JPWO2019188787A1 - the film - Google Patents

Abstract

An object of the present invention is to provide a film having mechanical properties necessary for use as a film and having excellent adhesion to a cloth or the like and handleability, and has a base material layer and an adhesive layer. The maximum value of Young's modulus is 0.05 MPa or more and 2.00 MPa or less, the base material layer contains more polyolefin resin than the adhesive layer, the adhesive layer is located on at least one outermost surface, and particles. The purpose of the film is to have a convex portion having a height of 20 μm or more on the surface thereof, and the area ratio of the convex portion to the entire surface is 2% or more and 20% or less. And.

Description

The present invention relates to a film having excellent adhesion to a material having an uneven surface such as cloth or non-woven fabric and having excellent handleability.

In recent years, there has been a demand for a single film having the mechanical properties necessary for use as a film and having another function. For example, in the field of medical and sanitary materials, materials such as cloth and non-woven fabric (hereinafter referred to as cloth, etc.) having the mechanical properties necessary for use as a film and having an uneven shape, elasticity, and flexibility. There is a demand for a film that has both adhesion and handleability.

So far, various developments have been made as films having adhesion to cloth and the like and excellent handleability. For example, Patent Document 1 discloses a pressure-sensitive adhesive layer containing expanded and foamed heat-expandable microcapsules to form air bubbles. Since the adhesive layer of such an adhesive tape is easily deformed by air bubbles, it is possible to improve the adhesiveness to a cloth or the like.

JP-A-2016-145353

However, although the technique of Patent Document 1 can improve the adhesion to cloth or the like to some extent, it is difficult to achieve both handleability. Specifically, there is a problem that blocking occurs when the film is stored as a roll, and its handleability is lowered.

An object of the present invention is to improve the drawbacks of the prior art, to provide a film having mechanical properties necessary for use as a film, and having excellent adhesion and handleability to a cloth or the like.

In order to solve the above problems, the present invention has the following configuration.
(1) It has a base material layer and an adhesive layer, and the maximum value of Young's modulus is 0.05 MPa or more and 2.00 MPa or less, the base material layer contains more polyolefin resin than the adhesive layer, and the adhesive The layer is located on at least one of the outermost surfaces, contains particles, has a convex portion having a height of 20 μm or more on the surface, and the area ratio of the convex portion to the entire surface is 2% or more and 20% or less. A film characterized by being.
(2) When the thickness of the adhesive layer is X μm and the average particle size of the particles contained in the adhesive layer is Y μm, X / Y is 0.1 or more and 2.0 or less. The film according to 1).
(3) When the frequency distribution was obtained at 1 μm intervals from the volume-based particle size distribution measured by the laser diffraction / scattering method of the particles contained in the adhesive layer, there were a plurality of peaks having a height of 3% or more, and the largest peak. When the particle size indicated by is the average particle size A and the particle size indicated by the second largest peak is the average particle size B, the difference between the average particle size A and the average particle size B is 10 μm or more. The film according to (1).
(4) When the thickness of the adhesive layer is X μm and the average particle diameter having a larger value among the average particle diameter A and the average particle diameter B is Z μm, X / Z is 0.1 or more and 2.0 or less. The film according to (3), which is characterized by being present.
(5) The film according to any one of (1) to (4), wherein the particles contain inorganic particles.
(6) When the rosin-based resin, the terpene-based resin, and the petroleum-based resin are used as the adhesive resin, the adhesive layer contains at least one kind of adhesive resin (1) to (5). The film described in any of.
(7) The film according to (6), wherein the adhesive layer contains more of the adhesive resin than the base material layer.
(8) The content of the adhesive resin in the adhesive layer is 10% by mass or more and 50% by mass or less when the total resin component in the adhesive layer is 100% by mass (6). ) Or the film according to (7).

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a film having mechanical properties necessary for use as a film and having excellent adhesion to cloth and the like and handleability.

It is an enlarged top view which shows the film which concerns on one Embodiment of this invention. It is a schematic diagram which shows the measuring direction of Young's modulus.

The film of the present invention has a base material layer and an adhesive layer, and has a maximum Young's modulus of 0.05 MPa or more and 2.00 MPa or less, and the base material layer contains more polyolefin-based resin than the adhesive layer. The adhesive layer is located on at least one of the outermost surfaces, contains particles, has a convex portion having a height of 20 μm or more on the surface, and the area ratio of the convex portion to the entire surface is 2% or more 20. It is characterized by being less than%.

(Film layer structure)
It is important that the film of the present invention has a base material layer and an adhesive layer. The base material layer in the film of the present invention contributes to the maintenance of mechanical properties as a film, and the adhesive layer contributes to the improvement of adhesion to cloth and the like and the improvement of handleability, the details of which will be described later. Therefore, by adopting such an aspect, it is possible to improve the adhesion and handleability to the cloth or the like while maintaining the mechanical properties of the film. At this time, another layer may exist between the base material layer and the adhesive layer as long as the effects of the present invention are not impaired.

(Base layer)
It is important that the base material layer in the film of the present invention contains more polyolefin-based resin than the adhesive layer described later. The fact that the base material layer contains more polyolefin-based resin than the adhesive layer means that the ratio (mass%) of the polyolefin-based resin to the total resin components constituting the base material layer is the polyolefin in the total resin components constituting the adhesive layer. It means that it is larger than the ratio (mass%) of the based resin. With such an embodiment, the base material layer can take on the function of maintaining the mechanical properties of the film. The composition of the base material layer is not particularly limited and can be arbitrarily determined as long as it contains a larger amount of polyolefin-based resin than the adhesive layer described later and can maintain mechanical properties to the extent that the effects of the present invention are not impaired. The adhesive layer does not necessarily have to contain a polyolefin resin.

However, from the viewpoint of improving the flexibility while maintaining the mechanical properties of the film, it is preferable that the base material layer contains a polyolefin resin as a main component. Here, the polyolefin-based resin means a homopolymer of olefins such as ethylene and propylene, or a copolymer with a dissimilar polyolefin, and when the polyolefin-based resin is the main component, the entire resin component constituting the layer is 100. When it is set to mass%, it means that the layer contains more than 50% by mass of the polyolefin resin. The "main component" can be interpreted in the same manner below.

Examples of homopolymers of olefins include polyethylene and polypropylene. Examples of the copolymer with the dissimilar polyolefin include an ethylene / propylene copolymer, an ethylene / vinyl acetate copolymer, an ethylene / vinyl alcohol copolymer, and an ethylene / vinyl chloride copolymer. Above all, from the viewpoint that the Young's modulus of the obtained film is easily within a preferable range described later, it is preferable that the base material layer in the film of the present invention contains polyethylene as a main component. Further, a plurality of polyolefin-based resins and other resins may be used in combination as long as the effects of the present invention are not impaired.

The base material layer may contain a filler as long as the effect is not impaired. The filler refers to a substance added to improve various properties, or an inert substance added for the purpose of increasing the amount, increasing the volume, or reducing the cost of the product. The type of filler is not particularly limited as long as the effect of the present invention is 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 a plurality of kinds as long as the effect of the present invention is not impaired. The filler is preferably an inorganic filler, and is preferably a metal carbonate such as calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, etc., from the viewpoint of easily setting the young ratio of the obtained film in a preferable range described later. It is possible to use at least one of metal sulfates, metal oxides such as titanium oxide and zinc oxide, and composite oxides such as silicon oxide (silica), aluminosilicate, mica, talc, kaolin, clay, and montmorillonite. Preferably, from the viewpoint of versatility and cost, it is more preferable to use calcium carbonate alone or in combination with other fillers.

The content of the filler in the base material layer is not particularly limited as long as the effect of the present invention is not impaired, but from the viewpoint of easily setting the Young's modulus of the obtained film to a preferable range described later, the entire resin component of the base material layer is used. When it is 100 parts by mass, it is preferably 5 parts by mass or more and 200 parts by mass or less, and more preferably 10 parts by mass or more and 150 parts by mass or less.

Further, the base material layer may contain components other than the above-mentioned components as long as the effects of the present invention are not impaired. Examples of such components include lubricants, antioxidants, UV stabilizers, matting agents, antibacterial agents, deodorants, weathering agents, antioxidants, ion exchangers, coloring pigments, dyes and the like. Be done.

(Adhesive layer and adhesive resin)
It is important that the adhesive layer in the film of the present invention is located on at least one of the outermost surfaces from the viewpoint of adhering to a cloth or the like. With such an aspect, the adhesive layer can be brought into direct contact with the cloth or the like.

The adhesive layer preferably contains an adhesive resin (at least one resin selected from a rosin resin, a terpene resin, and a petroleum resin) from the viewpoint of improving the adhesiveness between the film and the cloth or the like. When such an adhesive resin is blended with a polymer material, it exhibits adhesiveness due to a plasticizing action. Therefore, when the adhesive layer contains the adhesive resin, the adhesiveness between the film and the cloth or the like is improved.

The rosin-based resin is a resin containing rosin acid (abietic acid, palastolic acid, isopimalic acid, etc.) as a main component. The rosin-based resin that can be used in the film of the present invention can be obtained as a residue remaining after collecting balsams such as pine fat, which is the sap of a plant of the Pinaceae family, and distilling the terepine essential oil. Specific examples of the rosin-based resin include unmodified rosins such as gum rosin, wood rosin, and tall oil rosin, and modified rosins obtained by modifying these unmodified rosins by hydrogenation, disproportionation, polymerization, and other chemical modifications. And so on.

Petroleum-based resin refers to a resin obtained by polymerizing a part of naphtha-decomposed by-product oil (diene having high unsaturated property, etc.). Examples of the petroleum-based resin that can be used in the film of the present invention include aliphatic petroleum-based resins, aromatic petroleum-based resins, aliphatic / aromatic copolymer petroleum-based resins, and hydrogenated products thereof. Can be mentioned.

The terpene-based resin refers to a polymer of a terpene monomer, a copolymer of a terpene monomer and another monomer, and a derivative thereof. Examples of the terpene-based resin include α-pinene polymer, β-pinene polymer, dipentene polymer and the like, as well as terpene phenol resin, styrene-modified terpene resin, and modified terpene resin such as hydrogenated terpene resin. Be done.

In the film of the present invention, the adhesive layer preferably contains more adhesive resin than the base material layer. Here, "the adhesive layer contains the adhesive resin more than the base material layer" means the content of the adhesive resin in the adhesive layer when the total resin component constituting the adhesive layer is 100% by mass. It means that (% by mass) is larger than the content (mass%) of the adhesive resin in the base material layer when the total resin component constituting the base material layer is 100% by mass. At this time, the base material layer does not necessarily have to contain the adhesive resin. The adhesive resin can improve the adhesiveness to cloth and the like, but is inferior in mechanical strength to the resin that can be used in the above-mentioned base material layer. Therefore, by adopting such an aspect, it is possible to easily achieve both the mechanical properties of the film and the adhesion to the cloth or the like.

In the film of the present invention, the content of the adhesive resin in the adhesive layer is preferably 10% by mass or more and 50% by mass or less, preferably 30% by mass, when the total resin component constituting the adhesive layer is 100% by mass. More preferably, it is% or more and 50% by mass or less. When the content of the adhesive resin in the adhesive layer is 10% by mass or more when the total resin component constituting the adhesive layer is 100% by mass, the film has excellent adhesion to cloth or the like. .. On the other hand, when the total amount of the resin component constituting the adhesive layer is 100% by mass, it is 50% by mass or less, which facilitates processing at the time of manufacturing the film described later. When there are a plurality of types of adhesive resins in the adhesive layer, the content thereof shall be calculated by adding up all the corresponding components.

The adhesive layer in the film of the present invention preferably contains a resin other than the adhesive resin. The resin other than the adhesive resin may be one type or a plurality of types as long as the function of the adhesive layer is not impaired, and the type can be arbitrarily selected. However, it is preferable that the adhesive layer contains a thermoplastic elastomer from the viewpoint that the Young's modulus of the obtained film is easily within a preferable range described later.

Here, the thermoplastic elastomer has rubber elasticity at 25 ° C. by having a hard segment phase and a soft segment phase, while in a temperature range of 100 ° C. to 300 ° C., which is a general thermoplastic molding temperature range. It refers to a high molecular weight material that can be molded in the same manner as a general thermoplastic resin by developing fluidity in the hard segment phase. As the thermoplastic elastomer in the adhesive layer, for example, polyester-based elastomers, polyolefin-based elastomers, polyamide-based elastomers, polyurethane-based elastomers, styrene-based elastomers, polyacrylic elastomers, and the like can be used alone or in combination of two or more. Above all, it is preferable to use a styrene-based elastomer from the viewpoint of adhesion of the obtained film to cloth or the like.

Examples of the styrene-based elastomer include styrene-butadiene block copolymer, styrene-ethylenepropylene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, and styrene-ethylenebutylene-. Examples thereof include styrene block copolymers and styrene-ethylenepropylene-styrene block copolymers.

(particle)
In the film of the present invention, it is important that the adhesive layer contains particles. When the adhesive layer contains particles, it becomes possible to form a convex portion having a height of 20 μm or more on the surface thereof, and the handleability of the film is improved. More specifically, when the adhesive layer is brought into contact with a flat film or a material having no unevenness (hereinafter, may be referred to as a flat object), the contact area between the two is reduced by the uneven shape of the surface. Can be done. As a result, the film has low adhesiveness to a flat object, and the handleability of the film is improved. On the other hand, as for the adhesion to cloth or the like, the uneven shape of the film surface caused by the particles meshes with the uneven shape of the cloth or the like, so that the adhesion to a flat object is not deteriorated as much.

The particles in the film of the present invention are not particularly limited as long as the effects of the present invention are not impaired, and may be either inorganic particles or organic particles. However, it is preferable that the particles are inorganic particles from the viewpoint of reducing the decrease in adhesion to cloth or the like.

Examples of the inorganic particles that can be used in the film of the present invention include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, titanium oxide and the like. Be done. Examples of the organic particles that can be used in the film of the present invention include polyethylene resin, polyolefin resin, acrylic resin, urethane resin, styrene resin, urea resin, phenol resin, and epoxy resin.

The shape of the particles is not particularly limited as long as the effects of the present invention are not impaired, and may be spherical, lumpy, rod-shaped, flat, or the like, and different shapes may be used in combination as necessary. it can.

The film of the present invention preferably has an X / Y of 0.1 or more and 2.0 or less, where the thickness of the adhesive layer is X μm and the average particle size of the particles contained in the adhesive layer is Y μm. It is more preferably 5 or more and 2.0 or less, further preferably 0.5 or more and 1.5 or less, and particularly preferably 0.5 or more and 1.0 or less.

Here, the value of Y (μm) can be determined by the following procedure. First, the film is immersed in an aromatic hydrocarbon solvent such as toluene to dissolve the adhesive layer, a solution containing the particles is obtained, and the volume-based particle size distribution of the particles in the solution is obtained by a laser diffraction / scattering method. After that, from the volume-based particle size distribution, frequency distribution data in which the vertical axis is the frequency percentage display (%) and the horizontal axis is the particle size (μm) is acquired and made into a line graph (the interval on the horizontal axis at this time is 1 μm.). Next, check the number of intersections between the straight line parallel to the horizontal axis indicating that the value on the vertical axis is 3% and the line graph, and if there are two intersections, the grain with the highest frequency between the intersections. Let the diameter be Y (μm). At this time, if there are a plurality of particle diameters having the highest frequency between the intersections, the average value can be set to Y (μm). The number of intersections is an even number in principle of measurement, and the handling when the number of intersections exceeds two will be described later.

When X / Y is 0.1 or more and 2.0 or less, it means that the thickness of the adhesive layer / the average particle size of the particles contained in the adhesive layer is 0.1 or more and 2.0 or less. By setting X / Y to 0.1 or more, it is possible to reduce the functional deterioration of the adhesive layer due to falling off of particles and the like. Here, the thickness of the adhesive layer means the thickness of the adhesive layer in the portion where there are no particles. By setting X / Y to 2.0 or less, the thickness of the adhesive layer is not excessively increased, and it becomes easy to impart a convex portion having a height of 20 μm or more to the surface of the adhesive layer. When the adhesive layer is located on the outermost layers on both sides, it is sufficient that the X / Y of at least one of the adhesive layers is 0.1 or more and 2.0 or less.

The average particle size Y (μm) of the particles is not particularly limited as long as the effect of the present invention is not impaired, but is 20 μm or more and 80 μm or less from the viewpoint of forming a convex portion having a height of 20 μm or more on the surface of the adhesive layer. Is preferable, and more preferably 40 μm or more and 80 μm or less. When the average particle size of the particles is 20 μm or more, a convex portion having a height of 20 μm or more can be easily formed on the surface of the adhesive layer. Further, when the average particle size of the particles is 80 μm or less, the film formation of the film is more stable.

Further, in the film of the present invention, when the frequency distribution is determined at 1 μm intervals from the volume-based particle size distribution measured by the laser diffraction / scattering method of the particles contained in the adhesive layer, a plurality of peaks having a height of 3% or more are present. When the particle size indicated by the largest peak is the average particle size A and the particle size indicated by the second largest peak is the average particle size B, the difference between the average particle size A and the average particle size B is 10 μm or more. It is also preferable. Here, "peak of height 3% or more" means that a line graph of frequency distribution data is created according to the procedure for determining the value of Y (μm) described above, and the vertical axis indicates that the value is 3%. When a straight line parallel to is drawn, it means the area surrounded only by the line graph and the straight line.

Such an aspect means that the average particle size of the particles contained in the adhesive layer has two peaks, that is, the adhesive layer contains a plurality of particles having different average particle sizes. With such an aspect, in addition to improving the handleability of the film, it is possible to reduce the adhesion to a flat object. At this time, it does not matter whether or not the components of the particles showing the average particle size A and the components of the particles showing the average particle size B are the same, and the particles showing the average particle size A and the average particle size The number of components of the particles showing B does not matter.

The average particle size A and the average particle size B are parallel to the horizontal axis indicating that the value on the vertical axis is 3% by creating a line graph of the frequency distribution data according to the procedure for determining the value of Y (μm) described above. When the number of intersections between a straight line and the line graph is four or more, it can be determined by the following procedure. First, the portion where the value on the vertical axis is 3% or more at the peak between the first intersection and the second intersection counting from the smallest particle size is specified. Then, the same procedure is repeated for the peak between the third intersection and the fourth intersection, and thereafter, the same procedure is repeated until the peak between the last previous intersection and the last intersection is reached. .. After that, the "largest peak" and the "second largest peak" are identified by comparing the area of the portion where the value on the vertical axis is 3% or more for each obtained peak, and the frequency is highest in the largest peak. The particle size is defined as the average particle size A, and the particle size having the highest frequency at the second largest peak is defined as the average particle size B. At this time, if there are a plurality of particle sizes having the highest frequency at each peak, the average value thereof can be set to the average particle size A or the average particle size B.

The values of the average particle diameter A and the average particle diameter B in the film of the present invention are not particularly limited as long as the effects of the present invention are not impaired, but from the viewpoint of achieving both the formation of convex portions and the reduction of adhesion to flat objects, on the other hand. Is preferably 20 μm or more and 80 μm or less, and more preferably 40 μm or more and 80 μm or less. From the same viewpoint, the other is preferably 0.10 μm or more and 6.00 μm or less, and more preferably 0.10 μm or more and 1.00 μm or less. By setting the average particle size of the two types of particles contained in the adhesive layer to the above-mentioned preferable range, the particles having a large particle size contribute to the formation of the convex portion, and the particles having a small particle size provide adhesion to a flat object. Since it contributes to lowering, it is possible to more easily achieve both adhesion to cloth and the like and handleability.

The film of the present invention has an X / Z of 0.1 or more and 2.0 or less when the thickness of the adhesive layer is X μm and the average particle size of the average particle size A and the average particle size B is Z μm. It is preferably 0.5 or more and 2.0 or less, more preferably 0.5 or more and 1.5 or less, and particularly preferably 0.5 or more and 1.0 or less. By setting X / Z to 0.1 or more, it is possible to reduce the functional deterioration of the adhesive layer due to falling off of particles, etc., and by setting X / Z to 2.0 or less, the thickness of the adhesive layer becomes excessive. It does not become large, and it becomes easy to impart a convex portion having a height of 20 μm or more to the surface of the adhesive layer. When the adhesive layer is located on the outermost layers on both sides, it is sufficient that X / Z is 0.1 or more and 2.0 or less in at least one of the adhesive layers.

(Surface structure of film)
It is important that the film of the present invention has a convex portion having a height of 20 μm or more on the surface of the adhesive layer from the viewpoint of achieving both adhesion to cloth and the like and handleability. If there is one surface that meets the above requirements, the other surface is not particularly limited.

The method for forming a convex portion having a height of 20 μm or more on the surface of the adhesive layer is not particularly limited as long as the effect of the present invention is not impaired, and for example, the average particle size (Y or Z) of the particles is set within the above-mentioned preferable range. There is a method of adjustment. Specifically, the height of the convex portion can be increased by increasing the average particle size (Y or Z) of the particles within the above-mentioned preferable range.

Further, in the film of the present invention, it is important that the area ratio of the convex portion to the entire surface is 2% or more and 20% or less from the viewpoint of achieving both adhesion to cloth and the like and handleability. The term "surface" as used herein means the surface of the adhesive layer when the adhesive layer is located on one of the outermost surfaces, and means the surface of at least one adhesive layer when a plurality of adhesive layers are present. That is, a layer containing particles and having a convex portion having a height of 20 μm or more on the surface is located on the outermost surfaces on both sides, and the area ratio of the convex portion on one surface is 2% or more and 20% or less, and the other. Even when the area ratio of the convex portion on the surface of the surface is 2% or more and 20% or less, it can be considered that "the area ratio of the convex portion in the entire surface is 2% or more and 20% or less".

If the area ratio of the convex portion to the entire surface is 2% or more, unevenness having a height sufficient to improve the handleability is formed on the film surface, and the area ratio of the convex portion to the entire surface is 20% or less. If this is the case, the effect of improving the adhesion can be obtained by engaging the unevenness of the film with the unevenness of the cloth or the like. From the above viewpoint, the area ratio of the convex portion to the entire surface is more preferably 4% or more and 15% or less, further preferably 4% or more and 14% or less, and particularly preferably 7% or more and 14% or less.

As a means for achieving such an aspect, a method of adjusting the amount of particles in the adhesive layer is preferable. More specifically, by increasing the amount of particles having an average particle size of 20 μm or more and 80 μm or less, preferably 40 μm or more and 80 μm or less contained in the adhesive layer, the area ratio of the convex portion to the entire surface can be increased. ..

A method of measuring the height of the convex portion and the area ratio of the convex portion to the entire surface will be described with reference to the drawings. FIG. 1 is an enlarged top view showing a film according to an embodiment of the present invention. First, an arbitrary position on the surface of the adhesive layer is observed with a laser electron microscope having a surface shape measuring function. Next, when the position data in the height direction of the obtained image is acquired every 2 μm, the position having the largest distribution is set as the base surface (reference numeral 1), and the portion having a height of 20 μm or more with respect to the base surface. Is a convex portion (reference numeral 2). For each of the convex parts of the obtained image, draw a square or rectangle so as to completely surround the convex part and minimize the area, and in the case of a square, the sum of the squared values of one side, or a rectangle. In the case of, the sum of the squared values of the average values of the lengths of the long side and the short side is defined as the area of the convex portion. Next, the value obtained by dividing the area of the convex portion by the observed image area is taken as the occupied area of the convex portion in the field of view. This measurement is performed 10 times at different observation positions, the average value of the occupied area of the convex portion in the visual field is obtained, and this is taken as the area ratio (%) of the convex portion in the entire surface.

(Young's modulus of film)
The film of the present invention has a maximum Young's modulus of 0.05 MPa or more and 2.00 MPa or less in order to maintain the mechanical properties of the film and to ensure the followability to the cloth or the like when the film is brought into close contact with the cloth or the like. It is important that By setting the Young's modulus of the film to 0.05 MPa or more, the handleability of the film is improved. On the other hand, by setting the Young's modulus of the film to 2.00 MPa or less, the adhesion to the cloth or the like and the followability to the cloth or the like are improved.

The method for adjusting the Young's modulus of the film is not particularly limited as long as the effect of the present invention is not impaired, but a method for adjusting the content of the filler in the base material layer, a thickness ratio between the base material layer and the adhesive layer (group). A method of adjusting the thickness of the material layer / the thickness of the adhesive layer), a method of adjusting the resin composition of the base material layer and the adhesive layer, and the like can be mentioned. Specifically, Young's modulus can be increased by increasing the content of the filler in the base material layer or increasing the thickness of the base material layer / the thickness of the adhesive layer. From the above viewpoint, the more preferable range of the maximum value of Young's modulus is 0.05 MPa or more and 1.00 MPa.

A method for measuring the maximum value of Young's modulus of a film will be described with reference to FIG. 2, which is a schematic diagram showing a measurement direction of Young's modulus. First, a sample of 100 mm (width direction) × 10 mm (longitudinal direction) is prepared, and under the conditions of tensile strength of 200 mm / min, temperature of 23 ° C., and humidity of 65% RH, in the width direction according to ASTM-D882: 1990 (FIG. The Young's modulus of 4-4') in 2 is measured. The same measurement is repeated 5 times, and the average value of the obtained values is defined as Young's modulus in the width direction. Subsequently, the sample is cut out in the same manner so that the direction (5-5'in FIG. 2) rotated clockwise by 15 ° in the film plane from the width direction is the measurement direction, and the measurement is performed in the same manner. After that, as shown in FIG. 2, the measurement direction is shifted clockwise by 15 ° (6-6'→ 10-10' (longitudinal direction) in FIG. 2), and Young's modulus is measured in the same manner. The values of Young's modulus in the seven directions thus obtained are compared, and the largest value is taken as the maximum value of Young's modulus of the film. When the width direction and the longitudinal direction cannot be specified, the initial measurement direction can be arbitrarily determined, and the maximum value of Young's modulus of the film can be determined by the same procedure. Here, the longitudinal direction means the direction in which the film travels in the manufacturing process (in the case of a roll, the winding direction), and the width direction means a direction orthogonal to the longitudinal direction in the film plane.

(Film manufacturing method)
The method for producing the film of the present invention will be specifically described below. However, the method for producing a film of the present invention is not limited to this.

As a method for obtaining a molten resin composition for obtaining each layer (base material layer, adhesive layer, etc.) constituting the film of the present invention, a melt-kneading method for producing a composition by melt-kneading each component is used. Is preferable. The mixer for performing melt-kneading is not particularly limited, and a known mixer such as a kneader, a roll mill, a Banbury mixer, a single-screw or twin-screw extruder can be used. Above all, from the viewpoint of productivity, it is preferable to use a single-screw or twin-screw extruder.

Next, the molten resin composition obtained by the above method is laminated by a known laminating device, and an unoriented film is produced by a known film forming method such as an inflation method, a tubular method, or a T die casting method. Can be done. Further, from the viewpoint of improving mechanical properties, weight reduction, and moisture permeability, the non-oriented film obtained may be uniaxially or biaxially stretched, if necessary. Stretching can be performed by using the difference in peripheral speed of the rolls, or by using a tenter oven or the like.

Further, as another method, a method of extruding a composition for obtaining an adhesive layer on a sheet corresponding to a base material layer using a T-die or the like to form an adhesive layer, or an adhesive layer solubilized with a known solvent or the like is used. It is also possible to use a method of applying the composition for obtaining to the base material layer and drying, a method of separately forming a film corresponding to the base material layer and a sheet for obtaining the adhesive layer, and then heat laminating. .. Even when such a method is used, the film can be appropriately stretched.

The film thus obtained is wound as an intermediate product roll or a final product roll after cutting and removing the edge portions at both ends in the width direction, if necessary. When the film is wound as an intermediate product roll, the final product roll can be obtained by further unwinding the film from the intermediate product roll, cutting the film in parallel with the longitudinal direction so as to have a desired width, and winding the film. The final product roll obtained from one intermediate product roll may be one or a plurality of rolls.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto.

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

(1) Film Thickness A sample piece is cut out from the center portion in the width direction of the film, and a longitudinal-thickness direction cross section (hereinafter, may be referred to as a film cross section) of the sample piece is used as an observation surface using an ultramicrotome. As described above, ultrathin sections were collected at a knife inclination angle of 3 ° and -100 ° C. Next, a scanning electron microscope (S-3400N manufactured by Hitachi High-Technologies Corporation) was used to take a photograph of the cross section of the film at a magnification of 500 times, and the length measurement function of the microscope was used to determine the thickness of the portion not raised by particles. It was measured. The measurement was performed 10 times at different observation points, and the average value of the obtained values was taken as the film thickness (μm).

(2) Maximum Young's Modulus A method for measuring the maximum Young's modulus of a film will be described with reference to FIG. 2, which is a schematic diagram showing a measurement direction of Young's modulus. First, a sample of 100 mm (width direction) x 10 mm (longitudinal direction) is prepared, and a tensile tester (Tensilon type) manufactured by Orientec Co., Ltd. is used under the conditions of tensile strength 200 mm / min, temperature 23 ° C., and humidity 65% RH. Then, the Young's modulus in the width direction (4-4'in FIG. 2) was measured according to ASTM-D882: 1990. The same measurement was repeated 5 times, and the average value of the obtained values was taken as the Young's modulus in the width direction. Subsequently, the sample was cut out in the same manner so that the direction (5-5'in FIG. 2) rotated clockwise by 15 ° in the film plane from the width direction was the measurement direction, and the measurement was performed in the same manner. After that, as shown in FIG. 2, the measurement direction was shifted clockwise by 15 ° (6-6'→ 10-10' (longitudinal direction) in FIG. 2), and Young's modulus was measured in the same manner. The values of Young's modulus in the seven directions thus obtained were compared, and the largest value was taken as the maximum value of Young's modulus of the film.

(3) Ratio of the area of particles to the outermost surface An arbitrary position on the surface of the adhesive layer was observed with a laser electron microscope (VK-X100, manufactured by KEYENCE CORPORATION) having a surface shape measuring function. Next, when the position data in the height direction (thickness direction) of the obtained image is acquired every 2 μm, the position having the largest distribution is set as the base surface, and the portion having a height of 20 μm or more from the base surface is convex. It was a department. For each convex part in the obtained image, draw a square or rectangle so as to completely surround the convex part and minimize the area, and in the case of a square, the sum of the squared values of one side, and also In the case of a rectangle, the sum of the squares of the average lengths of the long and short sides is the area of the convex part in the visual field, and the area of the convex part in the visual field divided by the observed image area is the convex part in the visual field. Occupied area. The measurement was performed 10 times at different observation positions, and the average value of the obtained values was taken as the area (%) of the convex portion occupying the entire surface.

(4) 90 degree peel strength against cloth or the like A film was cut into strips of 100 mm × 10 mm and used as evaluation samples. The evaluation sample was attached to a cloth or the like (“Heise” (registered trademark) gauze NT-4 (manufactured by Asahi Kasei Co., Ltd.)) by reciprocating a laminating roller with a load of 2 kg once, and assuming a tensile speed of 300 mm / min, JIS Z 0237: The peel strength between the film and the cloth or the like was measured by the method specified in 2009. Sampling and measurement were performed 5 times for each film, and the average value of the obtained 5 values was classified according to the following criteria. If it is C or more, it is judged that the adhesiveness is such that there is no problem in practical use.
S: 400 mN / cm or more.
A: 200 mN / cm or more and less than 400 mN / cm.
B: 100 mN / cm or more and less than 200 mN / cm.
C: 50 mN / cm or more and less than 100 mN / cm.
D: Less than 50 mN / cm.

(5) 90-degree peel strength against flat objects Measured and evaluated in the same way as 90-degree peel strength against cloth, etc., except that the adherend is a polyethylene terephthalate film (“Lumilar” (registered trademark) S10 (manufactured by Toray Industries, Inc.)). did. If it is C or higher, it is judged that the handling property is not a problem in practical use.
S: Less than 0.1 N / cm.
A: 0.1 N / cm or more and less than 0.2 N / cm.
B: 0.2 N / cm or more and less than 0.5 N / cm.
C: 0.5 N / cm or more and less than 2.0 N / cm.
D: 2.0 N / cm or more.

(6) Blocking resistance The film was cut out to a size of 100 mm × 100 mm. The adhesive layer and the base material layer of the cut out film were laminated alternately and pressed at a temperature of 50 ° C. at a pressure of 1 MPa for 3 hours to prepare a sample for evaluation. The peel strength of the superposed evaluation samples was measured by the method specified in JIS Z 0237: 2009. The measurement was performed 5 times, and the average value of the obtained values was classified according to the following criteria, and if it was C or higher, it was judged that there was no practical problem.
S: Less than 0.5 N / cm.
A: 0.5 N / cm or more and less than 1.0 N / cm.
B: 1.0 N / cm or more and less than 2.0 N / cm.
C: 2.0 N / cm or more and less than 2.5 N / cm.
D: 2.5 N / cm or more (including cases where the film cannot be broken or peeled off).

(7) Followability to cloth, etc. The film was cut into strips of 100 mm × 10 mm and used as evaluation samples. The evaluation sample was attached to a cloth or the like (“Heise” (registered trademark) gauze NT-4 (manufactured by Asahi Kasei Corporation)) by reciprocating a laminating roller with a load of 2 kg once to prepare an evaluation sample. The evaluation sample was placed with the film on the upper side and the non-woven fabric on the lower side, and bent 90 degrees to the lower side. At this time, the presence or absence of peeling of the film was visually confirmed. The results were classified according to the following criteria. If it is A, it can be judged that there is no practical problem.
A: There was no peeling or floating of the film.
B: The film peeled off or floated.

(8) Average particle size of particles A film was cut out to a size of 50 mm × 50 mm and used as an evaluation sample. The evaluation sample was immersed in 100 g of toluene at 25 ° C. for 30 minutes with stirring to dissolve the adhesive layer, and a toluene solution containing particles was obtained. Next, the volume-based particle size distribution of the obtained toluene solution was measured using a laser diffraction type particle size distribution measuring device (Nikkiso Co., Ltd., Microtrac MT-300-II). After that, from the obtained volume-based particle size distribution, frequency distribution data with the vertical axis representing the frequency percentage (%) and the horizontal axis representing the particle size (μm) was acquired and made into a line graph (interval on the horizontal axis at this time). Is 1 μm.), The number of intersections between the straight line parallel to the horizontal axis indicating that the value on the vertical axis is 3% and the line graph was confirmed. If there are two intersections, the most frequent particle size between the intersections is Y (μm).

When there were four intersections, the average particle size A and the average particle size B were determined by the following procedure. First, at the peak between the first intersection and the second intersection counting from the smallest particle size, the portion where the value on the vertical axis is 3% or more was specified. Then, the same procedure was repeated for the peak between the third intersection and the fourth intersection. After that, the "largest peak" and the "second largest peak" are identified by comparing the area of the portion where the value on the vertical axis is 3% or more for each obtained peak, and the frequency is highest in the largest peak. The particle size was defined as the average particle size A, and the most frequent particle size at the second largest peak was defined as the average particle size B.

[Polyolefin-based resin of base material layer]
(A1) Low-density polyethylene (F200, manufactured by Sumitomo Chemical Co., Ltd.)
(A2) High-density polyethylene (HF560, manufactured by Japan Polyethylene Corporation)
(A3) Polypropylene (S131, manufactured by Sumitomo Chemical Co., Ltd.)
[Resin other than polyolefin resin of base material layer]
(B1) Block copolymer of methyl methacrylate and butyl acrylate (LA2330, manufactured by Kuraray Co., Ltd.)
(B2) Polybutylene succinate (FZ71, manufactured by Mitsubishi Chemical Corporation)
[Filler for base material layer]
(C1) Calcium carbonate (Softon 1000, manufactured by Shiraishi Calcium Co., Ltd.)
[Glidant for base material layer]
(D1) Stearic acid amide (fatty acid amide S, Kao Corporation)
[Thermoplastic resin of the adhesive layer]
(E1) Styrene / ethylene propylene / styrene block copolymer (2063, manufactured by Kuraray Co., Ltd.)
[Adhesive-imparting agent for adhesive layer]
(F1) Petroleum resin (P-140, manufactured by Arakawa Chemical Industry Co., Ltd.)
(F2) Terpene resin (PX-1250, manufactured by Yasuhara Chemical Co., Ltd.)
(F3) Rosin resin (A-100, manufactured by Arakawa Chemical Industry Co., Ltd.)
[Adhesive layer particles]
(G1) Calcium carbonate particles (BF-400, manufactured by Toyo Fine Chemical Co., Ltd.) Average particle size: 44 μm
(G2) Calcium carbonate particles (P-70, manufactured by Toyo Fine Chemical Co., Ltd.) Average particle size: 23 μm.
(G3) Calcium carbonate particles (P-30, manufactured by Toyo Fine Chemical Co., Ltd.) Average particle size: 5.6 μm.
(G4) Calcium carbonate particles (μ-POWDER 3S, manufactured by Bikita Powder Industry Co., Ltd.) Average particle size: 0.8 μm.
(G5) Calcium carbonate particles (CALSHITEC Vigot-15, manufactured by Shiraishi Kogyo Co., Ltd.) Average particle size: 0.15 μm
(Example 1)
The raw materials of the base material layer and the adhesive layer were each formulated as shown in Table 1 and supplied to a twin-screw extruder with a vacuum vent having a cylinder temperature of 190 ° C. and a screw diameter of 44 mm for melt-kneading, homogenizing, and then pelletizing. The obtained pellets are supplied to a single-screw extruder (L / D = 30 L represents the screw length and D represents the screw diameter), and the supply unit temperature is 150 ° C. and the subsequent temperatures are melted at 200 ° C. , A mirror surface drum (surface roughness: 0) whose temperature was controlled to 30 ° C. from a T die (lip gap: 1 mm) after being laminated so as to form a base material layer / adhesive layer in a feed block installed on the upper part of the die. .2s) The sheet was discharged onto the sheet. At that time, the film was obtained by niping with a silicone roll (nip pressure: 0.2 MPa). Table 1 shows the physical characteristics of the obtained film and the evaluation results.

(Examples 2 to 21, Comparative Examples 1 to 4)
A film was obtained in the same manner as in Example 1 except that the raw material formulations of the base material layer and the adhesive layer were as shown in Table 1. Table 1 shows the physical characteristics of the obtained film and the evaluation results.

The amount of resin component (mass%) of each layer was calculated assuming that the entire resin component in the layer was 100% by mass. The amount of other components in each layer was calculated with the entire resin component in the layer as 100 parts by mass. In Examples 19-21, X / Y is X / Z.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a film having mechanical properties necessary for use as a film and having excellent adhesion to cloth and the like and handleability. The film of the present invention is used for applications that require adhesion and handleability to cloth and the like, for example, medical / sanitary materials such as bed sheets, pillowcases, back sheets of absorbent articles such as sanitary napkins and paper diapers, and clothing for rainy weather. , Clothing materials such as gloves, garbage bags and compost bags, food bags such as vegetables and fruits, packaging materials such as bags for various industrial products, building materials such as buildings, houses and veneers, and in transport aircraft such as railroad vehicles, ships and aircraft. It can be preferably used as an interior material, a building material, etc.

1: Film 2: Base surface 3: Convex portion 4-4': Width direction 5-5': Direction rotated 15 ° clockwise with respect to the width direction in the film surface 6-6': 5 in the film surface Direction 7-7'clockwise rotated 15 ° with respect to -5': Direction 8-8' rotated 15 ° clockwise with respect to 6-6'in the film plane: 7-7 in the film plane 'Direction rotated 15 ° clockwise with respect to'9-9': Direction rotated 15 ° clockwise with respect to 8-8' in the film plane 10-10': Longitudinal direction

Claims (8)

It has a base material layer and an adhesive layer,
The maximum value of Young's modulus is 0.05 MPa or more and 2.00 MPa or less.
The base material layer contains more polyolefin resin than the adhesive layer, and the base material layer contains more polyolefin resin.
The adhesive layer is located on at least one of the outermost surfaces, contains particles, and has a convex portion having a height of 20 μm or more on the surface thereof.
Moreover, the film is characterized in that the area ratio of the convex portion to the entire surface is 2% or more and 20% or less. The first aspect of the present invention is characterized in that X / Y is 0.1 or more and 2.0 or less when the thickness of the adhesive layer is X μm and the average particle size of the particles contained in the adhesive layer is Y μm. The film described. When the frequency distribution was obtained at 1 μm intervals from the volume-based particle size distribution measured by the laser diffraction / scattering method of the particles contained in the adhesive layer, a plurality of peaks having a height of 3% or more existed.
When the particle size indicated by the largest peak is the average particle size A and the particle size indicated by the second largest peak is the average particle size B, the difference between the average particle size A and the average particle size B is 10 μm or more. The film according to claim 1, wherein the film is characterized by. When the thickness of the adhesive layer is X μm and the average particle size having a larger value among the average particle size A and the average particle size B is Z μm, X / Z is 0.1 or more and 2.0 or less. The film according to claim 3, which is characterized. The film according to any one of claims 1 to 4, wherein the particles contain inorganic particles. The invention according to any one of claims 1 to 5, wherein when the rosin-based resin, the terpene-based resin, and the petroleum-based resin are used as the adhesive resin, the adhesive layer contains at least one kind of adhesive resin. Film. The film according to claim 6, wherein the adhesive layer contains more of the adhesive resin than the base material layer. Claim 6 or 7 is characterized in that the content of the adhesive resin in the adhesive layer is 10% by mass or more and 50% by mass or less when the total resin component in the adhesive layer is 100% by mass. The film described in.

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