Vinyl chloride resin sheet material, laminated sheet, and method for manufacturing vinyl chloride resin sheet material

Abstract

The present invention provides a vinyl chloride resin sheet-like material, a laminated sheet equipped with a vinyl chloride resin sheet-like material, and a method for manufacturing a vinyl chloride resin sheet-like material, which can be manufactured at a lower cost without significantly impairing its coating properties and physical properties. [Solution] The vinyl chloride resin sheet 100 has a vinyl chloride resin layer 10, and the vinyl chloride resin layer contains vinyl chloride resin particles 20 with an average particle diameter of 40 μm to 200 μm and fiber powder 30 with a major diameter of 40 μm to 200 μm, the ratio of the mass of vinyl chloride resin particles to the mass of fiber powder is 90:10 to 50:50, and the total mass of vinyl chloride resin particles and fiber powder is 40 parts by mass or less with respect to 100 parts by mass of vinyl chloride resin constituting the vinyl chloride resin layer. The laminated sheet comprises a vinyl chloride resin sheet and a base material.

Description

Technical Field

[0001] The present invention relates to a vinyl chloride resin sheet-like material, a laminated sheet, and a method for producing a vinyl chloride resin sheet-like material.

Background Art

[0002] A vinyl chloride resin sheet-like material, which is a sheet-like material produced using a vinyl chloride resin, is widely used in various applications such as surface materials for synthetic leather and artificial leather, and building materials such as wallpapers and floor materials. These vinyl chloride resin sheet-like materials are produced, for example, using a paste vinyl chloride resin.

[0003] Specifically, Patent Document 1 discloses a method for producing a decorative floor material including a vinyl chloride resin layer formed by applying a sol-like paste vinyl chloride resin containing a white pigment onto the surface of a base material made of a glass fiber fabric.

[0004] Generally, a paste vinyl chloride resin refers to spherical fine particles polymerized by a polymerization method such as micro-suspension polymerization or emulsion polymerization, which are easily dispersed in a plasticizer to form a sol state and become a gel state at normal temperature or under heating. The above-mentioned fine particles are not limited to a specific particle size range. For example, they have a smaller particle size than the general-purpose vinyl chloride particles described later, with a primary particle size of several μm or less, and more preferably a primary particle size of 0.1 μm or more and 2 μm or less, which are widely used. The paste vinyl chloride resin related to the present invention described later is also defined in the same manner as above.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Incidentally, in addition to the paste vinyl chloride resins mentioned above, vinyl chloride resin particles with a primary particle size of several tens of micrometers to several hundred micrometers (hereinafter sometimes referred to as general-purpose PVC particles) are also known as vinyl chloride resin materials. General-purpose PVC particles are easier to manufacture and relatively cheaper than paste vinyl chloride resins.

[0007] Therefore, with the aim of reducing the cost of vinyl chloride resin sheets, the inventors attempted to manufacture sheet-like materials using a composition obtained by mixing a paste vinyl chloride resin with general-purpose vinyl chloride particles having a relatively large particle size. However, such compositions made it difficult to obtain good sheet-like materials due to poor coating properties, and the physical properties of the resulting sheet-like materials tended to be significantly inferior to those of sheet-like materials manufactured solely from paste vinyl chloride resin as the resin component.

[0008] The present invention has been made in view of the above problems, and aims to provide a vinyl chloride resin sheet-like material that can be manufactured at a low cost without significantly impairing its coating properties and physical properties, a laminated sheet equipped with the vinyl chloride resin sheet-like material, and a method for manufacturing the vinyl chloride resin sheet-like material. [Means for solving the problem]

[0009] The vinyl chloride resin sheet of the present invention has a vinyl chloride resin layer, and the vinyl chloride resin layer contains vinyl chloride resin particles with an average particle diameter of 40 μm to 200 μm and fiber powder with a major diameter of 40 μm to 200 μm, the ratio of the mass of the vinyl chloride resin particles to the mass of the fiber powder is 90:10 to 50:50, and the total mass of the vinyl chloride resin particles and the fiber powder is 40 parts by mass or less per 100 parts by mass of the vinyl chloride resin constituting the vinyl chloride resin layer.

[0010] The laminated sheet of the present invention is characterized by comprising a vinyl chloride resin sheet-like material of the present invention and a base material that supports the vinyl chloride resin sheet-like material.

[0011] A manufacturing method of the present invention for producing a vinyl chloride resin sheet-like material comprises: a sol member preparation step of preparing a paste-like sol member by adding a paste vinyl chloride resin, vinyl chloride resin particles with an average particle diameter of 40 μm or more and 200 μm or less, and fiber powder with a major axis of 40 μm or more and 200 μm or less to a plasticizer; a coating step of coating the paste-like sol member obtained in the sol member preparation step onto release paper or a substrate to obtain a presheet; and a gelling step of heating the presheet obtained in the coating step to gel the paste-like sol member constituting the presheet. [Effects of the Invention]

[0012] The vinyl chloride resin sheet material of the present invention having the above configuration can be manufactured at a lower cost without significantly impairing its coating properties and physical properties. Furthermore, the laminated sheet of the present invention comprises the vinyl chloride resin sheet material of the present invention, which is manufactured at a lower cost without significantly impairing its coating properties and physical properties, and enjoys the effects of the vinyl chloride resin sheet material of the present invention. In addition, the manufacturing method of the vinyl chloride resin sheet material of the present invention can produce a good quality sheet material at a lower cost without generating streaks or unevenness during coating. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic cross-sectional view of a vinyl chloride resin sheet-like material according to the first embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view of a vinyl chloride resin sheet-like material according to a second embodiment of the present invention. [Modes for carrying out the invention]

[0014] First, an overview of the vinyl chloride resin sheet-like material of the present invention will be described. In the following description, the vinyl chloride resin sheet-like material of the present invention may be referred to as the sheet-like material of the present invention. In relation to the present invention, the term "sheet-like material" refers to a thin molded product, and although the thickness is not particularly limited, it encompasses the concepts of films and sheets with a thickness of 0.05 mm or more and 3 mm or less. The sheet-like material of the present invention can be used as a single thin molded product, or it can form a resin layer laminated on any substrate.

[0015] The vinyl chloride resin sheet material of the present invention has a vinyl chloride resin layer, and the vinyl chloride resin layer contains vinyl chloride resin particles and fiber powder. The vinyl chloride resin particles have an average particle diameter of 40 μm to 200 μm, and the fiber powder has a major diameter of 40 μm to 200 μm. In the present invention, the ratio of the mass of vinyl chloride resin particles to the mass of fiber powder in the vinyl chloride resin layer is 90:10 to 50:50, and the total mass of vinyl chloride resin particles and fiber powder is adjusted to be 40 parts by mass or less per 100 parts by mass of vinyl chloride resin constituting the vinyl chloride resin layer. The sheet-like material of the present invention, having the above configuration, can be manufactured at a lower cost without significantly impairing the coating properties and physical properties compared to a vinyl chloride resin sheet-like material (hereinafter simply referred to as a conventional sheet-like material) that contains only paste-like vinyl chloride resin and does not contain vinyl chloride resin particles as a resin component. Specifically, the variation in physical properties described above in the present invention is evaluated by comparing the maximum breaking stress (MPa) of a conventional sheet and the sheet-like material of the present invention. Furthermore, in the present invention, coating properties are determined by whether or not streaks or uneven coating occur when a resin composition containing vinyl chloride resin is applied to any flat surface during the manufacture of the sheet-like material. In particular, when the coating thickness is 1 mm or less, and more especially when the coating thickness is 500 μm or less, the coating properties can be judged to be very good if no streaks or uneven coating occur during coating. The present invention will be described in more detail below.

[0016] [Vinyl chloride resin layer] The vinyl chloride resin layer is a series of resin layers composed of vinyl chloride resins, and the resin layer may be a non-foamed layer or a foamed layer.

[0017] The vinyl chloride resin layer in the present invention is preferably composed of, for example, a paste vinyl chloride resin. The paste vinyl chloride resin is composed of vinyl chloride resins which are spherical fine particles as described above, and becomes a paste state by being dispersed in a plasticizer and has excellent coatability. Therefore, the sheet-like material of the present invention can be preferably produced, for example, by a casting method.

[0018] The vinyl chloride resin in the present invention refers to a homopolymer of vinyl chloride, a copolymer of vinyl chloride and other copolymerizable monomers, or a mixture of these. The copolymer in the present invention refers to a copolymer mainly composed of vinyl chloride, specifically, a copolymer containing more than 50% by mass of structural units derived from vinyl chloride, and preferably contains 60% by mass or more. Examples of other copolymerizable monomers that can be contained in the copolymer include, but are not limited to, acrylic acid, methyl acrylate, methacrylic acid, vinyl acetate, vinylidene chloride, and the like.

[0019] [Vinyl chloride resin particles] The vinyl chloride resin particles in the present invention have an average particle diameter of 40 μm or more and 200 μm or less. By blending particles with an average particle diameter of 200 μm or less, good coatability is easily achieved, and physical properties comparable to those of conventional sheet-like materials are easily shown. From such a viewpoint, the average particle diameter of the vinyl chloride resin particles is preferably 180 μm or less, and more preferably 150 μm or less. Also, from the viewpoint of providing a vinyl chloride resin sheet-like material with reduced cost without significantly impairing coatability and physical properties, the average particle diameter of the vinyl chloride resin is 40 μm or more.

[0020] The vinyl chloride resin particles in the present invention are small particles as described above. The vinyl chloride resin particles may be spherical particles or non-spherical particles. Here, non-spherical particles include particles of any regular shape such as elliptical or cylindrical shapes and irregular random-shaped particles. In the present invention, even when non-spherical particles, particularly irregular random-shaped particles, are used as the vinyl chloride resin particles, a desired vinyl chloride resin sheet-like material can be provided. The average particle diameter of the vinyl chloride resin particles refers to the diameter of the spherical particles when the particles are spherical, and the major axis of the non-spherical particles when the particles are non-spherical. In the present invention, the average particle diameter of the vinyl chloride resin particles is determined by laser diffraction / scattering particle size distribution measurement. Specifically, using Partica mini LA-350 manufactured by Horiba, Ltd., 2 mg of vinyl chloride resin particles are dispersed in 2 mL of isopropyl alcohol, put into the measuring instrument, and then ultrasonic treatment is performed for 1 minute for measurement. Incidentally, the average particle diameter of the vinyl chloride resin particles may be a measured value obtained by observing the cross-section of the sheet-like material with a microscope instead of the laser diffraction / scattering particle size distribution measurement described above.

[0021] The method for obtaining the vinyl chloride resin particles is not particularly limited. For example, commercially available products of the general-purpose PVC particles described above having a desired average particle diameter can be used as the vinyl chloride resin particles in the present invention. Also, the vinyl chloride resin molded product may be pulverized until it becomes particles showing an average particle diameter within a desired range, or the vinyl chloride resin molded product may be pulverized and particles showing an average particle diameter within a desired range may be selected by a sieve or the like to prepare the vinyl chloride resin particles. The vinyl chloride resin molded product used for the preparation of the vinyl chloride resin particles may be a molded product manufactured for the preparation or a recovered product.

[0022] The shape of the vinyl chloride resin molded article described above is not particularly limited and may be a sheet or a molded article of any shape. Preferably, the vinyl chloride resin molded article contains more than 50% by mass of vinyl chloride resin, more preferably 70% by mass or more, even more preferably 90% by mass or more, and is particularly preferably substantially 100% by mass of vinyl chloride resin.

[0023] The above-mentioned recovered materials broadly include recovered components from used vinyl chloride resin sheets or molded vinyl chloride resin products, or scraps containing vinyl chloride resin generated during the manufacturing process. The above-mentioned collected materials can be obtained from used products, etc., and can be recycled as polyvinyl chloride resin, but the following are examples of components. • Used products consisting solely of polyvinyl chloride resin • Vinyl chloride resin components isolated from any used product • A composite member consisting of a polyvinyl chloride resin component isolated from any used product and other components. • Vinyl chloride resin components, which are scraps generated during manufacturing. • Composite components made from vinyl chloride resin scraps generated during manufacturing and other materials. Specific examples of used products include used vinyl chloride resin sheets (e.g., desk mats, table mats), vinyl chloride resin films (e.g., agricultural films), vinyl chloride resin components isolated from furniture and vehicles, and laminates comprising a base material and vinyl chloride resin laminated on the base material (e.g., synthetic leather, artificial leather, wallpaper, flooring materials).

[0024] In the present invention, the use of recycled materials in the preparation of vinyl chloride resin particles is preferable not only from the standpoint of reducing the cost of the sheet-like material provided, but also from the viewpoint of carbon neutrality, and can satisfy social demands as an environmentally friendly product. More specifically, in one aspect of the present invention, a vinyl chloride resin sheet comprising the following first element and / or the following second element is preferred. Details of the fiber powder described in the second element will be described later. First element: The vinyl chloride resin particles contained in the vinyl chloride resin layer are recycled material prepared from recovered materials. Second element: The vinyl chloride resin particles and fiber powder contained in the vinyl chloride resin layer are recycled materials prepared from recovered products comprising a substrate composed of fibers and a vinyl chloride resin layer laminated on the substrate.

[0025] In the second element described above, by crushing the recycled material and obtaining pulverized material of a desired diameter range, vinyl chloride resin particles and fiber powder used in the present invention can be prepared simultaneously. That is, embodiments of the present invention comprising the second element tend to be particularly superior in terms of cost reduction and carbon neutrality of the sheet material provided, as well as in terms of maintaining physical properties compared to conventional sheet materials, and are therefore preferred.

[0026] [Fiber powder] The sheet-like material of the present invention contains fiber powder with a major axis of 40 μm to 200 μm. As described above, when paste vinyl chloride resin and vinyl chloride resin particles are used in combination, the coating properties and physical properties tend to be significantly impaired compared to conventional sheet-like materials. In contrast, by mixing in fiber powder with a major axis of 40 μm to 200 μm, the above-mentioned deterioration of coating properties and physical properties can be prevented. If the major axis of the fiber powder is less than 40 μm or more than 200 μm, the effect of preventing the above-mentioned deterioration of coating properties and physical properties is not easily achieved.

[0027] The aspect ratio of the fiber powder in this invention is not particularly limited, but it is preferably 1.0 or higher, and more preferably 2.0 or higher.

[0028] The major axis of the fiber powder in this invention is determined by laser diffraction-scattering particle size distribution measurement. Specifically, using a Partica mini LA-350 manufactured by Horiba, Ltd., 2 mg of fiber powder is dispersed in 2 mL of isopropyl alcohol, placed in the measuring instrument, and then subjected to ultrasonic treatment for 1 minute before measurement. Alternatively, the major axis of the fiber powder may be measured by observing the cross-section of a sheet-like material with a microscope instead of the laser diffraction-scattering particle size distribution measurement described above.

[0029] The fiber powder in this invention may be any or a combination of natural fibers, chemical fibers, or inorganic fibers exhibiting a desired range of major diameters. The above-mentioned natural fibers may be plant fibers, animal fibers, or a combination thereof. Examples of plant fibers include cotton and fibers made primarily from pulp (paper), while examples of animal fibers include silk and fibers made primarily from wool, but are not limited to these. The above-mentioned chemical fibers may be synthetic fibers, regenerated fibers, or a combination thereof. Examples of synthetic fibers include polyester fibers and rayon fibers, while examples of regenerated fibers include fibers made primarily from rayon and Tencel, but are not limited to these. The inorganic fibers mentioned above include, but are not limited to, glass fibers.

[0030] The fiber powder may be made by preparing unused fibers to a desired major diameter (virgin fiber powder), or by preparing fibers obtained from recovered fiber products or products containing fibers to a desired major diameter (recycled fiber powder), or it may be fiber powder in recycled material prepared from crushed recovered material comprising a base material composed of fibers as shown in the second element described above and a vinyl chloride resin layer laminated on the base material. The recycled material may also include vinyl chloride resin particles along with the fiber powder. The fiber powder in the present invention may be other than those described above, and may be, for example, fiber powder derived from scraps generated during the manufacture of a laminate comprising a fiber layer and a vinyl chloride resin layer laminated on the fiber layer.

[0031] [Ratio of the mass of vinyl chloride resin particles to the mass of the fiber powder] In this invention, the ratio of the mass of vinyl chloride resin particles to the mass of fiber powder is adjusted to be between 90:10 and 50:50. If the mass ratio of fiber powder exceeds 50 in the above ratio, the texture of the sheet material may not be maintained well. On the other hand, if the ratio of vinyl chloride resin particles exceeds 90 in the above ratio, it becomes difficult to maintain good coating properties and physical properties.

[0032] [Total mass of vinyl chloride resin particles and the fiber powder] In this invention, the total mass of vinyl chloride resin particles and fiber powder is adjusted to be 40 parts by mass or less per 100 parts by mass of vinyl chloride resin constituting the vinyl chloride resin layer. This allows for good coating properties and physical properties to be exhibited even when a component constituting the vinyl chloride resin layer (for example, paste vinyl chloride resin) and vinyl chloride resin particles are used in combination. On the other hand, there is no particular lower limit to the total mass of the vinyl chloride resin particles and the fiber powder, but from the viewpoint of reducing the amount of material used to constitute the vinyl chloride resin layer (for example, paste vinyl chloride resin) and significantly reducing costs, it is preferable that it be 5 parts by mass or more, and more preferably 10 parts by mass or more.

[0033] [Sheet-like material] Embodiments of the sheet-like material of the present invention, configured as described above, will be explained with reference to Figures 1 and 2. Note that the embodiments shown in Figures 1 and 2 are schematic cross-sectional views and do not limit the sheet thickness, average particle diameter of resin particles, major axis dimensions of fiber powder, dimensional ratios, or mixing ratio of resin particles to fiber powder in the present invention.

[0034] (First Embodiment) Figure 1 shows a schematic cross-sectional view of a sheet-like material 100, which is a first embodiment of the present invention. The sheet-like material 100 is a single sheet-like material, and contains vinyl chloride resin particles 20 and fiber powder 30 in a series of vinyl chloride resin layers.

[0035] Physical properties: The physical properties of the sheet-like material 100 are specifically determined by the maximum breaking stress (MPa) measured according to JIS K 6772:1994. The maximum breaking stress of the sheet-like material of the present invention is not limited to a specific numerical range, but rather should be comparable to the maximum breaking stress (MPa) of a reference sheet-like material (conventional sheet-like material) manufactured in the same manner except that it does not contain vinyl chloride resin particles and fiber powder. Comparability means that the decrease in the maximum breaking stress (MPa) of the sheet-like material 100 compared to the maximum breaking stress (MPa) of the reference sheet-like material is preferably less than 20%, and preferably less than 10%.

[0036] Thickness: The thickness of the sheet-like material 100 is not particularly limited and can be determined appropriately depending on the application, but for example, it can be 50 μm or more and 200 μm or less. Furthermore, from the viewpoint of finishing the surface of the sheet-like material 100 smoothly, it is preferable that the average particle size of the vinyl chloride resin particles in the sheet-like material 100 is such that the thickness of the sheet-like material (μm) : the average particle size of the vinyl chloride resin particles (μm) = 1:1 to 1:0.2.

[0037] As a modified example of the sheet-like material 100 (not shown), the present invention also encompasses a vinyl chloride resin sheet-like material which is a foamed sheet containing a large number of air bubbles. In the present invention, a foamed sheet refers to a vinyl chloride resin sheet-like material containing a large number of air bubbles, wherein the walls separating the air bubbles are composed of a vinyl chloride resin layer, and vinyl chloride resin particles and fiber powder are contained between the air bubbles.

[0038] (Second embodiment) The sheet-like material of the present invention is not limited to being used alone. The present invention also includes laminated sheets, which are constructed by laminating and supporting the vinyl chloride resin layer according to the present invention on any substrate. For example, as shown in Figure 2, the present invention encompasses a sheet-like material which is a laminated sheet 200 comprising a vinyl chloride resin layer 150 directly or indirectly laminated onto a base material 40. Specifically, Figure 2 illustrates a laminated sheet 200 in which a vinyl chloride resin layer 150 is directly laminated onto a base material 40. The vinyl chloride resin layer 150 in this embodiment can be configured in the same way as the sheet-like material 100 in the first embodiment.

[0039] Base material: The base material 40 can be any member capable of supporting the sheet-like material of the present invention laminated on the base material. For example, the base material can be a woven fabric, a knitted fabric, a nonwoven fabric, a synthetic resin film, or a synthetic resin sheet. The fibers that make up the base material described above may be natural fibers or artificial fibers. The choice of which material the base material 40 is made of can be appropriately determined depending on the application of the laminated sheet 200. For example, when the laminated sheet 200 is used as synthetic leather or artificial leather, the vinyl chloride resin layer 150 constitutes the surface of the synthetic leather. The base fabric 40 should be made of a material that is suitable as the base material (base fabric) for synthetic leather. When the laminated sheet 200 is used as wallpaper or flooring, the vinyl chloride resin layer 150 should be placed on the side that is visible during use (the surface side).

[0040] Thickness: The thickness of the laminated sheet 200 and the thickness of the vinyl chloride resin layer 150 provided on the laminated sheet 200 are not particularly limited. The thickness of the laminated sheet 200 should be designed to be, for example, about 1000 μm to 3000 μm, and the thickness of the vinyl chloride resin layer 150 should be about 100 μm to 2500 μm.

[0041] Although Figure 2 shows a configuration in which one vinyl chloride resin layer 150 is provided in the laminated sheet 200, the laminated sheet (sheet-like material) of the present invention also includes configurations in which two or more vinyl chloride resin layers 150 are laminated. In this case, each of the two or more laminated vinyl chloride resin layers 150 may be composed of the same composition or different compositions, and the ratio of the compositions constituting each vinyl chloride resin layer 150 may be the same or different.

[0042] Although not shown in the illustration, as a modified example of the laminated sheet 200, an arbitrary layer such as a protective layer may be further laminated on the surface of the laminated sheet 200 shown in Figure 2 on the side with the vinyl chloride resin layer 150, or an arbitrary layer may be further laminated between the vinyl chloride resin layer 150 and the base material 40. Although Figure 2 shows a non-foamed sheet-like material 100, a foamed sheet-like material may be laminated onto the base material 40 instead of the non-foamed sheet-like material 100.

[0043] [Method for manufacturing vinyl chloride resin sheet material] Next, the method for producing a vinyl chloride resin sheet-like material of the present invention (hereinafter also simply referred to as the "production method of the present invention") will be described. The production method of the present invention is a preferred example of the production method of the sheet-like material of the present invention, but it is not limited to the production method of the sheet-like material of the present invention. The manufacturing method of the present invention comprises a sol component preparation step, a coating step, and a gelation step. Details of these steps are described below.

[0044] (Soluble component preparation process) The sol component preparation step involves preparing a paste-like sol component by adding a plasticizer, a paste vinyl chloride resin, vinyl chloride resin particles with an average particle diameter of 40 μm to 200 μm, and fiber powder with a major axis of 40 μm to 200 μm.

[0045] The plasticizers mentioned above can be appropriately selected from those generally used when mixing with paste vinyl chloride resins to prepare paste-like sol components, but specifically, phthalate esters are preferably used. Examples of phthalate esters include dioctyl phthalate such as bis(2-ethylhexyl) phthalate and dibutyl phthalate.

[0046] For paste vinyl chloride resin, vinyl chloride resin particles, and fiber powder, refer to the description of the sheet-like material of the present invention described above as appropriate.

[0047] When manufacturing a sheet-like material that is a foamed sheet, a foaming agent is added to the paste-like sol component described above, and an inorganic filler may also be added as an option. The above-mentioned foaming agent can be appropriately selected from foaming agents generally used to foam vinyl chloride resins, but specific examples include azodicarbonamide, azobisisobutyronitrile, barium azodicarboxylate, N,N'-dinitropentamethylenetetramine, p,p'-oxybis(benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide, etc. Examples of the inorganic fillers mentioned above include magnesium hydroxide, aluminum hydroxide, talc, kaolin, calcium carbonate, calcium oxide, barium sulfate, and barium carbonate.

[0048] (Other additives) The above paste-like sol member may further contain one or more additives selected from lubricants, inorganic fillers, etc. Examples of lubricants include polyoxyethylene polyoxypropylene decyl ether and olefin components having 7 to 24 carbon atoms.

[0049] (Coating process, gelling process) The coating process involves applying the paste-like sol component onto a release paper or substrate to obtain a pre-sheet. The pre-sheet, coated to a thin thickness by the coating process, is then gelled by the gelling process. The gelling process involves heating the pre-sheet to gel the paste-like sol component that constitutes the pre-sheet. This gelling process causes the pre-sheet to form a sheet. The gelling in the gelling process occurs due to the curing of the vinyl chloride resin. Therefore, the temperature at which the pre-sheet is heated should be adjusted to a temperature at which the vinyl chloride resin contained in the pre-sheet can be cured.

[0050] The above coating and gelling processes can be carried out, for example, by a casting method. The casting method, as used herein, is a method of obtaining a pre-sheet by directly or indirectly coating a paste-formed material with a plasticizer onto a flat surface such as a flat drum or release paper placed on the drum, and then heating the pre-sheet to obtain a sheet-like material. When manufacturing the sheet-like material of the present invention as a single unit, the paste-like sol member can be directly applied to the flat surface. When manufacturing a laminated sheet comprising the sheet-like material of the present invention, the single sheet-like material described above can be manufactured, and then the sheet-like material can be directly or indirectly laminated and bonded to a substrate to produce a laminated sheet. Alternatively, the above pre-sheet can be manufactured by a casting method, and the substrate can be laminated onto the pre-sheet and then heated, or the substrate can be laminated after the pre-sheet has been heated, to produce a laminated sheet in a series of steps.

[0051] The casting method is preferable to methods such as the calendering method because it does not involve physical stress and makes it easier to obtain thin, uniformly thick sheet-like materials. However, conventionally, when vinyl chloride resin particles were added to paste vinyl chloride resin, there was a problem that streaks and uneven coating were likely to occur during coating. However, according to the manufacturing method of the present invention, which is carried out by further blending fiber powder with paste vinyl chloride resin and vinyl chloride resin particles, the coating process can be carried out without causing streaks or uneven coating in the casting method, thus reducing costs and enabling the production of thin, high-quality sheet-like materials.

[0052] As described above, the manufacturing method of the present invention reduces costs by blending vinyl chloride resin particles having an average particle size within a predetermined range with a paste vinyl chloride resin, thereby reducing the amount of paste vinyl chloride resin used. Furthermore, by blending fiber powder with a major axis within a predetermined range, it becomes possible to coat the material without causing streaks or uneven coating, resulting in the production of a high-quality sheet-like material. The sheet-like material produced by the manufacturing method of the present invention has good physical properties as described above. [Examples]

[0053] Examples of the present invention are shown below, but the present invention is not limited in any way to these examples. Tables 1 and 2 show the composition and amount of the paste-like sol component used in each example, comparative example, and reference example. The unit of the amount in Tables 1 and 2 is parts by mass. The materials used in each example and comparative example are as follows. Note that "recycled polyvinyl chloride resin" refers to polyvinyl chloride resin recycled by any means. (Paste vinyl chloride resin) • ZEST PQHPN, manufactured by Tokuyama Corporation (Plasticizer) • Phthalate ester plasticizer; PL-200, manufactured by CG Ester Co., Ltd. (Vinyl chloride resin particles 1) • General-purpose vinyl chloride resin obtained by suspension polymerization, average particle size 200 μm (Vinyl chloride resin particles 2) Recycled polyvinyl chloride resin, average particle size 100 μm (Vinyl chloride resin particles 3) Recycled polyvinyl chloride resin, average particle size 300 μm (Fiber powder) • Polyester fiber; major axis 100 μm, aspect ratio (major axis / minor axis); 5.0 (Composite material of vinyl chloride resin particles and fiber powder) • Mass ratio in 100% composite material: 80% by mass of vinyl chloride resin / 20% by mass of polyester fiber, average particle size of vinyl chloride resin particles 100 μm, major axis of fiber powder 100 μm, aspect ratio (major axis / minor axis): 5.0 (Foaming agent) • Azodicarbonamide (Filler) Calcium carbonate

[0054] <Manufacturing of composite materials of vinyl chloride resin particles and fiber powder> The following components were used in the manufacture of the composite material of polyvinyl chloride resin particles and fiber powder. (Composition for forming epidermal layer) • 100 parts by mass of polyvinyl chloride resin (ZEST PQHPN, manufactured by Tokuyama Corporation) • Plasticizer (phthalate ester plasticizer, PL-200, manufactured by CG Ester Co., Ltd.) 80 parts by mass (Composition for forming foamed layer) • 100 parts by mass of polyvinyl chloride resin (ZEST PQHPN, manufactured by Tokuyama Corporation) • Phthalate-based ester plasticizer (PL-200, manufactured by CG Ester Co., Ltd.) 65 parts by mass • Foaming agent (azodicarbonamide) 0.8 parts by mass • Filler (calcium carbonate) 10 parts by mass (Composition for forming adhesive layer) • 100 parts by mass of polyvinyl chloride resin (ZEST PQHPN, manufactured by Tokuyama Corporation) • Plasticizer (phthalate ester plasticizer, PL-200, manufactured by CG Ester Co., Ltd.) 20 parts by mass (base material) • Fiber base material (polyester knit), 0.4mm thick, 110g / m² weight. 2

[0055] The above-mentioned epidermal layer-forming composition was applied onto release paper so that the thickness after curing was 200 μm, and cured in an oven at 180°C for 1 minute to obtain an epidermal layer. Next, a foam layer-forming composition was applied to the exposed side surface of the obtained epidermal layer so that its thickness after curing and foaming would be 300 μm, and it was cured in a 200°C oven for 1 minute to obtain a foam layer. Furthermore, an adhesive layer-forming composition was applied to the foamed layer to a coating thickness of 150 μm, a fiber substrate was bonded to it, and then it was cured at 200°C for 1 minute. The release paper was then peeled off to obtain synthetic leather. The synthetic leather obtained by the above method was cut to a size of 5 mm using a cutter mill, and then finely ground using a stone mill type grinder (Super Mascolloider MKZA10-40JIV, manufactured by Masuko Sangyo Co., Ltd.). The rotation speed was set to 1500 rpm. The average particle size after fine grinding was measured using a Partica mini LA-350 manufactured by Horiba, Ltd., by dispersing 2 mg of the finely ground material in 2 mL of isopropyl alcohol, placing it in the measuring instrument, and performing ultrasonic treatment for 1 minute. The compositions and base materials used in the above manufacturing method are as follows. In this example, synthetic leather manufactured for testing was crushed to obtain the composite material, but recycled composite materials obtained by crushing used and recovered synthetic leather or scraps generated in the manufacturing process of synthetic leather can also be used as a composite material of vinyl chloride resin particles and fiber powder.

[0056] <Manufacturing of vinyl chloride resin particles 2 and 3> The vinyl chloride resin particles 2 and 3 were obtained by recovering scraps of the resin layer, which consists of a surface layer, a foam layer, and an adhesive layer, formed on the release paper before lamination of the fiber base material during the manufacturing process of the synthetic leather described above. After peeling off the release paper, the resin particles 2 and 3 were obtained by finely grinding them in the same manner as the synthetic leather grinding method described above.

[0057] <Manufacturing of sheet-like materials for Examples 1-4, Comparative Examples 1-4, and Reference Example 1> A paste-like sol component prepared with the composition and proportions shown in Table 1 was coated onto release paper to create a pre-sheet with a cured thickness of 200 μm. This pre-sheet was then heated in an oven at 180°C for 1 minute to cure and gel, yielding sheet-like materials such as Examples 1-4, Comparative Examples 1-4, and Reference Example 1.

[0058] <Manufacturing of foamed sheet-like materials in Examples 5-8, Comparative Examples 5-8, and Reference Example 2> A paste-like sol material prepared with the composition and proportions shown in Table 2 was applied to a release paper with a coating liquid to a coating thickness of 200 μm to create a pre-sheet. The pre-sheet was heated in an oven at 140°C for 90 seconds to harden and gel it, and then heated in an oven at 200°C for another 90 seconds to foam it, thereby obtaining a foamed sheet.

[0059] The coating properties and physical properties of each example, comparative example, and reference example obtained as described above were evaluated as follows. The evaluation results are shown in Tables 1 and 2.

[0060] <Evaluation of coating properties> The surface condition of each paste-like sol component was visually observed after being applied to release paper and evaluated according to the following criteria. ○...The surface of the pre-coated sheet is free of streaks and uneven coating. △...Slight streaks and unevenness in the coating can be observed on the surface of the pre-coated sheet. ×...The viscosity of the paste-like sol component is too high, making it impossible to coat the entire surface of the release paper.

[0061] <Physical property evaluation: Examples 1-4, Comparative Examples 1-4, Reference Example 1> The maximum breaking stress (MPa) of each sheet material obtained as Examples 1-4, Comparative Examples 1-4, and Reference Example 1 was measured in accordance with JIS K 6772:1994. For the measurement, five 3cm x 25cm measurement samples were prepared from one sheet material, and the maximum breaking stress (MPa) of each sample was measured. The obtained values ​​were then arithmetic mean. The ratio of the maximum breaking stress (MPa) of each example and comparative example to the maximum breaking stress (MPa) of Reference Example 1 was determined and evaluated as follows. ◎...The above percentage was 90% or higher. ○...The above percentage was between 80% and 90%. ×...The above percentage was 80% or less.

[0062] <Physical property evaluation: Examples 5-8, Comparative Examples 5-8, Reference Example 2> The maximum breaking stress (MPa) of each foamed sheet obtained as Examples 5-8, Comparative Examples 5-8, and Reference Example 2 was measured in accordance with JIS K 6772:1994. For the measurement, five 3cm x 25cm measurement samples were prepared from one sheet, and the maximum breaking stress (MPa) of each was measured. The obtained values ​​were then arithmetic mean. The ratio of the maximum breaking stress (MPa) of each example and comparative example to the maximum breaking stress (MPa) of Reference Example 2 was determined and evaluated as follows. ◎...The above percentage was 90% or higher. ○...The above percentage was between 80% and 90%. ×...The above percentage was 80% or less.

[0063] [Table 1]

[0064] [Table 2] [Explanation of Symbols]

[0065] 10. Vinyl chloride resin layer 20. Vinyl chloride resin particles 30... Fiber powder 40...Base material 100...Vinyl chloride resin sheet material 150...Vinyl chloride resin layer 200... Laminated sheet

[0066] The above embodiment encompasses the following technical concepts. (1) Having a vinyl chloride resin layer, The vinyl chloride resin layer contains vinyl chloride resin particles with an average particle diameter of 40 μm to 200 μm and fiber powder with a major axis of 40 μm to 200 μm. The ratio of the mass of the vinyl chloride resin particles to the mass of the fiber powder is 90:10 to 50:50. A vinyl chloride resin sheet-like material characterized in that, with respect to 100 parts by mass of vinyl chloride resin constituting the vinyl chloride resin layer, the total mass of the vinyl chloride resin particles and the fiber powder is 40 parts by mass or less. (2) The vinyl chloride resin sheet-like material described in (1) above, wherein the vinyl chloride resin layer is composed of a paste vinyl chloride resin. (3) A vinyl chloride resin sheet-like material as described in (1) above, comprising the first element and / or the second element described below. First element: The vinyl chloride resin particles are recycled material prepared from recovered materials. Second element: The vinyl chloride resin particles and the fiber powder are recycled materials prepared from recovered products comprising a base material containing fibers and a vinyl chloride resin layer laminated on the base material. (4) A vinyl chloride resin sheet-like material as described in any one of the above items (1) to (3), A laminated sheet comprising a base material for supporting the vinyl chloride resin sheet-like material. (5) A method for producing a vinyl chloride resin sheet-like material as described in any one of the above items (1) to (3): A sol member preparation step involves preparing a paste-like sol member by adding a plasticizer, a paste vinyl chloride resin, vinyl chloride resin particles with an average particle size of 40 μm to 200 μm, and fiber powder with a major axis of 40 μm to 200 μm. A coating step is performed to obtain a pre-sheet by coating the paste-like sol member obtained in the sol member preparation step onto a release paper or substrate, A method for manufacturing a vinyl chloride resin sheet-like material, comprising a gelling step of heating the presheet obtained by the coating step to gel the paste-like sol member constituting the presheet.

Claims

1. Having a vinyl chloride resin layer, The vinyl chloride resin layer contains vinyl chloride resin particles with an average particle diameter of 40 μm to 200 μm and fiber powder with a major axis of 40 μm to 200 μm. The ratio of the mass of the vinyl chloride resin particles to the mass of the fiber powder is 90:10 to 50:

50. A vinyl chloride resin sheet-like material characterized in that, with respect to 100 parts by mass of vinyl chloride resin constituting the vinyl chloride resin layer, the total mass of the vinyl chloride resin particles and the fiber powder is 40 parts by mass or less.

2. The vinyl chloride resin sheet-like material according to claim 1, wherein the vinyl chloride resin layer is composed of a paste vinyl chloride resin.

3. A vinyl chloride resin sheet-like material according to claim 1, comprising the following first element and / or the following second element. First element: The vinyl chloride resin particles are recycled material prepared from recovered materials. Second element: The vinyl chloride resin particles and the fiber powder are recycled materials prepared from recovered products comprising a base material containing fibers and a vinyl chloride resin layer laminated on the base material.

4. A vinyl chloride resin sheet-like material according to any one of claims 1 to 3 above, A laminated sheet comprising a base material for supporting the vinyl chloride resin sheet-like material.

5. A method for producing a vinyl chloride resin sheet-like material according to any one of claims 1 to 3, A sol member preparation step involves preparing a paste-like sol member by adding a plasticizer, a paste vinyl chloride resin, vinyl chloride resin particles with an average particle diameter of 40 μm or more and 200 μm or less, and fiber powder with a major axis of 40 μm or more and 200 μm or less. A coating step is performed to obtain a pre-sheet by coating the paste-like sol member obtained in the sol member preparation step onto a release paper or substrate, A method for manufacturing a vinyl chloride resin sheet-like material, comprising a gelling step of heating the presheet obtained by the coating step to gel the paste-like sol member constituting the presheet.

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