Flame-retardant polyolefin decorative material and advertising medium using the same

Abstract

To provide a flame-retardant polyolefin-based decorative base material which has excellent flame retardancy, is excellent in weather resistance, mechanical strength and flexibility, and assumes to be recycled, and an advertisement medium.SOLUTION: A flame-retardant polyolefin-based decorative base material is obtained by sticking a flame-retardant polyolefin-based resin film obtained by film-forming a flame-retardant polyolefin-based resin containing a polyolefin-based resin, a white pigment and a shielding additive, and a fiber structure base fabric obtained by stretching a polyolefin-based resin having a stretching ratio of 3-15 times.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a flame-retardant polyolefin decorative material and an advertising medium using the same. [Background technology]

[0002] Conventionally, fiber-reinforced products obtained by using a synthetic fiber knitted or woven fabric as a core material and forming a conventional polyvinyl chloride resin layer on the surface thereof, or reinforced sheets such as tarpaulins and canvases formed by coating or laminating a vinyl chloride resin composition layer onto a fiber woven fabric, have been used for applications in buildings and structures, such as tents, sheet warehouses, construction site protection sheets, and soundproofing sheets for construction sites. In these cases, the use period is relatively long and the products can be reused at the next construction site.

[0003] On the other hand, similar materials are also used for large-scale advertising media such as "large board advertisements," "banners," "hanging banners," and "building wall display advertisements" that target consumers and are used on the rooftops and walls of buildings in business districts, downtown areas, and in front of stations. However, tarpaulins and other materials used as advertising media cannot be reused in their original state because the advertising period is short and advertisements are printed all over the surface.

[0004] Furthermore, because tarpaulin is a composite material consisting of a core of synthetic fiber knitted or woven polyester fabric and a surface layer of polyvinyl chloride resin, separating these materials is difficult for recycling. Because polyvinyl chloride resin contains chlorine in its molecular structure, it generates hydrogen chloride gas, a corrosive gas, when burned, and, depending on the combustion conditions, may also generate toxic gases such as dioxins. As a result, when it comes to disposal, tarpaulin material, which is primarily made of polyvinyl chloride and contains a large amount of chlorine, can damage furnaces when incinerated and can generate harmful substances such as hydrogen chloride, so landfilling, which is considered to be a high environmental burden, is the mainstream method.

[0005] Furthermore, in order to realize a sustainable society, as exemplified by the SDGs, attention is being paid to materials that do not rely on landfill disposal as much as possible. In recent years, environmental issues such as microplastics have become a growing concern, and Japan generates approximately 10 million tons of plastic waste per year, of which approximately 740,000 tons are landfilled and approximately 1.5 million tons are exported overseas. However, in July 2017, the Chinese government announced the "Implementation Plan for Reform of the Solid Waste Import Management System," which began a ban on imports from China in 2018. While exports to Malaysia, Vietnam, Thailand, and other countries have increased in response to China's measures, ASEAN countries are also moving to ban imports.

[0006] Furthermore, conventional canvas and tarpaulin materials for construction are primarily made of polyvinyl chloride resin, which itself has a high degree of flame retardancy. Therefore, flame retardancy can be imparted by adding a small amount of flame retardant such as antimony trioxide (5 to 20 parts by weight), making it possible to comply with the flame retardant standards set forth in the Fire Service Act (Article 4 of the Fire Service Act Enforcement Regulations: JIS Standard L-1091).

[0007] On the other hand, polyolefin resins such as polyethylene (PE) and polypropylene (PP), which do not contain halogens such as chlorine, are the most widely produced and are a type of general-purpose resin used in various fields in daily life. They are easy to recycle and have a well-established market as social infrastructure. However, when the constituent resins of these canvases and tarpaulins are replaced with polyolefin resins, the polyolefin resins themselves are flammable, making it essential to incorporate flame retardants to impart flame resistance to these resins. While technology has been proposed that uses flame retardants in combination with antioxidants (see Patent Document 1), it has sometimes been difficult to achieve sufficient flame retardancy depending on the type of antioxidant used. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Patent No. 5503071 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, the present invention was made in order to reduce the amount of halogen-based flame retardants added while still assuming the use of such additives, and aims to provide a flame-retardant polyolefin decorative material and advertising media using the same, which have excellent flame retardancy, weather resistance, mechanical strength, and flexibility, and which can be recycled without relying on incineration or landfill disposal when disposed of. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention This flame-retardant polyolefin decorative material is characterized by being a laminate consisting of at least three layers, including a flame-retardant polyolefin resin film formed from a flame-retardant polyolefin resin containing at least a polyolefin resin, a shielding additive which is a white pigment, and a flame retardant, and a fiber structure base fabric composed of fibers stretched from a polyolefin resin at a stretch ratio within a range of 2 to 15 times bonded to the front and back of the flame-retardant polyolefin resin film. This flame-retardant polyolefin decorative material is formulated with 100 parts by weight of polyolefin resin, 50 to 200 parts by weight of a metal hydrate as a flame retardant, and 20 to 80 parts by weight of a bromine-based flame retardant, with the total amount of polyolefin resin being 50 wt% or less.

[0011] The flame-retardant polyolefin decorative material is a laminate consisting of at least three layers, which is formed by bonding a fiber structure base fabric made of fibers stretched from polyolefin resin at a stretch ratio within a range of 2 to 15 times to the front and back of the fiber structure base fabric with flame-retardant polyolefin resin films formed from flame-retardant polyolefin resin containing at least polyolefin resin, a shielding additive which is a white pigment, and a flame retardant, and which is characterized in that the front and back surfaces are made of the flame-retardant polyolefin resin films. This flame-retardant polyolefin decorative material is formulated with 100 parts by weight of polyolefin resin, 50 to 200 parts by weight of a metal hydrate as a flame retardant, and 20 to 80 parts by weight of a bromine-based flame retardant, with the total amount of polyolefin resin being 50 wt% or less.

[0012] The flame-retardant polyolefin resin film is For 100 parts by weight of the polyolefin resin, the shielding additive 0.5 to 10 parts by weight It may also be a blend.

[0014] In addition, in the flame-retardant polyolefin resin film, 10 to 50 parts by weight of antimony trioxide is further added as the flame retardant to 100 parts by weight of the polyolefin resin. May be blended.

[0016] The flame-retardant polyolefin resin film has a melt flow rate (MFR) of 0.5 to 50.0 g / 10 min. may have

[0017] In addition, the fiber structure base fabric may have a shape selected from the group consisting of filament yarn, multifilament yarn, monofilament yarn, tape yarn, split yarn, and split yarn. May be chosen.

[0018] In addition, a printing image receiving layer is applied to the surface of the flame-retardant polyolefin decorative material. It may be provided.

[0019] Also, Claims 1 to 7 1. An advertising medium characterized by being formed by printing on the flame-retardant polyolefin decorative material described in 1.

[0020] The device is also characterized by having a resin eyelet on the outer periphery. Claim 8 It is an advertising medium described in. [Effects of the Invention]

[0021] According to the present invention, when the flame-retardant polyolefin resin film and the fiber structure base fabric melt during a combustion test, the residual stress in the stretched fiber structure base fabric is released, causing it to shrink thermally and move away from the fire source. At the same time, the physical action caused by the thermal shrinkage makes the remaining flame in the molten area more likely to fall off, thereby promoting the self-extinguishing function.

[0022] As a result, the polyolefin decorative material has excellent flame retardancy, weather resistance, mechanical strength, and flexibility.Furthermore, it is possible to provide a flame-retardant polyolefin decorative material and an advertising medium using the same, which are designed for recycling without relying on incineration or landfill disposal when disposed of. [Brief explanation of the drawings]

[0023] [Figure 1] 1 is a cross-sectional view showing the layer structure of a flame-retardant polyolefin decorative material according to the present invention. [Figure 2] FIG. 3 is a cross-sectional view showing another layer structure of the flame-retardant polyolefin decorative material according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments of the present invention will be described with reference to the drawings. Each of the embodiments shown below exemplifies a configuration for embodying the technical idea of ​​the present invention, and the technical idea of ​​the present invention is not limited to the materials, shapes, structures, etc. of the components described below. The technical idea of ​​the present invention can be variously modified within the technical scope defined by the claims.

[0025] Fig. 1 is a cross-sectional view showing the layer structure of a flame-retardant polyolefin decorative material according to the present invention. As shown in Fig. 1, the flame-retardant polyolefin decorative material according to the present invention is a laminate comprising a flame-retardant polyolefin resin film 10 and a fiber structure base fabric 20 bonded to both sides of the film.

[0026] The flame-retardant polyolefin resin film is a film formed from a flame-retardant polyolefin resin containing a polyolefin resin, a white pigment, a shielding additive, and a flame retardant, and the fiber structure base fabric 2 is composed of fibers stretched from a polyolefin resin at a stretch ratio within the range of 3 to 15 times.

[0027] <Flame-retardant polyolefin resin film> Examples of polyolefin resins used in flame-retardant polyolefin resin films include ethylene-α-olefin copolymers, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, ethylene-methacrylic acid copolymers, ethylene-methacrylic acid ester copolymers, ethylene-methyl methacrylic acid copolymers, ethylene-methyl methacrylic acid ester copolymers, ethylene-ethyl acrylic acid copolymers, ethylene-ethyl acrylic acid ester copolymers, and mixtures of two or more of these. The polyolefin resin used in the present invention can be produced by radical polymerization or ionic polymerization.

[0028] The polyethylene resin obtained by radical polymerization includes a polymer of ethylene alone and a copolymer obtained by copolymerizing ethylene with a monomer capable of radical polymerization with ethylene.

[0029] Flame retardants used in flame-retardant polyolefin resin films preferably include metal hydrates, bromine-based compounds, and inorganic compounds. Metal hydrates include aluminum hydroxide and magnesium hydroxide, which rapidly lower the combustion temperature by generating endothermic heat during dehydration during combustion, and are effective in suppressing the generation of flammable gases due to the thermal decomposition of plastics.

[0030] Brominated flame retardants include non-drip flame retardants that act directly on the combustion mechanism, such as by trapping OH radicals in the gas phase, by generating flame-retardant inert gases to block oxygen, and by diluting oxygen, and drip flame retardants that physically remove the burning part by reducing the viscosity of the plastic during combustion and causing the spark to fall.The preferred amounts of these additives are 50 to 200 parts by weight of metal hydrate and 20 to 80 parts by weight of brominated flame retardant per 100 parts by weight of polyolefin resin.

[0031] Inorganic flame retardants include antimony oxide compounds such as antimony trioxide and antimony pentoxide. Antimony trioxide is preferably added as a flame retardant, preferably in an amount of 10 to 50 parts by weight per 100 parts by weight of the polyolefin resin. When used in combination with a bromine-based flame retardant, a heavy flame-retardant gas containing antimony is generated, synergistically enhancing the oxygen blocking and oxygen dilution effects. Inorganic flame retardants such as zinc borate and zinc stannate also suppress smoke generation and reduce afterglow by promoting the formation of graphite-like char during combustion, and the formation of a gas barrier layer enhances the flame retardant effect.

[0032] Furthermore, adding excessive amounts of the above flame retardants to impart sufficient flame retardancy can reduce the processability of polyolefin resin compositions and significantly decrease the mechanical strength of processed products. In such cases, adding a small amount of modified polyolefin resin grafted with maleic anhydride is a good solution. The addition of maleic anhydride reduces the polarity of the polyolefin resin and significantly improves adhesion. Therefore, when inorganic fillers such as metal hydrate flame retardants are highly loaded, the interfacial adhesion between the filler and the resin improves, improving dispersibility and reducing voids in the resin, resulting in improved rigidity and strength of processed products. Furthermore, improving the dispersibility of metal hydrate flame retardants improves the efficiency of the endothermic reaction during combustion, thereby enhancing the flame retardant effect.

[0033] Furthermore, because the flame-retardant polyolefin-based decorative material of the present invention is intended for outdoor use, deterioration of the resin due to ultraviolet rays and color changes such as yellowing are important factors to control. Therefore, it is preferable to add a white pigment / shielding additive, preferably in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the polyolefin-based resin. Examples of white pigment / shielding additives include titanium oxide, zinc borate, and zinc oxide. Furthermore, there are two types of titanium oxide for industrial use: rutile and anatase. For the additive of the present invention, the rutile type, which has a high refractive index, is preferred.

[0034] The primary factor in the optical properties of inorganic pigments is the refractive index; the higher the refractive index, the greater the surface reflection, which improves light scattering in the resin and tends to increase hiding power. This can reduce the yellowing of resin due to ultraviolet rays. Rutile (Rutile): Refractive index 2.72. Anatase (Anatase): Refractive index 2.52.

[0035] Titanium dioxide also has the unique feature of absorbing light at wavelengths shorter than 400 nm while not absorbing visible light. This allows it to have similar effects to light stabilizers and UV absorbers, allowing for reduced amounts of these additives to be used. Titanium dioxide also has photocatalytic properties, exerting a powerful oxidizing power on its surface when exposed to light. This property is used industrially to decompose persistent substances. However, its oxidizing power in and on the surface of resins can lead to quality degradation, such as resin degradation and peeling of printed surfaces. Therefore, it is recommended to use titanium dioxide in a surface-treated form to suppress its oxidizing power. Surface treatment agents and dispersants include silica, aluminum hydroxide, dimethicone, cyclopentasiloxane, triethoxycaprylylsilane, hydrogen dimethicone, isostearic acid, stearic acid, alumina, and sodium polyacrylate.

[0036] In addition, it is desirable to add a light-blocking agent such as a UV absorber. UV absorbers include benzotriazoles and benzophenones, which absorb UV light in the 320-350 nm range, the wavelength range in which plastics are most susceptible. Furthermore, using them in combination with HALS can provide even greater light stability. Representative examples include BASF's Tinuvin series and Uvinul series, and ADEKA's LA series.

[0037] When compounding the flame-retardant polyolefin resin described above, additives for improving processing stability, weather resistance, strength, etc. may be added.

[0038] Examples of additives that can improve processability include lubricants, antioxidants, light stabilizers, UV absorbers, and antistatic agents. In particular, a significant amount of metal hydrate flame retardant is added to improve flame retardancy, which can easily generate shear heat during compounding and film-forming. Therefore, the addition of a lubricant is necessary. Adding a lubricant can reduce friction between the synthetic resin and the processing machine, as well as between the synthetic resin particles themselves. Lubricants that are used include hydrocarbons, fatty acids, aliphatic alcohols, aliphatic amides, and metal soaps. It is usually desirable to use multiple lubricants in combination, taking into account the balance between external and internal lubrication.

[0039] In addition, adding an antioxidant is recommended to prevent resin degradation due to shear heat and for outdoor use. Antioxidants are divided into primary antioxidants, which act as radical scavengers, and secondary antioxidants, which act as peroxide decomposers. Phenolic antioxidants are commonly used to scavenge radicals, stabilizing ROO· (alkoxy radicals) generated from radicals generated by ultraviolet light or thermal energy and oxygen. There are three types of chemical structures: hindered, semi-hindered, and less hindered, which differ in the number of radicals scavenged and the reaction rate. Olefin-based resins are generally relatively stable, so oxidation reactions proceed slowly. Therefore, slow-acting hindered antioxidants are effective. Representative antioxidants include the Irganox series from BASF and the AO series from ADEKA.

[0040] Furthermore, plastic peroxides (ROOH radicals) are generated as a reaction product of radical scavenging by phenolic antioxidants, and if left unattended, they will further decompose into radicals and deteriorate. To prevent this, sulfur- or phosphorus-based antioxidants, which have the peroxide decomposition ability to break down ROOH into stable substances, are used. However, sulfur-based antioxidants emit an odor at high temperatures and are difficult to color, making them unsuitable for creating white sheets; therefore, it is preferable to use phosphorus-based antioxidants. Representative phosphorus-based antioxidants include BASF's Irgafos 168 and ADEKA's PEP series and 2112.

[0041] Additionally, to improve weather resistance, it is desirable to add a light stabilizer (HALS), which captures radicals generated by ultraviolet light, preventing discoloration and maintaining gloss. However, when coexisting with brominated flame retardants, trace amounts of acidic substances are generated in the resin, and because regular HALS are alkaline, a neutralization reaction occurs in the resin, resulting in an antagonistic effect. For this reason, it is desirable to use NOR-type HALS, which is less likely to form salts with acidic substances. Typical examples include BASF's Tinuvin series and ADEKA's LA series.

[0042] In addition, it is preferable that the total amount of the polyolefin resin is 50 wt% (weight %) or less, and the melt flow rate (MFR) of the flame-retardant polyolefin resin is 0.5 to 50.0 g / 10 min in the flame-retardant polyolefin resin film 10. If the MFR is less than 0.5 g / 10 min, molding processing may become extremely difficult, and if it is more than 50.0 g / 10 min, the mechanical strength becomes insufficient.

[0043] Flame-retardant polyolefin resin films can be molded using T-die extrusion film production, calendar film production, inflation film production, and more. When manufacturing thin films of around 50 to 150 μm, T-die film production is suitable, as it allows for a wide range of adjustments in terms of extrusion volume, lip width, and take-up speed. On the other hand, when manufacturing films or sheets with thicknesses exceeding 150 μm, calendar film production is suitable, as it is easy to increase the extrusion volume and has high productivity.

[0044] <Fiber structure base fabric> The fiber structure base fabric 20 is preferably a nonwoven fabric or woven fabric made of polyolefin resin flat yarn, the shape of which is selected from filament yarn, multifilament yarn, monofilament yarn, tape yarn, split yarn, and split yarn.

[0045] The method for forming polyolefin multifilament yarn involves melt-kneading polyolefin resin in an extruder, extrusion molding it into a long, thin rod, and then heat-treating it while stretching it at 2 to 3 times the normal speed to homogenize the molecular orientation of the polyolefin resin and increase its strength, before turning it into fiber.

[0046] Considering strength, flexibility, and texture of the finished product, the yarn used in the reinforcing material of the present invention is generally preferably in the range of 80 to 200 denier. Furthermore, polyolefin resins have a lower melting point than polyester resins, which are typical chemical fibers, and are therefore more susceptible to breakage during fiber processing and subsequent weaving and knitting due to the effects of frictional heat. Therefore, it is desirable to set the filament count of the filament yarn to a low level. Furthermore, when using thin yarns, care must be taken to avoid problems such as fiber breakage during the subsequent fabric manufacturing process.

[0047] The method for forming the polyolefin flat yarn involves melt-kneading a polyolefin resin in an extruder, forming the film using an inflation method or a T-die method, slitting the film to a width of approximately 10 to 20 mm, stretching the film, and then heat-treating the film to form a flat yarn. The stretching is performed at a temperature below the melting point and above the softening point of the polyolefin. Any heating method, such as a hot roll method, a hot plate method, an infrared method, or a hot air method, can be used. The slit polyolefin film is heated and stretched by the difference in peripheral speed between the front and rear rolls. The stretching ratio is preferably 3 to 15 times, more preferably 5 to 10 times. If the stretching ratio is less than 3 times, the mechanical strength may be insufficient. On the other hand, if the stretching ratio exceeds 15 times, it may be difficult to stretch the film using conventional methods, and expensive equipment may be required. Multi-stage stretching is preferred to prevent uneven stretching.

[0048] The polyolefin flat yarn thus obtained is used as warp and weft yarns to form a woven or knitted fabric. The weave of the woven or knitted fabric is not particularly limited, and examples of woven fabrics include plain weave, twill weave, twill weave, ramie weave, and leno weave, while examples of knitted fabrics include raschel knit, tricot knit, and Milanese knit. The weft and warp yarn density is usually in the range of 5 to 40 threads / 2.54 cm, preferably 10 to 30 threads / 2.54 cm.

[0049] An example of a commercially available woven fabric is Tarpee Cloth (product name) manufactured by Hagiwara Kogyo Co., Ltd. In addition to woven and knitted fabrics, two sheets of the obtained polyolefin flat yarn are overlapped with the main fibers intersecting approximately perpendicularly to each other and then heated and welded together. A mesh nonwoven fabric may also be used. Representative commercially available examples of such mesh nonwoven fabrics include Warif (registered trademark) and CLAF (registered trademark) manufactured by JX ANCI, and Sof (product name) manufactured by Sekisui Film Co., Ltd. When such a fiber structure base fabric catches fire, the higher the draw ratio, the more volumetric shrinkage occurs, moving it away from the flame, resulting in improved flame retardancy.

[0050] The flame-retardant polyolefin resin film 10 and the fiber structure base fabric 20 are laminated by laminating the film on both sides of the base fabric. The lamination method may involve providing an adhesive layer between the film and the base fabric, or lamination and fusion without adhesive. In an embodiment of the present invention, a flame-retardant polyolefin resin film molded by a calendaring method and a fiber structure base fabric are laminated via an adhesive 3.

[0051] Before lamination, the flame-retardant polyolefin resin film 10 may be subjected to corona discharge treatment, chromic acid oxidation treatment (wet), flame treatment, hot air treatment, ozone plasma irradiation treatment, adhesion-enhancing treatment, or the like on the surface facing the print image-receiving layer 30. By applying these treatments, the surface of the flame-retardant polyolefin resin film 10 facing the print image-receiving layer 30 improves the wettability of the coating agent containing a metal material used in forming the print image-receiving layer 30, thereby improving the adhesion of the print image-receiving layer 30 to the flame-retardant polyolefin resin film 10. These surface treatment methods are appropriately selected depending on the type of flame-retardant polyolefin resin film 10, but corona discharge treatment and ozone plasma irradiation treatment are preferred in terms of the adhesion effect with the print image-receiving layer 30 and the operability of the processing equipment.

[0052] Furthermore, the adhesion of the print image-receiving layer 30 to the flame-retardant polyolefin resin film 10 may be improved by forming an anchor layer or a primer layer on the surface of the flame-retardant polyolefin resin film 10 facing the print image-receiving layer 30. There are various types of anchor agents and primer agents. For aqueous materials such as alcohol-based materials with high surface tension, it is desirable to increase the surface tension to about 70 dynes. For solvent-based materials or materials with low surface tension such as urethane, adequate coating may be possible even with a surface tension of about 50 dynes.

[0053] <Printing image-receiving layer> The print image-receiving layer 30 is a layer provided to improve printability and weather resistance of the print, and is provided by dissolving an acrylic or urethane resin in a solvent, applying it to a fiber structure base fabric and drying it, or by forming the resin into a film and adhering it. In addition, when the flame-retardant polyolefin decorative material and the advertising medium using it are used for an extremely short period of time, printing can be done directly with a UV inkjet printer without applying the print image-receiving layer 30 .

[0054] <Manufacturing advertising media> 1) Printing process When the flame-retardant polyolefin resin sheet obtained by the above method is used as an advertising medium, it is necessary to print a pattern on it. The most common method for printing images is by inkjet printers. There are several printing methods for inkjet printers, but they are not particularly limited. Typical inkjet printer methods include:

[0055] a) Latex inkjet printer: This is a printer that uses so-called "water-based pigment" ink, in which the pigment is dissolved in water. Latex ink contains four main components: water, latex (polymer), pigment (color component), and scratch-resistant material. It is characterized by having less odor than solvent-based volatile organic compounds (VOCs), and is often used for display purposes in hospitals, educational facilities, and stores.

[0056] b) Solvent inkjet printer: Solvent-based ink contains pigment in a dilute organic solvent. When the ink lands on the surface to be printed, the solvent components first attack the surface of the media. In other words, it dissolves the surface of the media, allowing the ink to penetrate a little into the media. After that, the solvent evaporates, allowing the pigment to adhere to the media and exhibit high weather resistance. Because it uses a solvent, a solvent smell remains after printing, making it unsuitable for indoor displays.

[0057] c) UV inkjet printer: When UV ink is exposed to UV light (ultraviolet) from the equipment, the monomer components contained in the ink polymerize and solidify, allowing the ink to set. While solvent ink erodes the surface of the media, UV printing forms an image in a state where the ink is solidified on the printing object. Because the ink solidifies the moment it is exposed to UV light, post-processing such as cutting and sewing can be done immediately after printing.

[0058] 2) Sewing and eyelet processing When manufacturing advertising media such as banners and hanging banners, it is necessary to fold back and sew the edges and then add grommets around the periphery to attach strings when displaying. Typically, sewing thread made from polyester resin is used, and the grommets are often made from metal materials such as aluminum or brass. However, these sewing threads and grommets must be removed during the recycling process after use, which is inefficient.

[0059] Therefore, it is desirable to use polyolefin resin for each component so that the sewing and eyelet processing processes can be carried out together in the recycling process. Representative examples of sewing threads include Toyobo's Izanas (registered trademark), Asahi Kuma's Pylen thread, Mitsubishi Chemical's Pylen (registered trademark), etc. Regardless of the above, any thread made of olefin resin is acceptable.

[0060] The eyelets are manufactured by injecting olefin resin into a mold. Conventional metal and polycarbonate eyelets are fastened by crimping like rivets, but olefin resin eyelets cannot be fastened by crimping due to the properties of the resin. Therefore, male-female mating resin eyelets are inserted into multiple holes on the periphery of the flame-retardant polyolefin decorative material.

[0061] Figure 2 shows the layer structure of another flame-retardant polyolefin decorative material. It comprises a fiber structure base fabric 50, flame-retardant polyolefin resin films 60 on both sides of the fiber structure base fabric 50, and a print image-receiving layer 70 on at least one side of the flame-retardant polyolefin resin film 60. The method for bonding the fiber structure base fabric 50 and the flame-retardant polyolefin resin film 60 is as described above. Even with this layer structure, a flame-retardant polyolefin decorative material that can be printed on both sides can be produced.

[0062] In the case of such a layer structure, in order to ensure the flexibility of the resulting structure, the thickness of the flame-retardant polyolefin resin film 60 must be thin, and it is desirable that it be configured to a thickness of 100 microns or less.

[0063] The molding process can be performed by extrusion molding using a T-die, lamination, or film formation using inflation molding. The lamination process is not limited to this method, although it is desirable from the viewpoint of manufacturing costs to use thermal lamination, which utilizes the heat generated during molding and is performed simultaneously with the molding process. Other methods include lamination using a heated roll in the next step, or spraying hot melt adhesive onto the film.

[0064] The subsequent formation of the print image receiving layer 70 and the manufacturing of the advertising medium are as described above. [Example]

[0065] The present invention will now be described in more detail with reference to examples.

[0066] Example 1 A compound with a melt flow rate (MFR) of 0.5-50.0 g / 10 min was prepared by blending 100-200 parts by weight of a metal hydrate as a flame retardant, 20-80 parts by weight of a bromine-based flame retardant, and 10-50 parts by weight of titanium oxide and antimony trioxide as white pigments and shielding additives per 100 parts by weight of polyolefin resin. The compound was then calendered at a temperature of 150-200°C using an inverted L-type four-roll calender to form a 230 μm thick flame-retardant polyolefin resin film. The resulting film was then coated with 2-30 g / m2 of hot-melt spray paint. 2 After applying an olefin hot melt adhesive in a weight of 100 denier, a plain weave base fabric of 100 denier multifilament yarn was attached to the front and back as a fiber structure base fabric to create a flame-retardant polyolefin decorative material. Note that, since the flame-retardant polyolefin decorative material of this example has a structure in which a flame-retardant polyolefin resin film is sandwiched between the fiber structure base fabric, wrinkles that occur in the flame-retardant polyolefin resin film are difficult to see from the outside.

[0067] <Example 2> The fiber structure base fabric is a mesh nonwoven fabric (CLAF, manufactured by JX Nippon Oil & Energy), and is applied at 2 to 30 g / m using a hot melt spray method. 2After applying an olefin-based hot melt adhesive in a weight of 100 parts by weight of polyolefin-based resin, a compound with a melt flow rate (MFR) of 0.5 to 50.0 g / 10 min was used, which was a mixture of 100 to 200 parts by weight of metal hydrate as a flame retardant, 20 to 80 parts by weight of bromine-based flame retardant, and 10 to 50 parts by weight of titanium oxide and antimony trioxide as white pigment and shielding additives. A 230 μm thick flame-retardant polyolefin-based resin film was then laminated on the mixture using an inverted L-type four-roll calendar at a temperature of 150 to 200°C to create a flame-retardant polyolefin-based decorative material.

[0068] The flame-retardant polyolefin decorative materials of Examples 1 and 2 were subjected to strength tests and flame retardancy tests.

[0069] <Strength test> Test 1) Tensile strength JIS P8113 3.1 Paper and paperboard -- Test methods for tensile properties -- Part 2: Constant rate of extension method -- Tensile strength applies Test piece width: 15 mm (test results converted to 1 m width) Grip spacing: 100 mm Test speed: 20 mm / min Equipment used: Shimadzu Autograph AG-X 10kN (load cell 1kN) Test 2) Tear strength JIS P8116 3.1 Paper - Tear strength test method Elmendorf type tear tester method Number of layers: 4 (test results converted to values ​​per layer) Equipment used: Yasuda Seiki Elmendorf type tear tester Test 3) Burst test JIS L 1096 Bursting Strength: The fabric is burst using a bursting tester to check the strength of the fabric. Equipment used: Burst testing machine manufactured by Yasuda Seiki Seisakusho.

[0070] Table 1 shows the test results.

[0071] [Table 1]

[0072] The reference example shown in Table 1 is the sheet itself molded from the compound described above, and Examples 1 and 2 are three sheets obtained by bonding together a reticular nonwoven fabric (CLAF, manufactured by JX Nippon Oil & Energy) as a fiber structure base fabric layer.

[0073] The results in Table 1 confirm that the strength is significantly improved by attaching the fiber structure base fabric layer.

[0074] <Flame retardancy test> Details of the flame retardancy test are as follows: Indoor and outdoor banners, hanging banners, and other decorative items are subject to flame retardancy regulations under the Fire Service Act, and must comply with the test methods outlined in Article 4-3, Paragraphs 3 to 7 of the Fire Service Act Enforcement Regulations. The test standard is JIS L 1091, Flammability Test Method for Textile Products, and the test method differs depending on the basis weight of the test object.

[0075] The flame-retardant polyolefin decorative material manufactured this time is 450g / m 2 Since the value exceeded this, testing was conducted using the A-2 method (45° microburner method) and the evaluation criteria for Category 3 were used. Table 2 shows the test criteria for Category 3 of the JIS L 1091A-1 method, and Table 3 shows the test results.

[0076] [Table 2]

[0077] [Table 3]

[0078] [Table 4]

[0079] The results in Tables 3 and 4 show that all flame-retardant polyolefin decorative materials achieved good results, meeting the criteria of JIS L 1091A-1, Category 3.

[0080] <Recycling test> Next, a recycling test was conducted to see if plastic flower pots could be made using samples of advertising media printed with the above flame-retardant polyolefin decorative material using a UV inkjet printer. The outline of the recycling test is as follows:

[0081] Purpose of the test: The advertising media samples were re-pelletized and their basic properties were measured. Also, it was confirmed whether they could be molded into flower pots and used. Test procedure: Crushing → Re-pelletization → Injection molding → Flowerpot creation Blend ratio: 100% recycled pellets

[0082] [Table 5]

[0083] As a result, it was confirmed that flowerpots with no problems in strength could be manufactured using the advertising medium samples after printing, even when re-pelletized. It was also confirmed that the flame-retardant polyolefin resin film of the flame-retardant polyolefin decorative material according to the present invention can be used.

[0084] Therefore, the flame-retardant polyolefin decorative material of the present invention has excellent flame retardancy, weather resistance, mechanical strength, and flexibility.Furthermore, when it is discarded after use as an advertising medium, it can be recycled without relying on incineration or landfill disposal. [Explanation of symbols]

[0085] 10: Flame-retardant polyolefin resin film 20: Fiber structure base fabric 30: Printing image receiving layer 50: Fiber structure base fabric 60: Flame-retardant polyolefin resin film 70: Printing image receiving layer

Claims

1. The laminate is composed of at least three layers, and includes a flame-retardant polyolefin resin film formed from a flame-retardant polyolefin resin containing at least a polyolefin resin, a shielding additive which is a white pigment, and a flame retardant, and a fiber structure base fabric made of fibers obtained by stretching a polyolefin resin at a stretch ratio within a range of 2 to 15 times bonded to the front and back of the flame-retardant polyolefin resin film, 50 to 200 parts by weight of a metal hydrate and 20 to 80 parts by weight of a bromine-based flame retardant are blended with 100 parts by weight of the polyolefin-based resin, The total amount of the polyolefin resin is 50 wt % or less A flame-retardant polyolefin decorative material characterized by:

2. A laminate consisting of at least three layers, comprising a fiber structure base fabric made of fibers obtained by stretching a polyolefin resin at a stretch ratio within a range of 2 to 15 times, and flame-retardant polyolefin resin films formed by forming films of a flame-retardant polyolefin resin containing at least a polyolefin resin, a shielding additive which is a white pigment, and a flame retardant on the front and back sides of the fiber structure base fabric, the front and back sides being made of the flame-retardant polyolefin resin films, 50 to 200 parts by weight of a metal hydrate and 20 to 80 parts by weight of a bromine-based flame retardant are blended with 100 parts by weight of the polyolefin-based resin, The total amount of the polyolefin resin is 50 wt % or less A flame-retardant polyolefin decorative material characterized by:

3. The flame-retardant polyolefin-based decorative material according to claim 1 or 2, characterized in that the flame-retardant polyolefin-based resin film contains 0.5 to 10 parts by weight of the shielding additive per 100 parts by weight of the polyolefin-based resin.

4. The flame-retardant polyolefin-based decorative material according to any one of claims 1 to 3, characterized in that the flame-retardant polyolefin-based resin film further contains 10 to 50 parts by weight of antimony trioxide as the flame retardant per 100 parts by weight of the polyolefin-based resin.

5. The flame-retardant polyolefin decorative material according to any one of claims 1 to 4, characterized in that the flame-retardant polyolefin resin film has a melt flow rate (MFR) of 0.5 to 50.0 g / 10 min.

6. 6. The flame-retardant polyolefin decorative material according to claim 1, wherein the fiber structure base fabric has a shape selected from the group consisting of filament yarn, multifilament yarn, monofilament yarn, tape yarn, split yarn, and split yarn.

7. 7. The flame-retardant polyolefin decorative material according to claim 1, wherein a print image-receiving layer is provided on the surface of the flame-retardant polyolefin decorative material.

8. An advertising medium characterized by being printed on a flame-retardant polyolefin-based decorative material described in any one of claims 1 to 7.

9. 9. The advertising medium according to claim 8, wherein a resin eyelet is provided on the outer periphery.

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