により1個の有機粒子を完全に囲みかつ面積が最も小さくなるように正方形または長方形を描いて、正方形の場合は1辺の長さ、長方形の場合は長辺と短辺の長さの平均値を該有機粒子の粒子径とした。同様の測定を100個の有機粒子について行い、得られた粒子径の値の平均値を有機粒子の平均粒子径(μm)とした。このとき、測定対象の有機粒子は、観察画像の中心部から近い順に100個選定するものとした。なお、顕微鏡の観察画像に含まれる粒子が100個未満の場合は、その観察画像に含まれる粒子は全て測定対象とし、さらに別の部位における観察画像より、合計が100個に達するまで中心部から近い順に選定するものとした。 (2) Average particle size of organic particles First, an ultramicrotome was used to cut the film at an angle of knife inclination (angle between the thickness direction and the knife surface) of 3 °, and the resulting cross section was scanned using an electron microscope (Corporation). In the case of a square, a magnified image is magnified 500 times with Hitachi High-Technologies S-3400N), and a square or rectangle is drawn so that one organic particle is completely enclosed and the area is minimized by the length measurement function of the microscope. Is the length of one side, and in the case of a rectangle, the average value of the length of the long side and the short side is taken as the particle diameter of the organic particles. The same measurement was performed on 100 organic particles, and the average value of the obtained particle diameter values was defined as the average particle diameter (μm) of the organic particles. At this time, 100 organic particles to be measured were selected in order from the center of the observation image. In addition, when 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.
(3)フィルムのせん断かたさ(G)
フィルムを12cm(機械方向)×12cm(幅方向)の大きさに切り取り試料とし、試験台に取り付けた。次いで、カトーテック社製のせん断試験機KES-FB1-Aを用いて、23℃、相対湿度65%の雰囲気下、強制荷重10gf、せん断ずり速度0.417mm/secの条件で、試料に-8°~8°のせん断変形を与え、せん断変形が-2.5°、-0.5°、0.5°、および2.5°である点におけるせん断応力を測定した(以下、各点におけるせん断応力をそれぞれHG-2.5、HG-0.5、HG0.5、HG2.5ということがある。)。HG0.5およびHG2.5より下記式2を用いて正方向のせん断かたさ(G(+))を、HG-2.5およびHG-0.5より下記式3を用いて負方向のせん断かたさ(G(-))をそれぞれ算出した。せん断応力の測定およびG(+)、G(-)の算出は、機械方向、幅方向ともに3回(合計6回)行い、その全てのG(+)、G(-)の値の平均値の小数第3位を四捨五入した値をそのフィルムのせん断かたさ(G)(gf/(cm・deg))とした。
式2:G(+)=(HG2.5-HG0.5)/(2.5°-0.5°)
式3:G(-)=(HG-2.5-HG-0.5)/(-2.5°-(-0.5°))
なお、機械方向のせん断かたさ(G)を測定する場合は、フィルムの機械方向がせん断変形方向と直交するように試料を取り付け、幅方向のせん断かたさ(G)を測定する場合は、フィルムの幅方向がせん断変形方向と直交するように試料を取り付けた。 (3) Film shear strength (G)
The film was cut into a size of 12 cm (machine direction) × 12 cm (width direction) and used as a sample, which was attached to a test bench. Next, using a shear tester KES-FB1-A manufactured by Kato Tech Co., Ltd., −8 was applied to the sample under the conditions of a forced load of 10 gf and a shear shear rate of 0.417 mm / sec in an atmosphere at 23 ° C. and a relative humidity of 65%. The shear stress was measured at points at which shear deformations of −8 ° to −2.5 °, −0.5 °, 0.5 °, and 2.5 ° were applied (hereinafter referred to as points at each point). (Shear stress may be HG −2.5 , HG −0.5 , HG 0.5 , and HG 2.5 , respectively.) From HG 0.5 and HG 2.5 , the followingformula 2 is used to determine the shear strength in the positive direction (G (+)). From HG −2.5 and HG −0.5 , 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.
Formula 2: G (+) = (HG 2.5 -HG 0.5 ) / (2.5 ° -0.5 °)
Formula 3: G (−) = (HG −2.5 −HG −0.5 ) / (− 2.5 ° − (− 0.5 °))
When measuring the shear strength (G) in the machine direction, attach the sample so that the machine direction of the film is orthogonal to the shear deformation direction, and when measuring the shear strength (G) in the width direction, The sample was mounted so that the direction was perpendicular to the shear deformation direction.
フィルムを12cm(機械方向)×12cm(幅方向)の大きさに切り取り試料とし、試験台に取り付けた。次いで、カトーテック社製のせん断試験機KES-FB1-Aを用いて、23℃、相対湿度65%の雰囲気下、強制荷重10gf、せん断ずり速度0.417mm/secの条件で、試料に-8°~8°のせん断変形を与え、せん断変形が-2.5°、-0.5°、0.5°、および2.5°である点におけるせん断応力を測定した(以下、各点におけるせん断応力をそれぞれHG-2.5、HG-0.5、HG0.5、HG2.5ということがある。)。HG0.5およびHG2.5より下記式2を用いて正方向のせん断かたさ(G(+))を、HG-2.5およびHG-0.5より下記式3を用いて負方向のせん断かたさ(G(-))をそれぞれ算出した。せん断応力の測定およびG(+)、G(-)の算出は、機械方向、幅方向ともに3回(合計6回)行い、その全てのG(+)、G(-)の値の平均値の小数第3位を四捨五入した値をそのフィルムのせん断かたさ(G)(gf/(cm・deg))とした。
式2:G(+)=(HG2.5-HG0.5)/(2.5°-0.5°)
式3:G(-)=(HG-2.5-HG-0.5)/(-2.5°-(-0.5°))
なお、機械方向のせん断かたさ(G)を測定する場合は、フィルムの機械方向がせん断変形方向と直交するように試料を取り付け、幅方向のせん断かたさ(G)を測定する場合は、フィルムの幅方向がせん断変形方向と直交するように試料を取り付けた。 (3) Film shear strength (G)
The film was cut into a size of 12 cm (machine direction) × 12 cm (width direction) and used as a sample, which was attached to a test bench. Next, using a shear tester KES-FB1-A manufactured by Kato Tech Co., Ltd., −8 was applied to the sample under the conditions of a forced load of 10 gf and a shear shear rate of 0.417 mm / sec in an atmosphere at 23 ° C. and a relative humidity of 65%. The shear stress was measured at points at which shear deformations of −8 ° to −2.5 °, −0.5 °, 0.5 °, and 2.5 ° were applied (hereinafter referred to as points at each point). (Shear stress may be HG −2.5 , HG −0.5 , HG 0.5 , and HG 2.5 , respectively.) From HG 0.5 and HG 2.5 , the following
Formula 2: G (+) = (HG 2.5 -HG 0.5 ) / (2.5 ° -0.5 °)
Formula 3: G (−) = (HG −2.5 −HG −0.5 ) / (− 2.5 ° − (− 0.5 °))
When measuring the shear strength (G) in the machine direction, attach the sample so that the machine direction of the film is orthogonal to the shear deformation direction, and when measuring the shear strength (G) in the width direction, The sample was mounted so that the direction was perpendicular to the shear deformation direction.
(4)フィルムの有機粒子を有する面の摩擦係数
カトーテック社製の表面特性試験機KES-SEを用いて、フィルムを12cm(機械方向)×12cm(幅方向)の大きさに切取り試料とし、フィルムの有機粒子を有する面が測定面となるように試験台に取り付けて、滑り子として標準摩擦子(指紋タイプ)を取り付け、荷重25gf、1mm/secの速度で滑り子をフィルムの有機粒子を有する面で移動させ、室温23℃、相対湿度65%の雰囲気の条件にて摩擦係数を測定した。機械方向、幅方向ともに測定をそれぞれ3回(合計6回)行い、その全てのデータの平均値をそのフィルムの有機粒子を有する面の摩擦係数とした。 (4) Coefficient of friction of the surface having organic particles of the film Using a surface property tester KES-SE manufactured by Kato Tech Co., Ltd., the film was cut into a size of 12 cm (machine direction) × 12 cm (width direction), and used as a sample. Attach a standard friction element (fingerprint type) as a slider and load the slider with the organic particles of the film at a load of 25 gf and 1 mm / sec. The coefficient of friction was measured under conditions of an atmosphere having a room temperature of 23 ° C. and a relative humidity of 65%. Measurement was performed three times in each of the machine direction and the width direction (6 times in total), and the average value of all the data was defined as the coefficient of friction of the surface of the film having organic particles.
カトーテック社製の表面特性試験機KES-SEを用いて、フィルムを12cm(機械方向)×12cm(幅方向)の大きさに切取り試料とし、フィルムの有機粒子を有する面が測定面となるように試験台に取り付けて、滑り子として標準摩擦子(指紋タイプ)を取り付け、荷重25gf、1mm/secの速度で滑り子をフィルムの有機粒子を有する面で移動させ、室温23℃、相対湿度65%の雰囲気の条件にて摩擦係数を測定した。機械方向、幅方向ともに測定をそれぞれ3回(合計6回)行い、その全てのデータの平均値をそのフィルムの有機粒子を有する面の摩擦係数とした。 (4) Coefficient of friction of the surface having organic particles of the film Using a surface property tester KES-SE manufactured by Kato Tech Co., Ltd., the film was cut into a size of 12 cm (machine direction) × 12 cm (width direction), and used as a sample. Attach a standard friction element (fingerprint type) as a slider and load the slider with the organic particles of the film at a load of 25 gf and 1 mm / sec. The coefficient of friction was measured under conditions of an atmosphere having a room temperature of 23 ° C. and a relative humidity of 65%. Measurement was performed three times in each of the machine direction and the width direction (6 times in total), and the average value of all the data was defined as the coefficient of friction of the surface of the film having organic particles.
(5)フィルムの透湿度
25℃、相対湿度90%に設定した恒温恒湿装置にて、JIS Z0208(1976)に規定された方法に従って測定した。測定は3回行い、得られた値の平均値をフィルムの透湿度(g/(m2・day))とした。なお、フィルムの透湿度は有機粒子を有する面から測定した。 (5) 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.
25℃、相対湿度90%に設定した恒温恒湿装置にて、JIS Z0208(1976)に規定された方法に従って測定した。測定は3回行い、得られた値の平均値をフィルムの透湿度(g/(m2・day))とした。なお、フィルムの透湿度は有機粒子を有する面から測定した。 (5) 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.
(6)フィルムの外観
有機粒子を有する面の外観について、24人にアンケートをとり、以下の基準で評価した。
A:布のような自然な外観であると回答した人数が20~24人。
B:布のような自然な外観であると回答した人数が15~19人。
C:布のような自然な外観であると回答した人数が10~14人。
D:布のような自然な外観であると回答した人数が5~9人。
E:布のような自然な外観であると回答した人数が0~4人。
外観はAが最も優れ、D以上の評価があれば実用性に耐えうると判断した。 (6) Appearance of film The appearance of the surface having organic particles was evaluated by the following criteria for 24 people.
A: There are 20 to 24 people who answered that they look natural like cloth.
B: The number of people who answered that it looks natural like cloth is 15-19.
C: The number of people who answered that it looks natural like cloth was 10-14.
D: The number of people who answered that it looks natural like a cloth is 5-9.
E: The number of people who answered that it looks natural like cloth is 0-4.
As for the appearance, A was the most excellent, and it was judged that if it had an evaluation of D or more, it could withstand practicality.
有機粒子を有する面の外観について、24人にアンケートをとり、以下の基準で評価した。
A:布のような自然な外観であると回答した人数が20~24人。
B:布のような自然な外観であると回答した人数が15~19人。
C:布のような自然な外観であると回答した人数が10~14人。
D:布のような自然な外観であると回答した人数が5~9人。
E:布のような自然な外観であると回答した人数が0~4人。
外観はAが最も優れ、D以上の評価があれば実用性に耐えうると判断した。 (6) Appearance of film The appearance of the surface having organic particles was evaluated by the following criteria for 24 people.
A: There are 20 to 24 people who answered that they look natural like cloth.
B: The number of people who answered that it looks natural like cloth is 15-19.
C: The number of people who answered that it looks natural like cloth was 10-14.
D: The number of people who answered that it looks natural like a cloth is 5-9.
E: The number of people who answered that it looks natural like cloth is 0-4.
As for the appearance, A was the most excellent, and it was judged that if it had an evaluation of D or more, it could withstand practicality.
(7)フィルムにおける有機粒子の占める面積の割合
まず、フィルムの有機粒子を有する面を走査型電子顕微鏡で200倍に拡大して観察し、フィルム表面の有機粒子の個数を数えた。次いで、フィルム表面における有機粒子の個数と「(2)有機粒子の平均粒径」に記載の方法で測定した有機粒子の平均粒径との積を有機粒子の面積とした。さらに、観察画像の面積をフィルム全体の面積とし、フィルム全体の面積に対する有機粒子の面積の割合を算出した。同様の測定をフィルムの有機粒子を有する面の任意の10箇所で行い、得られた値の平均値をフィルムにおける有機粒子の占める面積の割合とした。 (7) Ratio of the area occupied by organic particles in the film First, the surface of the film having the organic particles was magnified 200 times with a scanning electron microscope, and the number of organic particles on the film surface was counted. Next, the product of the number of organic particles on the film surface and the average particle size of the organic particles measured by the method described in “(2) Average particle size of organic particles” was defined as the area of the organic particles. Furthermore, the area of the observation image was defined as the area of the entire film, and the ratio of the area of the organic particles to the area of the entire film was calculated. The same measurement was performed at any 10 positions on the surface of the film having the organic particles, and the average value obtained was defined as the ratio of the area occupied by the organic particles in the film.
まず、フィルムの有機粒子を有する面を走査型電子顕微鏡で200倍に拡大して観察し、フィルム表面の有機粒子の個数を数えた。次いで、フィルム表面における有機粒子の個数と「(2)有機粒子の平均粒径」に記載の方法で測定した有機粒子の平均粒径との積を有機粒子の面積とした。さらに、観察画像の面積をフィルム全体の面積とし、フィルム全体の面積に対する有機粒子の面積の割合を算出した。同様の測定をフィルムの有機粒子を有する面の任意の10箇所で行い、得られた値の平均値をフィルムにおける有機粒子の占める面積の割合とした。 (7) Ratio of the area occupied by organic particles in the film First, the surface of the film having the organic particles was magnified 200 times with a scanning electron microscope, and the number of organic particles on the film surface was counted. Next, the product of the number of organic particles on the film surface and the average particle size of the organic particles measured by the method described in “(2) Average particle size of organic particles” was defined as the area of the organic particles. Furthermore, the area of the observation image was defined as the area of the entire film, and the ratio of the area of the organic particles to the area of the entire film was calculated. The same measurement was performed at any 10 positions on the surface of the film having the organic particles, and the average value obtained was defined as the ratio of the area occupied by the organic particles in the film.
(8)有機粒子の形状
フィルムの有機粒子を有する面を、(株)キーエンス製レーザー顕微鏡VK-9700を用いて対物レンズ倍率150倍で観察し、表面の高低差を色で表示したカラー画像を採取した。続いて同画像をpngファイル形式にて保存した後、アメリカ国立衛生研究所により開発された画像解析ソフトImageJ(バージョン:1.44p)により解析した。画像解析は以下の手順により行った。まず、得られたカラー画像をImageJにて赤、青、緑の3種類の輝度に分割した。次いで、赤の輝度を有する画像に対してImageJで大津の2値化機能による自動処理を施し、有機粒子部を赤色、それ以外の部分を白色とした。こうして得られた赤白画像に対してImageJで粒子解析の自動処理を施し、赤色の粒子部の円形度を求めた。なお、自動処理に際してはExclude on edges機能を用い、画像の端部と接する粒子は、解析対象から除外した。
なお、粒子解析を行う際の各設定パラメータは以下の通りとした。
Size:1-40,000μm2
circularity:0-1
show:outlines
上記方法により、有機粒子100個の円形度を測定し、その平均値を有機粒子の円形度とし、この円形度の値が0.3以上1.0以下である場合は有機粒子が球形状であるものと判断した。なお、観察画像に含まれる粒子が100個以上の場合は、中心部から近い順に100個の粒子を選定し、観察画像に含まれる粒子が100個未満の場合は、さらに別の部位における観察画像より、合計が100個に達するまで中心部から近い順に有機粒子を選定するものとした。 (8) 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. 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. In the automatic processing, the exclude on edges function was used, and particles in contact with the edge of the image were excluded from the analysis target.
In addition, each setting parameter at the time of performing particle analysis was as follows.
Size: 1-40,000 μm 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. In addition, 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.
フィルムの有機粒子を有する面を、(株)キーエンス製レーザー顕微鏡VK-9700を用いて対物レンズ倍率150倍で観察し、表面の高低差を色で表示したカラー画像を採取した。続いて同画像をpngファイル形式にて保存した後、アメリカ国立衛生研究所により開発された画像解析ソフトImageJ(バージョン:1.44p)により解析した。画像解析は以下の手順により行った。まず、得られたカラー画像をImageJにて赤、青、緑の3種類の輝度に分割した。次いで、赤の輝度を有する画像に対してImageJで大津の2値化機能による自動処理を施し、有機粒子部を赤色、それ以外の部分を白色とした。こうして得られた赤白画像に対してImageJで粒子解析の自動処理を施し、赤色の粒子部の円形度を求めた。なお、自動処理に際してはExclude on edges機能を用い、画像の端部と接する粒子は、解析対象から除外した。
なお、粒子解析を行う際の各設定パラメータは以下の通りとした。
Size:1-40,000μm2
circularity:0-1
show:outlines
上記方法により、有機粒子100個の円形度を測定し、その平均値を有機粒子の円形度とし、この円形度の値が0.3以上1.0以下である場合は有機粒子が球形状であるものと判断した。なお、観察画像に含まれる粒子が100個以上の場合は、中心部から近い順に100個の粒子を選定し、観察画像に含まれる粒子が100個未満の場合は、さらに別の部位における観察画像より、合計が100個に達するまで中心部から近い順に有機粒子を選定するものとした。 (8) 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. 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. In the automatic processing, the exclude on edges function was used, and particles in contact with the edge of the image were excluded from the analysis target.
In addition, each setting parameter at the time of performing particle analysis was as follows.
Size: 1-40,000 μm 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. In addition, 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.
(9)基材フィルムと有機粒子との剥離強度
フィルムサンプルの最表層に有機粒子を有する面に、25mm幅×30cm長のセロハンテープ(“セロテープ”(登録商標)CT405AP ニチバン(株)製)を、フィルムの機械方向とセロハンテープの長さ方向が平行となるように貼り付け、ハンドローラーで1.5kg/cm2の荷重で押しつけた。得られたサンプルを表面性測定機 “HEIDON”(登録商標)TYPE 14DR(新東科学(株)製)の試料台に、セロハンテープを貼り付けた面が上面になるようにサンプル周囲を固定し、同装置により以下の条件でセロハンテープを引き剥がし、その時に得られる剥離曲線において、試験開始後の変位量10cm~20cmの領域において観測される剥離力の平均値を求めた。同様の測定を、測定箇所を変えて5回行い、得られた値の平均値を有機粒子の剥離強度(gf/25mm)とした。
剥離角度:180°
剥離速度:100mm/分
剥離方向:機械方向
(10)溶解度パラメータ、基材フィルムと有機粒子との相溶性レベル
構造が既知である樹脂については、山本秀樹著「SP値 基礎・応用と計算方法」((株)情報機構発行(2005年)第66~67項)に記載のFedorの推算法に基づき溶解度パラメータを算出した。なお、樹脂の構造が不明瞭であり前記方法により計算できない場合においては、溶解度パラメータが既知である溶媒に対して溶解するか否かの判定による実験法(「ポリマーハンドブック 第4版(Polymer Handbook Fourth Edition)」 ジェー・ブランド(J.Brand)著、ワイリー(Wiley)社 1998年発行)によりSP値を算出し、その値を代用するものとした。但し、実施例において樹脂の構造が不明瞭な例はなく、全て先に記載の方法を用いた。 (9) Peel strength between base film and organic particles Cellophane tape ("Cello Tape" (registered trademark) CT405AP manufactured by Nichiban Co., Ltd.) having a width of 25 mm and a length of 30 cm is applied to the surface having organic particles on the outermost layer of the film sample. The film was attached so that the machine direction of the film and the length direction of the cellophane tape were parallel, and pressed with a load of 1.5 kg / cm 2 with a hand roller. Fix the sample periphery to the sample table of the surface property measuring instrument “HEIDON” (registered trademark) TYPE 14DR (manufactured by Shinto Kagaku Co., Ltd.) so that the surface on which the cellophane tape is attached becomes the upper surface. 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. (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) "The SP value was calculated by J. Brand, published in 1998 by Wiley, and the value was substituted. However, there are no examples in which the resin structure is unclear in the examples, and all the methods described above were used.
フィルムサンプルの最表層に有機粒子を有する面に、25mm幅×30cm長のセロハンテープ(“セロテープ”(登録商標)CT405AP ニチバン(株)製)を、フィルムの機械方向とセロハンテープの長さ方向が平行となるように貼り付け、ハンドローラーで1.5kg/cm2の荷重で押しつけた。得られたサンプルを表面性測定機 “HEIDON”(登録商標)TYPE 14DR(新東科学(株)製)の試料台に、セロハンテープを貼り付けた面が上面になるようにサンプル周囲を固定し、同装置により以下の条件でセロハンテープを引き剥がし、その時に得られる剥離曲線において、試験開始後の変位量10cm~20cmの領域において観測される剥離力の平均値を求めた。同様の測定を、測定箇所を変えて5回行い、得られた値の平均値を有機粒子の剥離強度(gf/25mm)とした。
剥離角度:180°
剥離速度:100mm/分
剥離方向:機械方向
(10)溶解度パラメータ、基材フィルムと有機粒子との相溶性レベル
構造が既知である樹脂については、山本秀樹著「SP値 基礎・応用と計算方法」((株)情報機構発行(2005年)第66~67項)に記載のFedorの推算法に基づき溶解度パラメータを算出した。なお、樹脂の構造が不明瞭であり前記方法により計算できない場合においては、溶解度パラメータが既知である溶媒に対して溶解するか否かの判定による実験法(「ポリマーハンドブック 第4版(Polymer Handbook Fourth Edition)」 ジェー・ブランド(J.Brand)著、ワイリー(Wiley)社 1998年発行)によりSP値を算出し、その値を代用するものとした。但し、実施例において樹脂の構造が不明瞭な例はなく、全て先に記載の方法を用いた。 (9) Peel strength between base film and organic particles Cellophane tape ("Cello Tape" (registered trademark) CT405AP manufactured by Nichiban Co., Ltd.) having a width of 25 mm and a length of 30 cm is applied to the surface having organic particles on the outermost layer of the film sample. The film was attached so that the machine direction of the film and the length direction of the cellophane tape were parallel, and pressed with a load of 1.5 kg / cm 2 with a hand roller. Fix the sample periphery to the sample table of the surface property measuring instrument “HEIDON” (registered trademark) TYPE 14DR (manufactured by Shinto Kagaku Co., Ltd.) so that the surface on which the cellophane tape is attached becomes the upper surface. 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. (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) "The SP value was calculated by J. Brand, published in 1998 by Wiley, and the value was substituted. However, there are no examples in which the resin structure is unclear in the examples, and all the methods described above were used.
得られた各樹脂の溶解度パラメータより、基材フィルムを構成する各樹脂と有機粒子を構成する樹脂の溶解度パラメータの差の絶対値を算出し、この値が最小となる基材フィルムを構成する樹脂を、有機粒子との相溶性が最も高い樹脂とした。なお、基材フィルムを構成する樹脂が1種類の場合は、該樹脂を有機粒子との相溶性が最も高い樹脂とした。次いで、有機粒子との相溶性が最も高い樹脂と有機粒子を構成する樹脂の溶解度パラメータの差の絶対値を求め、以下の基準で基材フィルムと有機粒子との相溶性レベルを評価した。
A.有機粒子との相溶性が最も高い樹脂と有機粒子を構成する樹脂の溶解度パラメータの差の絶対値が、0.10(MPa0.5)以下であった。
B.有機粒子との相溶性が最も高い樹脂と有機粒子を構成する樹脂の溶解度パラメータの差の絶対値が、0.10(MPa0.5)より大きかった。 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. In addition, when the resin which comprises a base film was 1 type, this resin was made into resin with the highest compatibility with an organic particle. Subsequently, 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.
B. 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 ).
A.有機粒子との相溶性が最も高い樹脂と有機粒子を構成する樹脂の溶解度パラメータの差の絶対値が、0.10(MPa0.5)以下であった。
B.有機粒子との相溶性が最も高い樹脂と有機粒子を構成する樹脂の溶解度パラメータの差の絶対値が、0.10(MPa0.5)より大きかった。 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. In addition, when the resin which comprises a base film was 1 type, this resin was made into resin with the highest compatibility with an organic particle. Subsequently, 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.
B. 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 ).
(11)有機粒子の重量平均分子量
有機粒子を構成する樹脂の重量平均分子量は、以下の条件で、ゲルパーミエーションクロマトグラフィー(GPC)法により測定した。有機粒子の構成成分が単一の樹脂である場合は、各測定値を有機粒子の重量平均分子量とした。有機粒子の構成成分が複数の樹脂である場合は、各測定値に含有比率(質量比)を掛け合わせて合計した値を有機粒子の重量平均分子量とした。
測定装置:Polymer Laboratories社製 PL-20
カラム:昭和電工(株)製“Shodex”(登録商標)UT806M
カラム温度:145℃
溶媒(移動相):o-ジクロルベンゼン
溶媒流速:1.0mL/分
試料調整:試料10mgに測定溶媒5mLを添加し、140~150℃で約20分加熱攪拌
インジェクション量:0.200mL
検出器:示差屈折率検出器RI
標準試料:単分散ポリスチレン
(12)フィルムの圧縮仕事量
フィルムを12cm角の大きさに切り取り試料とし、試験台に取り付けた。次いで、カトーテック社製の自動化圧縮試験装置KES-FB3-Aを用いて、室温23℃、相対湿度65%の雰囲気下において、取り付けた試料を面積2cm2の円形平面を持つ鋼板間で、圧縮速度20μm/sec、圧縮最大荷重10gf/cm2の条件で圧縮し、フィルムの圧縮仕事量(gf・cm/cm2)を測定した。フィルムの巻内面、巻外面の両面ともに測定をそれぞれ3回(合計6回)行い、その全てのデータの平均値の小数第3位を四捨五入した値をそのフィルムの圧縮仕事量とした。 (11) 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.
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. Then, using an automated compression tester KES-FB3-A manufactured by Kato Tech, 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 μm / 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.
有機粒子を構成する樹脂の重量平均分子量は、以下の条件で、ゲルパーミエーションクロマトグラフィー(GPC)法により測定した。有機粒子の構成成分が単一の樹脂である場合は、各測定値を有機粒子の重量平均分子量とした。有機粒子の構成成分が複数の樹脂である場合は、各測定値に含有比率(質量比)を掛け合わせて合計した値を有機粒子の重量平均分子量とした。
測定装置:Polymer Laboratories社製 PL-20
カラム:昭和電工(株)製“Shodex”(登録商標)UT806M
カラム温度:145℃
溶媒(移動相):o-ジクロルベンゼン
溶媒流速:1.0mL/分
試料調整:試料10mgに測定溶媒5mLを添加し、140~150℃で約20分加熱攪拌
インジェクション量:0.200mL
検出器:示差屈折率検出器RI
標準試料:単分散ポリスチレン
(12)フィルムの圧縮仕事量
フィルムを12cm角の大きさに切り取り試料とし、試験台に取り付けた。次いで、カトーテック社製の自動化圧縮試験装置KES-FB3-Aを用いて、室温23℃、相対湿度65%の雰囲気下において、取り付けた試料を面積2cm2の円形平面を持つ鋼板間で、圧縮速度20μm/sec、圧縮最大荷重10gf/cm2の条件で圧縮し、フィルムの圧縮仕事量(gf・cm/cm2)を測定した。フィルムの巻内面、巻外面の両面ともに測定をそれぞれ3回(合計6回)行い、その全てのデータの平均値の小数第3位を四捨五入した値をそのフィルムの圧縮仕事量とした。 (11) 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.
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. Then, using an automated compression tester KES-FB3-A manufactured by Kato Tech, 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 μm / 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.
(13)フィルムの触感
有機粒子を有する面の触感について、24人にアンケートをとり、以下の基準で評価した。
A:布のような自然な触感であると回答した人数が20~24人。
B:布のような自然な触感であると回答した人数が15~19人。
C:布のような自然な触感であると回答した人数が10~14人。
D:布のような自然な触感であると回答した人数が5~9人。
E:布のような自然な触感であると回答した人数が0~4人。
触感はAが最も優れ、D以上の評価があれば実用性に耐えうると判断した。 (13) Tactile sensation of the surface having organic particles of the film was evaluated by the following criteria for 24 people.
A: There are 20 to 24 people who answered that they had a natural tactile sensation like cloth.
B: The number of people who answered that it was a natural touch like cloth was 15-19.
C: The number of people who answered that they had a natural touch like cloth was 10-14.
D: The number of people who answered that they had a natural tactile sensation like cloth.
E: The number of people who answered that it was a natural touch like cloth was 0-4.
As for the tactile sensation, A was the most excellent, and it was judged that if there was an evaluation of D or higher, it could withstand practicality.
有機粒子を有する面の触感について、24人にアンケートをとり、以下の基準で評価した。
A:布のような自然な触感であると回答した人数が20~24人。
B:布のような自然な触感であると回答した人数が15~19人。
C:布のような自然な触感であると回答した人数が10~14人。
D:布のような自然な触感であると回答した人数が5~9人。
E:布のような自然な触感であると回答した人数が0~4人。
触感はAが最も優れ、D以上の評価があれば実用性に耐えうると判断した。 (13) Tactile sensation of the surface having organic particles of the film was evaluated by the following criteria for 24 people.
A: There are 20 to 24 people who answered that they had a natural tactile sensation like cloth.
B: The number of people who answered that it was a natural touch like cloth was 15-19.
C: The number of people who answered that they had a natural touch like cloth was 10-14.
D: The number of people who answered that they had a natural tactile sensation like cloth.
E: The number of people who answered that it was a natural touch like cloth was 0-4.
As for the tactile sensation, A was the most excellent, and it was judged that if there was an evaluation of D or higher, it could withstand practicality.
[基材フィルムの原料樹脂]
(A1)ポリエステル系エラストマー(商品名:“ハイトレル”(登録商標)G3548、東レ・デュポン(株)製)使用前には回転式真空乾燥機にて90℃で5時間乾燥した。結晶性の熱可塑性エラストマーである。
(A2)
ポリオレフィン系エラストマー(商品名:“アクリフト”(登録商標)WH303、住友化学工業(株)製) 結晶性の熱可塑性エラストマーである。
(A3)
低密度ポリエチレン(商品名:“スミカセン”(登録商標)F200、住友化学工業(株)製)
(A4)
アクリル系エラストマー(商品名:“クラリティ”(登録商標)LA4285、クラレ(株)製) 非晶性の熱可塑性エラストマーである。
[有機粒子]
(B1)ポリエチレン系粒子(商品名:“ミペロン”(登録商標)XM220、三井化学(株)製)
(B2)
超高分子量ポリエチレン(商品名:“ハイゼックスミリオン”(登録商標)240S、三井化学(株)製、重量平均分子量200万、平均粒子径120μm)を凍結粉砕により、平均粒径20μmの微粒子にしたもの。
(B3)
超高分子量ポリエチレン(商品名:“ハイゼックスミリオン”(登録商標)240S 、三井化学(株)製)。
(B4)
低密度ポリエチレン粉砕品(商品名:“フローセン”(登録商標)UF-4、住友精化(株)製)。
(B5)
ポリメチルメタアクリレート(商品名:“ガンツパール”(登録商標)GM2801、アイカ工業(株)製)。
[添加剤]
(C1)炭酸カルシウム(商品名:SCP E♯810、アスペクト比2、平均粒径3.0μm、三共精粉(株)製)
[フィルムの作製]
(実施例1)
基材フィルムの原料樹脂、添加剤を表1に記載の含有量でシリンダー温度175℃のスクリュー径44mmの真空ベント付二軸押出機に供給して溶融混練し、均質化した後にペレット化して組成物を得た。この組成物のペレットを、回転式ドラム型真空乾燥機を用いて、温度80℃で5時間真空乾燥した。真空乾燥した組成物のペレットをインフレーション法により、シリンダー温度190℃で、スクリュー径60mmの単軸押出機に供給し、直径250mm、リップクリアランス1.0mm、温度を175℃に設定した環状ダイスにより、ブロー比2.0にてバブル状に上向きに押出し、冷却リングにより空冷し、ダイス上方のニップロールで折りたたみながら、引き取りしてロール状に巻き取った。引き取り速度の調整により、表1に示す厚みの基材フィルムを得た。次いで、得られた基材フィルムを20cm×20cmのサイズにカットし、カットした基材フィルムの上から表1に記載の有機粒子について表1に記載の質量を150メッシュのふるいを用いて振りかけたのち、基材フィルムを垂直に引き上げ余分な有機粒子を落とした。樹脂粒子を振りかけた基材フィルムを熱ラミネーター((株)エム・シー・ケー製、MRK-600)で以下の条件で熱ラミネートすることで表面に有機粒子を有するフィルムを得た。得られたフィルムの物性および評価結果を表1に示す。
<熱ラミネート条件>
ロール温度:150度
ロール速度:1m/min
ロール線圧力:0.5MPa
(実施例2~15、実施例22~25、比較例1、3~5)
基材フィルムの原料樹脂、有機粒子、および添加剤を表1に記載の量としたこと以外は実施例1に記載の方法で表面に有機粒子を有するフィルムを得た。なお、実施例10および比較例5においては、50メッシュのふるいを使用した。得られたフィルムの物性および評価結果を表1~3に示す。 [Raw material resin for base film]
(A1) 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.
[Organic particles]
(B1) Polyethylene particles (trade name: “Miperon” (registered trademark) XM220, manufactured by Mitsui Chemicals, Inc.)
(B2)
Ultra high molecular weight polyethylene (trade name: “Hi-Zex Million” (registered trademark) 240S, manufactured by Mitsui Chemicals, Inc., weight averagemolecular weight 2 million, average particle diameter 120 μm) is freeze-pulverized into fine particles having an average particle diameter of 20 μm .
(B3)
Ultra high molecular weight polyethylene (trade name: “Hi-Zex Million” (registered trademark) 240S, manufactured by Mitsui Chemicals, Inc.).
(B4)
Low-density polyethylene pulverized product (trade name: “Flocene” (registered trademark) UF-4, manufactured by Sumitomo Seika Co., Ltd.).
(B5)
Polymethyl methacrylate (trade name: “Gantz Pearl” (registered trademark) GM2801, manufactured by Aika Industry Co., Ltd.).
[Additive]
(C1) Calcium carbonate (trade name: SCP E # 810,aspect ratio 2, average particle size 3.0 μm, manufactured by Sankyo Seiko Co., Ltd.)
[Production of film]
Example 1
The raw material resin and additives for the base film are supplied to a twin screw extruder with a vacuum vent of 44 mm with a cylinder diameter of 175 ° C. with the contents shown in Table 1, melt kneaded, homogenized, and then pelletized into a composition I got a thing. 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. Subsequently, 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 Roll speed: 1 m / min
Roll wire pressure: 0.5 MPa
(Examples 2 to 15, Examples 22 to 25, Comparative Examples 1 and 3 to 5)
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. In 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.
(A1)ポリエステル系エラストマー(商品名:“ハイトレル”(登録商標)G3548、東レ・デュポン(株)製)使用前には回転式真空乾燥機にて90℃で5時間乾燥した。結晶性の熱可塑性エラストマーである。
(A2)
ポリオレフィン系エラストマー(商品名:“アクリフト”(登録商標)WH303、住友化学工業(株)製) 結晶性の熱可塑性エラストマーである。
(A3)
低密度ポリエチレン(商品名:“スミカセン”(登録商標)F200、住友化学工業(株)製)
(A4)
アクリル系エラストマー(商品名:“クラリティ”(登録商標)LA4285、クラレ(株)製) 非晶性の熱可塑性エラストマーである。
[有機粒子]
(B1)ポリエチレン系粒子(商品名:“ミペロン”(登録商標)XM220、三井化学(株)製)
(B2)
超高分子量ポリエチレン(商品名:“ハイゼックスミリオン”(登録商標)240S、三井化学(株)製、重量平均分子量200万、平均粒子径120μm)を凍結粉砕により、平均粒径20μmの微粒子にしたもの。
(B3)
超高分子量ポリエチレン(商品名:“ハイゼックスミリオン”(登録商標)240S 、三井化学(株)製)。
(B4)
低密度ポリエチレン粉砕品(商品名:“フローセン”(登録商標)UF-4、住友精化(株)製)。
(B5)
ポリメチルメタアクリレート(商品名:“ガンツパール”(登録商標)GM2801、アイカ工業(株)製)。
[添加剤]
(C1)炭酸カルシウム(商品名:SCP E♯810、アスペクト比2、平均粒径3.0μm、三共精粉(株)製)
[フィルムの作製]
(実施例1)
基材フィルムの原料樹脂、添加剤を表1に記載の含有量でシリンダー温度175℃のスクリュー径44mmの真空ベント付二軸押出機に供給して溶融混練し、均質化した後にペレット化して組成物を得た。この組成物のペレットを、回転式ドラム型真空乾燥機を用いて、温度80℃で5時間真空乾燥した。真空乾燥した組成物のペレットをインフレーション法により、シリンダー温度190℃で、スクリュー径60mmの単軸押出機に供給し、直径250mm、リップクリアランス1.0mm、温度を175℃に設定した環状ダイスにより、ブロー比2.0にてバブル状に上向きに押出し、冷却リングにより空冷し、ダイス上方のニップロールで折りたたみながら、引き取りしてロール状に巻き取った。引き取り速度の調整により、表1に示す厚みの基材フィルムを得た。次いで、得られた基材フィルムを20cm×20cmのサイズにカットし、カットした基材フィルムの上から表1に記載の有機粒子について表1に記載の質量を150メッシュのふるいを用いて振りかけたのち、基材フィルムを垂直に引き上げ余分な有機粒子を落とした。樹脂粒子を振りかけた基材フィルムを熱ラミネーター((株)エム・シー・ケー製、MRK-600)で以下の条件で熱ラミネートすることで表面に有機粒子を有するフィルムを得た。得られたフィルムの物性および評価結果を表1に示す。
<熱ラミネート条件>
ロール温度:150度
ロール速度:1m/min
ロール線圧力:0.5MPa
(実施例2~15、実施例22~25、比較例1、3~5)
基材フィルムの原料樹脂、有機粒子、および添加剤を表1に記載の量としたこと以外は実施例1に記載の方法で表面に有機粒子を有するフィルムを得た。なお、実施例10および比較例5においては、50メッシュのふるいを使用した。得られたフィルムの物性および評価結果を表1~3に示す。 [Raw material resin for base film]
(A1) 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.
[Organic particles]
(B1) Polyethylene particles (trade name: “Miperon” (registered trademark) XM220, manufactured by Mitsui Chemicals, Inc.)
(B2)
Ultra high molecular weight polyethylene (trade name: “Hi-Zex Million” (registered trademark) 240S, manufactured by Mitsui Chemicals, Inc., weight average
(B3)
Ultra high molecular weight polyethylene (trade name: “Hi-Zex Million” (registered trademark) 240S, manufactured by Mitsui Chemicals, Inc.).
(B4)
Low-density polyethylene pulverized product (trade name: “Flocene” (registered trademark) UF-4, manufactured by Sumitomo Seika Co., Ltd.).
(B5)
Polymethyl methacrylate (trade name: “Gantz Pearl” (registered trademark) GM2801, manufactured by Aika Industry Co., Ltd.).
[Additive]
(C1) Calcium carbonate (trade name: SCP E # 810,
[Production of film]
Example 1
The raw material resin and additives for the base film are supplied to a twin screw extruder with a vacuum vent of 44 mm with a cylinder diameter of 175 ° C. with the contents shown in Table 1, melt kneaded, homogenized, and then pelletized into a composition I got a thing. 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. Subsequently, 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 Roll speed: 1 m / min
Roll wire pressure: 0.5 MPa
(Examples 2 to 15, Examples 22 to 25, Comparative Examples 1 and 3 to 5)
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. In 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.
(比較例2)
実施例1と同様の方法にて表1に示す厚みの基材フィルムを得た。得られた基材フィルムの片面に、バーコーターを使用して、コート厚みが約5μmとなるように、下記の樹脂層塗布液を塗布し、80度で乾燥してコート層を積層し、フィルムを得た。得られたフィルムの物性および評価結果を表3に示す。
<コート層塗布液>
ベンゾトリアゾール含有アクリル系共重合体樹脂((株)日本触媒製“ハルスハイブリッド”(登録商標)UV-G720T 濃度40質量%溶液)が70質量部、B1が12質量部、イソシアネート系架橋剤(日本ポリウレタン工業(株)“コロネート”(登録商標)HL、濃度75質量%)が2.7質量部、酢酸エチルが55質量部となるように混合した組成物を塗布液とした。 (Comparative 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 μm, and dry at 80 degrees to laminate the coating layer. Got. Table 3 shows the physical properties and evaluation results of the obtained film.
<Coating layer coating solution>
70 parts by mass of benzotriazole-containing acrylic copolymer resin (“HALS HYBRID” (registered trademark) UV-G720T concentration 40 mass% solution manufactured by Nippon Shokubai Co., Ltd.), 12 parts by mass of B1, isocyanate-based crosslinking agent (Japan) Polyurethane Industry Co., Ltd. “Coronate” (registered trademark) HL, concentration 75 mass%) was 2.7 parts by mass, and ethyl acetate was 55 parts by mass.
実施例1と同様の方法にて表1に示す厚みの基材フィルムを得た。得られた基材フィルムの片面に、バーコーターを使用して、コート厚みが約5μmとなるように、下記の樹脂層塗布液を塗布し、80度で乾燥してコート層を積層し、フィルムを得た。得られたフィルムの物性および評価結果を表3に示す。
<コート層塗布液>
ベンゾトリアゾール含有アクリル系共重合体樹脂((株)日本触媒製“ハルスハイブリッド”(登録商標)UV-G720T 濃度40質量%溶液)が70質量部、B1が12質量部、イソシアネート系架橋剤(日本ポリウレタン工業(株)“コロネート”(登録商標)HL、濃度75質量%)が2.7質量部、酢酸エチルが55質量部となるように混合した組成物を塗布液とした。 (Comparative 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 μm, and dry at 80 degrees to laminate the coating layer. Got. Table 3 shows the physical properties and evaluation results of the obtained film.
<Coating layer coating solution>
70 parts by mass of benzotriazole-containing acrylic copolymer resin (“HALS HYBRID” (registered trademark) UV-G720T concentration 40 mass% solution manufactured by Nippon Shokubai Co., Ltd.), 12 parts by mass of B1, isocyanate-based crosslinking agent (Japan) Polyurethane Industry Co., Ltd. “Coronate” (registered trademark) HL, concentration 75 mass%) was 2.7 parts by mass, and ethyl acetate was 55 parts by mass.
(実施例16)
実施例1で得られたフィルムを、由利ロール社製電気加熱式エンボス機“HTEM-300型”にセットした算術平均粗さ50μmの不織布柄エンボスロールとゴムロールの間を、有機粒子を有する面と反対の面を不織布柄エンボスロール側として、ロール温度120℃(上段、下段両方)、ニップ圧力(線圧)50kg/cm、ロール回転速度5.0m/minの条件で通した。得られたフィルムの物性および評価結果を表2に示す。 (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 μm 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.
実施例1で得られたフィルムを、由利ロール社製電気加熱式エンボス機“HTEM-300型”にセットした算術平均粗さ50μmの不織布柄エンボスロールとゴムロールの間を、有機粒子を有する面と反対の面を不織布柄エンボスロール側として、ロール温度120℃(上段、下段両方)、ニップ圧力(線圧)50kg/cm、ロール回転速度5.0m/minの条件で通した。得られたフィルムの物性および評価結果を表2に示す。 (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 μm 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.
(実施例17)
不織布柄エンボスロールとして算術平均粗さ80μmのロールを用いた以外は、実施例16と同様にフィルムを得た。得られたフィルムの物性および評価結果を表2に示す。 (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 μm was used as the nonwoven fabric pattern embossing roll. Table 2 shows the physical properties and evaluation results of the obtained film.
不織布柄エンボスロールとして算術平均粗さ80μmのロールを用いた以外は、実施例16と同様にフィルムを得た。得られたフィルムの物性および評価結果を表2に示す。 (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 μm was used as the nonwoven fabric pattern embossing roll. Table 2 shows the physical properties and evaluation results of the obtained film.
(実施例18、19)
A層用、およびB層用の各原料について、表2に記載の配合比となるようにシリンダー温度190℃のスクリュー径44mmの真空ベント付二軸押出機に供給して溶融混練し、均質化した後にペレット化して組成物を得た。この組成物のペレットを、回転式ドラム型真空乾燥機を用いて、温度90℃で5時間真空乾燥し、A層用、およびB層の組成物を得た。続いてこれらの組成物をシリンダー温度200℃、スクリュー径60mmの、それぞれ独立した層用単軸押出機に供給し、直径250mm、リップクリアランス1.0mm、温度190℃のスパイラル型環状ダイスより、A層/B層の2種2層構成となるように、ブロー比:2.0にてバブル状に上向きに押出し、冷却リングにより空冷し、ダイス上方のニップロールで折りたたみながら引き取ってロール状に巻き取った。得られた積層フィルムについて実施例1と同様の方法により表2に記載の有機粒子をA層側の面に散布し、有機粒子を有するフィルムを得た。得られたフィルムの物性および評価結果を表2に示す。 (Examples 18 and 19)
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. and a screw diameter of 60 mm, respectively, and from a spiral annular die having a diameter of 250 mm, a lip clearance of 1.0 mm, and a temperature of 190 ° C. Extruded upward in the form of bubbles at a blow ratio: 2.0, air-cooled with a cooling ring, taken up while being folded with a nip roll above the die, and wound up into a roll so as to form a two-layer structure oflayer 2 / layer B It was. About the obtained laminated | multilayer film, the organic particle of Table 2 was spread | dispersed on the surface by the side of A layer by the method similar to Example 1, and the film which has an organic particle was obtained. Table 2 shows the physical properties and evaluation results of the obtained film.
A層用、およびB層用の各原料について、表2に記載の配合比となるようにシリンダー温度190℃のスクリュー径44mmの真空ベント付二軸押出機に供給して溶融混練し、均質化した後にペレット化して組成物を得た。この組成物のペレットを、回転式ドラム型真空乾燥機を用いて、温度90℃で5時間真空乾燥し、A層用、およびB層の組成物を得た。続いてこれらの組成物をシリンダー温度200℃、スクリュー径60mmの、それぞれ独立した層用単軸押出機に供給し、直径250mm、リップクリアランス1.0mm、温度190℃のスパイラル型環状ダイスより、A層/B層の2種2層構成となるように、ブロー比:2.0にてバブル状に上向きに押出し、冷却リングにより空冷し、ダイス上方のニップロールで折りたたみながら引き取ってロール状に巻き取った。得られた積層フィルムについて実施例1と同様の方法により表2に記載の有機粒子をA層側の面に散布し、有機粒子を有するフィルムを得た。得られたフィルムの物性および評価結果を表2に示す。 (Examples 18 and 19)
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. and a screw diameter of 60 mm, respectively, and from a spiral annular die having a diameter of 250 mm, a lip clearance of 1.0 mm, and a temperature of 190 ° C. Extruded upward in the form of bubbles at a blow ratio: 2.0, air-cooled with a cooling ring, taken up while being folded with a nip roll above the die, and wound up into a roll so as to form a two-layer structure of
(実施例20)
実施例18で得られたフィルムに実施例16と同様の方法でエンボス加工を施した。得られたフィルムの物性および評価結果を表2に示す。 (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.
実施例18で得られたフィルムに実施例16と同様の方法でエンボス加工を施した。得られたフィルムの物性および評価結果を表2に示す。 (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.
(実施例21)
実施例18で得られたフィルムに実施例17と同様の方法でエンボス加工を施した。得られたフィルムの物性および評価結果を表2に示す。 (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.
実施例18で得られたフィルムに実施例17と同様の方法でエンボス加工を施した。得られたフィルムの物性および評価結果を表2に示す。 (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.
表1~3において、基材フィルムの原料樹脂(質量%)は基材フィルム中の樹脂成分全体を100質量%として算出した。また、添加剤(質量部)は基材フィルム中の樹脂成分全体を100質量部として算出した。
In Tables 1 to 3, the raw material resin (mass%) of the base film was calculated based on the total resin component in the base film as 100 mass%. Moreover, the additive (mass part) computed the whole resin component in a base film as 100 mass parts.
本発明のフィルムを用いることにより、せん断変形性およびすべり性に優れたフィルムを提供することができる。本発明のフィルムは、せん断変形性およびすべり性を必要とする用途、具体的には、ベッド用シーツ、枕カバー、衛生ナプキンや紙おむつなどの吸収性物品のバックシートといった医療・衛生材料、雨天用衣類、手袋などの衣料材料、ゴミ袋や堆肥袋、あるいは野菜や果物などの食品用袋、各種工業製品の袋などの包装材料、ビル、住宅、化粧板といった建材、鉄道車両、船舶、航空機といった輸送機内での内装材料、建築用材料などに好ましく用いることができる。
By using the film of the present invention, it is possible to provide a film having excellent shear deformability and slipperiness. 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.
1 有機粒子
2 基材フィルム
1Organic particle 2 Base film
2 基材フィルム
1
Claims (9)
- 基材フィルムの少なくとも一方の最表面に有機粒子を有し、前記有機粒子の平均粒径(μm)と、前記基材フィルムの平均厚み(μm)との比(基材フィルムの平均厚み/有機粒子の平均粒径)が0.5以上3.0以下であり、かつKES法におけるせん断かたさが0.1gf/(cm・deg)以上6.0gf/(cm・deg)以下であることを特徴とする、フィルム。 The organic film has organic particles on at least one outermost surface of the base film, and the ratio of the average particle diameter (μm) of the organic particles to the average thickness (μm) of the base film (average thickness of base film / organic The average particle diameter of the particles is 0.5 or more and 3.0 or less, and the shear hardness in the KES method is 0.1 gf / (cm · deg) or more and 6.0 gf / (cm · deg) or less. And a film.
- 有機粒子を有する面において、フィルム全体の面積を100%としたときに、有機粒子の占める面積の割合が20%以上100%未満であることを特徴とする、請求項1に記載のフィルム。 2. The film according to claim 1, wherein the ratio of the area occupied by the organic particles is 20% or more and less than 100% when the area of the whole film is 100% on the surface having the organic particles.
- 有機粒子を有する面において、KES法に従い測定される摩擦係数が0.05以上0.80以下であることを特徴とする、請求項1または2に記載のフィルム。 3. The film according to claim 1, wherein the surface having organic particles has a coefficient of friction of 0.05 to 0.80 measured according to the KES method.
- フィルムの透湿度が、500g/(m2・day)以上5,000g/(m2・day)以下であることを特徴とする請求項1~3のいずれかに記載のフィルム。 A film according to any one of claims 1 to 3, moisture permeability, characterized in that 500 g / are (m 2 · day) or more 5,000g / (m 2 · day) or less of the film.
- 前記有機粒子の形状が球形状であることを特徴とする、請求項1~4のいずれかに記載のフィルム。 The film according to any one of claims 1 to 4, wherein the organic particles have a spherical shape.
- 前記基材フィルムと前記有機粒子との剥離強度が30gf/25mm以上であることを特徴とする請求項1~5のいずれかに記載のフィルム。 The film according to any one of claims 1 to 5, wherein a peel strength between the base film and the organic particles is 30 gf / 25 mm or more.
- 前記基材フィルムが、熱可塑性エラストマーを含むことを特徴とする、請求項1~6のいずれかに記載のフィルム。 The film according to any one of claims 1 to 6, wherein the base film contains a thermoplastic elastomer.
- 前記基材フィルムが、少なくとも、前記有機粒子と接する層(A層)と、A層を挟んで前記有機粒子と反対側に位置する層(B層)の積層構成からなることを特徴とする、請求項1~7のいずれかに記載のフィルム。 The base film is composed of a layered 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 across the A layer, The film according to any one of claims 1 to 7.
- 溶解度パラメータの差の絶対値が最も小さくなるように、前記A層中の樹脂成分全体を100質量%としたときに、前記A層中に5質量%以上含まれる樹脂の中から1つの樹脂(樹脂A)を選択し、前記有機粒子の樹脂成分全体を100質量%としたときに、前記有機粒子中に5質量%以上含まれる樹脂の中から1つの樹脂(樹脂B)を選択した際に、前記樹脂Aと前記樹脂Bの溶解度パラメータの差の絶対値が0.10(MPa)0.5以下であることを特徴とする、請求項8に記載のフィルム。
When the total resin component in the A layer is 100% by mass so that the absolute value of the solubility parameter difference is minimized, one resin (from 5% by mass or more in the A layer) When the resin A) is selected and the total resin component of the organic particles is 100% by mass, when one resin (resin B) is selected from the resins contained in the organic particles by 5% by mass or more. The film according to claim 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.
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JP7439651B2 (en) | 2019-06-04 | 2024-02-28 | 東レ株式会社 | laminated film |
Citations (5)
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JPH07278441A (en) * | 1994-04-06 | 1995-10-24 | Idemitsu Petrochem Co Ltd | Thermoplastic resin composition containing ultrafine silk fibroin powder, film or sheet, and laminate using the same |
JPH08323931A (en) * | 1995-05-30 | 1996-12-10 | Sekisui Chem Co Ltd | Laminated sheet and production thereof |
JP2008207393A (en) * | 2007-02-23 | 2008-09-11 | Three M Innovative Properties Co | Waterproof sheet and its manufacturing method |
WO2012133824A1 (en) * | 2011-03-30 | 2012-10-04 | ユニ・チャーム株式会社 | Water retention assistant, and absorbent material, absorbent and absorbent article comprising same |
WO2016152670A1 (en) * | 2015-03-25 | 2016-09-29 | 東レ株式会社 | Film with excellent touch feeling and shear deformability |
-
2017
- 2017-09-27 JP JP2017553433A patent/JP6965750B2/en active Active
- 2017-09-27 WO PCT/JP2017/035049 patent/WO2018070250A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07278441A (en) * | 1994-04-06 | 1995-10-24 | Idemitsu Petrochem Co Ltd | Thermoplastic resin composition containing ultrafine silk fibroin powder, film or sheet, and laminate using the same |
JPH08323931A (en) * | 1995-05-30 | 1996-12-10 | Sekisui Chem Co Ltd | Laminated sheet and production thereof |
JP2008207393A (en) * | 2007-02-23 | 2008-09-11 | Three M Innovative Properties Co | Waterproof sheet and its manufacturing method |
WO2012133824A1 (en) * | 2011-03-30 | 2012-10-04 | ユニ・チャーム株式会社 | Water retention assistant, and absorbent material, absorbent and absorbent article comprising same |
WO2016152670A1 (en) * | 2015-03-25 | 2016-09-29 | 東レ株式会社 | Film with excellent touch feeling and shear deformability |
Cited By (1)
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JP7439651B2 (en) | 2019-06-04 | 2024-02-28 | 東レ株式会社 | laminated film |
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