JP2018062168A - Film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film which has mechanical characteristics necessary for used as the film, soft feeling like fabric and comfortable tactile.SOLUTION: A film has organic particles b has a single layer structure and a resin layer (X layer) a in contact with the organic particles b on the outermost surface layer of the film, where when the whole resin component in the X layer a is 100 mass% so that an absolute value of a difference between solubility parameters becomes the smallest, one resin (resin A) is selected from 5 mass% or more of resins contained in the X layer a, when the whole resin component of the organic particles b is 100 mass%, one resin (resin B) is selected from 5 mass% or more of resins contained in the organic particles b, an absolute value of the difference of the solubility parameters of the resin A and the resin B is 0.10(MPa)or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a film having mechanical properties necessary for use as a film, a soft texture like a cloth, and a pleasant touch.

  In recent years, there has been a demand for a single film having a mechanical function necessary for use as a film and further having another function. For example, in the field of medical and hygiene materials, in addition to the mechanical properties necessary for use as a film, a film having a soft texture such as cloth and a pleasant touch is desired.

  Various developments have been made so far to improve the texture of the film. For example, Patent Documents 1 and 2 disclose that a porous film with improved texture can be obtained by mixing a soft resin with a filler and stretching. Patent Documents 3 and 4 disclose that moisture permeability and film feel are improved by forming an uneven pattern by embossing. On the other hand, Patent Document 5 discloses a film whose surface is coated with particles.

Japanese Patent Laid-Open No. 10-237238 JP 2007-238822 A Japanese Examined Patent Publication No. 6-765015 WO2013 / 031755 pamphlet JP 2010-85843 A

  However, with the techniques described in Patent Documents 1 and 2, the tactile sensation of the film is improved to some extent, but it does not give a comfortable tactile sensation like cloth to the film. In addition, in the techniques described in Patent Documents 3 and 4, by setting the depth, height, and number of the concavo-convex patterns to values in an appropriate range, it is possible to impart softness and touch feeling like cloth to the film. The appearance of the film differs greatly from the cloth due to the presence of the uneven pattern. That is, these techniques have a problem that it is not possible to obtain a film having mechanical properties necessary for use as a film and having a soft texture such as a cloth and a pleasant touch.

  Moreover, since the film obtained by the technique described in Patent Document 5 is covered with particles, the film is excellent in slipperiness that 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.

  The object of the present invention is to provide a film having improved mechanical properties necessary for use as a film, a soft texture such as a cloth, and a pleasant tactile sensation.

In order to solve the above problems, the present invention has the following configuration.
(1) A film having organic particles having a single layer structure and a resin layer (X layer) in contact with the organic layer in the outermost layer of the film, wherein the X layer has the smallest difference in solubility parameter. When the total resin component is 100% by mass, one resin (resin A) is selected from the resins contained in the X layer at 5% by mass or more, 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 in an amount of 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) A film characterized by being ^0.5 or less.
(2) The film according to (1), wherein the X layer contains 5% by mass or more and 100% by mass or less of the resin A when the entire resin component in the X layer is 100% by mass.
(3) When the whole resin component in the organic particles is 100% by mass, the organic particles contain 50% by mass or more and 100% by mass or less of the resin B. (1) or (2) The film described.
(4) The film according to any one of (1) to (3), wherein the organic particles have a weight average molecular weight of 500,000 or more.
(5) Any of (1) to (4), wherein the X layer contains more than 50% by mass of a thermoplastic elastomer when the entire resin component in the X layer is 100% by mass. Film.
(6) The resin A and the resin B are both crystalline resins, and the X layer has at least one crystalline resin (resin C) having a melting point higher than that of the resin A. TmC1> TmB ≧ TmA, where the highest melting point is resin C1, the melting point of the resin A is TmA, the melting point of the resin B is TmB, and the melting point of the resin C1 is TmC1. The film according to any one of (1) to (5).
(7) The film according to (6), which has a layer (Y layer) having a melting point higher than that of TmB on the outermost surface opposite to the X layer.
(8) The resin A and the resin B are both amorphous resins, the X layer has at least one crystalline resin (resin D), and the resin D having the highest melting point is the resin D1, TgA is the glass transition point of the resin A, TgB is the glass transition point of the resin B, and TmD1 is the melting point of the resin D1, TmD1> TgB ≧ TgA. ) To (5).
(9) The film according to (8), having a layer (Z layer) having a melting point higher than that of TgB on the outermost surface opposite to the X layer.

  According to the present invention, it is possible to provide a film having mechanical properties necessary for use as a film, a soft texture like a cloth, and a pleasant touch.

It is sectional drawing of the film which has the organic particle of the single layer structure concerning one embodiment of this invention. It is sectional drawing of the film which has the organic particle of a multilayer structure. It is a schematic diagram showing the "holding angle of the adhesion part" used for the adhesive evaluation to the roll of a film (A is the figure which observed the roll from the direction perpendicular to the rotation axis, and B from the direction parallel to the rotation axis. .)

The film of the present invention is a film having organic particles having a single layer structure and a resin layer (X layer) in contact with the organic layer in the outermost layer of the film, and the absolute value of the difference in solubility parameter is minimized. When the entire resin component in the X layer is 100% by mass, one resin (resin A) is selected from the resins contained in the X layer in an amount of 5% by mass or more, and the entire resin component of the organic particles Of 100 mass%, when one resin (resin B) is selected from the resins contained in the organic particles at 5 mass% or more, the difference in solubility parameter between the resin A and the resin B The absolute value is 0.10 (MPa) ^0.5 or less.

  Although the desirable form for implementing this invention is demonstrated below, this invention is not limited to this.

(Organic particles)
It is important that the film of the present invention has organic particles having a single layer structure and a resin layer (X layer) in contact with the organic layer in the outermost layer of the film from the viewpoint of having a pleasant touch like cloth. Here, the single-layer structure means a state where only a single layer is observed when a cross section of the organic particles obtained by cutting with an ultramicrotome or the like is observed with an electron microscope or the like (FIG. 1). On the other hand, as an example different from the organic particles having a single layer structure, organic particles having a multilayer structure in which another layer is formed like a shell on the surface of organic particles serving as a nucleus can be cited (FIG. 2). As a method for fixing the organic particles on the surface of the film, a method of applying a coating liquid containing organic particles to the film surface and drying it (hereinafter sometimes referred to as a coating method) is generally used. The structure shown in FIG. 2 is a structure observed when the coating method is used.

  When the film of the present invention has organic particles having a single layer structure and a resin layer (X layer) in contact with the organic layer in the outermost layer of the film, fine irregularities such as the surface of a cloth are formed on the film surface. . Further, due to the presence of the unevenness, the contact area when the film is touched with a finger is reduced, and the friction coefficient of both is reduced accordingly, so that a smooth tactile sensation like a cloth can be realized.

  In the outermost layer, means for forming a film having organic particles having a single-layer structure and a resin layer (X layer) in contact therewith is not particularly limited as long as the effects of the present invention are not impaired. Ingredients that have strong interaction with the particles are included, and heat-history is used to heat-bond the organic particles present on the surface of the organic particles to the film surface. In addition, a method of holding the organic particles by the adhesive strength of the adhesive component may be mentioned.

  The average particle diameter of the organic particles of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 1 μm or more and 200 μm or less from the viewpoint of imparting a pleasant touch to the film. If the average particle size of the organic particles is smaller than 1 μm, the unevenness of the particles cannot be perceived when the surface of the film is touched by hand, and a comfortable touch feeling like a cloth may not be felt. On the other hand, when the average particle size of the organic particles is larger than 200 μm, when the film surface is touched with a hand, roughness may be felt stronger than smoothness. From the viewpoint of imparting a tactile sensation closer to a cloth, the average particle size is more preferably 3 μm or more and 150 μm or less, and further preferably 5 μm or more and 100 μm or less.

  The average particle size 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. 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.

In the film of the present invention, the amount of organic particles per 1 m ^{2 of} film surface (g / m ² ) is 0.1 g / m ² or more and 50 g / m ² from the viewpoint of maintaining a pleasant touch and softness to the film of the present invention. m is preferably ² or less. If the amount of organic particles per 1 m ^{2 of the} film surface (hereinafter sometimes simply referred to as the amount of organic particles) is less than 0.1 g / m ² , the number of organic particles is too small, and the film and finger made of organic particles The effect of reducing the contact area may be insufficient. On the other hand, if the amount of organic particles per 1 m ^{2 of} the film surface is larger than 50 g / m ² , the film mass will increase, and a thick layer will be formed by the organic particles, and the entire film will become hard and soft like cloth. May not be obtained. From the viewpoint of making the film feel comfortable and soft, the amount of organic particles per 1 m ^{2 of} the film surface is more preferably 0.5 g / m ² or more and 30 g / m ² or less, and even more preferably 1 g / m. ² or more and 10 g / m ² or less.

If the mass of the film before thermocompression bonding of the organic particles can be measured, measure the mass per unit area of the film before and after thermocompression bonding, and calculate the difference between the organic particles per unit area. This value can be obtained by converting this value per 1 m ² .

However, there are cases where the mass of the film before the organic particles are thermocompression bonded cannot be measured, as in the case where the organic particles are thermocompression bonded inline. In such a case, the amount of organic particles can be measured by the following method. First, using a scanning electron microscope, the surface having organic particles is used as an observation surface, the film is observed at a magnification of 500 times, and the number of organic particles is counted. Further, the total particle volume per 1 m ^{2 of} film is calculated from the obtained value of the number of organic particles, the area of the observation part, and the value of the particle size of the organic particles (at this time, the particle shape is spherical, the particle layer Is assumed to be one layer). In addition, using the value of the thickness of the film, the volume per 1 m ^{2 of} the film excluding the organic particles is calculated. Then, the value of the particle total volume per film 1 m ^2, the sum of the values of the particle total volume value and the film 1 m ² per volume of film 1 m ² per excluding the organic particles (of the entire film with organic grain volume The volume ratio of organic particles in the entire film having organic particles is calculated. Subsequently, assuming that the density of the organic particles and the film is the same, the amount of organic particles (g / m ^{2) is} calculated from the volume ratio of the organic particles to the entire film having organic particles and the mass of the film having organic particles. ) Is calculated.

  In the film of the present invention, the weight average molecular weight of the organic particles is preferably 500,000 or more from the viewpoint of suppressing the deformation of the particle shape due to the thermal history in the production process of the film of the present invention. By maintaining the particle shape within such a 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 tactile feel of the film is improved. The weight average molecular weight of the organic particles is more preferably 1 million or more, and further preferably 1.5 million or more. From the viewpoint of maintaining the particle shape, the higher the weight average molecular weight of the organic particles, the better. However, from a practical viewpoint, 10 million is the upper limit.

  The weight average molecular weight of the organic particles can be calculated from the composition ratio of the resin constituting the organic particles and the weight average molecular weight, and the weight average molecular weight of the resin can be measured by a gel permeation chromatography (GPC) method. (Detailed measurement conditions will be described later). In addition, when organic particles contain components other than resin, these components shall not be considered in the calculation of the weight average molecular weight of organic particles.

  The components constituting 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, homopolymers or copolymers of vinyl monomers such as divinylbenzene, styrene, acrylic acid, methacrylic acid, polytetra Fluoropolymers such as fluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, nylon resins such as nylon 6 and nylon 12, polypropylene, low density polyethylene, high density polyethylene, ultra high molecular weight polyethylene Polyolefin resins such as polyethylene terephthalate and polyester resins such as polybutylene terephthalate, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, thermosetting phenol resin Etc., and the like. Among these, from the viewpoints of cost, slipperiness, and the like, the organic particles preferably include a polyolefin resin as a main component. 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.

(Solubility parameters of resin component in X layer and organic particles, resin A and resin B)
In the film of the present invention, when the total resin component in the X layer is 100% by mass so that the absolute value of the difference in solubility parameter is minimized, the resin contained in the X layer is not less than 5% by mass. When one resin (resin A) was selected and the total resin component of the organic particles was 100% by mass, one resin (resin B) was selected from the resins contained in the organic particles at 5% by mass or more. In this case, it is important that 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.

  Here, the solubility parameter is a parameter calculated based on the cohesive energy density and molar molecular weight of each atomic group. Specifically, Hideki Yamamoto, “SP Value Basics / Applications and Calculation Methods” (Inc.) It is calculated based on Fedor's estimation method described in the mechanism 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.

  Resin A is determined by the absolute value of the difference in solubility parameter from each resin contained in the organic particles at 5 mass% or more when the total resin component of the organic particles is 100 mass%. On the other hand, the resin B is determined by the absolute value of the difference in solubility parameter with each resin contained in the X layer at 5 mass% or more when the entire resin component of the X layer is 100 mass%.

  In addition to the thermoplastic elastomer described later, the X layer may contain the components listed above as the components constituting the organic particles. 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 X 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 X layer by 5% by mass or more.

If the absolute value of the difference in solubility parameter between the resin A and the resin B is greater than 0.10 (MPa) ^0.5 , the adhesion between the X layer and the organic particles becomes insufficient, and the organic particles are exposed to load or contact with the film surface. The fabric may fall off and may not have a cloth-like feel. On the other hand, when 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 X layer and the organic particles becomes strong, and due to load or contact on the film surface. Since dropping off of the organic particles is reduced, it is possible to give the film a touch like cloth.

The higher the adhesion between the X layer and the organic particles, the more preferable it is to stably give the film a touch like 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 . By making the resin A and the resin B exactly the same resin, the difference in solubility parameter is 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. For example, it is included in the X layer. There is a method in which the chemical structures of the resin A and the resin B contained in the organic particles are as close as possible.

The above Fedor estimation method usually uses a value calculated for the unit when the number of repeating units constituting the polymer is a single repeating unit. When two or more components are present (for example, when the repeating unit A and the repeating unit B are present), 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)
In the film of the present invention, from the viewpoint of adhesion between the X layer and the organic particles, the X layer contains 5% by mass or more and 100% by mass or less of the resin A when the entire resin component in the X layer is 100% by mass. Is preferred. When the amount of the resin A in the X layer is less than 5% by mass when the entire resin component in the X layer is 100% by mass, even if the absolute value of the difference in solubility parameter from the resin B described later is small, 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 X layer and the organic particles. From the viewpoint of improving the adhesion between the X layer and the organic particles, the content of the resin A in the X layer when the entire resin component in the X 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%.

  From the viewpoint of adhesion between the X 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 X layer and the organic particles can be improved. From the viewpoint of improving the adhesion between the X 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.

  In the present invention, when there are a plurality of combinations that satisfy the conditions of the resin A and the resin B, the resin A having the largest content (% by mass) in the X layer is selected among the candidate resins. A combination shall be adopted. In addition, when there are a plurality of resins having the same content (% by mass) in the X layer, the resin A can be arbitrarily selected from the candidate resins.

(Crystallinity of the resin constituting the X layer)
The crystal characteristics of the resin A and the resin B in the film of the present invention are not particularly limited as long as the effects of the present invention are not impaired. However, from the viewpoint of controlling the adhesion between the organic particles and the X layer, both the resin A and the resin B are used. It is preferable that the resin is a crystalline resin, or that both the resin A and the resin B are amorphous resins. The crystalline resin is at least one 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 in a differential scanning calorimeter (DSC) measurement. A resin in which two melting points are observed. And when the melting | fusing point peak observed by this method is one, let the temperature be melting | fusing point of resin. When a plurality of melting point peaks are observed, the melting point peak showing the highest temperature among them is taken as the melting point of the resin. An amorphous resin refers to a resin in which a melting point peak is not observed when DSC measurement is performed under the same conditions.

  When both the resin A and the resin B are crystalline resins, the film of the present invention has at least a crystalline resin (resin C) whose X layer has a higher melting point than the resin A from the viewpoint of achieving both workability and tactile sensation. One type of resin C having the highest melting point is resin C1, the melting point of resin A is TmA, the melting point of resin B is TmB, and the melting point of resin C1 is TmC1, TmC1> TmB ≧ TmA Preferably there is.

  As TmC1 is higher than TmB and TmA, as a method of adding particles to the X layer, the organic particles are thermally fused to the surface of the film (X layer) by the thermal history using the interaction between the resin A and the resin B. When the method is used, a temperature located between TmC1 and TmB (hereinafter sometimes referred to as Tp1) can be adopted as the thermal fusion temperature. Therefore, the melting of the resin A and the resin B proceeds, and the adhesion between the organic particles and the X layer is improved. Furthermore, since the processing is performed at a temperature lower than the melting point of the resin C1, the resin C1 functions as a support during processing, and adhesion of the film to the roll is reduced when the heat fusion is performed roll-to-roll.

  Further, from the viewpoint of imparting a good tactile sensation to the film of the present invention, since it is preferable to reduce the deformation of the organic particles, it is preferable that the deformation of the organic particles due to the heat history in the thermal fusion is minimal. If TmB ≧ TmA, the X layer is more easily deformed than the organic particles when performing heat fusion at a temperature of Tp1, and the organic particles are thermally fused to the X layer while reducing deformation of the particles due to thermal history. be able to. As a result, it becomes easy to give a good tactile sensation to the film.

  When TmC1, TmB, and TmA satisfy the above relationship, the film of the present invention may have a layer (Y layer) having a higher melting point than TmB on the outermost surface opposite to the X layer from the viewpoint of workability. More preferred. By setting it as such an aspect, while a Y layer works as a support layer at the time of heat fusion, when performing heat fusion by a roll to roll, the adhesion to the roll of a film is further suppressed.

  When both the resin A and the resin B are amorphous resins, the film of the present invention has an X layer having at least one crystalline resin (resin D), and the resin D having the highest melting point is the resin. It is preferable that TmD1> TgB ≧ TgA where D1, the glass transition point of the resin A is TgA, the glass transition point of the resin B is TgB, and the melting point of the resin D1 is TmD1.

  As TmD1 is higher than TgB or TgA, as a method of adding particles to the X layer, the organic particles are thermally fused to the surface of the film (X layer) by the thermal history using the interaction between the resin A and the resin B. In the case of using the method, a temperature located between TmD1 and TgB (hereinafter sometimes referred to as Tp2) can be adopted as the thermal fusion temperature. Therefore, the softening of the resin A and the resin B proceeds, and the adhesion between the organic particles and the X layer is improved. Furthermore, since the processing is performed at a temperature lower than the melting point of the resin D1, the resin D1 functions as a support at the time of processing, and adhesion of the film to the roll is reduced when the heat fusion is performed roll-to-roll.

  Further, from the viewpoint of imparting a good tactile sensation to the film of the present invention, it is preferable that the amount of deformation of the organic particles due to the thermal history is the minimum necessary. If TgB ≧ TgA, the X layer is more easily deformed than the organic particles when heat-sealing at a temperature of Tp2, and the organic particles are thermally fused to the X-layer while reducing the deformation of the particles due to thermal history. be able to. As a result, it becomes easy to give a good tactile sensation to the film.

  When TmD1, TgB, and TgA satisfy the above relationship, the film of the present invention has a layer (Z layer) having a higher melting point than TgB on the outermost surface opposite to the X layer from the viewpoint of workability. Is more preferable. By setting it as such an aspect, while Z layer works as a support layer at the time of heat sealing | fusion, the adhesion to the roll of a film is further suppressed when performing heat sealing | bonding by a roll to roll.

  When the film of the present invention has a plurality of layers, the melting point and glass transition temperature of each layer can be measured by collecting a sample for each layer with an ultramicrotome or the like. In addition, a device for measuring the softening behavior accompanying heating of a micro area on the surface (for example, nano manufactured by Hitachi High-Tech Science Co., Ltd.), which performs a film cross-section and includes a microprobe having a heating mechanism in a scanning probe microscope for each layer. -TA).

(Thermoplastic elastomer in the X layer)
The film of the present invention has a layer (X layer) having organic particles on the outermost surface. From the viewpoint of imparting a soft texture like cloth in addition to flexibility and shear deformability to the film, the X layer is a thermoplastic elastomer when the entire resin component in the X layer is 100% by mass. It is preferable to contain more than 50 mass%. The thermoplastic elastomer means 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 as long as the effects of the present invention are not impaired, or a mixture of both. Here, the thermoplastic elastomer having crystallinity is 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 in DSC measurement. A thermoplastic elastomer in which a crystal melting peak 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.

  The thermoplastic elastomer having crystallinity in the film of the present invention is not particularly limited as long as the effects of the present invention are not impaired. For example, polyester elastomers, polyolefin elastomers, polyamide elastomers and the like are used alone or in combination. be able to. Among these, it is preferable to use a polyester-based elastomer and a polyamide-based elastomer alone or in combination of two or more from the viewpoints of the film's shear deformability, film-forming stability, heat resistance, and the like.

  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.

  Examples of the polyester elastomer include “Hytrel” (registered trademark) G3548, HTR 8206 grade, and the like manufactured by Toray DuPont.

  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.

  Examples of the polyamide-based elastomer include “PEBAX” (registered trademark) MV1074, MV1041, MV3000, MH1657 grade and the like manufactured by Arkema.

  The content of the thermoplastic elastomer having crystallinity in the 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 film formation stability, the total resin in the film of the present invention is 100 masses. % Is preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, and further preferably 30% by mass or more and 100% by mass or less. In addition, when there are multiple types of thermoplastic elastomers having crystallinity in the film, the content of the thermoplastic elastomer having crystallinity is calculated by adding up all the thermoplastic elastomers having crystallinity. .

  On the other hand, the amorphous thermoplastic elastomer in the film of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and acrylic elastomer, polystyrene elastomer, polyurethane elastomer and the like can be used. Among these, from the viewpoint of the shear deformability and moisture permeability of the film, it is preferable to use a polyurethane elastomer or an acrylic elastomer alone or in combination of two or more.

  As the polyurethane elastomer, it is preferable to use a polyether polyurethane elastomer from the viewpoint of imparting moisture permeability. Examples of such polyurethane elastomers include “Elastollan” (registered trademark) OP85A10MH grade and ET885FG grade manufactured by BASF.

  Examples of the acrylic elastomer include a block copolymer of polymethyl methacrylate and polybutyl methacrylate from the viewpoint of imparting flexibility and adhesion to organic particles. Specific examples include LA2330 grade and LA4285 grade of “Clarity” (registered trademark) manufactured by Kuraray Co., Ltd.

(Shear hardness (G))
The film of the present invention has a shear hardness (G) measured by the KES method of 0.1 gf / (cm · deg) or more and 2.5 gf / (cm · deg) or less from the viewpoint of imparting softness like cloth. It is preferable that Shear deformation refers to a deformation pattern that is most easily received by a cloth formed by 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 larger the shear deformation, that is, the smaller the shear strength (G), the more the curved surface like a human body fits. It is easy to do and a feeling of wear is good. That is, a film having a shear hardness (G) of 0.1 gf / (cm · deg) or more and 2.5 gf / (cm · deg) or less becomes a film that feels soft like a cloth.

The shear hardness (G) measured according to the KES method refers to the shear hardness (G) calculated from the shear stress in the longitudinal direction and the width direction measured according to the KES method. More specifically, the shear stress in the longitudinal 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 ), and the longitudinal direction and the width direction are expressed using the formula G1. Calculate the shear strength in the positive direction (G (+)) using the formula G2 to calculate the shear strength in the negative direction (G (-)), and average G (+) and G (-) in the longitudinal and width directions. The shear hardness (G) obtained in this way. The conditions at the time of measuring the shear stress are 23 ° C., 65% relative humidity atmosphere, forced load 10 gf, shear shear rate 0.417 mm / sec, and sample shear deformation range −8 ° to 8 °. Hereinafter, the shear hardness (G) measured according to the KES method may be simply referred to as shear hardness (G).

  Here, the longitudinal direction refers to the direction in which the film proceeds when producing the film, and the width direction refers to the direction that is parallel to the film transport surface and orthogonal to the longitudinal direction. When the film is wound on a roll, the longitudinal direction and the width direction can be easily specified. However, in the case of a sheet-like film that is not wound on a roll, the longitudinal direction and the width direction Cannot be easily identified. In such a case, after measuring the Young's modulus of the film in one direction arbitrarily selected by the method described later, the film is rotated 5 ° clockwise and the same measurement is performed, and this is repeated until 175 ° is reached. The direction with the largest Young's modulus is treated as the longitudinal direction. Hereinafter, the same applies to the present invention.

  Young's modulus is about 150 mm (measurement direction) × 10 mm strip-shaped film sample, with an initial tensile chuck distance of 50 mm and a tensile speed of 200 mm / min in an atmosphere of 23 ° C. and relative humidity of 65% in the longitudinal direction of the strip. It can be measured according to the method defined in JIS K-7127 (1999).

  In the film of the present invention, from the viewpoint of further improving the shear deformability of the film, the shear hardness (G) is 0.1 gf / (cm · deg) or more and 2.0 gf / (cm · deg) or less. More preferably, it is more preferably 0.1 gf / (cm · deg) or more and 1.5 gf / (cm · deg) or less.

  The method for setting the shear hardness (G) of the film of the present invention to 0.1 gf / (cm · deg) or more and 2.5 f / (cm · deg) or less, or the preferable range described above, impairs the effects of the present invention. The method is not particularly limited as long as it is not limited, and examples thereof include a method of adjusting the kind and content of the thermoplastic elastomer and organic particles, a method of adjusting the film thickness, and a method of imparting an uneven structure by embossing described later. . More specifically, the shear strength (G) can be reduced by increasing the depth of the recess or reducing the basis weight.

(Surface roughness variation (SMD))
The film of the present invention preferably has a surface roughness variation (SMD) measured in accordance with the KES method on the X plane of 0.5 μm or more and 15.0 μm or less from the viewpoint of imparting a pleasant touch to the film.

  Specifically, the surface roughness variation (SMD) measured according to the KES method is as follows: in an atmosphere of 23 ° C. and a relative humidity of 65%, the load is 5 gf and the moving speed of the slider is 1 mm / sec. This refers to the variation in surface roughness (SMD) measured by the method. Hereinafter, the surface roughness variation (SMD) measured according to the KES method may be simply referred to as the surface roughness variation (SMD).

  Focusing on improving the tactile feel of the film and improving the productivity of the film, the surface roughness variation (SMD) on the X plane is more preferably 1.0 μm or more and 10.0 μm or less, and 1.5 μm. More preferably, it is 5.0 μm or less.

  In the X plane of the film of the present invention, the method for setting the variation in surface roughness (SMD) to 0.5 μm or more and 15.0 μm or less, or the above preferable range is not particularly limited as long as the effect of the present invention is not impaired. However, for example, a method of adjusting the particle diameter and content of the organic particles, a method of adjusting the height of the concavo-convex portion by embossing described later, and the like can be mentioned. Specifically, the value can be increased by increasing the particle diameter of organic particles, which will be described later, and increasing the depth of the unevenness.

(Coefficient of friction)
The film of the present invention preferably has a friction coefficient on the X surface of 0.35 or less from the viewpoint of further improving the pleasant tactile sensation when touching the X surface. Here, the coefficient of friction refers to a coefficient of friction measured according to the KES method. Specifically, a standard friction element (fingerprint type) is attached as a slider under an atmosphere of 23 ° C. and a relative humidity of 65%, and a load of 25 gf. The friction coefficient measured by the KES method when the slider is moved on the surface of the sample at a speed of 1 mm / sec.

  From the viewpoint of coexistence of the touch feeling of the film, the anti-blocking property, the handling property, and the mechanical properties as the film, the friction coefficient of the X surface is more preferably 0.25 or less, and 0.15 or less. More preferably. Note that the lower limit of the friction coefficient of the X surface is preferably as low as possible, but the practical lower limit is 0.05.

  The method for adjusting the friction coefficient of the X surface to 0.35 or less is not particularly limited as long as the effects of the present invention are not impaired. For example, the method for adjusting the type and content of the organic particles and the particle diameter are adjusted. Method, etc. Specifically, by selecting organic particles with good slipperiness such as ultra high molecular weight polyethylene and polytetrafluoroethylene as the type of organic particles, increasing the content of organic particles, etc., the value is reduced. can do.

(Water permeability of film)
When the film of the present invention is used for applications requiring moisture permeability such as sanitary materials, the moisture permeability is preferably 1,000 g / (m ² · day) or more, and 1,500 g / (m ² · Day) or more, more preferably 2,000 g / (m ² · day) or more. The higher the moisture permeability of the film, the better, but there is no particular upper limit. However, from the viewpoint of application to sanitary materials, 8,000 g / (m ² · day) is sufficient.

  Here, the moisture permeability of the film refers to a moisture permeability obtained by measurement by a method defined in JIS Z-0208 (1976) with a constant temperature and humidity device set at 25 ° C. and a relative humidity of 90%. .

  The method for adjusting the moisture permeability of the film of the present invention to the above preferred range is not particularly limited as long as the effects of the present invention are not impaired. For example, the method for adjusting the kind and content of the thermoplastic elastomer, the basis weight And a method of adjusting Specifically, the moisture permeability of the film can be increased by using a thermoplastic elastomer having moisture permeability as a resin constituting the film, or by combining a moisture permeable material such as polyoxyethylene.

(filler)
The film of the present invention may contain a filler from the viewpoints of handling properties, winding properties and cost reduction. The filler refers to a substance added to improve various properties, or an inert substance added to the film for the purpose of increasing the amount, increasing the volume, or reducing the cost of the product.

  The filler is not particularly limited as long as the effects of the present invention are not impaired, and an inorganic filler and / or an organic filler can be used. Further, the filler may be one kind or a mixture of plural kinds. However, from the viewpoint of cost and versatility, the filler is preferably an inorganic filler, carbonates such as calcium carbonate, barium carbonate and magnesium carbonate, sulfates such as barium sulfate and calcium sulfate, silicon oxide (silica), It is preferable to use at least one of metal oxides such as titanium oxide and zinc oxide, and composite oxides such as aluminosilicate, mica, talc, kaolin, clay, and montmorillonite. From the viewpoint of versatility and cost, calcium carbonate and It is preferable to use barium sulfate.

  In the case of using organic particulates as the filler, the filler is positioned similar to the organic particles present on the X-plane of the film of the present invention. It is different in that the filler is present inside the film in the final film state after being put into the extruder together with the resin raw material to be used.

  The amount of the filler in the X layer of the present invention is not particularly limited, but is preferably 10 parts by mass or more and 120 parts by mass or less when the entire resin component in the X layer is 100 parts by mass.

(Film weight)
The basis weight of the film having organic particles having a single layer structure 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 handling properties and productivity, it is 10 g / m ² or more and 100 g / m ² or less. Preferably there is. By setting the basis weight of the film to 10 g / m ² or more, the stiffness of the film becomes stronger, so that the handleability is improved, and the roll winding shape and unwinding property are also improved. By setting the basis weight of the film to 100 g / m ² or less, the bubble is stabilized by its own weight, particularly in the inflation film forming method. In addition, the fabric weight of a film here means the value also including the mass of the organic particle of the single layer structure which exists in the outermost layer. The basis weight of the film can be measured according to JIS L-1913 (2010).

Furthermore, considering the viewpoint of further improvement in flexibility, stretchability, shear deformability, moisture permeability, film-forming stability, embossability, which is preferable for the film of the present invention, the basis weight of the film is 15 g / m ² or more and 45 g / m. m ² is more preferable, and 20 g / m ² or more and 40 g / m ² is more preferable.

(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, it contains antioxidants, UV stabilizers, anti-coloring agents, matting agents, antibacterial agents, deodorants, weathering agents, antioxidants, ion exchange agents, tackifiers, coloring pigments, dyes, etc. May be.

(Embossing)
The film of the present invention may be provided with an uneven structure by embossing from the viewpoint of bringing the feel and softness of the film closer to the cloth. By imparting a concavo-convex structure by embossing, the variation in surface roughness (SMD) can be easily within the preferred range. Moreover, since the degree of freedom of space is created by the concavo-convex structure, the shear hardness (G) can be easily set within the preferred range. As the unevenness depth on the surface of the embossing roll used for embossing is increased and the unevenness depth of the film is increased, the variation in surface roughness (SMD) tends to increase and the shearing degree (G) tends to decrease.

(Film production method)
Hereinafter, a film having no layers other than the X layer will be described as an example, and the method for producing the film of the present invention will be described more specifically. However, the film of the present invention and the production method thereof are limited to this. It is not a thing.

  A composition used for obtaining the film of the present invention, that is, a composition containing a resin A, a thermoplastic elastomer (this may correspond to the resin A in relation to the composition of organic particles), a filler and the like. Is preferably a melt-kneading method in which a composition is produced by melt-kneading each component. 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.

  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.

  The obtained non-oriented film may be subjected to uniaxial stretching or biaxial stretching, but the Young's modulus in the longitudinal direction of the film, the shear hardness (G), the work of compression, the water pressure resistance, and the elongation at break in the longitudinal direction of the film. In order to make the above-mentioned preferable range and to impart embossability, it is preferable not to perform stretching.

  After the film is formed, various surface treatments may be applied for the purpose of immobilizing organic particles having a single layer structure described later on the film surface. Examples of the surface treatment method include corona discharge treatment, plasma treatment, flame treatment, and acid treatment. Either method can be used, but a corona discharge treatment is more preferable from the viewpoint that continuous treatment is possible, the apparatus can be easily installed in an existing film forming facility, and the treatment is simple.

  The film formed by the method as described above is sprayed with organic particles having a single layer structure containing the resin B, and the film surface is coated with the organic particles having the single layer structure. Through a film laminator heated to a softening temperature or higher, the organic particles having a single layer structure and the film are thermocompression bonded to obtain a film having organic particles having a single layer structure on at least one outermost surface.

  Furthermore, when providing a concavo-convex structure to the film, embossing is performed between the embossing roll and the embossing roll to obtain a film having a concavo-convex structure. At this time, the roll temperature is preferably 20 to 150 ° C., the nip pressure (linear pressure) is preferably 20 to 100 kg / cm, and the roll rotation speed is preferably 0.5 to 30 m / min.

(Other uses)
The film of the present invention thus obtained is a film having mechanical properties necessary for use as a film, a soft texture like a cloth, a pleasant touch, and a natural appearance. For example, as a film for sanitary materials It can be used suitably. Furthermore, the film of the present invention may be a laminated film with another layer or a laminated body with a nonwoven fabric. Moreover, the sanitary material including the film of the present invention has both a soft texture and a pleasant touch.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto.

[Measurement and evaluation method]
Measurements and evaluations shown in the examples were performed under the following conditions.

(1) Thickness of film A sample piece is cut out from the center portion in the width direction of the film, and the longitudinal direction-thickness direction cross section (hereinafter sometimes referred to as a film cross section) of the sample piece is used as an observation surface 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 to 1,500 times, and measure the thickness of the film using the measuring function of the microscope. did. 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 each layer of the film. Note that the starting point and the ending point when measuring the thickness of the film using the length measuring function were positions not in contact with the organic particles on the outermost surface of the film, and the size of the organic particles was measured so as not to be included in the thickness measurement. The thickness of the film was a value obtained by rounding off the first decimal place. Here, the thickness direction means a direction perpendicular to the film surface.

(2) Weight per unit area (mass per unit area)
In accordance with JIS L-1913 (2010), 10 specimens of 10 cm square in the width direction and 10 cm square in the longitudinal direction were sampled in parallel with the longitudinal direction from the center in the width direction of the film, and the respective masses were measured. After calculating the average value, the weight per 1 m ² was converted to the mass per unit area (g / m ² ).

(3) Film shear strength (G)
The film was cut into a size of 12 cm (longitudinal 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., a sample having a load of 10 gf and a shear shear rate of 0.417 mm / sec in an atmosphere of 23 ° C. and a relative humidity of 65% was −8. A shear stress at a point where shear deformation of −2.5 °, −0.5 °, 0.5 °, and 2.5 ° was applied was given (hereinafter referred to as each point). the shear stress respectively _{HG -2.5, HG -0.5, HG 0.5} , sometimes referred _{HG 2.5.).} From HG _0.5 and HG _2.5 , the following equation G1 is used to determine the shear strength (G (+)) in the positive direction. From HG _-2.5 and HG _-0.5 , the following equation G2 is used to indicate the negative direction. Shear hardness (G (-)) was calculated. Measurement of shear stress and calculation of G (+) and G (-) are performed 3 times in the longitudinal direction and in the width direction (6 times in total), and the average value of all G (+) and G (-) values The value obtained by rounding off the second decimal place was taken as the shear hardness (G) (gf / (cm · deg)) of the film.
Formula G1: G (+) = (HG _2.5 −HG _0.5 ) / (2.5 ° −0.5 °)
Formula G2: G (−) = (HG _−2.5 −HG _−0.5 ) / (− 2.5 ° − (− 0.5 °))
When measuring the shear strength (G) in the longitudinal direction, the sample is attached so that the longitudinal direction of the film is orthogonal to the shear deformation direction, and when measuring the shear strength (G) in the width direction, the width of the film The sample was mounted so that the direction was perpendicular to the shear deformation direction.

(4) Variation in surface roughness of film (SMD)
The film was cut into a size of 12 cm (longitudinal direction) × 12 cm (width direction) and used as a sample, and the film was attached to the test stand so that the X plane was the measurement plane. Next, using a surface property tester KES-SE-SR-U manufactured by Kato Tech Co., Ltd., slipping on the measurement surface with a load of 5 gf and a speed of 1 mm / sec in an atmosphere of room temperature 23 ° C. and relative humidity 65%. The child was moved in parallel with the film longitudinal direction, and the variation of the surface roughness in the film longitudinal direction was measured. Thereafter, similarly, the slider was moved in parallel with the film width direction, and the variation of the surface roughness in the film width direction was measured. The variation of the surface roughness in the film longitudinal direction and the width direction was measured three times, and the value obtained by averaging the absolute values of all the values was defined as the variation (SMD) (μm) of the surface roughness of the film. As the slider, a piano wire having a length of 5 mm and a diameter of 0.5 mm was used.

(5) The film was measured with a constant temperature and humidity apparatus set at 25 ° C. and 90% relative humidity according to the method defined in JIS Z-0208 (1976). 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) Coefficient of friction 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 (longitudinal direction) × 12 cm (width direction), attached to the test bench, A standard friction element (fingerprint type) is attached as a slider, and the slider is moved on the surface having the organic particles of the film at a load of 25 gf and a speed of 1 mm / sec, and the room temperature is 23 ° C. and the relative humidity is 65%. The coefficient of friction of the surface having organic particles was measured. The measurement was performed 3 times in each of the longitudinal direction and the width direction (6 times in total), and the average value of all the data was defined as the friction coefficient of the film.

(7) Layer structure of organic particles (1) Similarly to the thickness measurement of the film, a sample piece is cut out from the center portion in the width direction of the film, and the longitudinal direction-thickness direction cross section of the sample piece (hereinafter, referred to as “ultramicrotome”). Ultrathin sections were collected at −100 ° C. so that the cross section of the film may be the observation surface. Using a scanning electron microscope (S-3400N manufactured by Hitachi High-Technologies Corporation), a photograph of the cross section of the film was taken at a magnification of 500 to 1,500 times, and the layer structure of the organic particles existing on the outermost surface (single layer) Or a multilayer structure) was observed. In addition, when the shape of the organic particles is intermediate between the single layer structure and the multilayer structure, that is, when a part of the outer peripheral portion of the organic particles has a multilayer structure, the entire outer peripheral portion has a single layer structure. When the ratio of the outer peripheral portion was 70% or more, it was regarded as a single layer structure.

(8) Adhesiveness between organic particles and X layer The degree of adhesion of organic particles to the finger when the surface of the X layer was traced with a finger was visually observed and evaluated in the following four stages. A is the best adhesion. On the other hand, in the case of D, it was judged that the drop-off of the particles was severely impractical.
A: Organic particles do not fall off, and even if the same place is traced with a finger five times, no organic particles adhere to the finger.
B: Dropping of organic particles is very small, and when the same place is traced with a finger five times, slight adhesion of organic particles to the finger is observed.
C: A small amount of organic particles fall off, and when the same place is traced five times with a finger, the adhesion of the organic particles to the finger is clearly observed.
D: The organic particles are not adhered to the film, and the organic particles do not remain on the film part touched with a finger.

(9) As a method of adding organic particles having an adhesive single-layer structure to a roll of film, when a method of thermocompression bonding organic particles onto a film by a film laminator is adopted, The adhesiveness to the roll was evaluated. Specifically, the film before thermocompression bonding is passed through a film laminator, and the film that has come out in the horizontal direction from the film laminator is transported while maintaining a horizontal state, and is disposed at a position closest to the outlet in the film laminator. In the two roll pairs for pressure bonding, the holding angle of the adhesive portion in the roll on the side where film adhesion occurred was measured, and the adhesion of the film to the roll was evaluated in the following three stages. In addition, when adhesion occurred in both rolls, the evaluation was performed with a roll having a large holding angle of the adhesion portion. The apparatus and conditions used for this evaluation are as follows.
<Equipment and conditions>
Film laminator: MCK, MRK-650Y roll material: Silicon roll speed: 2 m / min
Film transport speed after passing the film laminator: 2.2 m / min
<Evaluation criteria>
A: The holding angle of the adhesive part is 0 ° or more and less than 10 ° B: The holding angle of the adhesive part is 10 ° or more and less than 30 ° C: The holding angle of the adhesive part is 30 ° or more and the holding angle of the adhesive part is shown in FIG. Will be described. FIG. 3 is a schematic diagram showing the “holding angle of the adhesive portion” used for evaluating the adhesiveness of the film to the roll. Two points are taken on the outer periphery of the adhesive part f generated on the surface through which the film of the roll e passes, so that the distance when observed from the direction parallel to the rotation axis g is maximized, and the direction parallel to the rotation axis The angle formed by the center of the rotation axis g and the two points (h in FIG. 3) when observed from the above is defined as the holding angle of the adhesive portion. In the above evaluation, the holding angle of the adhesive portion is usually so small that adhesion does not occur, and the holding angle when no adhesion occurs is 0 °. That is, A is the most excellent evaluation of the adhesiveness to the roll of the film.

(10) A differential scanning calorimeter DSCII type (manufactured by Seiko Instrument Co., Ltd.) was used for measuring the melting point and glass transition point. The measurement sample was previously heated in a hot air oven at 100 ° C. for 24 hours in order to complete crystallization of the crystallizable component. A sample for measurement of 5 mg was taken from the measurement sample after heating, and the temperature was raised from 20 ° C. to 250 ° C. at a rate of temperature rise of 20 ° C./min. The temperature at the top of the endothermic peak accompanying melting observed was taken as the melting point. Moreover, the glass transition temperature was read from the change in the baseline curve in the same measurement. For each measurement sample, the measurement sample was changed five times at different locations where the measurement sample was collected, and the obtained melting point and glass transition temperature were rounded off to the first decimal place. And the glass transition point. In addition, the magnitude relationship between the melting point and the glass transition point between each component was judged using a value obtained by rounding off the first decimal place of the average value.

(11) Average particle diameter of organic particles First, the film was cut at an angle of knife inclination (angle formed by the thickness direction and the knife surface) 3 ° using an ultramicrotome, and the resulting cross section was scanned with an electron microscope (Corporation). S-3400N manufactured by Hitachi High-Technologies Corporation) and magnified observation at a magnification of 500 times, and by using the measuring function of the microscope, a square or rectangle was drawn so that one organic particle was completely enclosed and the area was minimized. In the case of a rectangle, the average value of the lengths of the long side and the short side in the case of a rectangle was defined 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 from the observation image in another part, from the central portion until the total reaches 100 particles. The selection was made in order of proximity.

(12) For resins with a known solubility parameter structure, Fedor estimates described in Hideki Yamamoto, “SP Value Basics, Applications, and Calculation Methods” (issued by Information Technology Corporation (2005), paragraphs 66-67) The solubility parameter was calculated based on the method. 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 was no example in which the resin structure was unclear in the examples, and all the methods described above were used.

(13) 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: Showa Denko "Shodex" (registered trademark) UT806M
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 (14) Quantity of Organic Particles The mass of the film before and after thermocompression bonding (both 400 cm ² ) was measured, and the difference was defined as the mass of organic particles per 400 cm ² . The value obtained by converting this value per 1 m ² was defined as the amount of organic particles (g / m ² ). In addition, when the mass of the film before thermocompression bonding of organic particles cannot be measured, it is necessary to use a different method as described above. This method was adopted in any of the examples.

[Thermoplastic elastomer]
(A1)
Before using the polyester elastomer (trade name: “Hytrel” (registered trademark) G3548, manufactured by Toray DuPont Co., Ltd.), it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.
(A2)
Polyolefin elastomer (trade name: “ACRlift” (registered trademark) WH303, manufactured by Sumitomo Chemical Co., Ltd.)
(A3)
Before using the polyamide-based elastomer (trade name: “PEBAX” (registered trademark) MV1074, manufactured by Arkema Co., Ltd.), it was dried in a rotary vacuum dryer at 90 ° C. for 5 hours.
(A4)
Low density polyethylene (trade name: “Sumikasen” (registered trademark) F200, manufactured by Sumitomo Chemical Co., Ltd.)
(A5)
Polyolefin elastomer (trade name: “ACRlift” (registered trademark) CM5022, manufactured by Sumitomo Chemical Co., Ltd.)
(A6)
Acrylic elastomer (trade name: “Clarity” (registered trademark) LA4285, manufactured by Kuraray Co., Ltd.)
[Organic particles]
(B1)
Ultra high molecular weight polyethylene (trade name: “Miperon” (registered trademark) XM-220, manufactured by Mitsui Chemicals, Inc.).
(B2)
Ultra high molecular weight polyethylene (trade name: “Hi-Zex Million” (registered trademark) 030S, manufactured by Mitsui Chemicals, Inc.).
(B3)
Ultra high molecular weight polyethylene (trade name: “Hi-Zex Million” (registered trademark) 145M, manufactured by Mitsui Chemicals, Inc.).
(B4)
Low density polyethylene (A4) pellets made into fine particles by freeze pulverization.
(B5)
Polymethylmethacrylate (trade name: “Delpet” (registered trademark) 80NH, manufactured by Asahi Kasei Co., Ltd.) pelletized by freeze pulverization.

[Filler (C)]
(C1)
Calcium carbonate (trade name: SCP E # 810, aspect ratio 2, average particle size 3.0 μm, manufactured by Sankyo Seimitsu Co., Ltd.)
[Production of film]
Example 1
Each raw material was supplied to a twin screw extruder with a vacuum vent of 44 mm with a cylinder diameter of 190 ° C. and melted and kneaded so as to have the blending ratio shown in Table 1, and homogenized and then pelletized to obtain a composition. . The pellets of this composition were vacuum-dried at a temperature of 90 ° 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 having a cylinder diameter of 200 ° C. and a screw diameter of 60 mm by an inflation method, and a circular die having a diameter of 250 mm, a lip clearance of 1.0 mm, and a temperature set to 190 ° C. The film 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 to obtain an unstretched film. Next, after spraying the organic particles shown in Table 1 on one side of the obtained unstretched film using a powder spraying device, it was passed through a thermal laminator (manufactured by MCK, MRK-650Y type) at 150 degrees. A film having organic particles on the surface was obtained. Furthermore, a roll temperature of 120 ° C. (both upper and lower tiers), nip between the nonwoven fabric pattern embossing roll having an arithmetic average roughness of 50 μm and a rubber roll set in an electric heating embossing machine “HTEM-300” manufactured by Yuri Roll Co., Ltd. It was embossed by passing under conditions of pressure (linear pressure) 50 kg / cm and roll rotation speed 5.0 m / min. The physical properties and evaluation results of the obtained film are shown in Table 1.

(Examples 2 to 18, Comparative Examples 1 and 3)
Except having set it as the composition of Tables 1-2, while obtaining the film which has an organic particle on one side by the method similar to Example 1, it embossed like Example 1 using the film. . The physical properties and evaluation results of the obtained films are shown in Tables 1-2. In addition, resin for obtaining the organic particle in Examples 11-13 describes the pellet of low density polyethylene (B4) and the pellet of polymethyl methacrylate (B5) in Table 2 using a twin screw extruder. A mixture obtained by melting and kneading at a mass ratio of 1 to 5 was used.

(Comparative Example 2)
A non-oriented film was obtained by the inflation method in the same manner as in Example 1 except that the composition shown in Table 1 was used. On the other hand, organic particles listed in Table 1 and water-soluble nylon (trade name: AQ nylon T70, manufactured by Toray Industries, Inc.) were mixed so that the mass ratio was 30:70, and then applied to the non-oriented film. Thereafter, the film was dried at 120 ° C. to remove moisture, and then embossed in the same manner as in Example 1. In the cross-sectional photograph of the obtained film, the organic particles were covered with the water-soluble nylon applied as shown in FIG. Further, the coating layer of 3 μm was formed by application of water-soluble nylon, so that the hardness of the film was increased and it did not have a soft texture like cloth.

(Examples 19 to 22)
Each raw material for X layer, Y layer or Z layer is supplied to a twin screw extruder with a vacuum vent with a cylinder diameter of 190 ° C. and a screw diameter of 44 mm so as to achieve the blending ratio shown in Table 3. And then homogenized and pelletized to obtain a composition. The pellets of this composition were vacuum-dried at a temperature of 90 ° C. for 5 hours using a rotary drum type vacuum drier, for the X layer, and for the Y layer (Examples 19 and 20) or the Z layer (Example 21, 22) was obtained. Subsequently, these compositions were applied to independent X-layer single-screw extruders having a cylinder temperature of 200 ° C. and a screw diameter of 60 mm, and single layers for Y-layers (Examples 19 and 20) or Z-layers (Examples 21 and 22). A spiral extruder having a diameter of 250 mm, a lip clearance of 1.0 mm, and a temperature of 190 ° C. is used to supply an X-layer / Y-layer (Examples 19 and 20) or an X-layer / Z-layer (Examples 21 and 22). ) To form a two-layer structure with a blow ratio of 2.0, extruded upward in a bubble shape, air-cooled with a cooling ring, air-cooled with a cooling ring, folded and folded with a nip roll above the die, and rolled. Rolled up. About the obtained laminated | multilayer film, while obtaining the film which has an organic particle on one side by the method similar to Example 1, embossing was performed like Example 1 using the film. Table 3 shows the physical properties and evaluation results of the obtained film.

In Comparative Examples 1 to 3, there is no resin A or resin B due to the solubility parameter. In the table, the combinations with the smallest absolute value of the solubility parameter difference are shown as Resin A and Resin B.

In Tables 1 to 3, “the resin component (mass%) of the X layer” was calculated based on 100% by mass of the entire resin of the X layer.
The “parts by mass” of the “filler” item in Tables 1 to 3 was calculated based on 100 parts by mass of the entire resin of the X layer.

  According to the present invention, it is possible to provide a film having mechanical properties necessary for use as a film, a soft texture like a cloth, and a pleasant touch. Specifically, the film of the present invention can be applied to medical / hygienic materials such as bed sheets, pillow covers, back sheets of absorbent articles such as sanitary napkins and paper diapers, clothing materials such as rainy clothing, gloves, garbage bags and compost. For packaging materials such as bags, bags for foods such as vegetables and fruits, bags for various industrial products, building materials such as buildings, houses, decorative panels, interior materials in construction equipment such as railway vehicles, ships, and aircraft, and building materials It can be preferably used.

a X layer b Organic particle c having a single layer structure c Film d Organic particle having a multilayer structure e Roll f Adhesive part g Rotating shaft h Holding angle of adhesive part

Claims (9)

In the outermost layer of the film, it is a film having organic particles having a single layer structure, and a resin layer (X layer) in contact therewith,
When the total resin component in the X 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 X 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 absolute value of the difference in solubility parameter between the resin A and the resin B is 0.10 (MPa) ^0.5 or less.   The film according to claim 1, wherein the X layer contains 5% by mass or more and 100% by mass or less of the resin A when the entire resin component in the X layer is 100% by mass.   The film according to claim 1 or 2, wherein the organic particles contain 50 mass% or more and 100 mass% or less of the resin B when the entire resin component in the organic particles is 100 mass%.   The film according to claim 1, wherein the organic particles have a weight average molecular weight of 500,000 or more.   The film according to any one of claims 1 to 4, wherein the X layer contains more than 50% by mass of a thermoplastic elastomer when the entire resin component in the X layer is 100% by mass. The resin A and the resin B are both crystalline resins, and the X layer has at least one crystalline resin (resin C) having a melting point higher than that of the resin A.
When the melting point of the resin C is the resin C1, the melting point of the resin A is TmA, the melting point of the resin B is TmB, and the melting point of the resin C1 is TmC1, TmC1> TmB ≧ TmA. The film according to claim 1, wherein the film is a film.   The film according to claim 6, further comprising a layer (Y layer) having a melting point higher than that of the TmB on the outermost surface opposite to the X layer. The resin A and the resin B are both amorphous resins, and the X layer has at least one kind of crystalline resin (resin D),
When the resin D has the highest melting point of the resin D, the glass transition point of the resin A is TgA, the glass transition point of the resin B is TgB, and the melting point of the resin D1 is TmD1, TmD1> TgB The film according to claim 1, wherein ≧ TgA. The film according to claim 8, further comprising a layer (Z layer) having a melting point higher than that of the TgB on the outermost surface opposite to the X layer.